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 ECerS2017
15th Conference & Exhibition
of the European Ceramic Society
July 9–13, 2017, Budapest, Hungary

BOOK OF ABSTRACTS
 ECerS2017
July 9–13, 2017, Budapest, Hungary

Book of Abstracts

AKCongress
P.O. Box 245, H-1519 Budapest, Hungary
Phone: +36 1 464 8220
E-mail: [email protected]

Please be aware that certain changes introduced in the Conference programme

after editing has been closed may not be included in this Book of Abstracts
due to the publishing deadline.

© Akadémiai Kiadó, Budapest, 2017

P.O. Box 245, H-1519 Budapest, Hungary
Phone: +36 1 464 8240
E-mail: [email protected]
www.akademiai.com / www.akademiaikiado.hu

ISBN 978-963-454-094-6
CONTENTS
Plenary lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

T01: New developments in processing and synthesis with a special focus

on additive manufacturing
Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Poster presentations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

T02: High temperature processes and advanced sintering

Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Poster presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

T03: Advanced structural ceramics

Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
Poster presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212

T04: Electroceramics and optical materials

Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
Poster presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361

T05: Ceramics for novel energy conversion, storage and use

Invited lectures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 418
Poster presentations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 469

T06: Ceramics and glasses for healthcare

Invited lectures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
Poster presentations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538

T07: Challenges and opportunities in industrial ceramics

Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 572
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
Poster presentations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591

T08: The ceramics genome: modelling, simulation and in-situ experimentation

Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 614
Poster presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 620
T09: Boron-based ceramics
Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 630
Poster presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 649

T10: Cultural heritage

Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 652
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 655
Poster presentations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661

T11: Refractories
Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
Poster presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675

T12: Art and ceramics

Invited lectures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
Oral presentations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693
Poster presentations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 697

Student speech contest. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 700

Plenary lectures
Silicon nitride – a promising candidate for the bioactive composite
implants
Miroslav Hnatko1, Pavol Šajgalík1, Martina Labudová2
1
Institute of Inorganic Chemistry, SAS, Bratislava, Slovakia;
e-mails: [email protected], [email protected]
2
Biomedical Centre, Institute of Virology, SAS, Bratislava, Slovakia; e-mail: [email protected]
Keywords: biomaterial, bioinert, bioactive, silicon nitride

Silicon nitride-based ceramics are characterized especially by high chemical resistance, su-
perior combination of fracture toughness, hardness, and thermal shock and wear resistance.
Recently also silicon nitride attracts interest for bio-applications in the human body as bio
inert material. Silicon nitride based biomaterials have a potential to be used as total hip-
joint replacements, mini-osteofixation systems, multiwall drug-release devices, interverte-
bral spacers and spinal surgery or implantations in otorhinolaryngology and traumatology.
However, the biological applications often require additional properties, e.g. bioactivity en-
abling stronger bonding to the host tissue and moreover ceramic bio-implants are of different
size, shape or form with foreseen mechanical, physical or chemical properties. In this work
porous or dense silicon nitride based substrate in the form of bulk or granules/microspheres
were prepared and subsequently covered by the hydroxyapatite/calcium phosphate phase
thin layer in order to change the substrate from bio-inert to bio-active. Four different silicon
nitride based bio-active materials will be presented with the aim to show a potential of silicon
nitride in bio applications:
1. Porous silicon nitride with bone-like pore structure prepared by replica method and
2. porous spheres of size about one millimeter (or more) on average prepared by water
silicon nitride suspension by freeze drying. Silicon nitride–hydroxyapatite composites
were prepared by infiltration of hydroxyapatite precursor sol into the silicon nitride based
porous ceramics (porosity up 80%). Cytotoxicity and in vitro bioactivity of Si3N4–HA
composites were tested in order to verify the effect of hydroxyapatite addition on the
biological properties of composite. After immersion of porous composite into simulated
body fluid (SBF) for 21 days, calcium phosphate (CP) layer was formed on the surface of
silicon nitride–hydroxyapatite composites, indicating their bioactivity.
3. Surface modification of dense silicon nitride body using an oxyacetylene torch at high
temperatures and the formation of a thin (2–5 µm) and porous bioactive layer based on
the grain boundary composition with chemical adhesion to substrate.
4. Porous silicon nitride microspheres of size about 10–100 µm prepared by flame synthesis.
The formation of thin layer utilizing of high temperature oxidation of dense silicon nitride
with different grain boundary phase (SiO2 or Ca3(PO4)2) by oxyacetylene torch was studied.
After short dwell time (30–60 sec.) at high temperature (aprox. 1480–1500 °C) two processes
were started – formation of a thin layer of glassy phase on the surface and decomposition of

5 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

Plenary lectures

silicon nitride (acting as a pore forming agent). This method of surface modification seems
to be a promising route for the bio-active layer formation. Finally, porous silicon nitride mi-
crospheres with different ratio of S3N4/Ca3(PO4)2 within starting mixture were prepared by
flame synthesis method. The influence of feed rate on the size distribution and porosity of
microspheres were studied.

Multiscale integration challenges in alternative and renewable energy

systems
Mrityunjay Singh
President, The American Ceramic Society (2015-16); Chief Scientist, Ohio Aerospace Institute;
Cleveland, OH, USA

It is estimated that globally 10 terawatts of power will be needed (equivalent to an additional

150 million barrels of oil) per day by 2050. Future energy production and distribution must
be sustainable, environmentally conscious, and less reliant on conventional fossil fuels that
are associated with a massive carbon footprint. Advanced ceramic materials and multiscale
ceramic integration technologies will dramatically impact the energy and environment land-
scape due to their wide scale applications in all aspects of alternative and renewable energy
production, storage, distribution, conservation, and efficiency. Examples include fuel cells,
thermoelectrics, gas turbine systems, distribution and transmission systems based on super-
conductors, nuclear power generation, NOx and COx reduction technologies, and a wide
variety of green and energy efficient manufacturing processes and technologies. Affordable
and reliable solar energy technologies could play key role in sustainable development around
the globe without major impact on environment since solar power is a clean, renewable, and
sustainable energy source. However, revolutionary approaches for thermal energy storage
(TES) system at elevated temperatures (>700 °C) for concentrated solar power (CSP) are
needed for reliable energy supply. Integration technologies are key to making these sys-
tems a reality. The development of robust and reliable integrated systems with optimum
performance requires the understanding of many thermochemical and thermomechanical fac-
tors, particularly for high temperature applications. In this presentation, various challenges
and opportunities in design, fabrication, and testing of integrated systems will be discussed.
Specific examples will be given for integration of fuel cell systems, thermal management,
and thermal energy storage devices. Potential opportunities and need for the development of
innovative design philosophies, approaches, and integrated system testing under simulated
conditions will also be discussed.

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 6

T01: New developments in processing
and synthesis with a special focus
on additive manufacturing
Invited lectures

242
Development of ceramic parts for semiconductor manufacturing
equipment using additive manufacturing
Masami Ando*, Takayuki Ide, Takero Tokizono
TOTO LTD., Chigasaki-City, KANAGAWA-PREF, Japan; *e-mail: [email protected]
Keywords: additive manufacturing, powder layer manufacturing, ceramics, reaction bonded SiC,
semiconductor manufacturing equipment

TOTO has been producing a variety of ceramic parts for semiconductor manufacturing
equipment such as stepper and plasma etcher, as well electrostatics chucks (ESC), plasma-
resistance Y2O3 film by aerosol deposition method, slip-casted large size alumina parts, low
thermal expansion ceramics (cordierite) and high rigidity ceramics (reaction bonded SiC).
We are also investigating joining and additive manufacturing technologies of reaction bond-
ed SiC to make complex shape and large size ceramic parts for semiconductor manufacturing
equipment.
Particularly we have been develop-
ing the additive manufacturing technol-
ogies in “High-Value Added Ceramic
Products Manufacturing Technologies”
project1, which has been conducted
since 2014 as a part of Strategic Inno-
vation Promotion Program under the
sponsorship of the Japanese govern-
ment. In this project, three kinds of
additive manufacturing technologies,
powder layer manufacturing (powder
bed fusion, or indirect selective laser
sintering), slurry layer manufacturing
(stereolithography) and ceramic laser
Fig. 1. Truss structure stage model
sintering (direct selective laser sinter-
ing), are investigated.

7 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T01: New developments in processing and synthesis – Invited lectures

We have developed the powder layer manufacturing technology for producing a reaction
bonded SiC parts which has excellent mechanical properties, furthermore having a complex
shape and large size. The reaction bonded SiC parts produced by this technology show al-
most the same mechanical properties as conventional forming method such as slip-casting,
having Young’s modulus of 340 GPa and flexural strength of 290 MPa. Fig. 1 shows the
truss structure stage model with the width of 20 cm, the length of 20 cm and the height of 8
cm, which has been made by this technology. This paper will introduce these latest research
achievements.

Acknowledgement
This work was conducted as a part of “High-value added ceramic products manufacturing technolo-
gies project” supported by CSTI, SIP, “Innovative design/manufacturing technologies (managed by
NEDO)”.

Reference
1. Website of “High-value added ceramic products manufacturing technologies project”: http://www.
hcmt.website/

666
Anisotropic hierarchical porosity ceramic electrodes for high
performance Li-ion batteries
Rajendra Bordia, Milad Azami-Ghadkolai, Stephen Creager
Clemson University, Clemson, SC 29634, USA

Porous electrodes are critically important for high performance Li-ion batteries. This applica-
tion demands optimization of a multitude of properties, which have conflicting requirements
on the microstructure. Using available models for the effect of the porous microstructure
on the important battery performance characteristics, it will be shown the electrodes with
designed anisotropic and hierarchical microstructures have the potential to optimally address
the different performance requirements.
Results will be presented on two processing approaches to make these designed micro-
structures. Both tape cast and partially sintered bulk electrodes have been investigated. With
the developed processing protocols, it will be shown that it is possible to independently
control several relevant microstructural parameters. The 3D microstructure has been char-
acterized at relevant length scales and these results will be presented. The electrochemical
performance of the designed porous electrodes will be compared to that of the uniformly
porous isotropic electrodes. It will be shown that, compared to uniform porosity electrodes,
due to reduced tortuosity leading to deeper electrolyte access, thick electrodes can be made.
These electrodes demonstrate high energy density and without significant capacity fade at
higher charge/discharge rate.

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 8

 T01: New developments in processing and synthesis – Invited lectures

172
Additive Manufacturing with inorganic polymers: an alternative to the
powder-binder approach
Giorgia Franchin1, Paolo Colombo1,2
1
Dipartimento di Ingegneria Industriale, University of Padova, via Marzolo 9, 35131 Padova, Italy
2
Department of Materials Science and Engineering, The Pennsylvania State University, University
Park, PA 16801, USA

Very few commercially available AM systems are suited for ceramic materials, and most of
them use ceramic powders as feedstock; AM technologies employing polymers are at a much
more advanced stage of development. We tried to exploit such advances and to provide alter-
natives to the ceramic powder-binder approach.
Preceramic polymers (e.g. silicones) convert into nanostructured Si-based ceramic materi-
als by high temperature pyrolysis; we employed them as a non-sacrificial, reactive binder to
develop inks for stereolithography and direct ink writing. We were able to fabricate porous
structures of advanced silicate ceramic phases, including bioceramics, starting from prece-
ramic polymers and (reactive) fillers. We also produced ceramic matrix composites (CMCs)
embedding fibers in the preceramic polymer matrix.
Geopolymers are inorganic 3D networks usually obtained through reaction of alumino-
silicate powders in a silicate alkaline solution. They consolidate at low or even room tem-
perature, show intrinsic micro- and meso-porosity, good mechanical properties, chemical
durability and high temperature stability.
We explored direct ink writing of highly porous lattices using a geopolymeric binder for
different potential applications. As the material in the inks consolidates with time forming
a continuous inorganic network, time becomes the 4th dimension in printing. It is therefore
necessary to control the characteristics of the system to allow for a suitable time window for
the process.

855
Porous ceramic foams and nanofibers
Gideon S. Grader
Chemical Engineering Department, Technion, Haifa, 32000, Israel; e-mail: [email protected]

Creation of porous ceramics has been an objective of much research for decades. The pore
architecture within the material is of key importance to specific applications such as catalysis,
filtration, adsorption and thermal insulation. This talk will concentrate on the mechanism of
pore formation driven by in-situ chemical transformations within two different systems.
On the one hand, the formation of ultralight bulk ceramics using a non-hydrolytic sol-gel
foaming process will be described. The unique foaming mechanism involves simultaneous
phase separation, gelation and drying, giving rise to ultralight foams with a porosity that can

9 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T01: New developments in processing and synthesis – Invited lectures

exceed 99%. The work has been demonstrated on alumina and alumino-silicate ceramics, and
is currently used commercially in India.
On the other hand, sub-micron fibers are of great interest for heterogeneous catalysis,
electrodes and adsorbents. The large pores between the fibers facilitates superior transport
properties between the fiber surface and the bulk. Furthermore, the presence of open and ac-
cessible nano porosity within the nanofibers increase the active surface, potentially improv-
ing the material performance. In catalysis applications lower deactivation rates are expected
due to confinement of the catalytic moieties. This part of the talk will focus the pore forma-
tion in Fe-Al-O ceramic nano fibers with core-shell architecture.
Both examples will demonstrate how internal chemical transformation can be harnessed
to generate controlled porosity in functional ceramics.

843
Processing of porous ceramic structures for efficient mass transport
Jonas Gurauskis1, Vanesa Gil2
1
Æneam ApS, Denmark; e-mail: [email protected]
2
Energy Conversion and Storage Department, Technical University of Denmark; e-mail: [email protected]

Ability to manufacture ceramic structures with efficient porosity and at the same time, suf-
ficient mechanical robustness is important for a broad range of applications, such as; catalyst
supports, filters, fuel cells, electrolysis electrodes, membrane reactors, CO2 capture and flue
gas purification.
The use of sacrificial pore formers, one of the most commonly used methods to generate
porous ceramic structures, delivers structures with random and inefficient porosity. There-
fore, alternative processing routes capable of delivering effective porosity are under high
demand.
Three approaches capable of accomplishing high mass transport ceramic structures will
be discussed: use of non-combustible pore formers, use of ice templating (freeze casting) and
additive manufacturing. Non-combustible pore former route is based on porosity formation
after final sintering step via reduction or mild leaching and results in a highly-interconnected
porosity. Ice templating route is based on porosity creation through generation and sublima-
tion of ice crystals and is capable of generating ceramic scaffolds with desired pore size and
orientation. Additive manufacturing technique is based on generation of complex large scale
ceramic bodies with programmed porosity channels. All these approaches proved to deliver
so called efficient porosity at different scales. Both ice templating and additive manufactur-
ing routes can be further tuned to generate structures with hierarchical porosity distribution.
The talk will be illustrated with some practical examples, where the challenges related to
fabrication of desired microstructures via these approaches will be presented.

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 10

 T01: New developments in processing and synthesis – Invited lectures

832
Advanced manufacturing of porous ceramic structures
for use in energy applications
A. Kaiser*, A.B. Haugen, W. Zhang, S. Ovtar, R. Kiebach, P.V. Hendriksen
DTU Energy, Department of Energy Conversion & Technical University of Denmark (DTU),
Frederiksborgvej 399, 4000 Roskilde, Denmark; *e-mail: [email protected]
Keywords: porous ceramics, multilayer, membrane, gas separation

Tailored porous ceramic materials and structures are utilized in energy devices at DTU En-
ergy, including electrochemical converters, membranes, adsorbents for gas separation and
storage and catalyst supports. These materials can contain pore sizes from the nanometers to
several millimeter, and can have oriented to random porosity or hierarchical porosity based
on various pore architectures. Ceramic structures with tailored porosity can be processed by a
variety of traditional or advanced shaping methods (phase inversion tape casting, templating,
freeze casting, electrospinning, etc.).
Often, some additional challenges need to be addressed if porous support or catalysts
layers with tailored porosity need to be integrated into asymmetric multilayer gas separation
devices to achieve high performance.
For the fabrication of oxygen transport membranes (OTM)1 or solid oxide fuel cells
(SOFC), the shaping, multi-layering and co-firing of porous support structures in ceramic
multilayer devices will be presented, which include the use of sacrificial templates (pore for-
mer) in extrusion2,3 or phase inversion tape casting4. The correlation between the fabrication,
the microstructure of the porous support structures and key performance parameters, such as
gas transport, mechanical properties, thermal stability or electrical conductivity in the final
ceramic multilayer structures and devices will be shown. Finally, a brief outlook on recently
started R&D activities with highly porous ceramic structures will be presented, including
novel concepts for the structuring of adsorbents in gas separation and storage.

References
1. D.K. Ramachandran, M. Søgaard, F. Clemens, J. Gurauskis, A. Kaiser, Fabrication and perfor-
mance of a tubular ceria based oxygen transport membrane on a low cost MgO support, Separation
and Purification Technology 147 (2015) 422–430.
2. D.K. Ramachandran, F. Clemens, A.J. Glasscock, M. Søgaard, A. Kaiser, Tailoring the microstruc-
ture of porous MgO supports for asymmetric oxygen separation membranes: Optimization of ther-
moplastic feedstock systems, Ceram. Int. 40 (2014) 10465–10473.
3. A.B. Haugen, J. Gurauskis, A. Kaiser, M. Søgaard, Graphite and PMMA as pore formers for ther-
moplastic extrusion of porous 3Y-TZP oxygen transport membrane supports, J. Eur. Ceram. Soc.
37 (2016) 1039–1047.
4. S. Cheng, H. Huang, S. Ovtar, S.B. Simonsen, M. Chen, W. Zhang, M. Søgaard, A. Kaiser, P.V.
Hendriksen, C. Chen, High-performance microchanneled asymmetric Gd FeO 3−δ-based mem-
branes for oxygen separation, ACS Appl. Mat. and Interf. 8 (2016) 4548–4560.

11 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T01: New developments in processing and synthesis – Invited lectures

834
Suspension plasma spraying: the meeting point for ceramic processing
and plasma spraying technique
E. Sánchez*, E. Cañas
Instituto de Tecnología Cerámica (ITC), Universitat Jaume I (UJI), Castellón, Spain;
*
e-mail: [email protected]
Keywords: suspension plasma spraying, suspensions stabilization, coatings characterisation

Plasma spraying represents a well-known deposition technique with numerous industrial ap-
plications in many diverse sectors such as aerospace, manufacturing, energy, biotechnology,
etc. because of the flexibility of the technique in terms of the composition and nature of the
feedstock used. Powders ready to be adequately sprayed have been traditionally employed in
plasma spraying. However, in the last years the use of liquid feedstocks has started to gain the
attention of scientific community owing to the simpler feedstock preparation as well as the
possibility of obtaining enhanced properties in the final coatings. Thus, Suspension Plasma
Spraying (SPS) or Solution Precursor Plasma Spraying (SPPS) have merged as alternative
or complementary methods to the state-of-the-art technique known as Atmospheric Plasma
Spaying (APS).
When a suspension instead of a powder is used as feedstock new challenges arise for the
plasma spraying process. This is because the suspension has to be prepared, stored, pumped
and finally, homogenously atomised into the plasma torch with the aim of producing coatings
with the targeted microstructure and properties. Therefore, concepts such as colloidal stabil-
ity, Z-potential, suspension stability, sedimentation, viscosity or suspension atomisation have
necessarily to be taken into account when a SPS process is designed.
This work presents different examples of the whole suspension plasma spraying process,
from suspension preparation to coating deposition, with the objective of showing the con-
nection between the ceramic processing and the plasma spraying operation. SPS processes to
obtain ceramic oxides coatings for wear-resistance applications (Al2O3-TiO2), photocatalytic
functionality (TiO2) or thermal barriers (Y-TZP), and bioactive glasses for implants are de-
scribed underlying the importance of the suspension preparation step on the performance of
the process as well as on the microstructure and properties of the final coatings. The effect
of the solid particle size (micro, submicro or nanometric size) and the solids content in the
suspensions are also addressed. Finally, some insights on the new challenges and future pos-
sibilities of the SPS technique are given.

Acknowledgement
This work has been supported by the Spanish Ministry of Economy and Competitiveness (ref.
MAT2015-67586-C3-R).

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 12

 T01: New developments in processing and synthesis – Invited lectures

812
New aluminosilicate nanoaggregates synthesis from low-temperature
geopolymerization processes
Dong-Kyun Seo
School of Molecular Sciences, Arizona State University, Tempe, Arizona, 85287-1604, USA

Nanoaggregates, such as carbon black and precipitated silica, have been one of the most
important classes of nanofiller materials in modern technologies. We report development of
new nanoaggregate materials with aluminosilicate compositions and their scalable high-yield
production methodologies based on low-temperature geopolymerization process. Unlike the
acid-base reaction process for known amorphous aluminosilicates, the geopolymerization
process allows products that have tetrahedral aluminosilicate network structures with nega-
tive surface charges, and are highly stable in water and in alkaline conditions. By simply
modifying the precursor compositions and reaction conditions, the new materials can be
controlled to have high surface area, high porosity, high structure, high aspect ratio, dif-
ferent crystal structures, crystallinity, or microporosity. Usefulness of the new materials in
large-scale applications is illustrated in rubber-composites, antimicrobials, catalysis and CO2
separation.

821
4D-printed hydrogel-based composite structures by additive processing
Ashok Vaseashta1*, Nimet Bolgen2
1
International Clean Water Institute, Herndon, VA, USA; *e-mail: [email protected]
2
Mersin University, Mersin, Turkey
Keywords: additive processes, 4D printing, hydrogels, bio-mimicking

Hydrogels are materials consisting of a permanent, three-dimensional network of hydrophilic

polymers and water filling the space between the polymer chains with applications in diverse
fields ranging from bio-medical applications and stimuli sensitive systems for agricultural,
personal care, environmental, and industrial applications. We have used multidisciplinary
approach and advances in programmable materials assembly to create transformable archi-
tectures. Using microscale 3D printing technology and fourth time dimensional parameter
by environmental response, we have developed 4D-printed hydrogel composite structures.
Although, the investigation is in its preliminary stages, we anticipate using meta-materials
to detect and capture organic materials, volatile organic compounds and an extension of
our work on capturing pharmaceuticals. Since, hydrogel composites contain cellulose fibrils
derived from wood, response to environment is likely to produce bio-mimicking to external
stimuli.

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T01: New developments in processing and synthesis – Invited lectures

Reference
1. Vaseashta, Nimet Bolgen, Didem Demir, Ashok Vasashta, Development of Polymeric Cryogels as
Potential Matrices for Removing Antibiotics from Wastewater, In: Vaseashta A., Khudaverdyan S.
(eds) Advanced Sensors for Safety and Security. NATO Science for Peace and Security Series B:
Physics and Biophysics. Springer, Dordrecht (2013).

836
Composite ceramic nanostructures for high-efficiency sunlight
conversion
Alberto Vomiero
Division of Materials Science, Department of Engineering Sciences and Mathematics, Luleå
University of Technology, SE-971 87 Luleå, Sweden

In several types of excitonic solar cells, nanomaterials can play a critical role in boosting
photoconversion efficiency by ameliorating the processes of charge photogeneration, exciton
dissociation and charge transport. Several strategies can be pursued, including broadening
of light absorbance to reduce solar light losses, fastening exciton dissociation and charge
injection from the photoactive medium to the charge transporting materials, reducing charge
recombination during charge transport and collection at the electrodes. In this lecture, a few
examples of application of ceramic composites will be thoroughly discussed in two specific
categories of excitonic solar cells, namely dye- and quantum dot-sensitized solar cells. Em-
phasis will be given to the investigation of both the photoactive medium (including compos-
ite and core-shell quantum dots) and the charge transporting scaffold (including metal oxide
hierarchical structures, nanowires, nanorods and carbon-based hybrids) towards a materials-
by-design approach.

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422
LSD-3D printing: a novel technology for the Additive Manufacturing
of ceramics
Andrea Zocca1*, Pedro Lima1, Thomas Mühler2, Jörg Lüchtenborg1, Jens Günster1
BAM Federal Institute for Materials Research and Testing, Division 5.4 Ceramic Processing and
1

Biomaterials, Unter den Eichen 44-46, 12203 Berlin, Germany; *e-mail: [email protected]
TU Clausthal, LaserAnwendungsCentrum, Arnold-Sommerfeld-Straße 6, 38678 Clausthal-Zellerfeld,
2

Germany
Keywords: 3D printing, Additive Manufacturing, layer-wise slurry deposition

The layer-wise slurry deposition (LSD) is an innovative process for the deposition of powder
layers with a high packing density for Additive Manufacturing (AM). A slurry with small
organic content is repetitively spread as thin layers on top of each other by means of a doctor
blade. During the deposition, the ceramic particles settle to form thin layers with a high pack-
ing density (55%–60%). Each layer is then dried, resulting in the stacking of a dry powder
bed with high powder packing. When coupled with a printing head or with a laser source, the
LSD enables novel AM technologies inspired to the 3D printing or selective laser sintering,
but taking advantage of having a highly dense powder bed.
The LSD-3D printing, in particular, offers the potential of producing large (>100 mm) and
high quality ceramic parts, with microstructure and properties similar to traditional process-
ing.
This presentation will give an overview of the milestones in the development of this tech-
nology, with focus on the latest results applied both to silicate and to technical ceramics.

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T01: New developments in processing and synthesis

Oral presentations

270
Light weight metallic additive effect on ballistic performance of spark
plasma sintered B4C
Burcu Apak, Gultekin Goller, Onuralp Yucel, Filiz Cinar Sahin
Metallurgical and Materials Engineering Department, Istanbul Technical University,
Ayazaga Campus, 34469, Istanbul, Turkey; e-mail: [email protected]
Keywords: boron carbide, ballistic performance, spark plasma sintering, fracture toughness

Boron carbide powders with different amounts of light weight metallic (Al and Si) additives
are spark plasma sintered in order to examine the ballistic effects of these additives on boron
carbide. As widely known, boron is a good candidate for body armours. Without increasing
the weight, the mentioned additions were made to improve main drawback of boron carbide
which is low fracture toughness. The final products having 61 mm diagonal, 10 mm height,
and 31 mm length have been produced by spark plasma sintering in the temperature range be-
tween 1400–1550 °C for 4 minutes, under an applied pressure of 40 MPa. After spark plasma
sintering procedure, the densification of composites were measured by Archimedes method
whereas the hardness and fracture toughness of boron carbide composites were measured by
Vickers indentation technique. The crack propagation behaviour of ceramics were observed
by using Scanning Electron Microscopy.

108
Additive manufacturing of Ti-B4C composites by 4M technology
Ľuboš Bača1*, Lilla Vály2, David Grech2, Nils Stelzer1, Erich Neubauer2,
Michael Kitzmantel2
1
Aerospace & Advanced Composites GmbH, 2700 Wiener Neustadt, Austria;
*
e-mail: [email protected]
2
RHP-Technology GmbH, Forschungs- und Technologiezentrum, 2444 Seibersdorf, Austria
Keywords: additive manufacturing, boron carbide, titanium, composites

Titanium Matrix Composites (TMCs) containing various volume fractions of boron carbide
particles have been deposited onto Ti Gd2.0 substrates from powder feedstock mixtures us-
ing a Machine for Multi-Material-Manufacturing (“4M-System”) developed by RHP-Tech-
nology GmbH. In this process plasma transfer arc (PTA) is used as a heat source for in-situ
reaction between Ti and B4C particles, which allows the formation of TiB and TiC phases
during the deposition. Additive layer manufacturing by using the “4M” system offers the
production of large and complex 3D components on one side and gradient structures or multi-
material concepts on the other side.

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 T01: New developments in processing and synthesis – Oral presentations

Various processing parameters such as deposition rate, travel speed of the torch as well as
plasma parameters (power/current/gas flow) have been investigated in order to obtain pore-
and crack-free B4C reinforced titanium composites.
As deposited specimens were cut and the cross sections were analysed by optical- and
scanning electron microscopy. Mechanical properties of such as hardness, tensile strength
and Young’s modulus were assessed.
Fully dense and crack free Ti specimens with 10 vol. % of B4C were obtained by additive
manufacturing with the optimized deposition parameters. In comparison to the pure titanium
grade 1.0 the Ti with 10 vol.% B4C test samples show higher Young’s modulus (150 GPa
against 103 GPa of the pure Ti1) as well as higher hardness values (374 ± 28 HV) and tensile
strength (572 ± 49 MPa). However, the total strain at break is very low showing ceramic like
behaviour. Further increase of the B4C content up to 30 vol. % led to the cracking of manu-
factured specimens.

Acknowledgement
This project has received funding from the European Union’s Horizon 2020 research and innovation
program under grant agreement No [673817].

Reference
1. R. Boyer, G. Welsch, E.W. Collings, Material Properties Handbook: Titanium Alloys, 1994.

105
Functional refractory molds for metal casting built by additive
manufacturing
Geoffroy Bister1*, Dominique Hautcoeur1, Dorian Deschuyteneer1, Pierre Nyssen2,
Michel Cambier1, Enrique Juste1, Anne Mertens3, Olivier Dedry3,
Jacqueline Lecomte-Beckers3, Véronique Lardot1, Francis Cambier1
1
Belgian Ceramic Research Centre, Member of EMRA, Avenue Gouverneur Cornez, 4, B-7000 Mons,
Belgium; *e-mail: [email protected]
2
CRM Group, Avenue du Bois Saint-Jean 21, B27 – Quartier Polytech 4, B-4000 Liège, Belgium
3
University of Liège, A&M Department, Metallic Materials Science, Quartier Polytech,
1 Allée de la Découverte 13A (B52/3), B-4000 Liège, Belgium
Keywords: casting mold, additive manufacturing, alumina, selective laser melting (SLM), rapid
prototyping

Additive manufacturing is more and more used in the field of industry. This technique is nota-
bly employed in investment casting process in order to build cores and models. Nevertheless
investment casting remains not cost effective in case of prototypes and very small series due
to the quite large amount time needed to build and dry the molds.
Additive manufacturing may also be used to directly shape metal parts but several prob-
lems are still linked to this technique as the presence of local defects in parts and the limita-
tion of the number of metal or alloy available for this technique on the market.

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We propose an intermediate method that permits to build directly molds and cores by ad-
ditive manufacturing using equipment initially dedicated to build metal parts. This method
presents the main advantage to cast with a large variety of metals or alloys using a single
ceramic material and only one set of building conditions. The properties of the casted parts
are very similar with those produced by investment casting.
This technique also permits the unique advantage to control the design of the shell thick-
ness and structure in order to have a better control of the thermal fluxes during metal cooling.
This would potentially ensure a better control of some casting defects.
The use of alumina processed by selective laser melting (SLM) is shown and its outstand-
ing resistance to temperature differential is demonstrated through casting trials with two dif-
ferent representative alloys. Casting trials in industrial conditions will be illustrated.

Acknowledgement
The project MOULFRIT is supported by the Public Service of Wallonia, DGO6, in the framework of
the 2014 Collective Research Call – convention n°1410087.

059
Flame spray synthesis of YAG:Ce nanoparticles
Mario Borlaf1*, Roman Kubrin1, Vladimir Aseev2, Alexander Petrov3, Nikolay Nikonorov2,
Thomas Graule1
1
Empa, Laboratory for High Performance Ceramics, Überlandstrasse 129, 8600 Dübendorf,
Switzerland; *e-mail: [email protected]
2
ITMO University, Kronverksky Pr. 49, 197101 St. Petersburg, Russia
3
Hamburg University of Technology, Institute of Optical and Electronic Materials,
Eißendorfer Str. 38, D-21073 Hamburg, Germany
Keywords: YAG, Ce, flame spray synthesis, photoluminescence, quantum yield

Yttrium aluminum garnet (YAG, Y3Al5O12) doped with cerium is a material widely applied
as a phosphor for blue-to-white light conversion. Over the last decade, various methods for
the synthesis of nanometric phosphor powders have been intensively studied because their
small particle size and weak scattering of light are very attractive for applications in imaging
and lighting. In this context, the preparation of submicrometric YAG:Ce particles with high
quantum yield (QY) is the main focus of this work. Nanoparticles with different concen-
trations of cerium were prepared by Liquid-Feed Flame Spray Synthesis. Evolution of the
crystalline phase, particle size and specific surface area (SSA) with increasing the thermal
post-treatment temperature were investigated by X-ray diffraction, Transmission Electron
Microscopy and N2 sorption-desorption, respectively. At T ≥ 900 °C, cubic-YAG phase is ob-
tained together with an increase of the particle size and a decrease of the SSA. The maximal
QY of 72% was obtained for particles containing 0.1 mol% cerium calcined at 1100 °C/1 h
resulting in the average particle size of 01–02 µm.

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125
Synthesis of Ce-TZP – Al2O3 for dental applications – shaping by
stereolithography
Sophie Cailliet1,2*, Marilyne Roumanie1,2, Guillaume Bernard-Granger1,3,
Richard Laucournet1,2
1
Univ. Grenoble Alpes, F-38000 Grenoble, France
2
CEA, LITEN, DTNM, LRVM, F-38054 Grenoble, France; *e-mail: [email protected]
3
CEA, DEN, MAR, DMRC, SFMA, F-30207 Bagnols-sur-Cèze, France
Keywords: composite, stereolithography, stabilized zirconia

Often opposing to the subtractive manufacturing, additive manufacturing (AM) technologies,

such as stereolithography (SLA), have the potential to produce, within a short time, unique,
accurate and dense objects, while limiting the loss of matter. SLA is a layered manufacturing
process based on the polymerization of an UV photocurable system (PS) composed of an UV
sensitive resin highly loaded with ceramic particles (>45%vol). This process is based on the
focussing of an UV light by digital projector screen on the system to cross-link the complex
shape components layer by layer. After manufacturing, components are cleaned to remove
the uncured PS, then debinded and sintered to obtain dense parts by a heat treatment. The
parameters for manufacturing (cross-link time, layer thickness) and related to the thermal
process are highly dependent on the PS.
The SLA known to enable the development of near-net shape components is well suitable
for dental field. In this technical area, Yttria-doped tetragonal zirconia polycrystal (Y-TZP)
is one of the most used material, and has been chosen as reference material. But, due to a
poor behaviour to hydrothermal degradation (HD) other materials have been considered such
as Ceria-doped tetragonal zirconia polycrystal (Ce-TZP). However, Ce-TZP shows lowest
flexural strength values.1 To obtain a material with high mechanical properties such as Y-TZP
and with excellent durability to HD, alumina is added to Ce-TZP to create Ce-TZP – Al2O3
composites. Such composites, according to their properties, seem to be better candidates in
the dental field.2,3 Investigations related to composite synthesis routes, phase distributions
and thermal treatments have been completed before adding this new ceramic system in the
photosensitive resin.
Parts manufactured by SLA performed from a Y-TZP based UV sensitive resin and me-
chanical characterisations will be presented as well as the Pechini and sol-gel routes to syn-
thesis Ce-TZP-Al2O3 powder, new filler in a PS.

References
1. J. Chevalier and L. Gremillard, “Ceramics for medical applications: A picture for the next 20 years,”
J. of the European Ceramic Society, 29 (7), pp.1245–1255, 2009.
2. K. Tanaka, J. Tamura, K. Kawanabe, M. Nawa, M. Oka, M. Uchida, T. Kokubo, and T. Nakamura,
“Ce-TZP/Al2O3 nanocomposite as a bearing material in total joint replacement,” J. Biomed. Mater.
Res., 63 (3), pp.262–270, 2002.
3. R. Benzaid, J. Chevalier, M. Saâdaoui, G. Fantozzi, M. Nawa, L.A. Diaz, and R. Torrecillas, “Frac-
ture toughness, strength and slow crack growth in a ceria stabilized zirconia–alumina nanocompos-
ite for medical applications,” Biomaterials, 29 (27), pp.3636–3641, 2008.

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850
Synthesis, characterisation and properties of perovskite ceramics
prepared by electric discharge assisted mechanical milling
A. Calka*, M. Wyszomirska, D. Wexler
University of Wollongong, Faculty of Engineering and Information Sciences, School of Mechanical,
Materials, Mechatronics and Bioengineering, Australia; *e-mail: [email protected]

Keywords: Perovskite ceramics, electro-mechano-chemistry

Many functional materials are traditionally synthesized by slow reaction processes that are
energy and time consuming. In the present world there is strong demand on development
of modern materials and materials processing methods that could offer rapid reaction rates,
energy efficiency and be environmentally safe.
Perovskite oxide ceramics have found wide applications in energy storage capacitors,
electromechanical transducers and piezoelectric, and ferroelectric devices.
The conventional method to prepare Perovskite oxide ceramics is ceramic-powder-based
processing, i.e., through solid-state reaction at high temperatures. This process has several
disadvantages, such as high-temperature reaction, limited degree of chemical homogene-
ity, and low sintering ability. Therefore, during past years, several chemical-based process-
ing routes, including freeze-drying, spray-pyrolysis, sol–gel, spray-drying, and pyrolysis
of complex compounds, have been developed to prepare powders with more homogeneous
composition, improved reactivity, and sintering ability at low temperatures. Recently, non-
conventional processing methods such as mechanical alloying and mechano-chemical ap-
proaches have been used to create reactions between species. However in this method the
reaction kinetics is very slow and processing time long.
The objective of the present study is to investigate the application of an Electric Discharge
Assisted Mechanical Milling (EDAMM)1 technique to synthesize various Perovskite oxide
ceramics, in particular formation of nano-phases and characterize the structural, physical,
and optical properties.
By using EDAMM, high purity single phase multi-element oxides can be formed in as
little as 0.1% of the processing time required in conventional solid-state techniques. An even
more important feature of EDAMM is that the crystallite size of the synthesized compound
is able to be reduced to nanometer size, by careful selection of electrical (voltage, current,
total power) and mechanical (vibration frequency and amplitude) experimental parameters.
We use EDAMM for (i) synthesis of oxides from elemental powders by oxidation in oxy-
gen plasma and for (ii) synthesis of single phase multi element oxides from pre-mixed oxides
as starting materials.
This presentation provides an overview of recent development of EDAMM method and
its application in rapid synthesis of Perovskite ABO3 type oxide ceramics such as BaHfO3,
BaTiO3, MnTiO3, PbZrO3 and others.

Reference
1. A. Calka and D. Wexler, Nature, 419, (2002) 147–151.

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956
Hydration layer: a potential key to manage colloidal processing of oxide
nanopowder suspensions
Simge Çınar1*, Mufit Akinc2
1
Dept. of Metallurgical and Materials Engineering, Middle East Technical University, 06800 Ankara,
Turkey; *e-mail: [email protected]
2
Dept. of Materials Science and Engineering, Iowa State University, Ames, IA 50011, USA
Keywords: hydration of oxides, colloidal processing of oxide nanopowders, rheology

The majority of ceramic processing techniques relies on the successful slurry preparation
that ensures homogeneous distribution of powders in a highly loaded slurry with manageable
flow characteristics. Only with effective slurry formulation, crack- and pore- free structures
can ultimately be manufactured. However, this still remain a challenging issue for advancing
technology of additive manufacturing. The available models to predict the colloidal proper-
ties of nanopowder slurries therefore require improvements. This presentation will show the
presence and importance of hydration layer around oxide nanopowders that has been over-
looked till very recently. Then, the influence of the hydration layer on the colloidal properties
of oxide nanopowder slurries has been discussed. When the Krieger-Dougherty relation is
modified according to the presence of hydration layer, the viscosity of suspensions can be
successfully estimated. The resultant improvement in green body quality achieved is also
demonstrated.

Fig. 1. DSC thermogram of water exhibits a secondary melting peak in the presence of oxide nanopowders
(a).1,2 Direct imaging of alumina nanopowders in an aqueous environment using fluid cell STEM proved the
presence of hydration layer around powders (a-inset).3 Control over the hydration and electrical double lay-
ers of oxide powders enabled to reduce the viscosity of suspension (b), and lead to the pore-free green bod-
ies with finer surface finish (c).4 Figure a, a-inset and c are adapted from references 1, 3 and 4, respectively

Acknowledgment
The part of this study was supported by the National Science Foundation (Grant No. CBET 0931038).

21 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

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References
1. S. Çinar, L. van Steenhuyse and M. Akinc, “Elucidation of Viscosity Reduction Mechanism of
Nano Alumina Suspensions with Fructose Addition by DSC”, J. Am. Ceram. Soc., 96, pp. 1077–
1084, 2013.
2. S. Çınar, D.D. Anderson and M. Akinc, “Influence of bound water layer on the viscosity of oxide
nanopowder suspensions”, J. Eur. Ceram. Soc., 35, pp. 613–622, 2015.
3. E. Firlar, S. Çınar, S. Kashyap, M. Akinc and T. Prozorov, “Direct Visualization of the Hydration
Layer on Alumina Nanoparticles with the Fluid Cell STEM in situ”, Sci. Rep., 5, 9830, pp. 1–7,
2015.
4. S. Çinar, D. D. Anderson and M. Akinc, “Combined effect of fructose and NaCl on the viscosity of
alumina nanopowder suspensions”, J. Eur. Cesram. Soc., pp. 377–382, 2014.

229
Highly porous B-doped hardystonite bioceramics from preceramic
polymers and engineered fillers: from foams to 3D-printed scaffolds
Hamada Elsayed1*, Paolo Colombo1,2, Enrico Bernardo1
Department of Industrial Engineering, University of Padova, Padova, Italy;
1

*
e-mail: [email protected]
Department of Materials Science and Engineering, the Pennsylvania State University, University
2

Park, PA 16801, USA

Keywords: hardystonite bioceramics, polymer-derivedsilicates, scaffolds, direct ink writing

Highly porous hardystonite-based bioceramics, in the form of foams and 3D scaffolds, were
obtained by thermal treatment in air (at 950 °C) of silicone resins and micro-sized oxide fill-
ers. Besides CaO and ZnO precursors (CaCO3 and ZnO powders), calcium borate, in both
hydrated and anhydrous form (Ca2B6O11·5H2O and Ca2B6O11, respectively) was added to
commercially available silicone resins. This latter addition had a significant impact on the
microstructural evolution of the bioceramics. In its hydrated form, calcium borate led to
a substantial foaming of silicone-based mixtures at low temperature (420 °C); after dehy-
dration, upon firing, the salt provided a liquid phase, favouring the development of novel
B-contaning hardystonite-based solid solutions (Ca2Zn1-xB2xSi2-xO7). This role in the phase
evolution upon firing was also maintained by the filler in anhydrous form, employed in for-
mulations used for direct ink writing of scaffolds. The bioceramic foams and scaffolds exhib-
ited remarkable mechanical properties (compressive strength exceeding 4 MPa, with a total
porosity above 67%). Preliminary investigations concerning ceramics based on even more
complex solid solutions ((Ca,Sr)2(Mg,Zn)1-xB2xSi2-xO7), embedding also SrO and MgO, will
be presented as well.

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354
Rheological properties of alumina formulations based on biosourced
additives for micro-extrusion application
Imane El Younsi*, Julie Bourret, Vincent Pateloup, Marguerite Bienia, Thierry Chartier
SPCTS, European Ceramic Center, UMR CNRS 7315, 12 Rue Atlantis 87068 Limoges, France;
*
e-mail: [email protected]
Keywords: alumina paste, rheology, micro-extrusion, green chemistry, mechanical properties

Paste extrusion has been widely used in many forming processes of ceramics for different
applications (biomedical, catalysts, electronic devices). However, the rheological behavior
of these pastes remains largely unexplored. Most rheological properties of high concentrated
paste extrusion are well described using typical empirical frameworks1,2 and then needs fur-
ther investigations to understand the impact of rheological properties on the green body ob-
tained by extrusion process.
This study is part of a process of sustainable development of resources and is based on the
respect of the principles of green chemistry. More particularly, the aim here is to quantify the
impact of the amount of constituents of alumina pastes based on bio-sourced organic materi-
als on their rheological behavior. Successful extrudability requires having rheological prop-
erties suited to the micro-extrusion process and conferring sufficient cohesion on the green
bodies. Rheological characterization is necessary to get clearer understanding of the paste
when the solid fraction is increased3. The nature of additives and their order of introduction
into the mixture is also a major factor influencing the rheological behavior and consequently
the paste extrudability. A feasibility study using an oscillatory experimental protocol was
carried out and yielded promising results which allowed to link the nature of polymers, the
amount of the constituents of the pastes with rheological properties. In addition, the effect
of alumina paste’s aging on the rheological properties was evaluated and discussed. It would
seem that rheological behavior evolution is a major factor for prediction of the extrudability
of the formulated pastes.
Finally, the mechanical properties of our pastes have been investigated to evaluate the
hardness and estimate the mechanical resistance of the extruded material after consolidation
with heat treatment.

References
1. J. Benbow, J. Bridgwater, “Paste flow and extrusion”. (1993), Oxford University Press.
2. S.L. Rough, D.I. Wilson, J. Bridgwater, “A model describing liquid phase migration within an ex-
truding microcrystalline cellulose paste”, Chem Eng Res Des. (2002), Vol. 80, 701–714.
3. D. Leighton, A. Acrivos, “The shear-induced migration of particles in concentrated suspensions”,
J. Fluid Mech. (1987), Vol. 181, 415–439.

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637
Osteoconductive ceramics of complex geometry fabricated by
stereolithography
Pavel Evdokimov1,2*, Valery Putlayev1,2, Tatiana Safronova1,2, Alexey Garshev1,3,
Elena Klimashina1,2, Yaroslav Filippov1,4, Nikolai Orlov1, Andrey Tikhonov1
1
Materials Science Department, Lomonosov Moscow State University, Moscow 119991, Russia;
*
e-mail: [email protected]
2
Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia
3
Baikov Institute for Metallurgy and Materials Science RAS, Moscow 119334, Russia
4
Institute for Mechanics, Lomonosov Moscow State University, Moscow 119991, Russia
Keywords: stereolithography, bioceramics, Kelvin structure, gyroid, permeability, calcium phos-
phates

The work tackles the issue of bioceramics with interconnected macropores with special ar-
chitecture of pores space. Kelvin structure and gyroid, as a member of triply-periodic mini-
mal surfaces family, were chosen to reach desirable permeability (up to 1000 Darcy) in order
to reveal osteoconductivity. FEM-analysis of loading and simulation of fluid flow through
the structure (SolidWorks 2013) facilitated making a choice. The above complex shapes were
reproduced as phosphate ceramics scaffolds via DLP-stereolithography of light-curable slur-
ries based on Ca3(PO4)2 and Са3-хМ2х(РО4)2 (x = 0 – 1, M = Na, K) ceramic powders. Optimi-
zation of the process parameters as well as reaching high lateral resolution of printing (up to
30 μm) were underlined with the study of photosensitivity of the slurries and light scattering
in them. To convert the as-printed scaffolds into the ceramics one, preserving their geometry,
a special regime of thermal treatment allowing release of polymer with the rate lower than
0.1 wt.%/min was elaborated. Time-temperature profile of the regime was stated through the
inspection of kinetics of polymer pyrolysis. Detailed study of densification and grain growth
in the course of sintering of ceramic scaffolds made us possible to fabricate prototypes of
bone implants (for small laboratory animals, cylinders with o.d. = 2–3 mm and height up to 6
mm) with overall porosity up to 80%, demonstrating compressive strength up to 12 MPa and
fracture toughness up to 0.7 MPa·m1/2.

Acknowledgement
The work was supported by RSF, grant #14-19-00752.

References
1. V.M. Ievlev, V.I. Putlyaev, T.V. Safronova, P.V. Evdokimov, “Additive technologies for making
highly permeable inorganic materials with tailored morphological architectonics for medicine”,
Inorg. Mat., 51, №13, pp. 1295–1313, 2015.
2. P.V. Evdokimov, V. I. Putlyaev, V. M. Ievlev, E. S. Klimashina, T. V. Safronova, “Osteoconductive
ceramics with a specified system of interconnected pores based on double calcium alkali metal
phosphates”, Dokl. Chem., 460 (Part 2), pp. 61–65, 2015.

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813
Porous and dense materials using bioplastics as structurers in colloidal
processing
A. Ferrandez-Montero1,2*, J. Yus1, F.J. Gonzalez1, M.P. Arrieta3, L. Peponi3, M. Lieblich2,
J.L. Gonzalez-Carrasco2, A.J. Sanchez-Herencia1, Z. Gonzalez1, B. Ferrari1
1
Ceramic and Glass Institute, (ICV-CSIC) Kelsen 5, 28049 Madrid, Spain;
*
e-mail: [email protected]
2
National Research Center for Metallurgy (CENIM-CSIC) Madrid, Spain
3
Institute of Polymer Science and Technology (ICTP-CSIC) Madrid, Spain
Keywords: hydroxyapatite, magnesium, nickel oxide, tape casting, electrospining, 3D printing, PLA

The aim of this work is to develop dense and porous films through the use of colloidal tech-
niques, such as tape casting and electrospinning, for health and energy applications. These
processing techniques required the use of a polymer as processing structurer or matrix. PLA
(Poly-L-lactic acid or Poly-L, D-lactic acid) is the front runner in the emerging bioresources
and bioplastics market with the best availability and the most attractive cost structure. The
production of the aliphatic polyester from lactic acid, a naturally occurring acid and bulk pro-
duced food additive, is relatively straightforward. PLA base materials were developed with
different inorganic loads which present diverse particles sizes such as Ni(OH)2 (200 nm),
Hydroxyapatite (3 μm) and Magnesium (30 μm). Differences on morphology and character-
istics of those powders have a strong influence on the limit of the inorganic load, properties
and applications of the processed materials.
PLA/Inorganic materials processing route is based on the homogeneous mixture of a sus-
pension of inorganic particles with a solution of PLA, where aqueous suspensions of inor-
ganic particles were prepared preserving the colloidal and chemical stability in terms of zeta
potential and packing density, varying the pH and the concentration of a stabilizer agent. On
the other hand, solution of PLA was optimized, and THF (tetrahydrofuran) resulted to be the
best solvent to prepare a homogeneous solution. The final suspension of PLA and Inorganic
particles served to obtain a feedstock to 3D printing, electrospinning and tape casting pro-
cesses. Those techniques allow us to obtain different inorganic and hybrid films and pieces,
as well as study the effect of the inorganic particle size in the processes. Finally, materials
were thermal treated if needed, and characterized focus on their applications, implants and/
or supercapacitors.

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259
Truly comprehensive solutions to produce ceramic parts with 3D
printing
Richard Gaignon
3DCERAM, Limoges, France; e-mail: [email protected]

3D printing lets users push back production limits. Ceramics are no exception to the rule, but
until now, the use of this material was reserved to ceramics experts. To open up this technol-
ogy to a wider spread of professionals 3DCeram is sharing its maker experience to propose
truly comprehensive solutions, depending both on users’ expertise and the type of production
they need.
Thanks to its large platform and high resolution, CERAMAKER 3D printer is particularly
suited to series production. High quality parts, made of 3DMix ceramic pastes developed by
3DCeram, get the same properties as those produced via traditional processes.
The company also offers a cleaning booth and furnaces to deliver a turnkey production
line to its customers. Assistance and support service will ensure they acquire the necessary
know-how to produce parts independently.

186
Additive manufacturing of monolithic catalysts
Johannes Homa1*, Robert-Jan Koopmans2, Carsten Scharlemann3, Yann Batonneau4,
Corentin Maleix4, Romain Beauchet4, Martin Schwentenwein1
1
Lithoz GmbH, Mollardgasse 85a/2/64-68, 1060 Vienna, Austria; *e-mail: [email protected]
2
Fotec GmbH, Viktor Kaplan-Straße 2, 2700 Wiener Neustadt, Austria
3
University of Applied Sciences Wiener Neustadt, Johannes-Gutenberg-Straße 3,
2700 Wiener Neustadt, Austria
4
Université de Poitiers, 4 rue Michel Brunet, 86073 Poitiers cedex 9, France
Keywords: additive manufacturing, catalysts, cordierite, silicon nitride, magnesia

Current manufacturing methods for catalysts are still in general 2D-based processes such
as extrusion with limited design freedom which do not allow the implementation of exist-
ing considerations for the improvement of catalyst designs and performance. Due to recent
developments in the area of additive manufacturing (AM), it is now possible to allow 3D
design freedom and therefore enables the implementation of new design features to improve
performance as well as lifetimes of catalysts.
This contribution discusses the manufacturing of 3D-printed catalysts using the lithogra-
phy-based ceramic manufacturing (LCM) process to produce monolithic structures based on
various ceramic materials such as alumina, cordierite, magnesia and silicon nitride. Using
this lithographic printing process allows the fabrication of highly detailed structures with de-

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fined feature sizes down to 150 µm. Such catalysts provide a high surface to volume area and
significantly reduce the pressure drop standard pellet type catalysts suffer from. Moreover,
it was shown, that the mechanical properties of the printed ceramic materials are similar to/
same as conventionally processed ceramics. First results indicate that the implementation
of advanced monolith designs enable the increase of the performance of the catalyst while
reducing the geometrical surface area of the construct, which means that the monoliths can be
miniaturized and there is less active phase is required. Thus, it would be possible to decrease
weight, size, and costs of the final catalyst. These findings underline the potential for a future
use of 3D printed catalysts, especially in the field of launcher and satellite propulsion where
a significant need for capable catalytic solutions exists.

Reference
1. M. Schwentenwein and J. Homa, “Additive Manufacturing of Dense Alumina Ceramics”, Int. J.
Appl. Ceram. Techn., 12, pp. 1–7, 2015.

394
Manufacturing of cemented tungsten carbide by hybrid machining
in green state
Enrique Juste1*, Grégory Martic1, Dominique Hautecoeur1, Nicolas Preux1, Fabrice Petit1,
Geoffrey Roy2, Valentin Marchal-Marchant2, Aude Simar2, Véronique Lardot1, Francis
Cambier1
1
Belgium Ceramic Research Center, avenue Gouverneur Cornez 4, 7000 Mons, Belgium;
*
e-mail: [email protected]
2
Université Catholique de Louvain (iMMC/IMAP), Louvain la Neuve, Belgium
Keywords: green machining, hybrid machining, hard material

Manufacturing of complex shapes of hard material/ceramics from dense bulk is carried out
mainly by two process routes:
–– hard machining through Computer Numerical Control (CNC) equipments; large areas
can be machined with a high removal rate. Despite technological advances since recent
years, this process remains considerably energy and time consuming. Beside, due to me-
chanical properties of hard materials/ceramics the wear of tools is very high.
–– physico-chemical processes such as electro-erosion or laser beam machining; such pro-
cesses are very selective, as a consequence these shaping routes are efficient to perform
high resolution details but not for large areas.
Green machining of hard material/ceramics through CNC is an alternative to manufacture
complex shape. However, the low mechanical properties of the green parts are not suitable
with high aspect ratio details realised by CNC machining. The use of a laser beam to perform
high resolution details is relevant in this case.
A combination of these two approaches in a hybrid process in green state: roughing by
machining then finishing by laser beam erosion, in the subtractive multi-scale approach was
recently carried out at BCRC.

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Green machining WC-Co12% is performed by the hybrid approach from powder to dense
complex 3D parts. A suitable additive was mixed with the ceramic powder to be machined by
conventional milling tools and laser beam. With the processing route reported here, complex
ceramic parts have been manufactured having a relative density up to 99%. The use of such
manufactured parts is relevant for drill bit application.
Some examples will be detailed in a case study.

Acknowledgment
Wallonia is gratefully acknowledged for it financial support to the research project HYLAFRU.

318
Porous ceramic by crystallization of combustible additive method
Ksenia Kamyshnaya*, Tamara Khabas
Department of Technology Silicates and Nanomaterials, Tomsk Polytechnic University,
30 Lenina st, Russia; *e-mail: [email protected]
Keywords: porous ceramic, carbamide, zirconium oxide

Requirements for new materials with unique properties are increased with the introduction of
new manufactures. Zirconium dioxide can be used such as material due to high physic-chem-
istry properties. Porous ceramics (including at the base of zirconium dioxide) are widely used
in different fields to develop filters, bioimplants, catalysts and etc.1,2 There are a lot of meth-
ods to investigate porous ceramics2. One of perspective method is the combustible additive
crystallization method. This method alloys to control size and direction pores, porosity and
to develop geometrically complicated parts. Carbamide is a very acceptable material for this
method. Carbamide dissolves in water very easily, solidifies in the form of thin needles at the
change of solution temperature and burns at the sintering. Micron and nanopowders of zir-
conium dioxide (amount of nanopowders from 10 to 50 vol%) were used to develop porous
ceramics. Two forms with different thermal conductivity were used to form porous samples
with unidirectional pores: polyurethane (0.315 Wm/°С) and metal (197 Wm/°С) forms. What
is more composite form on the base of polyurethane and metal was discovered to investigate
thin needles of carbamide. Porous samples were formed by freeze-casting method. Different
temperature conditions were used for freezing samples. The crystals of carbamide grew uni-
directional as the result of the gradient of temperature. The temperature of samples sintering
was 1580 °С. Porosity of development samples varies from 28% to 62%. Pores have sizes
from 0.2 to 200 μm. The samples strength is up to 82 MPa. Samples of porous ceramics with
thin permeable pores can be used as filters to clean air. The crystallization of combustible
additive method can be applied for different powders to develop porous samples.

References
1. A.R. Studart, “Processing routes to macroporous ceramics: a review”, J. Am. Ceram. Soc., 89 (6),
pp 1771–1789, 2006.
2. P.S. Liu, G.F. Chen, Porous materials processing and application. Elsevier Inc, USA, 2014.

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333
Micro- and mesopore structure control in silicon carbonitride-based
ceramics using molecular porogens
Thomas Konegger1*, Christina Drechsel1, Rajendra K. Bordia2
Institute of Chemical Technologies and Analytics, TU Wien, Getreidemarkt 9/164-CT, 1060 Vienna,
1

Austria; *e-mail: [email protected]

Department of Materials Science and Engineering, Clemson University, 161 Sirrine Hall, Clemson
2

SC 29634, USA
Keywords: polymer-derived ceramics, microporosity, pore generation, polysilazane, membrane

Micro- and mesoporous ceramics have gained increasing attention for prospective uses in the
fields of energy production and conversion, in particular for applications in the field of sepa-
ration of liquids or gases. Here, the high thermal and chemical stability of ceramic materials
is a decisive advantage over state-of-the-art polymer materials; however, the generation of
well-defined pore structures in the desired size range remains a major challenge.
In this contribution, we report on the generation and tailoring of micro- and mesoporosity
in polysilazane-derived silicon carbonitride. While microporosity is primarily created during
the polymer-to-ceramic conversion step, the addition of molecular porogens, including con-
ventional polymers, organometallic compounds, and solvents, was shown to further affect
both the micro- and the mesopore structure. Through a systematic investigation of various
candidate materials, polystyrene was found to have the most profound impact on the resulting
pore structure, which was characterized in detail using gas physisorption techniques. Finally,
selective layers of the polysilazane/polystyrene material were successfully deposited onto
oxide ceramic membrane supports. Single-gas permeance tests up to 300 °C demonstrated
the general suitability of this material combination for prospective gas separation applica-
tions.

268
Tribological behavior of HiTUS W-doped hydrogenated carbon based
coatings
František Lofaj*, Pavol Zubko, Dávid Medveď
Institute of Materials Research of SAS, Watsonova 47, 040 01 Košice, Slovakia; *e-mail: flofaj@
saske.sk

Friction behavior of carbon based coatings may be strongly affected by the presence of hy-
drogen used for the stabilization of the carbon structure. The aim of the work is to investigate
the influence of the addition of hydrogen into W-doped carbon based coatings prepared by
reactive High Target Utilization Sputtering (HiTUS) from the viewpoint of the control of its
tribological behavior under different conditions. The investigations of the influence of depo-

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sition conditions on the other properties including roughness, wear resistance, hardness and
elastic modulus are included and the results are compared with the properties of the conven-
tionally deposited W-C coatings.

543
Additive manufacturing of silicon nitride with Laser Induced Slip
Casting (LIS)
Jörg Lüchtenborg1*, Thomas Mühler2, Andrea Zocca1, Jens Günster1
Federal Institute for Materials Research and Testing (BAM), Division 5.4- Ceramic Processing and
1

Biomaterials, Unter den Eichen 87, Berlin, Germany; *e-mail: [email protected]

Clausthal University of Technology (TUC), Institute of Non-Metallic Materials, Clausthal-Zellerfeld,
2

Germany
Keywords: additive manufacturing, silicon nitride, LIS

Additive manufacturing opens the opportunity for new application of ceramic materials, but
until now there is a lack of methods for the additive manufacturing of large monolithic ce-
ramic parts which are dense and therefore have sufficient mechanical properties. Until now
voluminous additive manufactured ceramic parts are produced by powder bed based pro-
cesses. We have developed a new additive manufacturing method, the Laser Induced Slip
casting (LIS), based on the layerwise deposition of slurries and their sequent local drying
by intense laser radiation. Laser Induced Slip casting generates ceramic green bodies which
can be afterwards sintered like traditional produced ceramic parts. Green bodies and sintered
parts are presented and their microstructure and mechanical properties are discussed.

167
Ecofriendly alumina suspensions for tape casting process
Jérémy Marie1*, Pierre-Marie Geffroy1, Agnès Smith1, Julie Bourret1, Thierry Chartier1,
Vincent Chaleix2
1
SPCTS, European Ceramic Center, UMR CNRS 7315, 12 rue Atlantis, 87068 Limoges Cedex,
France; *e-mail: [email protected]
2
LCSN, EA 1069, FST, 123 avenue Albert Thomas, 87060 Limoges, France
Keywords: alumina, tape casting, green chemistry, aqueous suspensions

Tape casting process is widely used in the ceramic industry in order to produce thin and flat
ceramic tapes for microelectronics1 or membranes for gas separation2. The suspensions used
in the tape casting process are basically composed of a ceramic powder, a solvent, a disper-
sant, a binder and a plasticizer. The binder and plasticizer are usually polymers coming from

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the petrochemical sector and they may present risks for the operator health or the environ-
ment (in particular with organic solvents).
Due to the REACH regulation in Europe (Registration, Evaluation, Authorisation & re-
striction of Chemicals) and with respect to the “Green Chemistry” principles, the use of some
of these products could be forbidden in the near future.
The aim of this study is focused on the elaboration of new alumina suspensions with
biopolymer additives and rheological properties adapted to the tape casting process. Natural
polymers extracted from plants were identified as promising candidates in order to substitute
the classical organic additives. The interactions between different organic additives with alu-
mina were studied. The influence of the incorporation order of the different organic additives
on the viscosity of the suspension were evaluated. Then, mechanical properties of the green
and sintered tapes were determined in relation with the nature of bio-polymer additives.

References
1. T. Chartier, Tape-casting. In Encyclopedia of Advanced Materials, ed. D. Bloor, R.J. Brook, M.C.
Flemings, S. Mahajan. Pergamon Press (1994) 2763–2767.
2. P.-M. Geffroy, A. Vivet, L. Nguyena, E. Blond, N. Richet, T. Chartier, Elaboration of La1−xSrxFe1−
yGayO3−δ multilayer membranes by tape casting and co-firing for syngas application, J. Eur. Ceram.
Soc. 33 (10) (2013) 1849–1858.

095
Influence of different external lubricants and their deposition mode
on nuclear fuel green pellets during cold compaction
Ousseïni Marou Alzouma*, Anne-Charlotte Robisson
Laboratoire des Combustibles Uranium, CAD/DEN/DEC/SFER/LCU CEA Cadarache 13108 Saint-
Paul-Lez Durance, France; *e-mail: [email protected]
Keywords: lubrication, friction index, ejection force, pellets, compaction, nuclear fuel, zinc stearate

In the framework of the fabrication of future nuclear fuels, some solutions are attempted to
optimize the compaction process of the nuclear powder. In fact, lubrication is used for the
fabrication process in order to decrease the friction between actinide oxide grains and press
tools. A higher plutonium content and an isotopic composition including more 238Pu because
of plutonium multi-recycling would increase radioactivity and temperatures in future UO2
+ PuO2 powder mixtures. This temperature could be detrimental to maintaining lubricant
properties within the mixture.
A solution could be the replacement of the internal lubricant1 by a lubricant deposit on the
die wall (external lubrication)2 during compaction process. This lubrication technic, when
combined with the internal lubrication, is known to enhance mechanical strength and density
of the pellets resulting from the powder compaction3.
This paper investigates the influence of this kind of lubricant deposition on the die wall for
UO2 powder pelletization. Different lubricants and various ways of lubricant deposition on

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the die wall were investigated through sliding coefficient determination during powder com-
paction and pellets characterization. For example, depositing zinc stearate solid by lubricant
pelletization and spraying are compared. Results show that tensile strength of green pellets
is enhanced when lubricant is sprayed. Furthermore, the application of viscous oils on the
die wall does not allow the production of UO2 pellets probably due to the tribological inef-
ficiency of this form of lubricant in our conditions. The lubrication mechanism changes from
a lubricant to another and acts on the friction index, the slide friction and the characteristics
of the final green pellets.

References
1. Simchi, “Effects of lubrication procedure on the consolidation, sintering and microstructural fea-
tures of powder compacts”, Materials and Design, 24 (2003) 585–594.
2. K. Sudo, T. Takano, K. Takeuchi, Y. Kihara, M. Kato, “Development of Pressing Machine with
a Die Wall Lubrication System for the Simplified MOX Pellet Fabrication Method in the FaCT
Project”, Proceedings of GLOBAL 2011, Makuhari, Japan, Dec. 11–16, 2011, Paper No. 387512.
3. M. Uppalapati, D.J. Green, “Effect of external lubricant on mechanical properties of dry-pressed
green bodies”, J. Am. Ceram. Soc., 88(6) (2005)1397–1402.

244
Synthesis and characterization of nanometric gadolinia powders by low
temperature solid-state displacement reaction
Branko Matovic
Institute for Nuclear Sciences, Centre of Excellence-CextremeLab Vinca, University of Belgrade,
Belgrade, Serbia

Nanometric-sized gadolinia (Gd2O3) powders as well as Eu:Gd2O3 red phosphor were ob-
tained by applying solid-state displacement reaction at room temperature and low temper-
ature calcination. The structural properties have been carried out using X-ray diffraction,
Thermal analysis (DSC-TG), Field emission scanning electron microscopy (FE-SEM) and
Raman spectroscopy. The luminescence measurements were performed at room temperature
on the spectrofluorometric system, utilizing 500 W Xenon lamp as excitation source. Photo-
luminescence emission spectra were measured within the spectral region from 350 to 600 nm
and excitation from 250 to 400 nm.
The XRD analysis revealed that the room temperature product was gadolinium hydroxide,
Gd(OH)3 that upon calcining transforms to cubic Gd2O3 phase at 600 °C. The subsequent
calcination at 600~1200 °C of the room temperature reaction products was studied. Cubic
Gd2O3 phase is converted to monoclinic Gd2O3 phase between 1400 °C and 1600 °C.
High-density (96% of theoretical density) ceramic pellet free of any additives was ob-
tained after pressureless sintering at 1600 °C for 4 h in air. The red phosphor emits a strong
visible light, implying its potential application in the field of luminescence devices.

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078
Direct Ink Writing of boehmite gels: rheological understanding of
printability
Amin M’Barki1*, Lydéric Bocquet2, Adam J. Stevenson3
1
Saint-Gobain CREE LSFC Lab, Cavaillon / Claude Bernard Lyon I, France;
*
e-mail: [email protected]
2
Laboratoire de Physique Statistique – ENS, Paris, France
3
Saint-Gobain CREE, Cavaillon, France
Keywords: Direct Ink Writing, additive manufacturing, boehmite

Direct Ink Writing (DIW) is an additive manufacturing technique based on continuous layer-
by-layer filament deposition1. Suspensions must be tailored with specific rheological prop-
erties to ensure shape retention after printing. Among the required properties, suspensions
should be viscoelastic, shear-thinning, and have a sufficient yield stress to support stacking.
These behaviours are often intrinsically linked in complex fluids, such as controlling them
independently is impossible. Therefore, suspensions must be optimized to allow extrusion
through fine nozzles, but also layer stacking without deformation. The proper flow behaviour
for DIW suspensions has been thoroughly investigated to obtain porous spanning structures2.
However, literature lacks a clearer criterion to obtain ceramic objects that are free of print-
ing defects. In this work, we used boehmite as model suspensions to assess the rheological
properties required to print perfectly filled objects.
Boehmite gels undergo complex sol-gel reactions over time, considerably changing their
flow behaviour from Newtonian liquids, to solid-like yield stress fluids. This evolution is an
asset since it allows studying a broad range of rheological properties with a single suspen-
sion, only by changing the solids loading. As gelation occurs, we tracked well-established
rheological landmarks, like gelation point and the appearance of a measurable yield stress,
and show that they are strongly dependant of boehmite solids loadings, drastically changing
over time. By combining a clear objective definition of deformation to image analysis of
printed objects at different aging stages, we show that boehmite suspensions become print-
able when dynamic yield stress is able to overcome gravitational slumping, but also capil-
lary forces. Our work introduces a dimensionless number that provides a clear definition of
printability. We show that boehmite suspensions produce objects with shape fidelity greater
than 90% when this number is higher than unity. Even though the required shape fidelity may
be subject to the operator’s discretion, this number establishes a universal and direct link
between the rheological properties of a DIW suspension and the printed object shape fidelity.
We believe that this dimensionless number is a first step towards objects with potentially
enhanced properties, as it is the next challenge for DIW.

References
1. Zocca, A., Colombo, P., Gomes, C.M., Günster, J. Additive manufacturing of ceramics: issues,
potentialities, and opportunities. J. Am. Ceram. Soc. 98, 1983–2001 (2015).
2. Lewis, J.A. Direct-write assembly of ceramics from colloidal inks. 6, 245–250 (2002).

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705
Fabrication of transparent MgAl2O4 spinel using spark-plasma-
sintering (SPS) technique by suppressing discoloration
Koji Morita*, Byung-Nam Kim, Hidehiro Yoshida, Keijiro Hiraga, Yoshio Sakka
National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan;
*
e-mail: [email protected]
Keywords: spark-plasma-sintering, transparent, spinel, discoloration

Spark-plasma-sintering (SPS) technique has widely been utilized to consolidate various types
of materials. It is reported, however, that the SPS processed oxides such as Al2O3, ZrO2 and
spinel exhibit discoloration. Such a discoloration is known to be remarkable than the HIP/HP
processed oxides and affect the optical properties.
The discoloration in spinel can be explained by the combination of carbon contamina-
tions and lattice defects, which are introduced in the spinel matrix depending on the SPS
conditions. Although the carbon contamination and defects formations can be reduced with
decreasing the heating rate to some extent, those still remain in the oxide matrix. The lattice
defects can be removed by post-annealing in air. However, since the carbon phases transform
to CO/CO2 babbles within the materials by the post-annealing in air due to the reacting with
oxygen, it is very difficult to remove the carbon from the sintered bulk materials. Therefore,
the carbon contamination during the SPS processing should be suppressed, especially for at-
taining transparent ceramics.
In the presentation, we will mainly discuss the carbon contamination mechanism and dis-
cuss a possible SPS processing to suppress the carbon contamination.

145
Role of the interfaces in metal-ceramic nanocomposites processed by
novel routes in air
A. Moure1, A. Quesada1, C. Berges2, G. Larraz2, G. Herranz2, J.F. Fernández1
1
Instituto de Cerámica y Vidrio, CSIC, C/ Kelsen 5, Madrid 28049, Spain
2
Área de Ciencia e Ingeniería de los Materiales, E.T.S. Ingenieros Industriales, Universidad de
Castilla – La Mancha, Edificio Politécnico, Avda. Camilo Jose Cela s/n, 13071 Ciudad Real, Spain

Metal-ceramic composites in which a ceramic matrix is reinforced by a metal comprise a wide

range of compositions and applications in the field of construction, machining or biomedicine,
among others. A major difficulty for this type of material relates to its processing. High tem-
peratures and reducing or inert atmospheres to avoid the metal oxidation are needed. When
nanostructuring is needed, this make the problem even more complicated. In this work, we
present a novel and successful processing route that combines high energetic milling in air and
Spark Plasma Sintering to have metal-ceramic nanocomposites with particular properties. We

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recently reported1 that metal-oxide functional interfaces developed in-situ during the process-
ing give new and enhance properties in thermoelectric materials. This opens new application
possibilities beyond the traditional ones. In these sense, the mechanical and magnetic proper-
ties of alloys/oxides nanocomposites obtained by the mentioned route are shown in this work.

Reference
1. A. Moure et al. Thermoelectric Skutterudite/oxide nanocomposites: Effective decoupling of electri-
cal and thermal conductivity by functional interfaces. Nano Energy 31 (2017) 393–402.

605
LSD-based Selective Laser Sintering starts up to new quality of silicate
ceramic bodies
Thomas Mühler
TU Clausthal, Clausthal-Zellerfeld, Germany; e-mail: [email protected]

Selective Laser Sintering of ceramic powders is a promising technique for additive manufac-
turing (AM) of complex- and delicate-shaped parts. Most AM techniques have in common
that material is spread out as thin layers of a dried powder/granulate by a roller or a shaker
system. These layers are mostly characterized by a low packing rate. On the other hand, ap-
preciable densities can be reached by the use of ceramic slurries. Therefore, the layer-wise
slurry deposition (LSD) has been developed. Powder beds built up by employing the LSD
technology exhibit a density comparable to ceramic compacts by means of conventional
forming technologies. By the right choice of laser parameters for creating a homogenous
energy distribution across the entire cross section of the sliced object, parts could be manu-
factured which can be post sintered to dense ceramics.

124
Ceramic powder synthesis by spray pyrolysis: aerosol formation and
evolution
Mariana Munoz*, Simon Goutier, Sylvie Foucaud, Gilles Mariaux
SPCTS UMR 7315, Centre Européen de la Céramique, 12 Rue Atlantis, 87068 Limoges Cedex,
France; *e-mail: [email protected]
Keywords: aerosol generation, droplet size distribution, non-oxide ceramics, spray pyrolysis

Spray pyrolysis is a process developed for the synthesis of ceramic powders from liquid pre-
cursors which allows composition and size modulation of the particles. This technique, based
on the ultrasonic generation of a hexamethyldisilazane (HMDS) liquid precursor aerosol that
is heat-treated in a furnace, has been used to obtain Si/C/N sub-micron powder ceramics with
a high thermal stability1.

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The process is based on one droplet one particle (ODOP) mechanism corresponding to the
formation of one particle from one aerosol drop2. The final aim of this work is to model the
process, improving its comprehension, from the liquid precursor to the formed aerosol char-
acterization, its transport and the chemical-physical phenomena involved in this stage. At
first, to understand the relation between the precursor physical properties and the synthesized
particles size, aerosol characterization is an important aspect to obtain information about the
influence of droplet size on final particle size. However, modelling the aerosol formation was
not considered due to the complexity of two involved interdependent mechanisms, the liquid
surface wave instability development and the cavitation phenomena. Thus, the choice was
made to experimentally determine the spray’s droplet size distribution using the shadow­
graphy technique in similar conditions to synthesis ones. Different natures of fluids close to
HMDS one were used, and the evolution of the spray size distribution was evaluated at three
positions of the aerosol generating device. The results show a bimodal distribution of drop
size for the three positions, precursors and operating parameters of the nebulization device.
In order to predict the aerosol mean droplet size according to liquid properties and nebu-
lizer operating conditions, measured droplet diameters were compared with values issued
from correlations laws proposed in the literature. Furthermore, these correlations developed
for a slightly different generating system but nevertheless involving the same aerosol forma-
tion mechanisms were adapted and used to estimate the mean droplet diameter generated by
our system. Droplet size distribution represents the input information for decomposition and
recombination phenomena, next stage of the process. To clarify the mechanisms responsible
of particle formation, the precursor behavior at high temperature is being studied. These
experimental results will complete the numerical model of the process leading to its entire
comprehension.

References
1. Salles, V, et al. J. Europ. Ceram. Soc., 27, 357–366, 2007.
2. Wang, W, et al. Ind. Eng. Chem. Res., 47, 1650–1659, 2008.

620
Influence of specific interactions between processing additives
and the surface of oxide particles on Epoxy Gel Casting
S.M. Olhero, E. Lopes, J.M.F. Ferreira*
Department of Materials and Ceramics Engineering, CICECO-Aveiro Institute of Materials,
University of Aveiro, Aveiro 3810-193, Portugal; *e-mail: [email protected]
Keywords: Epoxy Gel Casting, surface interaction, epoxy cure reaction, ceramic oxides, MEMS

Epoxy Gel Casting (EGC) revealed to be a suitable direct consolidation technique to fabri-
cate high green strength micro-components for advanced applications such as in microelec-
tromechanical systems (MEMS) and biomedical devices (Bio-MEMS). The process involves
casting well dispersed high solid loading suspensions with added epoxy resin and hardener

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 T01: New developments in processing and synthesis – Oral presentations

into silicon rubber moulds.1,2 Very high green strength values were achieved, enabling over-
coming the elevated shear stresses upon un-moulding micro-components with high aspect
and surface to volume ratios. This is an essential and unique feature of EGC conferred by the
in situ polymerization of epoxy resins in the presence of suitable amine-based crosslinking
agents. The specific interactions between the surface of the powder particles and the process-
ing additives are likely to determine different partitions of the crosslinking species, dissolved
in the bulk solution, or adsorbed at the surface of the particles, and affect the EGC process.
The present work aims at evaluating the influence of surface chemistry on the extent of the
specific interactions at the solid/liquid interface and how it affects the polymerization kinet-
ics and the properties of ceramic green bodies consolidated by EGC. Different ceramic ox-
ides (alumina, zirconia and fused silica) having similar particle size distributions were used.
Stable colloidal suspensions with 45 vol.% solids were prepared by dispersing the powders
in aqueous solutions containing a fixed amount of a common dispersant and various dis-
solved amounts of an epoxy resin. Zeta potential, rheological measurements and calorimetry
were used to assess the specific interactions and their effects on the consolidation kinetics
upon adding a polyamine hardener, and on the final properties of consolidated parts. With
the isoelectric point of the naked particle surface decreasing, there were noticeable decreases
in gelation time, shrinkage, green density, and flexural strength of the green ceramic body’s
properties. An interaction model is proposed to explain the observed differences.

References
1. Olhero, S.M., Garcia-Gancedo, L., Button, T.W., Alves, F.J., Ferreira, J.M.F. “An innovative col-
loidal approach to fabricate PZT pillar arrays”, J. Eur. Ceram. Soc., 32(5), 1067–1075, 2012.
2. Olhero, S.M., Lopes E., Ferreira J.M.F. “Fabrication of ceramic microneedles - The role of specific
interactions between processing additives and the surface of oxide particles in Epoxy Gel Casting”,
J. of Europ. Ceram. Soc., 36(16), 4131–4140, 2016.

361
Additive manufacturing of ceramics from preceramic polymers:
from nanometers to centimeters
Johanna Schmidt1, Laura Brigo1, Gioia Della Giustina1, Giovanna Brusatin1, Paolo
Colombo1,2
1
Department of Industrial Engineering, University of Padua, Padua 35131, Italy
2
Department of Materials Science and Engineering, The Pennsylvania State University, University
Park, PA 16802, USA
Keywords: Additive Manufacturing, Digital Light Processing, 2-Photon-Polymerization, preceramic
polymer, macrofabrication, microfabrication

Ceramic structures across different length scales were fabricated by additive manufacturing
using stereolithography of preceramic polymer solutions. Commercially available polysilox-
anes were selected, physically combined and photocrosslinked using the visible light range

37 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T01: New developments in processing and synthesis – Oral presentations

of the Digital Light Processing (DLP) printer for macrofabrication and the IR-wavelength of
the 2-Photon-Polymerization (TPP) printer for microfabrication.
Compatible polysiloxanes were combined with one material possessing the necessary
photocrosslinkable groups for fabrication and the other a high ceramic yield. The printing
process and solutions were optimised regarding printing parameters and additives like sol-
vent, photoinitiator and photoabsorber to print 3D structures with accurate geometry in an
appropriate time frame as well as preserve the shape after pyrolysis.
We present the DLP and TPP fabrication of SiOC ceramic macro- (heights up to several
cm) and micro-fabricated parts (features down to a few hundreds of nm) starting from com-
mercially available preceramic polysiloxanes. Complex ceramic structures, with a chemical
composition which is not realizable other than from the preceramic polymer route, were man-
ufactured with ceramic yields up to 60.2 wt%. In comparison to other additive manufacturing
techniques, DLP offers higher resolution and the possibility of achieving dense ceramic parts,
while sub-micron resolution can be achieved with TPP.

Fig. 1. PSA/Pol2 = 1/1 (not pyrolysed produced by DLP)

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 T01: New developments in processing and synthesis – Oral presentations

Fig. 2. PSA/Pol2 = 1/1 (pyrolysed produced by DLP)

Fig. 3. PSA (not pyrolysed produced by TPP)

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720
Laser melting initiated deeper structural heterogeneity in oxide ceramics
Lu Song1*, Jing Ma1, Yafei Wang1, Qinghua Zhang1, Ben Xu1, Zhijian Shen1,2
School of Materials Science and Engineering, Tsinghua University, Beijing 100084, P. R. China;
1

*
e-mail: [email protected]
Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University,
2

S-106 91 Stockholm, Sweden

Keywords: laser melting, nonstoichiometric oxides, nonequilibrium, physical properties, structure-
performance relationship

Selective laser melting, as a kind of additive manufacturing process, has proven itself a pow-
erful method in manufacturing of customized parts, made especially of metals and alloys. Be-
sides the success in 3D net-shape forming, this process has been recognized by its dynamic
and non-equilibrium characteristics, which has enabled the formation of amorphous metals
and high-entropy alloys. In ceramics, this process introduces deeper structural heterogeneity
that would alter their properties. In our work the selective laser melting process was used to
treat oxide ceramics. Here we demonstrate that complicated multi-scale structures and rich
defects can be implanted. Thus, nano-crystallites, with size much smaller than that of the
precursor particles, were found to form in laser melted oxide ceramics, which assembled
together to form larger grains with identical crystallographic orientation as the constitutional
nano-crystallites. Such deeper structural heterogeneity further results in significant changes
in the electric, magnetic and optical properties of these functional oxides. The process thus
is proven to be an efficient way for synthesis and modification of oxide ceramics with novel
properties that would add more benefits to the additively manufactured ceramic parts, en-
abling the manufacture of customized ceramic parts with customized performances.

References
1. B. Qian, C.H. Xiao, J. Zou, Y. Zhong, Z.J. Shen, “Assembled Nano-Structures from Micron-Sized
Precursors”, RSC Adv., 4, pp. 30754–30757, 2014.
2. D. Grüner, Z.J. Shen, “Ordered Coalescence of Nano-Crystals during Rapid Solidification of Ce-
ramic Melts”, CrystEngComm, 13, pp. 5303–5305, 2011.

523
MgTi2O5 and related pseudobrookite-type ceramics
Yoshikazu Suzuki
Faculty of Pure and Applied Sciences, University of Tsukuba, Ibaraki 305-8573, Japan;
e-mail: [email protected]
Keywords: pseudobrookite, low bulk thermal expansion, anisotropic structure, spherical porous
granules

Magnesium dititanate (MgTi2O5, MT21) has the pseudobrookite structure (general for-
mula Me3O5), corresponding to Mg-enriched artificial endmember of Fe2TiO5–FeTi2O5–
Mg0.5Fe0.5Ti2O5 (pseudobrookite–ferropseudobrookite–armalcolite) solid solution found in
ECerS2017 / July 9–13, 2017 / Budapest, Hungary 40
 T01: New developments in processing and synthesis – Oral presentations

natural igneous rocks. MgTi2O5 was named ‘karrooite,’ but it is not an official mineral name.
Apollo 11 mission in 1969 found a new mineral, Mg0.5Fe0.5Ti2O5 in lunar rocks collected
by the astronauts Armstrong, Aldrin and Collins; it was termed armalcolite after them. The
discovery of Mg0.5Fe0.5Ti2O5 stimulated renovated interests on MgTi2O5. To date, studies on
­MgTi2O5 mainly focus on basic properties such as cation order–disorder and anisotropic ther-
mal expansion. Also, MgTi2O5 is used as a ‘pseudobrookite-phase stabilizer’ for Al2TiO5,
which is widely known as a low-thermal-expansion ceramic.
Recently, our group have developed a variety of MgTi2O5 and related pseudobrookite-type
porous and dense ceramics for energy and environmental applications2–8. In this presentation,
we introduce various functional applications of these pseudobrookite-type ceramics.

Fig. 1. Pseudobrookite-type spherical porous granules by one-step reactive sintering8

References
1. Y. Suzuki and Y. Shinoda, Sci. Tech. Adv. Mater., 12, no. 034301 (2011).
2. Y. Suzuki, T.S. Suzuki, Y. Shinoda, and K. Yoshida, Adv. Eng. Mater, 14, 1134–1138 (2012).
3. T. Hono, N. Inoue, M. Morimoto, and Y. Suzuki, J. Asian Ceram. Soc., 1, 178–183 (2013).
4. Y. Nakagoshi and Y. Suzuki, J. Asian Ceram. Soc., 3, 334–338 (2015).
5. R.S.S. Maki and Y. Suzuki, J. Ceram. Soc. Jpn., 124, 1–6 (2016).
6. Y. Nakagoshi, J. Sato, M. Morimoto, and Y. Suzuki, Ceram. Int., 42, 9139–9144 (2016).
7. H.-W. Son, R.S.S. Maki, B.-N. Kim, and Y. Suzuki, J. Ceram. Soc. Jpn., 124, 838–840 (2016).
8. Y. Suzuki, H. Tokoro, and H. Abe, Mater. Lett., 163, 43–46 (2016).

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935
From primary particle coating to sintered ceramics – an alternative
method to create homogenous ZTA ceramics
Caroline Tschirpke*, Uwe Reichel, Sabine Begand
Fraunhofer Institut für keramische Technologien und Systeme IKTS, Hermdorf, Germany;
*
e-mail: [email protected]
Keywords: ZTA, core-shell, coating, sintering

Zirconia toughened alumina (ZTA) ceramics exhibit many favorable properties. They are
less inclined towards low temperature degradation and therefore suitable for medical appli-
cations. Furthermore ZTA exhibits higher toughness and strength than alumina with reduced
costs compared to pure zirconia ceramics, which allows a mass market usage e.g. as pump
components, sensors. As for all composite ceramics, the phase distribution as well as grain
size and density are main features of the ceramic mechanical properties. It stands to reason
that a more homogenous phase distribution at comparable grain size and density leads to
increased toughness and strength values. The aim of this project was to investigate whether
significant differences in the phase distribution can be observed when either ball-milled pow-
der mixtures or coated primary particles are used as ZTA raw material.
The coating of primary particles can be achieved by various technologies e.g. by fluid-
ized bed drying or flame spraying technology. In this project a wet chemical synthesis – a
modified Pechini process1,2 – was established. Zirconyl nitrate was dissolved in an ethylene
glycol, citric acid and water mixture and afterwards mixed with an alumina-water suspension
(particle size of alumina in the range of 200 nm). After rotary evaporation and calcination
for removing the volatile parts, the generated powder was grounded, pressed and sintered.
At every step of the process several characterization methods were carried out. The primary
and coated particles were analyzed by SEM, XRD, DTA and TG. The sintered ceramics were
characterized by microstructure, XRD and density measurements were carried out.
Results of the powder coating showed a disturbed layer of ZrO2 on the alumina core.
Nevertheless, first SEM images of the sintered ceramic show a locally very homogenous dis-
tribution of the zirconia phase. The zirconia grains are uniformly located at the interparticle
grain boundary.
Due to the high additive content an insufficient densification occured during sintering and
no defect free sampled could be produced so far. Modification of the drying process could
be the main challenge for the production of these kinds of ceramics and the main focus for
further research.

Acknowledgment
We kindly thank the BMBF for financial support of this project in connection with PADES Thüringen
(03WKCN03H).

References
1. US 3330,697; Method of preparing lead and alkaline earth titanates and niobates and coating meth-
od using the same to form a capacitor, Maggio P. Pechini, 1967.
2. Nanocoating of Al2O3 additive on ZrO2 powder and its effect on the sintering behaviour in ZrO2
ceramic, R.F. Gonçalves, M.J. Godinho, E.R. Leite, A.P. Maciel, E. Longo, J.A. Varela, J. Mater.
Sci, 2007.

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178
Sol–gel routes in different media to obtain nanostructured,
superhydrophobic coatings on copper surfaces
Federico Veronesi*, Mariarosa Raimondo, Magda Blosi, Giulio Boveri, Guia Guarini
Institute of Science and Technology for Ceramics, National Research Council, Via Granarolo 64,
48018 Faenza (RA), Italy, *e-mail: [email protected]
Keywords: copper, nanostructured coatings, superhydrophobic surfaces, sol-gel

Due to peculiar properties like thermal and electrical conductivity, alloyability, malleability
and so on, copper is widely used as reference material for a great number of industrial com-
ponents, such as heating/cooling devices and electronics. When copper is in contact with a
water flow, it could become crucial to control its surface wetting properties to enhance ef-
ficiency in such devices. With this aim, copper surfaces were functionalized by deposition of
hybrid, nanostructured layers to achieve advanced water repellence, e.g. superhydrophobic-
ity. First, alumina nanoparticles obtained by sol-gel routes were deposited to form a thin gel
layer, which, after treatment in boiling water, turned into a nanostructured boehmite coating
with a peculiar flower-like morphology. Two sol-gel syntheses of Al2O3 nanoparticles were
attempted, namely in water and in isopropyl alcohol. This latter revealed to be able to pro-
vide a better organized nanostructured coating with higher superhydrophobicity after chemi-
cal grafting of a fluoroalkylsilane moieties with respect to the water-based one. The further
analyses of XPS spectra confirmed these circumstances.
Moreover, the effect of thermal treatment temperature on surface morphology were also
evaluated. After formation of the gel film, the surfaces were heat-treated at either 200, 300
or 400 °C. SEM investigations showed that flower-like boehmite prevailed when T ≤ 300 °C,
while at T = 400 °C CuO microwires grew, displacing boehmite itself. Even though all coated
samples displayed superhydrophobic behavior, the 400 °C-treated surface was extremely
brittle, while the 200 °C-treated sample could perfectly withstand ultrasonic treatment with
no loss in superhydrophobicity. These results suggest that it is necessary to strictly control
both the synthesis of coatings precursors and the processing variables when copper surfaces
modifications leading to advanced water repellence have to be designed.

References
1. N. Miljkovic, R. Enright, Y. Nam, K. Lopez, N. Dou, J. Sack and E. Wang, “Jumping-Droplet-
Enhanced Condensation on Scalable Superhydrophobic Nanostructured Surfaces”, Nano Lett., 13,
pp.179–187, 2013.
2. A. Caldarelli, M. Raimondo, F. Veronesi, G. Boveri and G. Guarini, “Sol–gel route for the build-
ing up of superhydrophobic nanostructured hybrid-coatings on copper surfaces”, Surf. Coat. Tech.,
276, pp. 408–415, 2015.

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056
Fabrication of silica glass from mesoporous powder by SPS
Lianjun Wang*, Minghui Wang
College of Material Science & Engineering, Donghua University, Shanghai, 201620, China;
*
e-mail: [email protected]

Silica glasses containing noble metal nanoparticles are of great interest due to the surface
plasmon resonances of these nanoparticles which behave as optically functional phases.
These composite materials are expected to be exploited in photonic devices. Despite the
prospects of application, the traditional fabrication methods impair homogenously nucleation
of nanoparticales resulting in an obstacle to control the size and dispersion of nanoparticles
dopnant. Here, a new versatile processing strategy based on solid-state sintering is reported
for preparation such bulk transparent glass composite. Mesoporous silica SBA-15 powders
encapsulating Au, Ag and Pt nanoparticles are prepared via host-guest synthesis method
and then dynamically consolidated to form a bulk transparent specimen by Spark Plasma
Sintering(SPS). The whole sintering process takes place under much lower temperature
(1020 °C) and within very short times (10 min) than traditional melting-quenching method.
The obtained composite glasses show different colors due to the surface plasmon resonance
differences from Au, Ag, Pt nanoparticles and exhibit large nonlinear optical susceptibilities
(ranging in 10–12~10–11 esu) regarding with the extreme low dopnant (ca. 0.05 wt%). This ap-
proach should be applicable to the synthesis of silica glasses embedded with a wide variety
of nobel metal and semiconductor nanoparticles.

References
1. X. Zhang, W. Luo, L.J. Wang and W. Jiang, J. Mater. Chem. C, 2, 6966(2014).
2. X. Zhang, X.W. Yu, W. Luo, L.J. Wang, Z.J. Shen and W. Jiang, J. Am. Ceram. Soc., 98[2]1056(2015).
3. X. Zhang, S.J. Gu, B.Y. Zhou, L.W. Shi, L.J. Wang and W. Jiang, J. Am. Ceram. Soc., 2016, DOI:
10.1111/jace.14172.

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758
Freeze-cast cylindrical silicon oxycarbide shells fabricated by cryo
thiol-ene photopolymerization
Xifan Wang1, Franziska Schmidt1, Sara Zavareh1, Paul H. Kamm2, John Banhart2,
Sören Selve3, Jörg Nissen3, Dirk Berger3, Aleksander Gurlo1
Fachgebiet Keramische Werkstoffe / Chair of Advanced Ceramic Materials, Institut für
1

Werkstoffwissenschaften und –technologien, Technische Universitaet Berlin, Hardenbergstrasse 40,

10623 Berlin, Germany; e-mail: [email protected]
Institut für Angewandte Materialforschung / Institute of Applied Materials, Helmholtz-Zentrum
2

Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin, Germany;

e-mail: [email protected]
Zentraleinrichtung Elektronenmikroskopie (ZELMI), Technische Universitaet Berlin, Straße des 17.
3

Juni 135, 10623 Berlin, Germany; e-mail: [email protected]

Keywords: freeze casting, ice templating, polymer derived ceramic, cryo photopolymerization, thiol-
ene click chemistry, graphene oxide, ceramic shell

Porous ceramics are of interest for various applications including filtration, separation and
catalysis. They demand extensive research towards new processing routes. Among them,
freeze casting technique (also called ice templating) attracted a considerable attention in the
recent years.
Herein, we report the first example of low temperature thiol-ene click photopolymeriza-
tion combined with ice templating that allows for fabrication of macroporous ceramics from
liquid preceramic precursor. We show that this technique is highly suitable for directional
freeze casting of the UV active polymers, which cannot be produced by conventional freeze
casting method. Furthermore, we observe that a hollow monolith with a cylindrical shape and
radial density gradient is produced when introducing the graphene oxide (GO) suspension
into the preceramic polymer. The whole reaction, especially the UV light absorption rate and
the degree of polymerization, are strongly affected even by adding only one weight percent
of GO. GO sheets define the material’s architecture by limiting the depth of the penetrating
UV light as well as the volume which is cross-linked by UV light. As a result the size of the
void inside the ceramic monolith can be easily controlled by adjusting the GO concentration.

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252
Porous γ-(Y1-xHox)2Si2O7 thermal insulator with excellent strength
retention at high temperature
Zhen Wu1, Jingyang Wang2
High-performance Ceramics Division, Institute of Metal Research CAS, 72 Wenhua Road, Shenyang
1

110016, China; e-mail: [email protected]

High-performance Ceramics Division, Institute of Metal Research CAS, Shenyang, China;
2

e-mail: [email protected]
Keywords: porous γ-(Y1-xHox)2Si2O7 solid solution, high temperature thermal insulator, in situ reac-
tion foam-gelcasting method, strength retention, low thermal conductivity

High temperature thermal insulation materials challenge extensive candidates with good me-
chanical, thermal and chemical reliability at high temperature. Recently, porous γ-Y2Si2O7
was shown a promising thermal insulator in harsh environment; however its strength at 1300
o
C degraded to 38% of the magnitude at room temperature. In this work, we significantly
improved its high temperature strength by doping Ho. Highly porous γ-(Y1-xHox)2Si2O7 solid
solution was fabricated by in situ foam-gelcasting method and has low thermal conductivity
(~0.19 W/(m·K)) and high compressive strength (~12 MPa) with the porosity of 80%. SEM
and X-ray tomography observations showed interesting multiple pore structures, including
large pores (30–230 μm) and small pores (0.1–2 μm), in the as-prepared porous samples.
Porous γ-(Y2/3Ho1/3)2Si2O7 demonstrated the best optimization on strength, 65% retention at
1300 °C. Porous solid solution samples also displayed obviously lower thermal conductivity
than the two end pure-phase porous materials. Porous γ-(Y1-xHox)2Si2O7 ceramic is highlight-
ed as a promising high-temperature thermal protection material with optimal low thermal
conductivity and excellent strength retention.

References
1. A.R. Studart, U.T. Gonzenbach, E. Tervoort and L. Gauckler, “Processing routes to macroporous
ceramics: A review”, J. Am. Ceram. Soc., 89, pp. 1771–1789, 2006.
2. Z. Wu, L.C. Sun, P. Wan and J.Y. Wang, “Preparation, microstructure and high temperature perfor-
mances of porous γ-Y2Si2O7 by in situ foam-gelcasting using gelatin”, Ceram. Int., 41, pp. 14230–
14238, 2015.
3. P. Sepulveda and J.G.P. Binner, “Processing of cellular ceramics by foaming and in situ polymerisa-
tion of organic monomers”, J. Eur. Ceram. Soc., 19, pp. 2059–2066, 1999.

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526
Borothermal reduction of group IV and V metal oxide with NaBH4:
synthesis and characterization of metal diboride nanocrystals
Luca Zoli, Laura Silvestroni, Diletta Sciti
CNR-ISTEC, National Research Council of Italy, Institute of Science and Technology for Ceramics,
Via Granarolo 64, I-48018 Faenza, Italy

Group IV and V metal diboride (MB2) have very high melting point (>3000 °C), high hard-
ness, good solid-state phase stability, high thermal and electrical conductivity. Metal dibo-
ride-based ceramics are expected to be potential candidate materials for ultra-high-tempera-
ture applications in the aerospace industry1. Availability of submicrometric/nanometric bo-
ride particles has indeed the potential to improve several stages of ceramic processing2, or for
instance to facilitate the sintering of bulk ceramics3, due to enhanced particle reactivity. Meta
diboride nanocrystals can be synthesized by various methods: chemical route from inorganic
precursors such as metal halides and NaBH4, mechanical alloying and self-propagating high-
temperature synthesis4–6. However these processes often require expensive facilities or raw
materials and are carried out under extreme conditions.
In this work group IV and V metal diboride (MB2, M = Ti, Zr, Hf, Nb, Ta) nanocrystals
were successfully synthesized by a thermal treatment of metal oxide and sodium borohydride
(NaBH4) at 700 °C under atmospheric pressure7. The reaction occurs first via decomposition
of NaBH4, followed by the formation of amorphous boron and crystalline ternary species
with general formula NaxMyOz and NaxByOz. Finally all of the intermediary species yield
metal diboride (MB2) and sodium meta-borate (NaBO2).
Synthesized TiB2 nanocrystals have an average size of 11 nm and the powder has a specific
surface area (s.s.a) of 33.45 m2/g. ZrB2 has grains have a platelet morphology with aspect
ratio of 10, with average size of 22.5 nm and s.s.a of 24.97 m2/g; HfB2 has a similar morphol-
ogy with a crystals size of 28 nm, while the s.s.a is even higher, 36.36 m2/g. As far as we
know, the latter is the finest powder obtained via borothermal reduction of metal oxides ever
reported. Synthesized NbB2 powder consists of crystallites around 12 nm and has an s.s.a of
21.09 m2/g. TaB2 powder has an s.s.a of 11.38 m2/g and consists of 200 nm agglomerates of
spherical and needle-shaped nanocrystals with average size of 11 nm.

References
1. R.A. Cutler, Engineering Properties of Borides, in: Ceramics and Glasses, Engineered Materials
Handbook, Vol. 4, Edited by S. J. Schneider. ASM International, Materials Park, OH, 1992, pp.
787–803.
2. S. Carenco, D. Portehault, C. Boissière, N. Mézailles, and C. Sanchez, Chem. Rev., vol. 113, no.
10, pp. 7981–8065, 2013.
3. J.K. Sonber and A.K. Suri, Adv. Appl. Ceram., vol. 110, no. 6, pp. 321–334, 2011.
4. W.G. Fahrenholtz, G.E. Hilmas, J. Am. Ceram. Soc. 90 (2007) 1347–1364.
5. E.-Y. Jung, J.-H. Kim, S.-H. Jung, S.-C. Choi, J. Alloys Compd. 538 (2012) 164.
6. T. Tsuchida, S. Yamamoto, J. Eur. Ceram. Soc. 24 (2004) 45.
7. L. Zoli, A. L. Costa, and D. Sciti, “Synthesis of nanosized zirconium diboride powder via oxide-
borohydride solid-state reaction,” Scr. Mater., vol. 109, pp. 100–103, 2015.

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Poster presentations

887
Fabrication of Cu-Mo composites combining SHS and SLS technologies
Sofiya Aydinyan1, Tatevik Minasyan1, Hasmik Kirakosyan2,4, Marina Aghayan1,
Irina Hussainova1,3, Suren Kharatyan2,4
1
Tallinn University of Technology, Ehitajate 5, 19086, Tallinn, Estonia
2
A.B. Nalbandyan Institute of Chemical Physics, P. Sevak 5/2, 0014, Yerevan, Armenia
3
ITMO University, Kronverksky 49, 197101, St. Petersburg, Russian Federation
4
Yerevan State University, A. Manukyan 1, 0025, Yerevan, Armenia

Cu-Mo alloys have been attracted tremendous interest in the recent past due to excellent
combination of high thermal conductivity of copper and low thermal expansion coefficient
of molybdenum. Primary applications of these materials are high power electronic devices
and electrical contacts especially at high voltage, welding electrodes, electric discharge ma-
chine, and heat sinks.1 Because of the mutual insolubility of molybdenum and copper the
main densification mechanism is considered to be the particle rearrangement associated with
the movement of the liquid phase. However, Cu-Mo compacts show very poor sinterability
even above the melting point of copper. In this regard, a novel approach has been explored
to enhance Cu-Mo composite densification by energy-saving combustion processes (SHS)
combined with selective laser sintering (SLS).2,3 As high-dense Cu-Mo materials with homo-
geneous microstructure are required for high performance, attempts were made to prepare
ultra-fine and well-dispersed Cu-Mo powders. For this purpose the co-reduction of metal-
constituents from oxygen containing compounds was performed using Mg+C mixture as
combined reducers. It was demonstrated that at certain amount of reducers and slow propaga-
tion of combustion wave, the joint and complete reduction of both metals becomes possible.
Cu-Mo alloys developed by SHS process and subjected to consolidation using SLS technol-
ogy possess uniform distribution of consisting phases and high density. The combination
of SHS and SLS undoubtedly is advantageous in comparison with the other technologies
and may be considered as an alternative pathway to fabricate Cu-Mo alloys with enhanced
properties.

References
1. Joseph R. Davis, “Copper and Copper Alloys”, ASM International, p. 621, 2001.
2. A.G. Merzhanov, A.S. Mukasyan, Solid-flame combustion, Torus Press, Moscow, p. 280–282,
2007.
3. A. Zocca, P. Colombo, C.M. Gomes, J. Günster, Additive manufacturing of ceramics: issues, poten-
tialities, and opportunities, J. American Cer. Soc. 98(7), pp. 1983–2001, 2015.

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 T01: New developments in processing and synthesis – Poster presentations

461
Solid state sintering and thermal expansion behavior of cordierite with
CeO2 and MgF2 additions
Demet Aydogmus, Erdem Demirkesen
Department of Metallurgical and Materials Engineering, Istanbul Technical University, Maslak,
Istanbul, Turkey; e-mails: [email protected], [email protected]
Keywords: cordierite, solid state sintering, quantitative X-ray diffraction analysis

Due to excellent thermal and electrical properties, cordierite (2MgO.2Al2O3.5SiO2) ceramics

have a wide range of industrial applications. Conventional solid state sintering of cordierite
exhibits some limitations. Firstly, the cordierite formation process via solid state reaction is
extremely slow. Since there is an interface area between reactants leading to cordierite forma-
tion, in order to proceed the reaction, the reactants should diffuse through the generated cor-
dierite barrier. Therefore the interdiffusion of reactants through this barrier of product slows
down the overall reaction rate. Particularly the determinative step of the overall reaction rate
is the interface controlled diffusion of reactants. Another limitation is the narrow sintering
range of cordierite due to the eutectic and peritectic points near incongruent melting point of
cordierite as can be noticed from MgO-Al2O3-SiO2 ternary phase diagram. The temperature
range between these invariant points is around 100 oC. The slow reaction rates and the narrow
sintering temperature range result in meeting some difficulties about cordierite formation via
solid state sintering. Different researchers have tried to employ different sintering additives
so far, to be able to withstand these sintering problems. However, the individual effects of
additives on cordierite formation at constant temperature, pressing pressure has not been
determined yet.
In this study, the specific effects of 2-5 wt.% CeO2 and MgF2 additives on the forma-
tion rate and thermal expansion behavior of cordierite were investigated. The stoichiometric
amount of spinel (MgO.Al2O3) and quartz (SiO2) powders were pressed and sintered at 1350
o
C for 10 to 50 hours. Qualitative and quantitative X-ray diffraction phase analysis, dilato-
metric analysis and density measurements using Archimedes principle were carried out. Re-
garding with the overlapping problem in spinel-cordierite phases, two different quantitative
XRD methods were applied and the results were compared according to accuracy.

References
1. J.M. Benito, X. Turrillas, G.J. Cuello, A.H. De Aza, S. De Aza, M.A. Rodríguez, “Cordierite syn-
thesis. A time-resolved neutron diffraction study”, Journal of the European Ceramic Society, 32(2),
pp. 371–379, 2012.
2. M.E. Brown, D. Dollimore, A. K. Galwey. Theory of Solid State Reaction Kinetics. Elsevier, New
York, 1980.
3. Z.M. Shi, K.M. Liang, S.R. Gu, “Effects of CeO2 on phase transformation towards cordierite in
MgO-Al2O3-SiO2 system”, Materials Letters, 51, pp. 68–72, 2001.

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871
Manufacture of alkali activated polymers from clay with
mechanochemical activation
Ida Balczár*, Tamás Korim
Institute of Materials Engineering, University of Pannonia, Egyetem utca 10, H-8200 Veszprém,
Hungary; *e-mail: [email protected]
Keywords: alkali activated cements, mortars, grinding, compressive strength

Alkali activated cements play an increasing role as a successful substitute of ordinary Port-
land cements due to their superior durability and environment friendliness. Raw materials
commonly used for alkali activated cement synthesis are those which are rich in alumino-sil-
icates such as natural pozzolans, fly ashes, calcined kaolins and also calcined clay minerals.1
Present research focused on the manufacture of this novel binding material system based
on two clay minerals with different composition. The raw materials were activated before
setting with two different methods; one hand with thermal activation on two different tem-
peratures (700 and 850 °C) and with two chosen heat treatment time (1 h, 3 h). The other
hand a novel, possibly cost-effective method, mechanochemical activation, was applied, a
short but intensive grinding. The grinding time was altered during the experiment, and the
physical performance of the obtained mortars were compared.
The degree of amorphous phase of differently treated samples was determined using x-ray
diffraction which may have a direct effect on reactivity. 28 days of compressive strength was
also determined of the mortar samples. In summary, alkali activated cement samples (pro-
duced from clay minerals) activated with mechanochemical activation have better physical
properties as the samples derived by thermal activation.

Reference
1. J. Davidovits, “Geopolymers: inorganic polymeric new materials”, J. Therm. Anal. 37, pp. 1633–
1656, 1991.

796
Synthesis of mesoporous tin dioxide powder using polystyrene latex and
CTAB
Fereshteh Bayat, Ali Beitollahi, Seyyed Mohammad Mirkazemi
Centre of Excellence for Ceramic Materials, School of Metallurgy and Materials Engineering, Iran
University of Science and Technology (IUST), Narmak, Tehran 16846, Iran
Keywords: tin dioxide, mesoporous, polystyrene, CTAB

In recent years, semiconductor metal oxides have considered much attention due to their
wide range of applications. Tin dioxide (SnO2) is a functional wide band gap (3.6 eV at
300K) n-type semiconductor and possesses special properties which provide applications in

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gas sensors, Li-ion batteries, dye-synthesized solar cells and photocatalytic devices1,2. Meso-
porous materials have attracted considerable interest because of having large surface areas
which makes them suitable candidates for distinctive applications. Different hard and soft
templates have been used to fabricate nanostructured tin dioxide so far3. Using hard and soft
templates simultaneously have enabled the formation of porous structures with high surface
area and special properties4.
Here, a facile method for the synthesis of mesoporous SnO2 powder is reported. Mesopo-
rous SnO2 nanoparticles were synthesized using SnCl2.2H2O precursor and polystyrene (PS)
latex and cetyltrimethylammonium bromide (CTAB) surfactant as hard and soft templates re-
spectively. Polystyrene nanospheres were prepared using conventional emulsion polymeriza-
tion and they were analysed using Dynamic Light Scattering (DLS), Field emission electron
microscopy (FESEM), and Fourier transformed infrared analysis (FTIR). Results showed
successful synthesis of Polystyrene latex with spherical morphology and the mean particle
size of 78 nm. In the synthesis process, CTAB micelles covered the polystyrene surface and
then the precursor precipitated on templates. After optimizing synthesis parameters, tem-
plates were removed via different calcination procedures in air to protect the mesostructure.
The obtained mesoporous SnO2 powder was characterized using X-Ray diffraction (XRD),
FESEM, FTIR, and Nitrogen adsorption/desorption. The powder had nearly spherical mor-
phology and the specific surface area and the pore size value of the synthesized SnO2 powder
were 177.67 m2/g and 12.5 nm, respectively.

References
1. J. Hu, M. Chen, X. Fang, L. Wu, “Fabrication and application of inorganic hollow spheres,” Chem.
Soc. Rev., vol. 40, no. 11, pp. 5472–5491, 2011.
2. P. Manjula, R. Boppella, S.V. Manorama, “A facile and green approach for the controlled synthesis
of porous SnO 2 nanospheres: Application as an efficient photocatalyst and an excellent gas sensing
material,” ACS Appl. Mater. Interfaces, vol. 4, pp. 6252–6260, 2012.
3. D. Gu, F. Schüth, “Synthesis of non-siliceous mesoporous oxides,” Chem. Soc. Rev., vol. 43, no.
1, pp. 313–44, 2014.
4. X.-Y. Yang, Y. Li, A. Lemaire, J.-G. Yu, B.-L. Su, “Hierarchically structured functional materials:
Synthesis strategies for multimodal porous networks,” vol. 81, no. 12. 2009.

872
Production of inorganic polymers with different raw material activating
methods based on kaolin
Adrienn Boros*, Ida Balczár, Tamás Korim, Éva Makó
Institute of Materials Engineering, University of Pannonia, Egyetem utca 10, H-8200 Veszprém,
Hungary; *e-mail: [email protected]
Keywords: calcination, milling, mechanical properties, geopolymer mortars

During the past decades, manufacturing of binders has increased rapidly, and concrete has be-
come an essential structural material, but cement manufacture causes massive CO2 emissions
and landscape destruction. A new kind of inorganic binders, called alkali activated cements

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provide solution for the listed problems. Alkali activated cements can be synthesised from
alumina-silicate rich materials, such as natural pozzolans, fly ashes and calcined kaolins.
The present study compares two different activating methods of kaolin for the purpose of
manufacturing these binding materials. Thermal activation is a well-known procedure, but
here, the investigation focused on the influence of heat-treatment temperature and time. In
this case a new method, called mechanochemical activation, was applied in parallel using
various grinding parameters (grinding time, the mass ratio of sample to grinding body, and
rotation speed). The structural and morphological changes of thermally and mechanochemi-
cally activated kaolinite were followed by X-ray diffraction (XRD), scanning electronmi-
croscopy (SEM). The effectiveness of thermal and mechanochemical activation was charac-
terised by compressive strength at 28 days and a calculated “degree of amorphisation”. The
results demonstrate that mechanochemical activation is an effective method for producing
geopolymers, the maximum compressive strength (55.6 MPa) of mechanochemically acti-
vated samples surpassed the best thermally activated one (43.0 MPa).

430
An innovative extrudable alumina paste containing bio-sourced organic
binder
Julie Bourret*, Imane El Younsi, Thierry Chartier, Vincent Pateloup
SPCTS, European Ceramic Center, UMR CNRS 7315, 12 Rue Atlantis 87068 Limoges, France;
*
e-mail: [email protected]
Keywords: micro-extrusion, natural additives, alumina, rheology, Young’s modulus

Micro-extrusion is a shaping process which is used to make geometrically 3D complex ce-

ramic green bodies from a paste on the micrometric scale1. This technique has a wide range
of potential applications in various domains: health, energy, information and communication
technologies. Moreover, it has great flexibility because parts can be made “on demand” from
the modelling of the part in a CAD format without requiring machining or realization of
tooling. However, its success depends strongly on the composition and consequently on the
rheological behaviour of the used paste.
To obtain a ceramic paste which can be extruded correctly, its rheological behaviour must
be controlled. For this, several additives are used (dispersant, plasticizer, binder). These addi-
tives come mainly from the petrochemical industry and could have a negative impact on the
environment. In the context of developing low-cost and environmentally-friendly processes
and in accordance with the development of the principles of green chemistry, a new formu-
lation based on natural additives is studied. The challenge is to obtain a concentrated aque-
ous alumina ceramic particle systems based on bio-based polymers which is suitable for the
micro-extrusion process and which ensures satisfactory structural and mechanical properties.
In this work, alumina pastes (widespread oxide ceramic material) are produced in an
aqueous medium with a natural binder derived from plants and not chemically transformed
(in comparison with cellulose derivatives). The amount of alumina in pastes is around 50%vol.

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The pastes are extruded with a digital controlled device consisting of an XYZ displacement
platform and a home-made extrusion head. With this head, extrusion at pressures up to 600
bar is possible. The green parts are porous cubes made of 1 mm or 400 μm diameter alumina
cords (Fig. 1).

a) CAD model of the part b) Green part c) Scaffold after heat treatment at 1600 °C

Fig. 1. Presentation of alumina parts made from a paste containing a natural binder

After having successfully produced parts from these pastes based on bio-sourced binder, their
structural, micro-structural and mechanical characteristics are determined.

Reference
1. S. Michna, W. Wu, J.A. Lewis, “Concentrated hydroxyapatite inks for direct-write assembly of 3-D
periodic scaffolds,” Biomaterials, vol. 26, no. 28, pp. 5632–5639, 2005.

934
Development of LTCC tapes for silicon-ceramics composites
Beate Capraro1*, Uwe Partsch2
1
Fraunhofer IKTS, Department of Tape Casting, Hermsdorf, Germany;
*
e-mail: [email protected]
2
Fraunhofer IKTS, Department of Tape Casting, Dresden, Germany
Keywords: tape casting, LTCC, Si-LTCC-composites

The LTCC technology (Low Temperature Cofired Ceramics) is a state-of-the-art technol-

ogy that allows for miniaturization and integration of electronic circuits in a ceramic multi-
layer matrix. The processability of LTCC green tapes enables completely new interconnec-
tion and packaging solutions. The green sheets are mechanically structured, conduction lines
are printed with thick film technique, and finally the multilayer stack is laminated and then
sintered at about 900°C. In addition, there are favorable dielectric properties and the low
resistance of internal conductor paths, which enable various HF applications. The result is a
highly integrated three-dimensional cross-linked multilayer ceramic board.

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Silicon and LTCC are used as semiconductor and ceramic packages for a variety of mi-
cro-sensors and microsystems technologies. Micro-technology methods, such as photoli-
thography and micro-structuring, thick-film and thin-film techniques, as well as methods
of assembly and packaging, are used for both materials. This allows efficient fabrication of
microsystems in different product areas. By integrating both, silicon and LTCC, into one
multi-material multilayer systems, microsystems with significantly greater complexity and
application potential might be created. For the combination of silicon with LTCC two differ-
ent methods can be used.
One method for the realization of silicon-ceramic composites is anodic bonding of silicon
to an anodically bondable LTCC multilayer. The starting material consists of a powder mix-
ture (particle size in the sub micrometer range) of alumina, cordierite or SiO2 and a sodium-
containing glass as well as a polymer binder in the non-sintered state. The LTCC wafer is
manufactured separately using standard LTCC technologies. After sintering, the LTCC wafer
has a relatively high surface roughness (about 200 nm Ra). A lower roughness of Ra <50
nm is required for anodic bonding at the bonding surface, therefore the prefabricated LTCC
wafer has to be lapped and polished in an elaborate manner. Silicon and LTCC wafers are
then aligned with one another, heated to about 400 °C and subjected to a direct voltage of up
to 600 V.
A second technology for bonding of silicon with LTCC ceramics is the newly developed
SiCer process. For this purpose, a new ceramic LTCC material system was investigated
which can be co-sintered with structured silicon leading to high-strength composite sub-
strates. During the cofiring process, a solid bonding to the silicon is established. The formed
SiCer substrate is a material composite, which is thermally completely adapted to silicon
over a wide temperature range up to above 500 °C.
The poster presents the LTCC material classes developed for both connection technolo-
gies. Materials compositions, properties and some application examples will be discussed.

115
Preparation of La2NiO4 powders using oxalic acid process
Tzu Hsuan Chiang*, Chen-Kai Weng
Department of Energy Engineering, National United University, 2, Lienda, Nan-Shi Li, Miaoli,
Taiwan; *e-mail: [email protected]
Keywords: oxalic acid, dielectric constant, structure, XRD data

In this work, synthesis of La2NiO4 via a simple oxalic acid process, the nickel oxalate dis-
solved using ammonia as solvent then mixed with 0.1M of lanthanum nitrate and 0.1M of
strontium nitrate as shown in Eqs. (1) to (4). The SEM image of La2NiO4 powders and XRD
patterns of the different temperature calcined were shown in Fig. 1. The peaks as black spots
at 2θ were corresponded to the La2NiO4 structure (JCPDS 34-0314) with the Ruddlesden-
Popper structure and the white spots at 2θ were corresponded to the NiO structure (JCPDS
44-1159) in Fig. 1. However, the peaks of Sr compounds do not appear in XRD data although

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the process had been added 0.1M of strontium nitrate. This phenomenon has been described
previously by Nie et al.1, who stated that the formation of A2-xA’xBO4 structure is partially
related to the oxidation state of cation at B-site and that the valence of the B cation should be
approximately +2 for the K2NiF4 structure. This is an indication that Sr substitution on A sites
helps stabilize the Ruddlesden-Popper structure.
1. NiC2O4·2H2O + NH4OH→Ni+2 + C2O4‒2 + NH3 + 3H2O
2. La(NO3)3·6H2O +H2O→La3+ + 3NO3‒ + 7H2O
3. Sr(NO3)3 +H2O→Sr3+ + 3NO3‒ + H2O
4. 2Ni+2 +2 La3+ + Sr3++ 5/2O2→La2NiO4 +NiO

(a)

(b)
Fig. 1. (a) SEM image of La2NiO4 powders;
(b) XRD patterns of the different temperature calcined of La2NiO4 powders

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References
1. H.W. Nie, T.-L. Wen, S.R. Wang, Y.S. Wang, U. Guth, V. Vashook, “Preparation, thermal expansion,
chemical compatibility, electrical conductivity and polarization of A2−αA′αMO4 (A=Pr, Sm; A′=Sr;
M=Mn, Ni; α=0.3, 0.6) as a new cathode for SOFC,” Solid State Ionics, 2006, 177, pp. 1929–1932.
2. T.T. Inprasit, S. Wongkasemjit, S. J. Skinner, M. Burriel, P. Limthongkul, “Effect of Sr substituted
La2-xSrxNiO4+δ (x = 0, 0.2, 0.4, 0.6, and 0.8) on oxygen stoichiometry and oxygen transport proper-
ties,” RSC Adv., 2015, 5, pp. 2486–2492.

057
Growth of Si3N4 nanowires from amorphous Si3N4 powders synthesized
by low-temperature vapor-phase reaction
Yong-Kwon Chung1,2, Jae-Hong Koo1, Shin-A Kim1, Eun-Ok Chi1, Jun-Young Cho2,
Woon-Bae Sohn2, Mi-Young Kim2,3, Jin-Sang Kim4, Chan Park2,3
1
Research and Development Center, OCI company Ltd., Seongnam 462-120, Republic of Korea
Department of Materials Science and Engineering, Seoul National University, Seoul 151-744,
2

Republic of Korea
Research Institute of Advanced Materials, Seoul National University, Seoul 151-744, Republic of
3

Korea
Center for Electronic Materials Research, Korea Institute of Science and Technology, Seoul,
4

130-650, Republic of Korea

Keywords: silicon nitride, nanowire, amorphous

A novel synthesis method of Si3N4 nanowires from the amorphous silicon nitride (a-Si3N4)
powder synthesized by low-temperature vapor-phase reaction method was investigated.
Highly crystallized α-Si3N4 nanowires were synthesized from the heat-treatment of a-Si3N4
powder under ammonia atmosphere. The surface of the nanowires was smooth and clean
without any attached particles. The thickness of the nanowires was in the range of 200 ~
300 nm with lengths of tens of micrometers. The nucleation of nanowires from the reaction
between SiO and N2 occurs on the surface of a-Si3N4 powder which is covered by a thin layer
of SiO2, and the nanowires grow from the re-arrangement of Si and N atoms of the a-Si3N4
powder. The reduction of SiO2 to SiO by ammonia was promoted by the presence of Ni cata-
lyst, and so the growth was observed at lower temperature when Ni was added to the a-Si3N4
powder than when Fe was added. The growth of α-Si3N4 nanowires occurs along the [100]
and [101] direction and follows Vapor-Solid-Solid mechanism.

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130
Wet chemistry routes for morphology-controlled actinide oxides
powders
Nicolas Clavier*, Jérôme Maynadié, Adel Mesbah, Nicolas Dacheux
ICSM, UMR 5257 CEA/CNRS/ENSCM/Univ. Montpellier, Site de Marcoule, BP 17171, 30207
Bagnols/Cèze, France; *e-mail: [email protected]
Keywords: oxides, actinides, wet chemistry, synthesis, hydrothermal

The development of future generations of nuclear reactors led to consider wet chemistry
routes for the fabrication of the fuel ceramics (e.g. UO2 and (U,Pu)O2 solid solutions) as they
provide interesting powder properties (homogeneity, sintering capability) and enhance the re-
sistance toward proliferation. Such processes are mainly based on the initial precipitation of
low-temperature precursors (such as nitrates, carbonates or oxalates) which are further con-
verted into the final compounds through a heat treatment step operated at high temperature.
However, the resulting oxide powders can still incorporate some impurities1 and frequently
suffer from a poor flowability inherited from the morphology of the parent precursor.
In this context, we developed several wet chemistry routes aiming to precipitate directly
hydrated actinides oxides in solution, with a particular attention paid to the control of their
morphology. The first method retained is based on the formation of hydroxides colloids
which rapidly aged in solution to yield nanocrystalline AnO2.nH2O2. Preliminary tests indi-
cated that such powders can be directly sintered (i.e. without any prior heating step). They led
to a significant decrease of the temperature required for a complete densification and allowed
the preparation of a wide range of microstructures, particularly in term of final grain size.
On the other hand, the hydrolysis of actinides under mild hydrothermal conditions in
presence of aspartic acid as a shaping agent3, was investigated to prepare UO2.nH2O micro-
spheres. In this case, different operating parameters were studied (such as temperature, dura-
tion and aspartic acid concentration) and can be used to tailor the final grain size, typically
between 100 and 500 nm. Both methods thus directly provided oxide powders with original
microstructural features which can be of interest for future nuclear fuel cycles.

References
1. J. Martinez, N. Clavier, T. Ducasse, A. Mesbah, F. Audubert, B. Corso, N. Vigier, N. Dacheux,
“From uranium(IV) oxalate to sintered UO2 : consequences of the powders’ thermal history on the
microstructure”, J. Europ. Ceram. Soc., 35, pp. 4535–4546, 2015.
2. J. Martinez, N. Clavier, A. Mesbah, F. Audubert, X.F. Le Goff, N. Vigier, N. Dacheux, “An original
precipitation route toward the preparation and the sintering of highly reactive uranium cerium diox-
ide powders”, J. Nucl. Mater., 462, pp. 173–181, 2015.
3. N. Clavier, J. Maynadié, A. Mesbah, J. Hidalgo, R. Lauwerier, G.I. Nkou Bouala, S. Parrès-
Maynadié, D. Meyer, N. Dacheux, R. Podor, “Characterization of thorium aspartate tetrahydrate
and comparison of hydrothermal and thermal conversions into ThO2”, submitted to J. Nucl. Mater.,
2017.

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910
Selective composite metal/ceramic coatings made by two-step laser
cladding
D. Deschuyteneer1*, F. Petit1, V. Lardot1, F. Cambier1, M. Belting2, I. Ross2, D. Maischner2,
A. Weisheit2
1
Belgian Ceramic Research Centre (BCRC), Avenue Gouverneur Cornez 4 – 7000 Mons, Belgium;
*
e-mail: [email protected]
2
Fraunhofer-Institut fur LaserTechnik ILT, Steinbachstrasse 15 – 52074 Aachen, Germany
Keywords: composites, two-step cladding, coatings, selective, laser

The aim of this work is to develop a composite two-step laser coating process for metallic
subtrates/parts with no need for post-machining. In the first step the coating is deposited
via air spraying a slurry. The slurry contains the coating material as powder, some organic
additives and a solvent. Drying is carried out either by an air stream at room temperature
or laser radiation in case a higher temperature is required. In the second step the coating
is remelted by laser radiation which densifies the layer, ensures a metallurgical bonding to
the substrate by remelting a thin layer (only a few microns) of the substrate and produces
a smooth (polished-like) surface finish. The overall innovation target is to develop a novel
coating process which provides functional layers with a thickness between 20 and 300 µm
and a smooth surface finish which spares post-machining. In detail the main innovations are
slurries formulations adapted for spraying thin layers with high accuracy and minimum effort
for drying, a spraying method adapted for high spray rates and high level of reproducibility,
layers free of porosity and cracks after remelting, high area rates for laser remelting (Å ≥ 0.5
cm2/s) and a smooth surface finish (Ra ≤ 0.5 µm).
In the addressed thickness range (20–300 µm) no other technique providing both features
is available. This technology allows depositing protective materials in a cost-effective and a
sustainable process. The potential for exploitation is very high. The materials used and the
applications considered are only a limited choice of potential applications. On the material
side the process can be exploited towards corrosion protection of large areas, e.g. for marine
applications. The process is also interesting for wear resistance applications by the reinforce-
ment of superalloy metal matrix with carbide particles.

Acknowledgements
This work was realized in the framework of a CORNET (network of ministries and funding agencies
in Europe) project: 2SLAC (2015-2017) and was funded by SPW (Belgium-Wallonia) and AIF (Ger-
many).

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211
Fabrication of Si3N4/SiCN layer structures with graded multiscalar porosity
Christina Drechsel*, Thomas Konegger
Institute of Chemical Technologies and Analytics, TU Wien, Getreidemarkt 9/164-CT, 1060 Vienna,
Austria; *e-mail: [email protected]
Keywords: polymer-derived ceramics, porosity, dip coating, polysilazane

Layered Si3N4/SiCN structures with multi-scale porosity were prepared with the future aim
of using them as membrane materials. The focus was set on the deposition of continuous
selective layers onto macroporous supports by dip coating with a preceramic polymer. The
planar (disk shaped) supports were prepared in two different ways, via conventional slipcast-
ing (resulting in Si3N4), and via the polymer precursor route (resulting in SiCN) including the
use of polyethylene as a sacrificial filler. Before deposition of the top layers, it was necessary
to generate an intermediate layer on top of the support, which was prepared by dip coating/
slip casting with an Si3N4/preceramic polymer dispersion. The deposition of a continuous top
layer was then tested on these two-layered structures using masking techniques.
Additional experiments were conducted to set up a model correlating the withdrawal
speed and the resulting layer thickness applicable to the dipping solutions that were used to
prepare the selective layer. These experiments were carried out on dense model substrates.
Properties such as viscosity and surface tension of the dipping solutions were determined to
see if the existing model by Landau-Levich fits the experimental data or has to be adapted.
On both support structures, the slip cast type and the polymer derived ceramic (PDC) type,
an intermediate layer (with a thickness of around 30 µm) could be successfully deposited.
A surface modification (silanisation) of the Si3N4 powder of the intermediate layer slip was
necessary. Using polystyrene as sacrificial mask for the intermediate layer (and the support
structure), a continuous top layer was successfully prepared in the crosslinked stage on both
of the support types. The porosity of the underlying layers was preserved after pyrolysis. The
Landau-Levich model could be easily adapted to the used polymer-solvent-systems.

240
Fabrication of complex shaped boron carbide by robocasting and
pressureless spark-plasma sintering
Siamak Eqtesadi1*, Azadeh Motealleh1, Fidel H. Perrera2, Pedro Miranda2, Antonia
Pajares2, Rune Wendelbo1, Fernando Guiberteau2, Angel L. Ortiz2
1
Abalonyx AS, Oslo, Norway; *e-mail: [email protected]
2
Engineering School, University of Extremadura, Spain
Keywords: robocasting, B4C, spark-plasma sintering

Boron carbide (B4C) is an interesting material for a wide variety of applications due to its
low density, high melting point, low chemical reactivity, and high hardness. The main ap-
plications for B4C include nuclear industry and armour applications.1 However challenges

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associated with both shaping and sintering of morphologically complex components are the
main hurdles for using B4C.2
Robocating, as an additive manufacturing method (AMM), has opened new doors for
fabricating green component ceramics with complex shapes. Robocasting is unique among
the AMMs because it allows one to build 3Dstructures using water-based inks (highly con-
centrated suspension of desired materials for fabrication of the 3D structures) with minimal
organic content capable of fully supporting their own weight during assembly. Colloidal
gels are excellent candidate materials for direct ink writing of such complex 3D structures.
The inks must fulfil two important requirements. First, they must exhibit a well-controlled
viscoelastic response, so they flow through the deposition nozzle and then set immediately to
facilitate shape retention of the deposited features even as they span gaps in the underlying
layers. Second, they must contain a high colloid volume fraction to minimize drying-induced
shrinkage after assembly is complete, so that the particle network is able to resist compres-
sive stresses arising from capillary tension.3
The present work aims to fabricate complex-shaped B4C by combining robocasting of
highly loaded aqueous suspensions for the initial shaping stage with pressureless spark-plas-
ma sintering (SPS) for the subsequent consolidation stage with shape retention. It will be
shown that this combination allows the fast and energy-efficient manufacture of geometri-
cally complex boron carbide components for a wide range of possible applications.

References
1. P. Dünner, H.-J. Heuvel, M. Hörle, “Absorber materials for control rod systems of fast breeder reac-
tors,” J. Nucl. Mater. 124, pp. 185–194, 1984.
2. W.G. Fahrenholtz, E.W. Neuman, H.J. Brown-Shaklee, G.E. Hilmas, “Super hard Boride–Carbide
particulate composites,” J. Am. Ceram. Soc. 93, pp. 3580–3583, 2010.
3. S. Eqtesadi, A. Motealleh, P. Miranda, A. Lemos, A. Rebelo, J.M.F. Ferreira, “A simple recipe for
direct writing complex 45S5 Bioglass® 3D scaffolds,” Mater. Lett. 93, pp. 68–71, 2013.

052
Cold sintering process of magnetodielectrics for radio frequency (RF)
applications
Sinan S. Faouri1, Ian M. Reaney2
Department of Engineering Materials, University of Sheffield, Sheffield, S1 3JD, UK;
1

e-mail: [email protected]
Department of Engineering Materials, University of Sheffield, Sheffield, S1 3JD, UK;
2

e-mail: [email protected]
Keywords: magnetodielectrics, cold sintering process, thermal stability, radio frequency

M-type hexaferrites, e.g. BaFe12O19, have attracted a lot of attention because of their excellent
magnetic properties and potential application in various fields1. They are utilized throughout
the electroceramic industry not only in magnetic storage systems2,3,4 but also as RF substrates
in the fabrication of filters and antennas.

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The cold sintering processing (CSP) is a novel technique developed recently to achieve
dense ceramics at extremely low temperatures (<180 °C) across a variety of ceramics, ce-
ramic/ceramics and ceramic/metal and polymer/ceramic composites5. The process utilises a
small volume fraction of aqueous-based solutions as transient solvents to aid densification by
a nonequilibrium mediated dissolution–precipitation process6.
Magnetodielectric composites have been fabricated using CSP at 120 °C from BaFe12O19
and Li2MoO4 end members. The microstructure, structure and properties of these compos-
ites have been studied with a view to developing substrates with bespoke permeability and
permittivity for RF applications.

References
1. Xiuna Chen, Guolong Tan. Multiferroic Properties of BaFe12O19 Ceramics. Wuhan University of
Technology, Wuhan 430070, China.
2. J.A. Cortés, J H. Marin, M.A. Ramirez. Microstructural and magnetic characterization of
BaFe12O19.
3. M.J. Molaei, M.R. Rahimipour. Microwave Reflection loss of magnetic/ dielectric nanocomposites
of BaFe12O19/TiO2, Materials Chemistry and Physics 167 (2015) 145–151.
4. Ping Xu, Xijiang Han, Jingjing Jiang, Xiahong Wang, Xuandong Li, Aihua Wen. Synthesis and
Characterization of Novel Coralloid Polyaniline/BaFe12O19 Nanocomposites, J. Phys. Chem. C
2007, 111, 12603–12608.
5. Hanzheng Guo, Jing Guo, Amanda Baker, Clive A. Randall. Hydrothermal-Assisted Cold Sintering
Process: A New Guidance for Low-Temperature Ceramic Sintering. ACS Appl. Mater. Interfaces
2016, 8, 20909−20915.
6. Jing Guo, Amanda L. Baker, Hanzheng Guo, Michael Lanagan, Clive A. Randall. Cold Sintering
Process: A New Era for Ceramic Packaging and Microwave Device Development. J. Am. Ceram.
Soc., 1–7 (2016).

342
Preparation of porous beta-alumina and application for water
treatment filter
Kazuki Fukui1, Yoshikazu Suzuki2
Graduate School of Pure and applied Sciences, University of Tsukuba, Ibaraski, Japan;
1

e-mail: [email protected]
Faculty of Pure and Applied Sciences, University of Tsukuba, Ibaraski, Japan;
2

e-mail: [email protected]
Keywords: plate-like, β-alumina, porous ceramics, water treatment, reactive sintering

Introduction: For water treatment filters, rapid loss of filtration efficiency is one of the most
serious problems. To solve this problem, anisotropic porous ceramics is focused. In this
study, porous materials made of plate-like β-alumina were prepared by reactive sintering.
Experiment: α-alumina and sodium carbonate powders were ball-mixed by 5:1 molar ra-
tio to obtain β”-alumina composition. Besides, 0.5 wt. % of LiF was added as a mineralizer.
Each mixed powder was uniaxially pressed to obtain green pellets with the dimensions of ~2
mm in thickness and 30 mmφ in diameter. The green pellets were sintered at 1200 °C for 2 h

61 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

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to prepare disc-shape water filters. The obtained samples were characterized by XRD, SEM
and filteration test via turbidity measurement.
Results: Plate-like porous structure of β-alumina was presented in Fig. 1. Turbidity was
sharply decreased in non-doped β-alumina and clear water was obtained in Fig. 2.

Fig. 1. SEM images of β-alumina plate-like porous structure

Fig. 2. Turbidity test for water treatment

Acknowledgment
This research is granted by Nippon Sheet Glass Foundation for Materials Science and Engineering.

References
1. S. Ichikawa, T. Takahashi, J. Ceram. Soc. Jpn., 102[1] 5–7 (1994).
2. Y. Nakagoshi, Y. Suzuki, J. Asian Ceram. Soc., 3[3] 334–338 (2015).

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529
Influence of the starting conditions to tobermorite synthesis from CaO-
SiO2-H2O system
Lucie Galvankova*, Tomas Opravil, Jiri Masilko, Eva Bartonickova
Faculty of Chemistry, Brno University of Technology, Purkynova 118, 612 00 Brno, Czech Republic;
*
e-mail: [email protected]
Keywords: C-S-H system, tobermorite, hydrothermal synthesis, XRD

Tobermorite is a mineral which crystalizes under hydrothermal conditions in system CaO-

SiO2-H2O1,2. This system is very complicated and many variable factors have an influence on
the creation of pure well crystalize tobermorite. Thanks to his microstructure, tobermorite is
the key mineral in autoclaved aerated concrete3. From this point of view is very important to
determine the real structure of the phase pure tobermorite. Up to this point of the research,
the fully crystallised structure of the tobermorite was not synthetized yet, so the further study
is required1,2,4,5.
The main aim of this contribution is to study the influence of variable conditions and
various starting materials of hydrothermal reaction to formation of tobermorite. As was
mentioned before tobermorite crystallises from the CaO-SiO2-H2O system, so the sources
of calcium and silicon oxides are very important. The cost effective Ca and Si sources was
favoured. As the source of CaO a grounded calcinated limestone was used. As a source of
SiO2 two different sources differing in particle size were chosen, milled quartz sand (d50 =
28.33 µm) and silica sand Dorsilit (d50 = 3.53 µm). The C/S ratio was set to 0.83. Solubility
of starting materials influences the hydrothermal reaction as well, so different water to solid
ratios was used. All synthesis were performed at 180 °C in laboratory steel autoclaves. The
prepared samples were characterized in order to determine the phase composition (by X-Ray
diffractometery). Morphology and particle size of synthetized powdered products was stud-
ied by scanning electron microscopy. The influence of the procedure on the final particle size
distribution was studied by laser diffraction.

References
1. I. G. Richardson, “The calcium silicate hydrates”, Cem. Concr. Res., 38, pp. 137–158, 2008.
2. S. Merlino, E. Bonaccorsi and T. Armbruster, “Tobermorities: Their real structure and order-disor-
der (OD) character”, Am. Mineral., 84, pp. 1613–1621, 1999.
3. D. Tunega and A. Zaoui, “Understanding of Bonding and Mechanical Characteristic of Cementious
Mineral Tobermorite From First Principles”, J. Comput. Chem., 32, pp. 306–314, 2012.
4. N. Isu, H. Ishida and T. Mitsuda, “Influence of quartz particle size on the chemical and mechanical
properties of autoclaved aerated concrete (I) tobermorite formation”, Cem. Concr. Res., 25, pp.
243–248, 1995.
5. J. Kikuma and M. Tsunashima, “Effect of quartz particle size and water-to-solid ration on hydro-
thermal synthesis of tobermorite studied by in-situ time-resolved X-ray diffraction”, J. Solid State
Chem., 184, pp. 2066–2074, 2011.

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129
Application of solution combustion synthesis induced by microwave
radiation for fabrication of yttria nanopowder
Magdalena Gizowska*, Izabela Kobus, Krzysztof Perkowski, Milena Zalewska,
Gustaw Konopka, Irena Witosławska, Marcin Osuchowski
Nanotechnology Department, Institute of Ceramics and Building Materials, 9 Postepu Street,
02-676 Warsaw, Poland; *e-mail: [email protected]
Keywords: solution combustion synthesis, YAG nanopowder, microwave induced SCS

The work presents results of solution combustion method utilization for yttria (Y2O3) ceramic
nanopowder fabrication. One of the most recent applications, in which yttria ceramics gains
much interest, is for solid state lasers. Yttria ceramics sintered to near theoretical density
shows transparency in broad spectrum of electromagnetic radiation. Thus it can serve as the
matrix for laser active ions. It should be also noted that the radius of yttrium ion is very simi-
lar as the ion radius of neodymium, erbium and ytterbium (rY3+ = 104 pm; rNd3+ = 112.3 pm;
rEr3+ = 103 pm; rYb3+ = 100.8) so the dopant can be built in the yttria lattice.
The combustion method is based on the high energy reaction between the metal nitrates
and reducing agent. In the researches the reaction was induced by microwave radiation,
which makes the process much faster than one with conventional heating. In this study com-
bustion synthesis was performed using urea and glycine in stoichiometric quantities. After
synthesis the reaction products were analyzed in terms of phase composition, particle size
and morphology.

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912
Additive manufacturing of functionalized LTCC ceramic material for
electronic devices
J. Gonçalves1,2*, A. Muguruza3, J. Bonada3, E. Xuriguera4, M. Blanes1,2, A. Gómez3,
J. Minguella-Canela3, F. Ramos1, E.A. Cirera2
Francisco Albero S.A.U, C/Rafael Barradas, 19, Polig. Gran Via Sud, 08908 L’Hospitalet Barcelona,
1

Spain; *e-mail: [email protected]

Universitat de Barcelona, Dept. of Engineering: Electronics, C/ Martí i Franquès, 1,
2

08028 Barcelona, Spain

Universitat Politècnica de Catalunya - BarcelonaTECH, Centre CIM, C/Llorens i Artigas, 12,
3

08028 Barcelona, Spain

Universitat de Barcelona, Dept. of Mat. Sci. and Physical Chemistry, C/ Martí i Franquès, 1,
4

08028 Barcelona, Spain

Keywords: additive manufacturing, DLP, inkjet, LTCC

The hybridization of Digital Light Processing (DLP) and two-dimensional (2D) Drop on De-
mand Inkjet technologies is presented in this work. This novel combination allows the fabri-
cation of an electric circuit embedded within a three dimensional (3D) ceramic structure, that
holds the promise of exploring new materials and designing with new levels of functionality.
The DLP technology, based on digital micromirror devices (DMDs), was used to build
3D geometries layer upon layer by polymerization of photosensitive resins, while the inkjet
printing system accurately deposits droplets of conductive inks onto the generated substrate.
Therefore, one of the main goals is the development of a slurry with appropriate features
concerning the scattering phenomena and viscosity for DLP technology. In our approach the
improvement and characterization of Low Temperature Co-firing Ceramic (LTCC) suspen-
sion was optimized considering the rheological behavior and its photopolymerization in the
developed DLP machine.
The hybrid printed parts were characterized after the sintering process regarding their
mechanical properties, density and electrical properties.

Acknowledgments
NHIBRID has been funded by the Spain Ministry of Economy and Competitiveness with the aim of
promoting technological development, innovation and quality research.

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809
Materials based on shaping of core-shell nanostructures prepared by
chemical precipitation of hydroxides nanoparticles on the surface of
particles in aqueous suspensions
Z. Gonzalez1, J. Yus1, M. Dios1,2, A. Rodriguez1, E. Gordo2, B. Ferrari1
1
Institute of Ceramic and Glass, CSIC, C/Kelsen 5, 28049 Madrid, Spain
2
Department of Materials Science and Engineering and Chemical Engineering,
University Carlos III of Madrid, Avda. Universidad 30, 28911 Leganés, Madrid, Spain
Keywords: core-shell, heterogeneous precipitation, pseudocapacitors, photoactive films, cermets

In the area of particle engineering, core-shell nanostructures with non-symmetrical shapes

and compositions have been handled depending on the final application. Among all of them,
inorganic/ inorganic core-shells have been proved to be extremely useful. In this work the
chemical precipitation of hydroxides, under the influence of ultrasound, in the surface of
particles in aqueous suspensions is proposed to produce inorganic/inorganic core-shell nano-
structures to improve processing and properties of functional and structural materials. Three
examples of the method efficiency are presented: the processing of photoactive TiO2 and ZnO
based films, supercapacitor electrodes and cermets.
The heterogeneous growth of Al(OH)3 nanoparticles (2-5 nm in diameter) on semiconduc-
tor nanoparticles provides an effective doped nanostructure after sintering, which effectively
modifies the photoactive response of the films in terms of degradation of organic molecules
dissolved in liquid. Following a similar method, core-shell Ni(OH)2-NiO flowerlike nano-
structures were shaped by electrophoretic deposition (EPD) forming electroactive coatings
leading to elevated capacity (around 1000 Fa/g at 2 mA) as a ceramic pseudocapacitor. Fi-
nally, Ni(OH)2 nanoplatelets can be also precipitated on Ti(C,N) particles in suspension and,
after the cermet shaping and sintering in vacuum, the ceramic particles appear imbibed in a
Ni-based matrix. Those microstructures exhibit improved hardness and mechanical proper-
ties if compare with regular microstructures fabricated by conventional powder metallurgy
techniques.

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882
Influence of printed layer’s orientation on dental ceramics
manufactured by stereolithography
Jean-Christophe Hornez1, Marion Dehurtevent1,2, Pascal Béhin2, Anthony Thuault1,
Lieven Robberecht1,2, Anne Leriche1, Fabrice Petit3, Francis Cambier3
1
LMCPA-University of Valenciennes, Maubeuge, France
2
Dental Faculty-University of Lille, Lille, France
3
Belgian Ceramic Research Center, Mons, Belgium
Keywords: stereolithography, alumina, orientation

Subtractive computer-aided design (CAD) and computer-aided manufacturing (CAM) tech-

nologies have led to major improvements in dentistry. They make it possible to produce
reliable restorations with accurate dimensions and to reduce manufacturing time. However,
these processes are limited by the waste of raw material (loss of unused portions of blocks
and difficulty in recycling excess material) and heavy wear of milling tools. Microscopic
cracks, which can weaken restorations, can also appear in objects due to the milling process.
Additive manufacturing processes avoid these limitations by building objects layer-by-layer.
Several researchers investigated the impact of slurry composition on mechanical properties.
However, no data is available with regard to the impact of layer orientation manufacturing.
The aim of this study was to compare mechanical properties of alumina and zirconia tough-
ened alumina manufactured by stereolithography with different layer orientations.
Samples for this study were designed by CAD software (Catia, Dassault Systèmes) and
were fabricated within 3 orientations (XY, ZX and ZY). Samples were sliced by Creation
Workshop software (Envisionlabs) and transferred to the stereolithography software and
equipment (CryoCeram Printer, CryoBeryl Software) for manufacturing. After sintering,
sample size was 1.3 × 4 × 22 mm (ISO 6872:2008).
The physical and mechanical properties of stereolithographied ceramics prepared from
alumina slurries (mean particle size = 1.56 ± 0.04 µm, dry matter content = 80%) were
evaluated by microstructural analysis, hydrostatic weighing, fracture toughness, three-point
flexural strength measurements with Weibull analysis.
No difference of density was found regarding the orientation of printed layers. The frac-
ture toughness of XY was significantly higher than that found in the ZX group. All samples
had large grains whose major axis was parallel to the layer orientation. The fracture surfaces
of XY and ZY manufactured samples were trans-granular and inter-granular for ZX manu-
factured samples. These results were sixmilar to those exposed by Suzuki1who showed that
samples produced by electrophoretic deposition with grains perpendicular to the load had
trans-granular fracture surfaces and higher mechanical strength than when the load was par-
allel to the grain axis.
To conclude, the microstructural texture of alumina stereolithographied ceramics influ-
enced the flexural strength, the crack propagation and the fracture mode.

Reference
1. Suzuki TS, Uchikoshi T, Sakka Y. “Control of texture in alumina by colloidal processing in a strong
magnetic field.” Sci Technol Adv Mater., 7(4), pp. 356–364, 2006.

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261
Influences of organic agents on the aluminium nitride tape casting
process
Chi-Shiung Hsi1*, Min-Yu Yang1, Kuan-Ting Lai2, Kun-Ru Liu1
Department of Materials Science, National United University, Miaoli, Taiwan;
1

*
e-mail: [email protected]
Chemical System Research Division, National Chung-Shan Institute of Science and Technology,
2

Taoyuan, Taiwan
Keywords: tape casting, aluminium nitride, polyvinyl butyral, viscosity

Aluminium nitride (AlN) substrate has high thermal conductivity, high electric insulation,
low dielectric constant, and high mechanical strength, which can be implemented to high
power electronic packaging and modulus. Tape casting process is one of the efficient process
to fabricate AlN substrates. In the tape casting process, AlN slurry is poured into a reservoir
and casted onto a mylar carrier surface through the gap between blade and carrier.1 In this
study, the AlN slurry is prepared by mixing aluminium nitride powder with different ratios of
Polyvinyl butyral (PVB) series binders, plasticizer and organic solvent to prepare appropriate
viscosity slurry, and the slurry was coated uniformly on PET films via the tape casting pro-
cess. The AlN raw materials are very sensitive to the humidity in the forming process2, it eas-
ily reacted with vapor to form amorphous as well as porous AlOOH (boehmite) and Al(OH)3
(bayerite). Since ethyl alcohol had hydrogen bond with deliquescence and absorb vapor in
air, different ethyl alcohol/toluene solutions were selected as solvent in order to investigate
a stable AlN slurry. Blown Menhanden Fish Oil, polyoxyalkylene, and Triton X100 were
used as dispersing agents. A low volatilisity and non-phthalic acid derivative plasticizer was
applied to develop plasticizing characteristics of the green tape. Types and ratios of mixed
adhesive/plasticizer determined the viscosities of the slurries and tensile strength of the alu-
minium nitride green films. Green tapes with smooth surfaces were prepared by the slurries
with viscosities in the range between 2000–4000 mPa·s. The highest yielding strength of
green films was 0.159 kg/mm2, the tapes had good machinability and laminating property.
The green tapes were laminated and de-bindered at 450 oC for 2 hours. The aluminium nitride
substrates were obtained after sintering of de-bindered tapes at temperature of 1700 oC for 6
hours in the nitrogen atmosphere.

References
1. R.E. Mistler and E.R. Twiname. Tape Casting Theory and Practice. The American Ceramic Society,
Ohio, 2000.
2. M. Oliveira, S. Olhero, J. Rocha and J.M. Ferreira, “Controlling hydrolysis and dispersion of AlN
powders in aqueous media.” Journal of Colloid and Interface Science, 261, pp. 456–463, 2003.

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488
Preparation and water-filter application of porous spinel ceramics
Yoko Kamato1, Yoshikazu Suzuki2
Graduate School of Pure and Applied Sciences, University of Tsukuba, Ibaraki, 305-8573, Japan;
1

e-mail: [email protected]
Faculty of Pure and Applied Sciences, University of Tsukuba, Ibaraki, 305-8573, Japan;
2

e-mail:[email protected]
Keywords: porous material, MgAl2O4, reactive sintering, alumina powder, grain growth

Introduction: Water is indispensable in our lives. To maintain our life, it is recommended to

drink 2 to 2.5 L water a day. However, many people, especially in Africa or in Southeast Asia,
suffer from polluted water or water shortage. Water purification using porous ceramics is a
key technology to solve the problem. In this research, porous MgAl2O4 microfiltration filters
(MF filter) from different starting materials have been developed.
Experimental: As an MgO source, hydromagneasite powder (MgCO3 (basic)) was used,
and as Al2O3 sources, α-Al2O3, γ-Al2O3 and AlOOH were used. Besides, α-Al2O3 mixed pow-
ders doped with LiF as mineralizer were prepared. These powders were mixed by wet ball-
milling. They were dried and sieved to obtain mixed powders. The mixed powders were
uniaxialy pressed to obtain green compacts. These green compacts were reactively sintered
at 1200 ºC–1600 ºC for 2 h. The samples were characterized by XRD, SEM observation and
density calculation. MgAl2O4 thin plate filters were evaluated by filtration test and turbidity
measurement.
Result and discussion: Almost single phase MgAl2O4 was synthesized in all samples con-
firmed by XRD. Fig. 1 shows SEM micrographs of porous MgAl2O4 sintered at 1600 ºC by
using α-Al2O3, γ-Al2O3 and AlOOH as starting materials. In the order of α-Al2O3, AlOOH,
and γ-Al2O3, density became higher. This difference may be caused by grain and grain size
distribution of raw material powders. For this reason the filters prepared by each mixed pow-
der show different result of filtration efficiency. Also in the samples sintered at 1400 ºC with
LiF, grain growth was observed in microstructure. At 1600 ºC, suppression of densification
was observed with increasing amount of LiF.

Fig. 1. SEM micrographs: (left) α-Al2O3, (middle) γ-Al2O3 and (right) AlOOH

Acknowledgments
This research is supported by grants from Nippon Sheet Glass Foundation for Materials Science and
Engineering.

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521
Compaction of high dense metal-ceramic composite using powerful
ultrasound assistance
Oleg Khasanov*, Edgar Dvilis, Oleg Tolkachev
Department of Nanomaterials, Tomsk Polytechnic University, 30, Lenin Ave., Tomsk, 634050, Russia;
*
e-mail: [email protected]
Keywords: metal-ceramic composite, dry pressing, powerful ultrasound assistance, spark plasma
sintering

The optimal content of the light metal-ceramic composite has been modeled by the discrete
element method and experimentally verified: powder of Al/Mg matrix (74 wt.%) with inclu-
sions of B4C powder (6 wt.%), W nanopowder (20 wt.%). This content provides the maxi-
mum dense particle packing for all the components and strong alloy matrix with the coordi-
nation number greater than 4 and packing density of 0.67. Fully dense composite (density of
3.14 g/cm3) has been consolidated by the spark plasma sintering at 490 oC, 39 MPa, 10 min
while the known method of hot extrusion provides 95% relative density only1.
Characterization of the compressibility of the dry powder mixture has been performed by
plotting the compaction curves obtained for the conditions of uniaxial pressing with load-
ing–reloading cycles and using an approximation by a logarithmic equation in a dimension-
less form2. At pressure of 800 MPa the composite powder green compacts with a density of
92.6% were obtained by the conventional quasi-static pressing at room temperature. These
samples were consolidated by free vacuum sintering at 590 oC up to density of 93.4%. How-
ever the uniaxial pressing of the composite powder at 800 MPa and using simultaneous
non-cavitation powerful ultrasound assistance in the special mold – ultrasonic waveguide2
allowed to reach the green density of 95.1% which is comparable with the density provided
for the consolidated composite by the hot extrusion method. Following free vacuum sintering
(590 oC) of the sonicated green compacts led to the density of 96.8%.
Thus the opportunity to press the dry composite powder mixture up to high density (95.1%)
owing to application of the powerful ultrasound assistance has been shown. Free solid state
sintering is not suitable for the complete consolidation of the composite. To achieve full
density of the composite it is necessary to use spark plasma sintering (pulsed electric current
sintering).

References
1. E.S. Dvilis, O.L. Khasanov, V.N. Gulbin, M.S. Petyukevich, A.O. Khasanov and E.A. Olevsky,
“Spark plasma sintering of aluminum-magnesium-matrix composites with boron carbide and tung-
sten nano-powder inclusions: modeling and experimentation”, JOM, 68, pp. 908–919, 2016.
2. O.L. Khasanov and E.S. Dvilis, “Compressibility of the structural and functional ceramic nanopo-
wders”, J. Eur. Ceram. Soc., 27, pp. 749–752, 2007.

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904
Microwave-assisted one-step SCS synthesis of composite ceramic
nanomaterials
Alexander Khort1, Kirill Podbolotov2
Department of Thermophysics, A.V. Luikov Heat and Mass Transfer Institute of the National
1

Academy of Sciences of Belarus, Minsk, 220072, Belarus; e-mail: [email protected]

Physico-Technical Institute of the National Academy of Sciences of Belarus, Minsk, 220141,
2

Belarus; e-mail: [email protected]

Keywords: microwave, solution combustion synthesis, composite ceramic nanomaterials

Composite cerametallic nanomaterials have attached great research and practical interest due
to their unique properties that allow using them successfully for catalysis, microwave scatter-
ing, in microelectronics and etc. Nickel containing alumina based composite nanomaterials
are one of the most broadly used. However, production of nickel nanoparticles in any form
by solution combustion technique requires the usage of protective atmosphere or additional
post reducing of metal oxides. To obtain cerametallic composite nanomaterial by one-step
solution combustion method, where Al-containing phase acts a strong oxidizer, is even more
complicated. In this case Ni and Al have a tendency to form a spinel phase, which is not so
attractive.
In this work, we report a new modified solution combustion synthesis technique for one-
step production of cerametallic alumina – nickel composite nanomaterials. The main unique
feature of our approach is the use of microwave assisted foam preparation and ignition of
combustion of precursors in combination with effective fuel. That allows us to obtain alumi-
na-nickel composites under normal air atmosphere without any post reduction. Also, the ef-
fect of different components’ concentration on the phase composition and grain size of resul-
tant solid products were investigated. Moreover, nanomaterials prepared by the microwave-
assisted and high-temperature radiation-convective ignitions of combustion were compared.
It was found that the microwave assistant accelerates water removal, decomposition of
fuels, alumina and nickel oxide phases nucleation and then reduction of obtained NiO to Ni
metal bonded nanoparticles during combustion process due to promotion of reducing spe-
cies access to whole volume of reaction mixture. It was observed the formation of alumina
nanoparticles on which Ni metal nanoparticles with the average grain size ~ 28 nm distrib-
uted.
The prepared materials are characterized by high coercivity (166 Oe and 64 Oe for micro-
wave- and high-temperature-assisted method respectively). The formation of great amount
of reduction gaseous mixture during fuel decomposition and rapid combustion reaction in
metals nitrate – fuel systems promotes full Ni oxides reduction and prevents metallic Ni
reoxidation. Moreover high velocity of reaction prevents spinel phase formation. In addition,
our method allows to get nanoparticles with high degree of magnetostructural anisotropy,
which strongly enhances magnetic properties of ferromagnetic nanoparticles.

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519
Complex shapes PLA/TCP constructions for bone regeneration
obtained by 3D printing
Elena S. Klimashina1,2*, Dmitry M. Zuev2, Pavel V. Evdokimov1,2, Valery I. Putlayev1,2,
Dmitry S. Larionov2
Department of Chemistry, Lomonosov Moscow State University, 119991, Leninskie Gory, 1, GSP-3,
1

Moscow, Russia; *e-mail: [email protected]

Department of Materials Science, Lomonosov Moscow State University, 119991, Leninskie Gory, 1,
2

GSP-3, Moscow, Russia

Keywords: polylactid, tricalcium phosphate, 3D printing, composite

Modern regenerative medicine has a great need in resorbable bioactive composite materials
for bone implants. Biodegradable polymers, e.g. polylactide (PLA), filled with resorbable
calcium phosphate (with the ratio Ca/P ≤ 1.5, e.g. tricalcium phosphate) are good candidates.
Specific macroporous architecture for osteoconductivity enhancing can be achieved by 3D-
printing process. In the case of 3D thermal extrusion technique it is necessary to produce
composite filament (PLA/TCP) with uniform distribution of the phosphate particles inside
PLA prior to printing and to develop printing regimes1.
The aim of this work is to create bioactive macroporous composites based on calcium
phosphate and biopolymers, of predetermined complex shape for bone regeneration.
Composite filaments were fabricated with a different ratio β-TCP/biopolymer. 3D thermal
extrusion technique was used for printing of 3D periodic structures with different mesh size
and more complex shape implants. We have obtained macroporous bioactive PLA/TCP com-
posites with computed complex architecture.
It was shown that osteoconductive composite implants made of degradable polymer and
bioresorbable calcium phosphate with complex shapes can be fabricated by thermal extru-
sion 3D-printing technique.

Acknowledgments
The authors would like to thank the RF President Grant (project MK-8668.2016.8), the RFBR and Mos-
cow city Government (research project №15-38-70047 «mol_а_mos»), the RFBR (research project
№15-08-99597«а» and №16-38-60203\16), for providing financial support to this project.

Reference
1. Ievlev V.M. et al. J. Inorganic Materials. 51, 1297–1315, 2015.

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873
Solvothermal synthesis of kaolinite nanoscrolls
András Kovács1, Éva Makó2
Institute of Materials Engineering, University of Pannonia, Egyetem utca 10, Veszprém, Hungary;
1

e-mail: [email protected]
Institute of Materials Engineering, University of Pannonia, Egyetem utca 10, Veszprém, Hungary;
2

e-mail: [email protected]
Keywords: kaolinite, intercalation, nanoscroll, solvothermal

Kaolinite nanoscrolls are of interest in the research area of functional nanocomposites and
nanohybrids. We present a simple, convenient and effective a solvothermal synthesis pro-
cedure for preparing kaolinite nanoscrolls. This solvothermal synthesis procedure produces
high-quality kaolinite-cetyltrimethylammonium chloride complex from kaolinite-urea pre-
cursor. The desired kaolinite-cetyltrimethylammonium chloride complex is attained without
prior (weeks-long, conventional stirring) treatments of the samples with methanol. We also
investigate the factors that affect the efficiency of this solvothermal treatment using X-ray
diffraction, thermal analysis, Fourier transform infrared spectroscopy, and electron micros-
copy. The eco-friend precursor proved to be suitable to directly intercalate cetyltrimethylam-
monium chloride using a short-term (16-h) solvothermal treatment at 100 °C. Our findings
reveal that the formed kaolinite-cetyltrimethylammonium chloride complex can easily trans-
form into kaolinite nanoscrolls. This conceptually new synthesis procedure using cheap urea
and methanol as reagents is expected to be broadly applicable for a cost-efficient production
of nanoscrolls-based functional materials.

914
Direct Inkjet Printing of ceramic materials
Alexander Kremer*, Michael Kramer, Rainer Telle
Institute of Mineral Engineering, RWTH Aachen University, Aachen, Germany;
*
e-mail: [email protected]
Keywords: additive manufacturing, Direct Inkjet Printing, ceramic materials

Direct Inkjet Printing (DIP) is a promising process for ceramic manufacturing. By applying
aqueous suspensions with high solid contents (of up to 30 vol.-%) directly (through nozzles)
onto a substrate, intricate and detailed structures can be fabricated. The ceramic inks have to
be precisely conditioned in regard to their rheological properties (i.e. viscosity and surface
tension) and particle size distribution in order to guarantee a steady flow of ink through the
narrow channels of the printhead and thus minimize nozzle clogging. Consequently, any ma-
terial that can be dispersed in water with the required rheological properties can be converted
into printable suspensions. At the Institute of Mineral Engineering, RWTH Aachen, zirconi-

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T01: New developments in processing and synthesis – Poster presentations

um oxide, aluminum oxide and silicon nitride have been successfully printed by DIP. Due to
a low porosity and homogeneous micro structure, directly printed objects show a mechanical
behavior comparable to slip casted or pressed specimens. The direct and droplet-wise deposi-
tion of material allows a simultaneous and spatially free combination of multiple materials in
one manufactured part. Such functionally graded materials (FGM) enable a tailored adjust-
ment of material properties by purposefully adding further materials whose properties suit
the application and load of the part.

525
Calcium phosphates powders synthesized in non-aqueous media to
fabricate osteoconductive resorbable bioceramics
Dmitry S. Larionov1*, Mariia A. Kuzina1, Pavel V. Evdokimov1,2, Elena S. Klimashina1,2,
Valery I. Putlyaev1,2
Materials Science Department, Lomonosov Moscow State University, Leninskiye Gory d.1, Moscow,
1

Russia; *e-mail: [email protected]

Department of Chemistry, Lomonosov Moscow State University, Leninskiye Gory d.1, Moscow,
2

Russia
Keywords: calcium phosphates, biomaterials, ionic liquids, non-aqueous synthesis

The topical issues of modern biomaterials science include the manufacture of nanosized bio-
ceramics for bone tissue replacement. The latest developments are related to regenerative
approach, which requires the investigation of calcium phosphate based materials with Ca/P
ratio < 1.5. The usage of non-aqueous media is a promising way to eliminate water influ-
ence, avoid the impurities and gain strong control over the material. Another advantage of
non-aqueous media is the ability to explore low-temperature synthesis and thus to liquidate
calcination stage.
The key objects of the research were tricalcium orthophosphate (Ca3(PO4)2, TCP) and
several condensed calcium phosphates (e.g. Ca2P2O7, CPP). The main requirement was the
usage of liquids with high boiling point and fusible salts.
Ethylene glycol was chosen due to its solvent abilities and the fact that the only coproduct
of the reaction should be the solvent itself. The precursors, such as calcium glycolate, crystal
orthophosphoric acid, ammonium pyrophosphate were obtained previously. TCP was ob-
tained by adding orthophosphoric acid or commercial ammonium hydrophosphate solutions
in ethylene glycol to calcium glycolate solution. CPP was obtained in ethylene glycol using
the same technique: ammonium pyrophosphate solution was added to calcium glycolate so-
lution. The syntheses were carried out in the range from 30 to 150 °C.
The usage of ionic liquids is the key idea of the second approach. Temperature range
from 150 to 350 °C was chosen for the calcium phosphates synthesis according to the
KNO3-NaNO3 phase diagram. Calcium phosphates were obtained by mixing Ca(NO3)2-
NaNO3-KNO3 melt with suspension of corresponding sodium phosphate in molten KNO3-
NaNO3. By-products were washed out with alcohol.

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The main aspects of the samples sintering, as well as the microstructure and qualities,
were analysed using X-ray diffraction (XRD), scanning electron microscopy (SEM), trans-
mission electron microscopy (TEM) and dynamic light scattering (DLS).
We have developed a unique method of microcrystalline calcium ortho- and pyrophos-
phate powder synthesis in non-aqueous media. Also we have investigated low-temperature
range for calcium phosphate synthesis.
Development of the novel phosphate synthesis method makes possible obtainment of pure
calcium phosphate phases without impurities of hydrophosphates. XRD data have confirmed
the obtainment of pure crystalline TCP and CPP phases. DLS, SEM and TEM have demon-
strated that phosphate particle size from 100 to 200 nm can be obtained.

Acknowledgement
The authors would like to thank the Russian Foundation for Basic Research (Grant No: 16-38-60203\16)
for providing financial support to this project.

118
Synthesis, characterization and applications of environmentally friendly
water-soluble tantalum and niobium precursors
Ai-Dong Li*, Hai-Fa Zhai, Ji-Zhou Kong, Di-Wu
National Laboratory of Solid State Microstructures and Department of Materials Science and
Engineering, College of Engineering and Applied Sciences, Collaborative Innovation Center of
Advanced Microstructures, Nanjing University, Nanjing 210093, P. R. China;
*
e-mail: [email protected]
Keywords: water-soluble precursor, polymerizable complex route, Ta or Nb-based oxide, photocata-
lyst, ferroelectrics

Owing to the remarkable potentials of tantalate and niobate materials in ferroelectric and
photocatalytic fields, development of environmentally friendly tantalum or niobium precur-
sors becomes urgent. During wet chemical synthesis of Ta- or Nb-based oxide such as sol-gel
and metalorganic decomposition, alkoxides of tantalum and niobium are most frequently
used as starting sources. Nevertheless, some inherent issues are associated with Ta or Nb
alkoxides, such as great sensitivity to moisture and relatively high cost. Recently a simple
polymerizable complex (PC) route, known originally as the Pechini method, has been de-
veloped to solve these problems. However, air-stable water-soluble tantalum and niobium
precursors are not easily available yet. In this work, a simple flexible route to synthesize
aqueous tantalum and niobium precursors has been developed using cheap and stable Nb2O5
or Ta2O5 as starting source, based on the basic flux technique. Various analytical techniques
have been used to characterize the formation mechanism, purity, and thermal decomposition
features of the precursors. The synthesis processing has been optimized. These Ta or Nb
precursor solutions have higher Ta or Nb ion purity over 99% among detectable positive ions
with the higher yield. IR analyses confirms that the element Ta or Nb exists in the precursor
solution as the group of COO-Ta (Nb)-O. Using home-made Ta and Nb precursors, several

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photocatalytic nanopowders such as Ta-doped ZnO and BiNbO4, and ferroelectric ceramics
such as 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 (PMN-PT), have been prepared by a modified PC
method. Compared to conventional solid phase reaction, these powders have pure crystalline
phases with uniform sizes of 20-100nm and larger specific surface area in the range of 9–30
m2/g. The related ferroelectric and photocatalytical properties have also been examined, im-
plying that this is an attractive and flexible approach for fabrication of tantalate and nibonate
functional materials.

References
1. A.D. Li, J.Z. Kong, H.F. Zhai, J.B. Cheng, H.Li, D. Wu, “Synthesis, Characterization, and Applica-
tions of Water-Soluble Tantalum Carboxylate Precursors via a Flux Method”, J. Amer. Ceram. Soc.,
92, PP1959–1965, 2009.
2. H.F. Zhai, J.Z. Kong, A.Z. Wang, H.J. Li, T.T. Zhang, A.D. Li, D. Wu, “The Polymerization Effect
on Synthesis and Visible-Light Photocatalytic Properties of Low-Temperature β-BiNbO4 Using
NbCitrate Precursor”, Nanoscale Res. Lett. 10, PP457, 2015.

278
Strength of alumina ceramic produced by the LCM additive
manufacturing technology
Tanja Lube1*, Josef Schlacher1, Walter Harrer1, Gerald Mitteramskogler2,
Martin Schwentenwein2, Robert Danzer1
1
Institut für Struktur- und Funktionskeramik, Montanuniversität Leoben, 8700 Leoben, Austria;
*
e-mail: [email protected]
2
Lithoz GmbH, 1060 Wien, Austria
Keywords: additive manufacturing, bending strength, fractography, microstructure

The strength of ceramic components and specimens is governed by inhomogeneities (called

defects) which are present in the bulk, on the surface or on edges of the part. These defects
are introduced during processing. Type and size of these defects may be influenced by chang-
ing process parameters with the goal to increase the strength. This principle is also valid for
additive manufactured components.
A specific aspect of the strength of additive manufactured components and specimens is
the building direction. The interface between adjacent layers may have properties that deviate
from the properties of the layers themselves1. In a prismatic bar as usually used for strength
testing of ceramics the layers may be oriented parallel to each of the specimens faces. During
flexural strength testing the applied stress then acts normal or parallel to the interfaces. This
enables an investigation of properties in relation to the building direction.
In this contribution we present mechanical properties obtained on specimens from addi-
tive manufactured alumina components. Specimens tested in different orientations with re-
spect to the building direction are investigated. The relation between applied stress direction,
strength and building direction is presented. It is shown that specific defects resulting either

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from printing, cleaning or the thermal postprocessing are responsible for failure Depending
on the testing direction and testing conditions these specific defects may be identified or
remain hidden.

Reference
1. M. Schwentenwein und J. Homa, “Additive Manufacturing of Dense Alumina Ceramics,” Interna-
tional Journal of Applied Ceramic Technology, Bd. 12, Nr. 1, pp. 1–7, 2015.

507
Hydrothermal synthesis of ferrite nanocomposites with core/shell
structure
Marija Milanović, Ivan Stijepović, Vladimir V. Srdić
Department of Materials Engineering, Faculty of Technology Novi Sad, University of Novi Sad,
Novi Sad, Serbia

In this work, we have prepared different ferrite nanoparticles, such as nickel ferrite, zinc fer-
rite and iron oxides and combined them in different manner in order to investigate the possi-
bility to obtain the core/shell structure. Nickel ferrite and iron oxide are mainly used as a core
material, while zinc ferrite owing to its low toxicity was used as a shell. Simple preparation
of the samples, high physical and chemical stability and magnetic properties which can be
easily controlled with the size of the particles, make these materials a good starting point for
obtaining multifunctional particles used in biomedicine. XRD, TEM, DLS, Raman and VSM
methods were used in order to investigate their structural and magnetic properties. Spinel
structure was confirmed by X-ray and Raman measurements. TEM analysis indicated that
synthesized nanoparticles are agglomerated, with possibility to obtain the core/shell struc-
ture. Magnetic measurement have shown that magnetic properties are increased by addition
of zinc ferrite layer on to the nickel ferrite core.

590
Selective laser melting for manufacturing of MoSi2/Si3N4 composites
Tatevik Minasyan1, Miguel A. Rodríguez2, Le Liu1, Marina Aghayan1, Lauri Kollo1,
Irina Hussainova1,3,4
1
Tallinn University of Technology, Ehitajate 5, 19086 Tallinn, Estonia
2
Instituto de Ceramica y Vidrio (ICV-CSIC), C/Kelsen, 5, 28049 Madrid, Spain
3
ITMO University, Kronverksky 49, St. Petersburg, 197101, Russian Federation
4
University of Illinois at Urbana-Champaign, Department of Mechanical Science and Engineering,
Urbana, IL 61801, USA

Selective laser melting (SLM) technique has a potential to revolutionize the global parts
manufacturing and logistics landscape and has been recognized as a blasting technology to
manufacture customize designed, geometrically and functionally complex structures with a

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good dimensional tolerance. Despite of many advantages of SLM over conventional meth-
ods, high heating and cooling rates of materials restrict its use for manufacturing ceramic
components. Moreover, usually the ceramics have low laser absorptivity to be manufactured
by SLM.
To address this issue, we proposed a new approach for preparation of MoSi2/Si3N4 com-
posite by SLM. Thus, newly designed powders (MoSi2/Si) with unique structure were syn-
thesized by self-propagating high temperature synthesis method. The as-synthesized powders
were shaped by SLM and reactive sintered in nitrogen. As a result, MoSi2/Si3N4 composite
with designed complex shape was performed. Morphology of the synthesized Si3N4 powders
could be regulated from spherical to fibrous shape using different catalysts. The suggested
design of the powders and strategy of consolidation will expand the possibility and applica-
tion of SLM technology, find scientific interest and huge industrial usage.

418
Adsorptive removal of methylene blue by high surface area mesoporous
tungsten oxide
Banafsheh Mirtaheri, Mohammadreza Shokouhimehr, Ali Beitollahi
Centre of Excellence for Ceramic Materials, School of Metallurgy and Materials Engineering,
Iran University of Science and Technology (IUST), Narmak, Tehran 16846, Iran;
e-mails: [email protected], Beitolla@ iust.ac.ir
Keywords: mesoporous, tungsten oxide, soft-template, tungstic acid, methylene blue

Dyes are widely used in various industries. The inevitable released related wastewater
and contaminating our nature are major concerns. Therefore, the removal of synthetic dyes
is very important from the environmental viewpoint because most of them are toxic and
carcinogenic1. Methylene blue is one of these dangerous dyes with chemical formula of
C16H18N3SCl2. Various techniques have been applied to eliminate this dye from wastewater,
e.g. adsorption on the surface of metal oxide as adsorbents3. Increasing the specific surface
area by providing a mesoporous structure can improve the interaction between adsorbate and
adsorbent materials4. Among several synthetic methods for producing mesoporous materials,
soft- templating approach is commonly used, in which self-assembly of organic molecules
such as block-copolymers forms the pores5.
In this study, mesoporous tungsten oxide powder was synthesized by soft-templating route
as an adsorbent for the removal of methylene blue from an aqueous solution. Inexpensive
peroxo tungstic acid precursor and P123 block-copolymer were selected as metal oxide pre-
cursor and organic template, respectively. The resulting gel was calcined at 500 °C. An ap-
propriate heating program was adjusted to protect the mesopores from destruction during
calcination process. The inorganic networks were formed around the template through a sol-
gel process during the synthesis development. Fourier transformed infrared spectroscopy
confirmed complete elimination of the organic template after calcination step. X-ray diffrac-

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 T01: New developments in processing and synthesis – Poster presentations

tion analysis demonstrated the formation of orthorhombic crystalline structure. In addition,

the morphology of powder was studied using a field emission scanning electron microscopy.
The specific surface area of the resulting product was found to be 67 m2/g using nitrogen
adsorption/desorption analysis. The methylene blue adsorption potential of the synthesized
mesoporous tungsten oxide was investigated in various concentration of solutions. The dye
removal sufficiency of the designed adsorbent was verified by maximum methylene blue
adsorption capacity of 85% (43.6 mg/g) in a short time.

References
1. J.Y. Luo et al. “Strong aggregation adsorption of methylene blue from water using amorphous WO3
nanosheets”, Appl. Surf. Sci., vol. 287, pp. 270–275, 2013.
2. D. Hidayat et al. “Preparation of size-controlled tungsten oxide nanoparticles and evaluation of
their adsorption performance”, Mater. Res. Bull., vol. 45, no. 2, pp. 165–173, 2010.
3. S.M. Miraboutalebi et al. “Methylene blue adsorption via maize silk powder: Kinetic, equilib-
rium, thermodynamic studies and residual error analysis”, Process Saf. Environ. Prot., vol. 106,
pp. 191–202, 2017.
4. Chi-Ping Li et al. “Scalable synthesis of improved nanocrystalline, mesoporous tungsten oxide
films with exceptional electrochromic performance”, Sol. Energy Mater. Sol. Cells, vol. 132, pp.
6–14, 2015.
5. RUREN XU et al. Chemistry of Zeolites and Related Porous Materials : Synthesis and Structure.
John Wiley & Sons (Asia) Pte Ltd, 2007.

263
Pozzolanic reactivity assessment of Turkish calcined clay as a cement
substitution
Pozhhan Mokhtari, Sorour Semsari Parapari, Noyan Ozkan, Mehmet Ali Gulgun
Department of Material Sciences and Nano-Engineering, Sabanci University, Tuzla, Istanbul, Turkey;
e-mails: [email protected], [email protected],
[email protected], [email protected]
Keywords: calcined clay, cement substitute, pozzalanic activity, SEM, XRD, TGA, conductivity

Cement manufacturing is a major source of greenhouse gases and it causes more than 5
percent of CO2 production. Few studies tried to solve the emission production by the cement
industry concentrating on intervention of the other affordable and attainable materials such
as clay. In fact, an ordinary way to reduce the CO2 emission attributed to cement production
is to substitute a large portion of Portland clinker in cement to create blended cements, or
replace an OPC in concrete mixture with proper supplementary cementing materials (SCM).
Recently, the usage of the industrial by-products such as fly-ash and blast-furnace slag as
substitution was widespread, but the amount of these materials is significantly less than the
cement production and industrial demands. So, alternative sources like calcined clay were
considered by the manufactures. Clays are the widely available material on the earth crust
and in some part of it, the specifications of clay or schist type materials are proper enough to
evaluate them as cement substitute. In this study the pozzolanic activity of 3 common clay

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type raw materials (C1, C2, C3) coming from mining quarries have been investigated. This in-
terest is a part of widely spread attention directed towards the utilization of waste by-products
in cement industry to minimize the OPC consumption. Also, the mortars and concrete which
contain pozzolanic materials exhibit tangible enhancement in durability properties. To evalu-
ate the raw materials, several types of analyses have been performed. First, the potential reac-
tivity of normal clays is analyzed by the thermo-gravimetry method to identify the optimum
dehydroxylation temperature. Then, the phase analysis has done by means of X-ray diffract-
meter (XRD) while the scanning electron microscopy (SEM) photos elaborate phases present
in the raw material. Another method which is used to evaluate the pozzolanic activity is based
on the measurement of compensated electrical conductivity of calcium hydroxide saturated
solution, to which the material is added over time. The same characterization methods are
used for Kaolin to compare the potential of calcined C1 to C3 with meta-kaolin. Results rep-
resent that the all samples could be feasible candidate as cement substitute while there is an
assumption that C1 could have the chance for more than 30% of replacement.

References
1. Jackcon, M.D, Landis, E., Brune, P.F., Vitti, M., Li, Q.F.I., “Mechanical resilience and cementitious
processes in Imperial Roman architectural mortar”, PNAS, vol. 111, no. 52, 18484–18489.
2. Kingery, W.D., Bowen, H.K., Uhlmann, D.R., “Introduction to Ceramics”, 2nd Edition, Wiley Pub-
lication, 1976, ISBN-13: 978-0471478607.
3. Sabir, B.B., Wild, S., Bai, J., “Metakaolin and calcined clays as pozzolans for concrete: a review”,
Cement and Composite 23. 2001, pp. 441–454.
4. Scrivener, K., Antoni, M., Favier, A., Martirena, F., “Low Carbon Cement Based on Cliner, Cal-
cined Clay and Limestone”, Journal of the American Ceramic Society, 2011, 94(6): pp. 1901–1910.
5. Davidovits, F., Davidovits, J., “Long-Lasting Roman Cements and Concrete”, Geopolymer Confer-
ence Proceeding 99, 2003, pp. 315–320.
6. Davidovits, J., “Egyptian made stone statues in 2000 B.C: Deciphering the irtysen steel, (Louvre C
14).” Geopolymer Conference Proceeding 99, 2003, pp. 321–330,

533
Preparation and characterization of carbon nano/microfiber
membranes for ceramic matrix composite applications
Erika Mudra*, Magdalena Streckova, Ivan Shepa, Jan Dusza
Institute of Materials Research, Slovak Academy of Sciences, Watsonava 47, 040 01 Kosice,
Slovak Republic, *e-mail: [email protected]
Keywords: electrospinning, fiber, carbon, membrane

The needle-less electrospinning was employed for a preparation of two types of carbon nano/
microfiber membranes with extraordinary high specific surface area. The prepared fiber
membranes were produced in a large scale as potential heat-management materials, for rein-
forcement, high-temperature catalysis, membrane-based separation, and as components for
nanoelectronics and photonics1,2. The polyacrylonitrile (PAN) and polyvinyl alcohol (PVA)
were used as base polymers for preparation of electrospinning solution and subsequent pre-

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cursor fiber membranes formation by needle-less electrospinning on device called “Nanospi-

der”. The exactly defined temperature schedules and atmosphere were suggested according
to the results obtained from differential scanning calorimetry/thermogravimetric (TG/DSC)
analyses for all heat treatments. The final heat treatments consisted of preoxidation process
in air and carbonization in the pure Ar atmosphere3. The preoxidation process is respon-
sible for the final geometry, strength and defectless structure of the individual nanofibers and
the carbonization in Ar provides amorphous carbon character of final flexible membranes.
The structural characterization of the precursor and final carbon membranes was visualized
and evaluated by X-ray diffraction (XRD), scanning and transmission electron (SEM and
TEM) microscopy and average diameter of PAN-based fibers was 450 nm and PVA-based
fibers 220 nm. The roughness of fiber surfaces was measured by the atomic-force microscopy
(AFM) and the values of specific surface area SBET of the studied material were processed by
the Brunauer, Emmett, Teller (BET) isotherms. The higher roughness was observed on the
PVA-based fibers membranes what is in accordance with the higher specific surface area and
porosity. These cost-effective electrospun membranes have obvious importance as reinforce-
ment of ceramic matrix composites, especially multilayer systems.

References
1. E. Zussman, X. Chen, W. Ding, L. Calabri, D.A. Dikin, J.P. Quintana, R.S. Ruoff. “Mechanical
and structural characterization of electrospun PAN-derived carbon nanofibers”, Carbon, 43, pp.
2175–2185, 2005.
2. E. Hammel, X. Tang, M. Trampert, T. Schmitt, K. Mauthner, A. Eder, et al. “Carbon nanofibers for
composite applications”, Carbon 42, pp. 1153–1158, 2004.
3. M. Streckova, E. Mudra, R. Orinakova, L. Markusova-Buckova, M. Sebek, A. Kovalcikova, T.
Sopcak, V. Girman, Z. Dankova, M. Micusik, J. Dusza. “Nickel and nickel phosphide nanoparti-
cles embedded in electrospun carbon fibers as favourable electrocatalysts for hydrogen evolution”,
Chem. Eng. J. 303, pp. 167–181, 201.

789
Very fine AlN powder production from Al(OH)3 using dynamic
carbothermal reduction and nitridation
Nurşen Mutlu, Nuray Canikoğlu, Ali Osman Kurt
Depart. of Metall. and Mater. Eng., Sakarya Uni., 54187, Sakarya, Turkey;
e-mails: nurş[email protected], [email protected], [email protected]
Keywords: aluminium nitride, dynamic carbothermal reduction, powder production

Carbothermal reduction and nitridation (CRN) method used in nitride-based ceramic powder
production is an effective and economic technique that has been studied extensively. In this
study, CRN process was carried out in an atmosphere controlled modified tube furnace. Un-
like conventional CRN method, this novel approach in producing ceramic powders called
the dynamic CRN method (designated as DCRN for the nitride powder production) where
granulated reactants in a cylindrical reactor are rolled continuously rotary-type tube furnace

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during the process by means of using a servo motor1. It is believed that the diffusivity within
the reactants increases with the dynamic motion of the particles in the system during reactor`s
rotation. Thanks to this dynamic movement, quality of final products/powders improved sig-
nificantly after the DCRN process. The resulting product of narrow size distribution of very
fine (below 300nm) equiaxed aluminium nitride (AlN) powders were produced in a relative
short period of time and lower reaction temperature compared to conventional static system
of CRN method2. New technique is also suitable for the industrial scale production of the
high quality and economic nitride based ceramic powder production. Results of this study
shows that high yield, high quality, uniax homogeneous powders of very fine size aluminium
nitride (AlN) could be produced using DCRN method from Al(OH)3+carbon granules. Based
on the new powder production technique, the conditions of the manufacturing process and
new design parameters for AlN powder production have been determined and demonstrated.
High conversation ratio with single-phase of submicron AlN powders were synthesised at
1450 °C for 90 min from Al(OH)3 using DCRN method.

References
1. A. O. Kurt. “A production method of high-tech ceramic powders in atmosphere-controlled rotary
kiln”, Turkish Patent, TR 2011 02804 B.
2. S. Erçayhan, “Production of aluminum nitride powder from Seydişehir aluminum hydroxide”,
M.Sc. Thesis, İstanbul Technical University, 2003.

891
Solid oxide fuel cells electrolytes fabrication by stereolithography
technologies
David Rodríguez Vidal
FAE, L’Hospitalet de Llobregat, Spain; e-mail: [email protected]

Solid oxide fuel cells (SOFCs) are one of the more promising future power generation tech-
nologies due to their high efficiency and fuel flexibility1,2. Even though their reliability and
their clear thermodynamic advantages compared to other technologies, the number of steps
to build-up a stack of fuel cells and the complexity associated has made the technology not
being completely mature3.
Additive manufacturing technologies represents a breakthrough on ceramics processing
which could make SOFCs widely industrial competitive and assure its fast market adop-
tion4–6. Going through this idea, Cell3Ditor project is developing the fabrication of mono-
lithic SOFC stacks which could reduce in a half the estimated cost of a stack.
In this work 8YSZ electrolytes fabricated by additive manufacturing at 3DCeram have
been analyzed taking into account the sintering behavior, microstructural and mechanical
properties.
These tests demonstrated that the technology is suitable to produce electrolytes for SOFCs.

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Acknowledgments
This project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant
agreement No 700266. This Joint Undertaking receives support from the European Union’s Horizon
2020 research and innovation programme and Hydrogen Europe and N.ERGHY.

References
1. A. Choudhury, H. Chandra, A. Arora, Renew. Sust. Ener. Rev. 20 (2013) 430–442.
2. A. Boudghene Stambouli, E. Traversa, Renew. Sust. Ener. Rev. 6 (2002) 433–455.
3. Solid Oxide Fuel Cell. Manufacturing Overview. Hydrogen and Fuel Cell Technologies. Manufac-
turing R&D Workshop. August 11–12, 2011. Washington, DC.
4. http://web.ornl.gov/info/news/pulse/no421/feature.shtml consulted March 30th, 2017.
5. A. Ghazanfari, W. Li, M.C. Leu, J.L. Watts, G.E. Hilmas, Ceramics International, 43(8) (2017)
6082–6088.
6. Y. Du, A. Maar, K. Zhao, Ceramic Engineering and Science Proceedings, 37(5) (2017) 73.

985
Magnetic exchange coupling in RSPS-consolidated hexaferrites
Gabriela Vazquez-Victorio1,2, Nancy Flores-Martinez2, Sophie Nowak2, Souad Ammar2,
Raul Valenzuela1*
1
IIM, Universidad Nacional Autonoma de Mexico, 04510, Mexico; *e-mail: [email protected]
2
ITODYS, Paris Diderot University, 15 rue Jean Antoine de Baif, Paris, France
Keywords: permanent magnets, spring magnet, spark plasma sintering, nano-structured ceramics

In spite of impressive progress in rare-earth permanent magnet (PM) technology, bulk hexa-
ferrites M2+Fe12O19 (M2+ is a divalent cation, typically Ba, Sr) still retain a dominant fraction
of the world permanent market, due to their inexpensive primary sources and a well-known
“mature” technology1. The recent developments on soft chemistry and sintering can give
still a new place to nanostructured hexaferrites. In this work, we show that a combination of
polyol synthesized precursors subsequently consolidated by Reactive Spark Plasma Sintering
(RSPS) can lead to materials with a very high energy product, and hence a large variety of
PM applications, Fig. 1. The experimental parameters can be tailored to produce the hexago-
nal phase with a small content of other iron oxides (hematite, magnetite), with fine interfaces
between these components and therefore the onset of exchange coupling.

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Fig. 1. Comparison of hysteresis loops (at RT) of pure BaFe12O19 (BFO) and BFO + iron oxide second
phase. Saturation magnetization was normalized

Reference
1. R. C. Pullar, Prog. Mat. Sci. 57, 1191 (2012).

761
Sol-gel transparent nano-glass-ceramics base on SiO2-GdF3 matrix for
optics applications
J.J. Velazquez1, J. Mosa1, G. Gorni1, R. Balda2, J. Fernández2, A. Duran1, Y. Castro1
1
Grupo GlaSS, Instituto de Cerámica y Vidrio-CSIC, C/ Kelsen 5, 28049, Madrid, Spain
2
Applied Physic Department I, Superior school of Engineering, Pais Vasco University, Bilbao, Spain
Keywords: glass-ceramics, sol-gel, photonics applications

In recent years, Rare-earth (RE) doped transparent oxyfluoride nano-glass-ceramics (nGCs)

materials obtained by sol-gel method at low-temperature processes have attracted much at-
tention due to the possibility of use in a large variety of optic and photonic applications, such
as infrared and tunable phosphors1–3. The inherent advantages of this method are the low

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sintering temperature, the versatility of the processing method (thin-films and bulk materials)
and high purity and homogeneity of the materials obtained4–6. Moreover, this method also al-
lows the incorporation of high quantities of fluoride precursors.
However, in the bibliography, oxyfluoride nGCs with composition up to 10 mol% of fluo-
ride host without cracking has been only reported for its use in photonics applications. This
fact was enough to carry out a study increasing the amount of fluoride. In the present work,
undoped and RE3+-doped transparent nGCs with composition of (100-x)SiO2-xGdF3, (x = 10
and 20 mol%), were prepared by a novel sol-gel route. Structural analyses have been realized
by XRD, ATG/ATD, Raman, FTIR and HRTEM, revealing the GdF3 nanocrystals precipita-
tion. Photoluminescence studies confirm that RE3+ ions are located in the fluoride nanocrys-
tals. As a result, adequate optical properties have been observed in these materials, showing
up potential photonics applications.

References
1. W. Xu, G. Zhu, X. Zhou and Y. Wang, Dalton Trans., 44, (2015) 9241.
2. S. Fujihara, S. Koji and T. Kimura, J. Mater. Chem., 14, (2004) 1331.
3. B. Szpikowska-Sroka, L. ˙Zur, R. Czoik, T. Goryczka, M. Za˛dłoand W.A. Pisarski, Opt. Lett., 39,
(2014) 3181.
4. S. Fujihara,T. Kato and T. Kimura, J. Am. Ceram. Soc., 84 (2001) 2716.
5. A.C. Yanes, J.J. Velázquez, J. Del-Castillo, J. Méndez-Ramos and V.D. Rodríguez, Nanotech. 19,
(2008) 295707.
6. B. Szpikowska-Sroka, N. Pawlik, T. Goryczka and W.A. Pisarski RSC Adv., 5(2015), 98773.

471
Analysis of melt pool characterization during selective laser melting by
numerical simulation
Hsuan-Chung Wu*, Ju-Han Yang
Department of Materials Engineering, Ming Chi University of Technology, Taipei 24301, Taiwan;
e-mail: [email protected]
Keywords: selective laser melting, melt pool, numerical simulation, additive manufacturing

Selective laser melting (SLM) is one of the promising additive manufacturing processes and
has been widely used for the fabrication of implants and aerospace components. However,
many issues regarding process stability and the quality of the final parts arise during SLM
manufacturing. One of the concern issues is the stability of melt pool, which may affect
the formation of the so-called balling effect, pores, and other defects. This study adopted
ANSYS-FLUENT software package based on the thermo-fluid dynamical multi-phase model
to simulate the molten pool dynamics during SLM. In addition, the effects of various process
parameters, such as laser power, scan speed, hatch spacing and layer thickness on velocity
field, temperature gradient, cooling rate, melt pool sizes and surface morphology, and relative
density were also investigated.

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941
Robocasting and co-sintering of a multimaterial device for
radiofrequency applications
E. Xuriguera1*, E. Feilden-Irving2, J. Gonçalves3,4, E. Saiz2
Universitat de Barcelona, Dept. of Material Science and Physical Chemistry, C/ Martí i Franquès, 1,
1

08028 Barcelona, Spain; *e-mail: [email protected]

Centre of Advanced Structural Ceramics, Department of Materials, Imperial College London,
2

SW7 2AZ, UK
Universitat de Barcelona, Dept. of Engineering: Electronics, C/ Martí i Franquès, 1, 08028
3

Barcelona, Spain
Francisco Albero S.A.U, C/Rafael Barradas, 19, Polig. Gran Via Sud, 08908 L'Hospitalet Barcelona,
4

Spain
Keywords: robocasting, co-sintering, mutimaterial, radiofrequency

Additive Manufacturing (AM) comprises a broad range of different techniques to build three
dimensional objects layer-by-layer. It allows the design and rapid manufacturing of highly
complex shapes with very few geometric limitations compared to traditional manufacturing
processes. AM technologies enable the fabrication of complex and fully customizable parts
made of functional or structural materials such as ceramic or metals. One of the main chal-
lenges in robocasting is the development of suitable paste formulations to print multimate-
rial devices with high resolution. Here we describe the printing of a copper/ceramic (low
temperature co-fired ceramic) structure using robocasting with water-based inks. The solid
content, the particle dispersion and the influence of the addition of Pluronic as rheology
modifier are studied in order to achieve the optimal formulation. A co-sintering process has
been developed to build an inductor for radiofrequency applications.

Acknowledgment
This work has been financially supported by the research fund of Universitat de Barcelona under the
project Ajut en el Marc del programa de formació per professorat amb contractació temporal 2016.

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528
Additive manufacturing of ceramics enabled by flash pyrolysis
technique of polysilazane based polymers with nanoscale layers and
oxidation resistance of final composites
Luca Zoli1,2, Diletta Sciti1, Rishi Raj2
CNR-ISTEC, National Research Council of Italy, Institute of Science and Technology for Ceramics,
1

Via Granarolo 64, I-48018 Faenza, Italy

Department of Mechanical Engineering, University of Colorado at Boulder, Boulder, Colorado
2

80309-0427, USA

The key impediment to additive manufacturing of net shapes from Polymer derived ceramics
(PDCs) has been the very slow heating rates with a process period of about 10 h, which are
required to preempt fissures in the ceramic caused by shrinkage, and to allow hydrogen, as
the polymer evolves into the ceramic phase, to escape.1 For these reasons, the infiltration of
fiber preforms from the polymer route, by the process known as PIP or polymer-infiltration-
pyrolysis has been difficult. An additive manufacturing novel design has been developed at
Colorado University to achieve CMC via preceramic route by reducing the time for pyrolysis
to about few seconds (the so-called flash pyrolysis).2 The goal of flash pyrolysis is to deposit
preceramic polymer films around fibers having a thickness of few hundred nm; the pyrolysis
of thin polymeric films leads to crack-free ceramic coating even when the heating treatment
of curing and pyrolysis is carried out in few seconds. Full dense composites can be manufac-
tured by repeating procedure of deposition and pyrolysis cycles. The wettability of fibers has
been studied to permit a three-dimensional coating as well as the maximum thickness of the
coating during infiltration to avoid cracks during shrinkage. Polysilazane polymer was used,
pure or doped with [Hafnium(IV) tetra-isopropoxide], to achieve carbonitride (SiCN) and
HfSiCN matrix respectively. The resulting CMCs were characterized by RAMAN spectros-
copy to highlight the conversion of polymer into ceramic phase while microscopy analysis
revealed the morphology of the coating from few deposition cycles to nearly-full infiltrated
composite. Finally the oxidation resistance of coated single fibers and full infiltrated com-
posites barriers has been investigated via TGA at increasing temperature and holding time.

References
1. P. Colombo, G. Mera, R. Riedel, G. D. Soraru, “Polymer-Derived Ceramics: 40 Years of Research
and Innovation in Advanced Ceramics,” J. Am. Ceram. Soc., 93 [7] 1805–1837 (2010).
2. L. Zoli, D. Sciti, Li-A. Liew, K. Terauds, S. Azarnoush, R. Raj, “Additive Manufacturing of Ceram-
ics Enabled by Flash Pyrolysis of Polymer Precursors with Nanoscale Layers,” J. Am. Ceram. Soc.
99, 57–63 (2016).

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T02: H
 igh temperature processes and advanced
sintering
Invited lectures

271
Spark plasma sintering technique: a powerful research tool for
developing new ceramic materials
Manuel Belmonte*, Pilar Miranzo, M. Isabel Osendi
Institute of Ceramics and Glass (ICV-CSIC), Campus Cantoblanco, 28049 Madrid, Spain;
*
e-mail: [email protected]
Keywords: SPS, ceramics, composites, graphene, carbon nanotubes

The search of new materials able to fulfil the increasing demanding operating conditions
is frequently stopped by technological challenges. In this way, the spark plasma sintering
(SPS), a pressure assisted pulsed direct current sintering technique, arises as a powerful re-
search tool for developing bulk materials and ceramic composites with enhanced properties.
As proof of concept, here we present few examples of new ceramics developed during the
SPS process; in particular, a one-step approach for tailoring continuous in-situ functionally
graded non-oxide ceramics from a sole homogenous powder composition, and the in-situ
development of different multifunctional ceramic/carbon nanostructures (graphene or nano-
tubes) composites.
In the first example, continuous gradual mechanical properties (hardness and toughness)
in the direction of the pressing axis for silicon nitride specimens were produced through the
control of the temperature profile within the powder compact. This was achieved by both
varying the SPS die-punches contact sections and introducing electrical insulators between
the punch and the compact.1 In the case of ceramic/carbon nanostructures composites with
superior electrical and/or mechanical properties, different in-situ synthesis processes are pre-
sented: i) the growth of graphene sheets into a sole homogenous silicon carbide starting
powder during the ceramics densification,2 ii) the in-situ thermal reduction of graphene oxide
films to graphene that takes place along with multilayered ceramics composite sintering,3 iii)
the carbothermal reduction of a 3D silica coated carbon nanotube network to in-situ develop
silicon carbide/carbon nanotubes composites.4

References
1. M. Belmonte, P. Miranzo, M.I. Osendi, “Enhanced microstructural and mechanical gradients on
silicon nitride ceramics”, Ceram. Int., 41, pp. 2594–2598, 2015.
2. P. Miranzo et al. “In situ processing of electrically conducting graphene/SiC nanocomposites”, J.
Eur. Ceram. Soc., 33, pp. 1665–1674, 2013.
3. M. Belmonte et al. “Directional electrical transport in tough multifunctional layered graphene-
ceramic composites”, Adv. Electron. Mater., 1, pp. 1500132, 2015.
4. L. P. Rajukumar, M. Belmonte et al. “3D nanocomposites of covalently interconnected
­multi-walled carbon nanotubes with SiC with enhanced thermal and electrical properties”,
Adv. Func. Mater., 25, pp. 4985–4993, 2015.
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856
Sintering of ultra-fine nanocrystalline ceramics and how to avoid their
growth
Ricardo H.R. Castro
Department of Materials Science & Engineering, University of California-Davis, USA

Contradicting past reports, nanocrystalline dense ceramics have been recently shown to pres-
ent mechanical properties that largely surpass those of the microcrystalline counterparts. The
success in showing these properties relies on a highly controlled processing of nanoparticles
followed by a densification process that minimizes grain growth and eliminates porosity. In
this talk we discuss the novel Deformable Punch Spark Plasma Sintering method, in which
a complaint tool is used to destabilize porosity at the final stage of densification of nanopar-
ticles. The products are highly dense parts with grain sizes below 10 nm and unprecedented
hardness. While these are interesting products by themselves, it is well known that coarsen-
ing can occur in such samples during operation conditions or further processing, limiting life
time of the nanostructures at high temperatures due to the inherent excess energy coming
from interfaces. Therefore, we further discuss in this talk how, by targeting a decrease in
grain boundary energy, one can enable the creation of highly stable nanocrystalline ceramics,
with virtually zero excess energy coming from interfaces.

825
Reactive sintering activated by SPS
Mirva Eriksson*, Zhijian Shen
Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University,
S-106 91 Stockholm, Sweden; *e-mail: [email protected]

The Spark plasma sintering gives new possibilities to sinter ceramics and composites which
are traditionally very difficult to sinter. Together with the electric field, the rapid heating rate
and short holding time give an additional driving force for the sintering making it possible to
reach the eligible microstructure as well gives possibilities for the reactive sintering and syn-
thesis. The reactions can be controlled during the sintering by changing the sintering profile
giving possibilities to tailor the product and their microstructures simultaneously.1,2
Boride based materials are interesting for their good physical and chemical properties.
They have high melting point and are chemically very stable against oxidation, thus can
particularly be used in extreme environments at ultra-high temperatures. Due to the very
high hardness but modest toughness and low self-diffusion coefficient their sintering is very
difficult by conventional methods.
In order to improve the density of TiB2, reactive sintering from the precursor powders was
conducted. The reaction was aided by a small addition of conducting magnesium which in-
creased the current flow inside the sample. This created many ignition points for the reaction

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between Ti and B which continued then in a self-propagating manner.3 The rapid reaction and
sintering improved the microstructure compared to the mixture without magnesium. When
similar test to react TiB from precursor powder was tried in SPS it was obvious that the fast
process could not finish to equilibrium during the short sintering times in SPS but reaction
products were mixtures of different borides. When zirconium diboride based composites was
sintered by reactive spark plasma sintering (RSPS) a significant grain refinement was ob-
served increasing the grain size control and improvements of the properties. Also, by inten-
tionally choosing a mixture of coarse and fine powders as the reactants, dual microstructure
ceramics with simultaneously improved toughness and strength could be obtained.4
It is also possible to improve sintering and plastic deformation of sialon while adding a
LiCO3 in order it to react during the sintering with the glassy phase and in that way decrease
the viscosity of the liquid phase and improve the non-equilibrium sintering and deformation
of the sialon.
The SPS in argon atmosphere will open the possibility to sinter reaction-sensitive mate-
rials. Lithium hydride compounds has been tried to synthesize in SPS in protective atmo-
sphere. The evaporation of lithium and its intercalation with graphite during the synthesis
was avoided by inserting a closed crucible inside the graphite die. The protective atmosphere
has also been shown to be beneficial to avoid the formation of ZnO in ZnSb compounds. The
formation of ZnO was decreased to undetectable by X-ray.

References
1. Shen, Z., Nygren, M., Microstructural prototyping of ceramics by kinetic engineering: Applications
of spark plasma sintering, Chemical Record, 2005, 5(3), 173–184.
2. M. Nygren and Z.-J. Shen , “Hot Pressing and Spark Plasma Synthesis,” in "Ceramics Science and
Technology" edited by Ralf Riedel and I-Wei Chen, Wiley-VCH Germany, 2010.
3. David Salamon, Mirva Eriksson,w Mats Nygren, and Zhijian Shen, Homogeneous TiB2 Ceramics
Achieved by Electric Current-Assisted, Self-Propagating Reaction Sintering, J. Am. Ceram. Soc.,
90 [10] 3303–3306 (2007).
4. Zou, J.; Zhang, G. J.; Shen, Z. J.; Binner, J., Ultra-low temperature reactive spark plasma sintering
of ZrB2-hBN ceramics. J. Eur. Ceram. Soc. 2016.

838
Segregation and surface excess during ceramic process and sintering
Douglas Gouvêa
Department of Metallurgical and Materials Engineering – Polytechnic School – University of
Sao Paulo, Av. Prof. Mello Moraes, 2463 – Sao Paulo – SP – Brazil; e-mail: [email protected]
Keywords: segregation, surface excess, sintering, surface energy, nanoparticle

Segregation is the process that differentiates the composition at an interface or surface from
the average or bulk composition, and it is well-known in the metallurgical processes. How-
ever, it can often be mistaken as a process that occurs out of equilibrium due to the rapid
cooling. Surface excess is a more generally term used in the thermodynamic of equilibrium
for adsorption processes. In ceramic, the interface excess has been observed as a common

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phenomenon due to gas adsorption in surface and additive segregation in surface and grain
boundaries and, consequently, changing the chemical compositions of the interfaces. That
has a significant influence in the colloidal process, nanoparticle size stability, phase stability
and sintering as well as in the ceramic application due to the reduction in the interface energy.
The aim of this work is to point out the main mechanisms of interface segregation in ceramic
materials and to present some consequences in the colloidal process, nanoparticle size stabil-
ity, phase stability and sintering.

Reference
1. R.H.R. Castro and D. Gouvêa, “Sintering and Nanostability: The Thermodynamic Perspective,” J.
Am. Ceram. Soc., 99(4), pp. 1105–1121, 2016.

085
Fundamentals of sintering and their future research directions
Suk-Joong L. Kang
KICET/KAIST, Jinju/Daejeon, South Korea; e-mail: [email protected]

Sintering, the oldest human technology with the firing of pottery, is an essential technique
for fabricating ceramic materials and components. Although the technique has been used for
over several thousand years, its scientific studies began only in the middle of the 20th century.
During the past 70 years, sintering models and theories have been developed under the as-
sumption that only the atom transport governs the sintering kinetics, and the results of sinter-
ing studies have been interpreted in view of the developed theories. The classical assumption,
however, was recently found to be valid only for systems with rough interfaces.
This presentation will first review the classical descriptions of solid–state sintering (SSS)
and then liquid–phase sintering (LPS) as well. For SSS, densification models and kinetics are
presented. For LPS, the fundamental difference between two existing models of densifica-
tion, contact flattening and pore filling, are explained. Microstructural evolution with normal
grain growth during SSS and LPS are described.
At the beginning of the 2000s, we found that densification, grain growth and microstruc-
tural evolution are largely governed by the structure of grain boundaries (for SSS) and solid/
liquid interfaces (for LPS).1–5 When the driving force is smaller than a critical value, the re-
action of atoms at the interface governs the sintering behavior and kinetics for systems with
faceted (even partially) boundaries and interfaces. For faceted systems, the classical theories
of sintering are, therefore, not valid and new theories need to be developed to properly de-
scribe the sintering kinetics and microstructural evolution. Remaining issues are suggested
to achieve this goal.

References
1. B.-K. Lee, et al., Acta Mater., 48, 1575–1580 (2000).
2. S.-Y Choi and S.-J. L. Kang, Acta Mater., 52, 2937–2943 (2004).
3. B.-K. Yoon, et al., Acta Mater., 53, 4677–4685 (2005).
4. S.-J. L. Kang, et al., J. Am. Ceram. Soc., 92, 1464–1471 (2009).
5. M.-G. Lee, et al., Acta Mater., 59, 692–698 (2011).

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026
Reactive metal infiltration for manufacturing of ceramic
matrix composites
Dietmar Koch, Marius Kütemeyer, Bernd Mainzer
German Aerospace Center, Institute of Structures and Design, Stuttgart, Germany

The reactive melt infiltration process is a versatile route to manufacture nonoxide fiber re-
inforced ceramics (CMC). In general a fibrous preform is manufactured with Carbon or SiC
fibers. The fibers are surrounded by a porous matrix which shows an adjusted pore morphol-
ogy for the succeeding melt infiltration process. Depending on the composition of the reac-
tive alloy melt and the desired final matrix state Carbon, SiC or filler particles as borides are
introduced in the porous matrix. Ideally all constituents react in the desired manner with the
alloy to a more or less dense matrix.
The process strategy to manufacture damage tolerant tough and dense composites is
shown. The resulting properties of C/SiC, SiC/SiC as well as ultra high temperature ceramic
matrix composites UHTCMC are discussed and correlated with the key aspects of manufac-
turing steps. One example is the design of the fiber matrix interphase which needs to survive
the reactive melt infiltration and furthermore must provide crack deflection in order to pre-
vent brittle failure of the composite.

853
RMI-derived ceramic matrix composites based on the liquid-phase
pyrolysis of carbon/carbon
Walter Krenkel
Ceramic Materials Engineering, University of Bayreuth, Germany
Keywords: ceramic matrix composites, RMI, thermoplastics

Ceramic matrix composites (CMC) manufactured via Reactive Melt Infiltration (RMI) pro-
cesses, in particular by Liquid Silicon Infiltration (LSI), are well-established structural ce-
ramic materials, used in gas turbines, thermal protection systems of spacecraft or brake sys-
tems. Typically, the requirements on these applications differ widely with the consequence
that the microstructure should be tailored to different properties.The RMI-process offers
unique opportunities for microstructure modifications as the fiber/matrix interphase can be
modified easily by thermal fiber pre-treatments which varies the functional groups on the
fiber surface. Also, a post-treatment of the amorphic carbon matrix beyond 1600 °C result in
different microstructures.
Carbon/Carbon (C/C) composites derived from thermoplastics like PEI or PEEK were
pyrolized up to 1000 °C and subsequently carbonized in inert atmosphere up to 2200 °C.
The increased carbonization temperature leads to a higher carbon order as well as an incipi-

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ent stress-induced graphitization of the carbon matrix close to the fiber surface at 2200 °C.
The C/C-SiC composites show a maximum flexural strength of 180 MPa and monotonically
increasing Young’s moduli ranging from 49 GPa with C/C preforms treated at 1600 °C up to
59 GPa after carbonization at 2200 °C. The correlations between the mechanical properties,
the microstructure and the material’s composition is discussed. whole text should fit to this
single page.

583
Cold, flash, sparks, nano – where are sintering processes headed?
Gary Messing, Tobias Frueh, Elizabeth Kupp
Pennsylvania State University, Department of Materials Science and Engineering, USA

Recent times have seen an explosion of innovative means to densify ceramics at significantly
lower temperatures and much shorter times. These innovations have capitalized on either
massive increases in driving force by using >100 MPa pressures, or exceptional changes in
kinetic processes that enable faster diffusion over short-range distances. This presentation
analyzes the spectrum of conditions reported using the sintering approaches listed in the
title and summarizes these novel processes in terms of sintering driving force differences
and mechanistic alterations in transport required for densification of ceramics powders. In
the end, we project how these novel sintering processes will impact commercial sintering
technology.

735
Novel processing for unique porous ceramics
Tatsuki Ohji*, Manabu Fukushima
National Institute of Advanced Industrial Science and Technology (AIST), Nagoya, Japan;
*
e-mail: [email protected]
Keywords: pore, processing, freeze-dry, ceramics, microstructure, mechanical properties

Porous ceramics are now being used for environmental protection such as diesel particulate
filters (DPF), coal gasification gas filters, separation membrane supports, and catalyst sup-
ports. It is expected that these applications will be further expanded in future, as the concerns
over environmental issues become more crucial in all the countries over the world. A number
of innovative processing routes developed for critical control of pores are described, along
with some important properties. This paper intends to give an overview on the recent pro-
gresses of porous ceramics (mainly macro-porous ceramics whose pore size is larger than 50
nm) prepared via powder processing routes. The partial sintering of powder compacts, the
most conventional technique for making porous ceramics, has been substantially sophisti-
cated in recent years. Very homogeneous porous ceramics with extremely narrow size dis-

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tribution have been successfully prepared through sintering combined with in-situ chemical
synthesis. Carefully tailored microstructure (size, morphology and orientation of grains and
pores, etc.) of porous ceramics has led to unique mechanical properties, which cannot be
attained even in the dense materials. Powder processing with various types of the sacrifi-
cial fugitives also has been examined for obtaining well-tuned shape and size of pores. The
freeze-dry techniques using water or liquid as fugitive materials have been most frequently
studied in recent years. Controlling growth of ice during freezing has led to unique porous
structures and excellent performances of porous ceramics.
As an novel processing approach for unique porous structure, special emphasis is placed
on the advanced gelation-freezing methodology for macroporous ceramic components, that
can create nearly honeycomb shaped pore channels, unlike either ellipsoidal or dendric or la-
mellar structures obtained via conventional aqueous freeze casting. Three main technological
features will be discussed in terms of 1) honeycomb shaped porous structures, 2) relationship
between carefully selected freezing conditions and cell properties generated, 3) mechanical
properties and applications of the obtained porous ceramics. This simple, ecofriendly and ver-
satile approach tailors porous architecture with engineered porosity and yields macro-cellular
component with distinctive characteristics of fluid permeability, mechanical properties, ma-
chinability, and thermal insulation properties, suitable for a variety of industrial applications.

638
Ultra high temperature ceramic matrix composites based on carbon
fibres
Virtudes Rubio*, William Hillman, Jon Binner
School of Metallurgy and Materials, University of Birmingham, UK,
*
e-mail: [email protected]
Keywords: UHTCMC, carbon fibre, infiltration

Ultra High Temperature Ceramics (UHTCs) are potentially excellent materials for use in
severe aerospace environments, for example as nozzle inserts and/or thermal protection sys-
tems (TPS). However, although they are refractory materials and have melting temperatures
above 3000 °C1–3, their poor thermal shock means that they need to be reinforced and used as
CMCs. The use of carbon fibre reinforcement is possible as long as it can be protected at the
application temperatures. In the present work, carbon fibre preforms have been impregnated
by different UHTC slurries to fill the inter-tow porosity between the different orientation
plies of the preform and then infiltrated with a UHTC matrix using a CVI technique based
on radio frequency (RF) heating to fill both the intra-tow porosity and the residual inter-tow
porosity. Operating at 150–400 kHz and with a maximum of 4.2 kW, the temperature of the
sample was controlled using a 2 colour pyrometer and the pressure used was in the rage of
15–100 mbar. The advantage of RF heating is the inverse temperature profile that develops in
the sample, which means that the infiltration starts from inside out. The consequent reduction
in process time is significant in comparison with a more conventional CVI process.

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References
1. E. Wuchina, E. Opila, M. Opeka, W. Fahrenholtz, I. Talmy, “UHTCs: ultra-high temperature ce-
ramic materials for extreme environments applications”, Electrochem. Soc. Interface, 16:30, 2007.
2. F. Monteverde, A. Bellosi, L. Scatteia, “Processing and properties of ultra-high temperature ceram-
ics for space applications”, Mater. Sci. Eng. A, 485, pp. 415–421, 2008.
3. W.G. Fahrenholtz, G.E. Hilmas, I.G. Talmy, J.A. Zaykoski, “Refractory diborides of zirconium and
hafnium”, J. Am. Ceram. Soc., 90, pp. 1347–1364, 2007.
4. I.G. Talmy, J.A. Zaykoski, M.M. Opeka, “Synthesis, processing and properties of TaC-TaB2-C ce-
ramics”, J. Eur. Ceram. Soc., 30, pp. 2253–2263, 2010.

824
Recent advances in current assisted sintering
Theo Saunders, Salvatore Grasso, Francesco Gucci, Michael J. Reece
School of Engineering and Material Science, Queen Mary University of London, London,
E1 4NS, UK

In recent year there has been much excitement and debate about flash sintering, which has
reinvigorated interest in other processes involving direct Joule heating. SPS is still the domi-
nant electric current sintering technology and has already been be used to Flash SPS (FSPS)
various materials. This talk will discuss some simple methods to evaluate the possibility of
flash sintering different materials using SPS equipment. A more complex model of the en-
tire sintering process was also developed. But this required revaluating many assumptions
used in the previous work, in light of the highly no equilibrium conditions of flash sintering.
With a robust model in place optimized tooling and heating profiles have been developed for
FSPS. Thermoelectric materials proved to be an excellent test case for this technique due to
the significant effect of microstructure on the functional properties. Skutterudite thermoelec-
tric materials was successfully FSPSed to near full density and samples with unique micro-
structures and properties were achieved.

Acknowledgements
The project leading to this research was funded by the EPSRC throught the XMat grant (EP/K008749/1)
and from the European Union’s Horizon 2020 research and innovation programme under the Marie
Sklodowska-Curie grant agreement No 642557.

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109
Densification strategies for Ultra High Temperature Ceramics prepared
by Near-Net-Shaping Techniques
Carolina Tallon
Department of Materials Science and Engineering, Virginia Polytechnic Institute and State University,
Blacksburg, VA, 24061, USA; e-mail: [email protected]

Components for hypersonic applications have relied on Ultra High Temperature Ceramics
to withstand high temperatures, high stagnation pressures, vibrations and extreme oxidation
conditions associated with the speed, flight and reentry conditions. These components often
require a complex geometry and a fully dense, fine and controlled microstructure. The current
state-of-the-art processing of these materials allow their full densification but not the shap-
ing capability. Near-Net-Shaping Techniques involving the colloidal processing of UHTC
powders can afford to provide near-net-shaped pieces, but because of the shape, the sintering
needs to be done using pressureless conditions. This work will discuss the strategies to en-
hance the densification of these materials: particle packing in the green bodies (by the control
of the interparticle forces in solution), sintering temperature and profiles and additives, and
how these results compare with the current state-of-the-art densification. These strategies
have allowed to reach 93% TD without sintering aids at 2100 oC and 98% TD with sintering
aids and modified sintering profiles. This work also show some of the shapes and some of the
temperature testing performed in samples produced using colloidal processing and pressure-
less sintering combined approach.

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Oral presentations

266
Effect of sintering temperature on crystallization of nepheline-leucite
glass-ceramics
Ali Alzahrani*, Robert Allaker, Robert Hill
Institute of Dentistry, Queen Mary University of London, Mile End Road, London E1 4NS,
United Kingdom; *e-mail: [email protected]

Ball milling is an effective method of mechanically reducing the crystallite size after crys-
tallisation. However, pre-crystalised glass particles tend to hinder the densification process
during sintering. Introducing a green compact to a sintering temperature higher than the
crystallisation one can allow for sufficient viscous flow to occur in some cases. However this
can result in changes of the crystalline phase/s, size and morphology as well as the residual
glassy phase composition. Therefore, the aims of this study were to investigate the effect
of sintering temperature on crystallisation of alkali rich alumina silicate glasses. Wherein,
two different glass compositions based on a multicomponent system were synthesised using
melt-quench method. The experimental glass powders were prepared by ball milling for 2
hours and sieving below <125 µm (mean glass powder particles, D50 = 25µm). Thereafter
the prepared powders were divided into two groups one of which (group A, G1 and G2) was
left as glass powders for sinter-crystallisation experiment from green compact; whereas the
second (group B, GC1 and GC2) was heat-treated to produce glass-ceramics powders. The
prepared glass-ceramics were ball milled for 2 hours back to find powders. Thus, sintering
experiments were conducted on glass powders (G) and pre-crystalised glass powders (GC).
Glasses and glass-ceramics were characterised before and after sintering using differential
scanning calorimetry (DSC) Dilatometry (DIL), X-ray diffraction (XRD) and Nuclear Mag-
netic Resonance (NMR). The crystalline microstructures of the glass-ceramics were analysed
using scanning electron microscopy (SEM) before and after sintering. Results illustrated a
tendency towards a decrease in grain size with increasing the sintering temperature in group
B (GC1 and GC2). This paper will discuss further the sintering results for both groups in
relation to crystallisation, different crystalline phase developments, crystallite size and mor-
phology.

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444
New insights into field assisted sintering through synchrotron X-rays
computed tomography investigations
Yann Aman1,2, Kai Zhu3, Wenbo Yu3
1
NIMTE CNITECH Chinese Academy of Sciences, Ningbo, China
2
Laboratoire de Chimie-Physique, Université Félix Houphouët Boigny Abidjan, Côte d’Ivoire
3
School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
Keywords: spark plasma sintering, alumina, synchrotron X-ray, computed tomography

The emergence of spark plasma sintering (SPS) has been seen as one of the most effective sin-
tering technologies for powdered materials including metals, ceramics, glass, biomaterials and
even polymers.1–5 Since the first patent of Inoue half a century ago,6 SPS has been developed
based on the assumption that using discharge or plasma induced by pulsed electric currents
coupled with the application of uniaxial mechanical pressure could favor the short time and low
temperature sintering of advanced nanostructured materials. However, despite the tremendous
technological advances in electric current-activated/assisted sintering,6 a large gap still exists
between the numerous experimental studies of the process parameters and the fundamental
understanding of the underlying mechanisms of SPS. This difficulty in understanding the sa-
lient mechanisms could be due to the numerous physical couplings (electrical–thermal–me-
chanical)7,8 encountered in this process. Among the non-elucidated hypothetical mechanisms,
such as plasma (or micro-discharge) cleaning of particle surfaces before sintering activation,9
Joule heating,10 electromigration,11 local melting and evaporation, 12 or thermal diffusion by
Soret effect, the existence of plasma has been cited routinely without providing evidence or
justification. In the present investigation, we propose a novel experimental approach to high-
light the SPS mechanisms during early –stage sintering of non-conductive ceramics. We use
ex-situ synchrotron X-ray beamlight (SSRF Beamline BL13W1), and computed tomography
techniques to reveal particular details of the sintering necks and mechanisms during SPS. We
discuss these results in the framework of thermal instabilities theories.

References
1. Zhang ZH, Wang FC, Wang L, Li S-K (2008) Mater Sci Eng A 476:201.
2. Shen Z, Johnsson M, Zhao Z, Nygren M (2002) J Am Ceram Soc 85:1921.
3. Riello P, Bucella S, Zamengo L, Anselmi-Tamburini U, Francini R, Pietrantoni S, Munir ZA (2006)
J Eur Ceram Soc 26:3301.
4. Gu YW, Loh NH, Khor KA, Tor SB, Cheang P (2002) Biomaterials 23:37.
5. Omori M (2000) Mater Sci Eng A 287:183 6. Grasso S, Sakka Y, Maizza G (2009) Sci Technol Adv
Mater 10:053001.
6. Mondalek P, Silva L, Durand L, Belleta M (2010) AIP Conf Proc 1252:697.
7. Vanmeensel K, Laptev A, Hennicke J, Vleugels J, Van der Biest O (2005) Acta Mater 53:4379.
8. Groza JR, Zavaliangos A (2000) Mater Sci Eng A 287:171.
9. Carney CM, Mah TI (2008) J Am Ceram Soc 91:3448.
10. Munir ZA, Anselmi-Tamburini U, Ohyanagi M (2006) J Mater Sci 41:763. doi:10.1007/s10853-
006-6555-2.
11. Chaim RJ (2006) J Mater Sci 41:7862. doi:10.1007/s10853- 006-0605-7.
12. Olevsky E, Froyen L (2009) J Am Ceram Soc 92:S122.

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070
Strong junctions of Alumina to TZM alloy obtained by coupling
oxidation of the alloy and diffusion bonding
Réda Berkouch*, Stéphane Valette, Joseph Absi, PierreLefort
SPCTS – European Ceramic Center – 12 Rue Atlantis, 87068 LIMOGES Cedex, France; *e-mail:
[email protected]
Keywords: ceramic to metal joining, diffusion bonding, TZM oxidation, adherence, ASTM C633

The new ceramic to metal junctions must make possible to use the pieces at high temperatures
in aggressive environments, with good mechanical properties, including fracture toughness.
First of all, the materials to be joined must have high Tammann’s temperatures, for avoid-
ing the effects of unwanted diffusions leading to the recrystallization of the metal and to
creep; moreover, their coefficients of thermal expansion (CTE) must be close.
The TZM alloy (Mo99/Ti0.5/Zr0.1) melts at 2600 °C and recrystallizes at 1400 °C, which
is better than pure molybdenum, with identical physical and corrosion properties.
Hence it seemed well suited for a ceramic to metal assembly with alumina (TF = 2072 °C),
the CTE of which being close to that of TZM, respectively 5.4 × 10–6 and 5.3 × 10–6 K–1 at
room temperature.

Fig. 1. SEM photograpy of an alumina to TZM interface by diffusion bonding

In this study a joining approach without filler alloys interphases, or metallization is in-
vestigated. The proposed method is based on diffusion bonding by thermocompression. Of
course, the direct joining of TZM to alumina is thermodynamically impossible and an impor-
tant preliminary step is required. This step consists in the preoxidation of TZM in air.1

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The ceramic to metal adherence of the obtained assemblies (Fig. 1) was tested via the
mechanical ASTM C633-13 traction test, but the adherence values could not be determined
because the fractures occurred in the glue during the test, for a rupture stress of 45 MPa. This
means that the adherence of the alumina /TZM adherence was higher than 45 MPa.

Reference
1. G.R. Smolik, D.A. Petti, S.T. Schuetz, Journal of Nuclear Materials. 283 (2000) 1458–1462.

547
Flash sintering of alumina
Mattia Biesuz, Vincenzo M. Sglavo
Department of Industrial Engineering, University of Trento, Via Sommarive 9- 38123 Trento, Italy;
e-mails: [email protected], [email protected]
Keywords: flash sintering; alumina; sintering

Flash sintering is an innovative energy saving densification technology, which allows a con-
sistent reduction of the consolidation time and temperature for many ceramic materials.1,2
Flash sintering belongs to the family of field/current assisted sintering technique; however,
it possesses some peculiar characteristics mainly associated to the presence of the so called
flash event. This is characterized by a very rapid heating of the specimen based on Joule
effect, which is in the order of 104 K min–1.3 Meanwhile, a drop in the electrical resistivity
takes place and the material densifies in few seconds. Such phenomenon is also associated to
a strong bright light emission.
In this work, we apply flash sintering to 99.8% pure α-alumina using different combina-
tions of DC current/field. Densification and microstructural evolution are studied as a func-
tion of the process parameters. Different microstructures are pointed out in proximity to the
electrodes. Such asymmetry is very likely associated to partial reduction of the oxide upon
the final stage of the process, after the flash event. Finally, the analysis of the light emission
points out its fundamental thermal origin.

References
1. M. Cologna, B. Rashkova, R. Raj, “Flash sintering of nanograin zirconia in <5 s at 850°C”, J. Am.
Ceram. Soc., 93, pp. 3556–3559, 2010.
2. J.A. Downs, V.M. Sglavo, “Electric field assisted sintering of cubic zirconia at 390°C”, J. Am.
Ceram. Soc., 96, pp. 1342–1344, 2013.
3. S. Grasso, Y. Sakka, N. Rendtorff, C. Hu, G. Maizza, H. Borodianska, O. Vasylkiv, “Modeling of
the temperature distribution of flash sintered zirconia”, J. Ceram. Soc. Japan., 119, pp. 144–146,
2011.

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359
Joining steel to yttria doped hafnia with a reactive brazing for
a potentiometric oxygen sensor in sodium
L. Brissonneau1, P. Trabuc, C. Chabert, T. Matonne, H. Sassoulas, F. Bianchi2
1
CEA/DEN/DTN/SMTA/LIPC, Cadarache, 13108 St-Paul lez Durance, France
2
CEA/DRT/LITEN/DTCB/LTCA, 17 rue des martyrs, 38054 Grenoble cedex 9, France
Keywords: SFR, potentiometric sensors, yttria-dopped hafnia, reactive brazing, steel

Within the framework of the development of the fourth generation of nuclear reactors, a
Sodium cooled Fast Reactor (SFR), named ASTRID (Advanced Sodium Fast Reactor for In-
dustrial Demonstration) is in a basic design phase. A SFR operates in a specified oxygen con-
tent range in order to control the corrosion of the steel structures of the core (claddings…).
Potentiometric sensors allow to obtain a fast and specific measure complementary to others
devices (plugging indicator). In most advanced designs, the solid electrolyte of the sensor,
generally made of yttria-doped thoria (YDT) or more rarely hafnia (YDH) is brazed on a steel
with a controlled thermal expansion coefficient, in order to limit the size of the ceramic tube
and to insure that it is fully immerged in sodium at constant temperature.
As no potentiometric sensors specifically designed for liquid sodium are commercially
available, the CEA decided to develop its own. In the past, brazing was found to be a critical
part of the success of the sensor, so a new assembling method was investigated and a reactive
brazing was developed and patented.1 The first tests are conducted on YDH, as a surrogate
material for YDT (similar expansion coefficients). Their purpose was to ensure that a correct
mechanical strength could be obtained for the joint and to examine the effect of the brazing
parameters on the reactive layer.
The brazing between the steel and the oxide ceramic is performed by forming an eutectic
between a zirconium foil and the Fe-Ni steel on one interface and by the formation of an
oxide layer on the other interface, zirconium reducing the ceramic. The Fe-Ni-Zr eutectic
temperature is about 940 °C and the oxygen diffusion in the ceramics must be fast enough
so the layer can be formed in a few minutes at the interface. The yttrium doping provides
oxygen vacancies, which induce a high ionic conductivity in the oxide.
Tests were performed in induction and tubular furnaces under vacuum at temperatures
between 980 °C and 1080 °C. It was found that too high temperatures do not allow good
quality joint, because of a too large reduced area in the ceramics and too important wetting
of the steel by the zirconium foil. Obviously, the formation of the oxide layer is not limited
by the diffusion in the oxide. It was also found that this layer is enriched in iron, which could
be a drawback for sodium corrosion resistance of the joint. Cracks were often found at the
interface or at 45° in the YDH oxygen depleted zone. Better mechanical resistance and lower
cracking were obtained by using a Zr machined ring rather than a foil.

Reference
1. O. Mailliart, Procédé d'assemblage d’au moins deux éléments par brasage, assemblage com-
prenant au moins deux éléments et un joint de brasage obtenu par ledit procédé in CEA, Patent
WO2015092317 A1, France, 2015.

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800
Emulsion detonation synthesis (EDS) as an alternative route for YSZ
outstanding based materials
J. Calado, S. Pratas, M. Rodrigues, N. Vitorino, J. Macias, P. Newbatt, R. Calinas
Innovnano, iParque, 3040-570 Coimbra, Portugal
Keywords: EDS, Y-TZP, mechanical properties, Metal Matrix Ceramic

Emulsion detonation synthesis (EDS) is a unique manufacturing powder synthesis process

that through the high pressure thermodynamic variable enables the manufacture of nano-
structured powders with customizable properties and excellent mechanical performance.
Involving a cycle of high temperatures, pressures and rapid quenching, EDS produces
nanostructured ceramic powder with extremely favorable properties compared to conven-
tional micro-structured powders ensuring the control of powder chemistry, uniform grain
sizes, low sintering temperatures and enhanced physical and chemical properties.
ZrO2 doped with 2% mol Y2O3 ceramic powders was synthesized through this method, ob-
taining outstanding mechanical properties for sintered ceramics (14 MPa m0.5, 1200 MPa and
1250 MPa of fracture toughness, biaxial flexural strength and hardness (HV10) respectively)
without being significantly affected by the ageing process typically for 2YSZ ceramics syn-
thesized by other methods.
New Metal Matrix Ceramic (MMC) inter-granular composites with remarkable dielectric,
magnetic and mechanical properties can be prepared through EDS. Through the control of
the detonation atmosphere (reduced atmosphere), these composites can be supplied to the
market with well distributed reduced metal on the surface of the base ceramics. This configu-
ration excludes the reduction step during processing, increasing the yield of the production
process of these specialties by the Ceramic Industry.

569
Study of the shaping and sintering ability of lanthanide oxide powders
Séverin Chaigne1,2, Alexandre Maître1, Rémy Boulesteix1, Bénédicte Arab-Chapelet2,
Thibaud Delahaye2
Laboratoire Sciences des Procédés Céramiques et de Traitements de Surface, UMR CNRS 7315,
1

12 rue Atlantis, 87068 Limoges, France

CEA, Nuclear Energy Division, RadioChemistry & Processes Department, SERA, LCAR,
2

F-30207 Bagnols sur Cèze, France

Keywords: cerium oxide(IV), spent nuclear fuel, powder morphology, sintering

This research is focused on reprocessing and recycling of future spent nuclear fuels. Some
previous studies1,2 have shown that recovering actinides such as uranium and plutonium from
the spent nuclear fuels through an oxalic co-conversion process can be a suitable route to syn-
thetize actinide mixed oxides. At last, this latter could be used to fabricate new nuclear fuel.

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The main objective of this study is to evaluate the shaping and sintering abilities of these
ceramic powders. In particular, it appears critical to find correlations between powder mor-
phology, green body’s characteristics and sintering behaviour. This preliminary work was
carried out on a surrogate of actinide oxides3: ceria CeO2 and then transposed to the uranium
dioxide UO2. The first experimentations were related to the using of uniaxial pressing fol-
lowed by pressure-less sintering treatment under air or argon hydrogenated atmosphere.
A commercial powder and a powder synthetized by oxalic precipitation of different mor-
phology (crystallite size, agglomeration state, etc.) were used. They showed different shap-
ing and sintering abilities depending on their initial morphology. First, it appears that the
green density of pellets obtained after pressing depends on the size, the morphology and
the agglomeration state of the elementary particles. For example, aggregation of particles
resulting from the oxalic precipitation way inhibits the compaction ability during shaping.
Secondly, the densification phenomenon observed during pressure-less sintering under air
occurs in the 1000–1400 °C temperature range for both powders. This temperature remains
significantly low compared to the refractoriness of CeO2 and can be attributed to the high
reactivity of submicronic size powder particles. Beyond this temperature, the grain growth
becomes quicker and leads to micro-sized grains after sintering. Aggregated nanoparticles
obtained from oxalic precipitation way show a differential sintering ability due to firstly the
densification of intra-agglomerate porosity at low temperature (T < 1000 °C) and secondly
to the inter-agglomerate porosity at higher temperature (1000 °C < T < 1400°C). To prevent
this differential densification, it would be pertinent to improve powder characteristics by
employing supplementary grinding and/or deagglomeration step. Finally, green bodies with
more uniform crystallite and pore size could be thus obtained leading to higher densification
ability and more uniform microstructure evolution during sintering.

References
1. B. Arab-Chapelet et al., “Synthesis of new mixed actinides oxalates as precursors of actinides oxide
solid solutions”, J. Alloys Compd., vol. 444445, no SPEC. ISS., p. 387390, 2007.
2. S. Vaudez et al., “A new fabrication route for SFR fuel using (U, Pu)O2 powder obtained by oxalic
co-conversion”, J. Nucl. Mater., vol. 442, no 1–3, p. 227234, nov. 2013.
3. H. S. Kim et al., “Applicability of CeO2 as a surrogate for PuO2 in a MOX fuel development”, J.
Nucl. Mater., vol. 378, no 1, p. 98104, août 2008.

176
Invasive percolation model for flash sintering of ceramic powders
densified by liquid film capillary
Rachman Chaim
Department of Materials Science and Engineering, Technion – Israel Institute of Technology,
Haifa 32000 Israel

Rapid sintering and densification of ceramic nano-powder compacts by spark plasma sinter-
ing (SPS) and flash sintering (FS) are attractive and novel fabrication methods for the near
future. During the last decade, enormous efforts invested towards the modeling of the densifi-
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cation mechanisms during the SPS and FS. The high densification rates observed during SPS
explained by the formation of local spark and plasma due to the particle surface discharges,
materials jets, liquid assisted particle rearrangement and densification, as well as local plastic
deformation. However, many aspects of the densification mechanisms during FS are still
unclear and subject to scholarly debate. Here invasive percolation model used to describe the
universal rapid densification of ceramic powder compacts subjected to flash sintering. The
electrical system is composed of two types of resistances of the particles and their contact
points. The particle contact points with the highest relative resistance first melt due to pre-
ferred local Joule heating followed by thermal runaway. Further local melting has a hierarchi-
cal nature and its occurrence propagates as a front. The flash event represents the percolation
threshold by invasive nature of melt at the particle surfaces between the two electrodes. The
rapid densification is associated with local particle rearrangements due to attractive capillary
forces induced by the liquid film at the particle surfaces.

254
Microstuctural and electromagnetic study of a CuNiZn ferrite obtained
by a non-traditional ceramic process
Carolina Clausell-Terol1, Antonio Barba-Juan1, Lucyna Jawroska2, Miguel A. Rodríguez-
Barbero3
1
Instituto Universitario de Tecnología Cerámica, Departamento de Ingeniería Química, Universitat
Jaume I, 12071 Castellón, Spain
2
The Institute of Advanced Manufacturing Technology, Wroclawska street 37a, 30-011 Cracow,
Poland
3
Instituto de Cerámica y Vidrio (CSIC), Campus Cantoblanco, 28049 Madrid, Spain
Keywords: ferrites, sintering, microstructure, electromagnetic properties, grain size

Ferrite powders containing nickel, zinc and different amounts of copper are typically used
as electromagnetic wave absorbers. It is very difficult to control the absorption capacity of
a given material, as the attenuation properties of electromagnetic wave absorbers depend on
several factors, such as complex permeability, complex permittivity, frequency, and thick-
ness. Moreover, certain magnetic properties such as the saturation magnetic moment depend
only on the material’s chemical composition, whereas others, such as permeability loss, also
depend on other factors, of which material microstructure is the most critical. Thus, for a ma-
terial to act satisfactorily as an electromagnetic wave absorber, high sintered relative density
(low porosity), little average grain size growth, and narrow grain size distribution width are
required.
Numerous studies have shown that the mechanical and/or physical properties of ce-
ramic bodies improve when particle-size distribution decreases from the microscale to the
nanoscale, but controlling the grain growth of the nanometric particles by a conventional
sintering process is really hard work. In this line, a non-traditional ceramic process has been
used for sintering nano-sized copper nickel zinc ferrites in order to control the grain growth

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process. The microstructure of the sintered ferrites has been analysed by SEM and EDX,
determining the grain size distribution, pore size distribution, grain boundary morphology
and precipitate second phases nature. The electrical permittivity and magnetic permeability
of the sintered ferrites has been determined, as well as the evolution of the ferrite absorbance
with frequency, and correlated with the microstructure results and with the physical proper-
ties of the samples. These results have been compared with the ones obtained by a traditional
ceramic process.

437
Powder chemistry effects on the sintering of Bayer alumina
Tobias Frueh1, Elizabeth R. Kupp1, Charles Compson2, Joe Atria2, Gary L. Messing1
1
Department of Materials Science and Engineering, Pennsylvania State University, University Park,
PA, USA, 16802; e-mail: [email protected]
2
Almatis, Inc., Leetsdale, PA, USA, 15056
Keywords: sintering, alumina

Commercial high purity Bayer aluminas are typically 99.8%–99.9% pure and contain Na2O,
SiO2, Fe2O3, and CaO as main impurities. During heating these impurities can combine to
form a nanometer thick liquid phase at the grain boundary that controls the sintering behav-
ior of the powder. We show that the viscosity and solubility of Al2O3 in the liquid phase are
strongly affected by impurity chemistry. In this work we systematically show how the sinter-
ing kinetics and fundamental sintering mechanisms of Bayer alumina change as a function of
the total amount and fractions of the different impurities and dopants. High-resolution TEM
and EDS studies reveal how physical and chemical characteristics of the grain boundaries
change as a function of powder chemistry, leading to an understanding of the observed sinter-
ing behavior. By comparing the sintering kinetics, grain boundary chemistries and structures
of MgO-free and MgO-doped Bayer aluminas, we identify when MgO affects sintering and
gain some insight about the role of MgO during the sintering of Bayer alumina.

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021
Densification and mechanical behavior of spark plasma sintered
Ta0.8Hf0.2–xZrxC (x = 0–0.2)
Seyed Amir Ghaffari1*, Ali Celik2, Mohammad Ali Faghihi-Sani3, Farhad Golestani-Fard1,
Hasan Mandal4, Mohammad Khoshkalam3
1
School of Metallurgy and Materials Engineering, Iran University of Science and Technology, P.O.
Box: 16845-161, Tehran, Iran; *e-mail: [email protected]
2
Department of Materials Science and Engineering, Anadolu University, Iki Eylul Campus, Eskişehir,
Turkey
3
Department of Materials Science and Engineering, Sharif University of Technology,
Tehran 11365-9466, Iran
4
Faculty of Engineering and Natural Sciences, Sabanci University, Istanbul, Turkey, P.O. Box: 34956
Keywords: spark plasma sintering, ultra-high temperature ceramics, carbides, mechanical properties

TaC, HfC and ZrC are known as ultra high temperature ceramics with the melting point above
3400 °C. Spark plasma sintering is a new route for consolidation of materials, specially these
UHTCs, which are difficult to be sintered at temperatures lower than 2000 °C. The purpose of
this study was to consolidate Ta0.8Hf0.2-xZrxC ceramics by spark plasma sintering using MoSi2
and TaSi2 as sintering aid and investigate their mechanical properties. Fully consolidation
of Ta0.8Hf0.2-xZrxC was achieved in presence of 12 vol.% sintering aid at 1650 °C for 5 min
under 30 MPa. Sintering procedure consisted of two stages: the first stage occurred via plastic
deformation of sintering aid particles, while the second stage was due to Ta0.8Hf0.2-xZrxC solid
solution and liquid phase formation. XRD patterns, SEM images and micro indentation test
revealed that insitu formed SiC significantly increased the fracture toughness.

216
Fracture toughness properties of spark plasma sintered boron carbide
ceramics using Ti and TiO2
Busra Guney*, Rojda Sara, F. Duygu Ersan, Burcu Apak, Ipek Akin Karadayi,
Gultekin Goller, Onuralp Yucel, Filiz Cinar Sahin
Metallurgical and Materials Engineering Department, Istanbul Technical University, Ayazaga
Campus, 34469, Istanbul, Turkey; *e-mail: [email protected]
Keywords: boron carbide, titanium, titanium oxide, spark plasma sintering, fracture toughness

B4C-TiB2 composites were produced by spark plasma sintering (SPS) technique with 5 and
10 vol. % in two different ways. In first set of experiments, metallic titanium with different
particle sizes are used to form TiB2 whereas in second set of experiments reactive spark plas-
ma sintering is attained by adding titanium oxide and C-black to B4C. All of the experiments
were carried out at 1550 °C by applying 40 MPa pressure under vacuum atmosphere with

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4 minutes holding time. The final products having hexagonal geometry (61 mm diagonal,
10 mm height, and 31 mm length) were spark plasma sintered for the first time in literature.
The relative density were examined by Archimedes method, hardness and fracture toughness
of samples were evaluated by the Vickers indentation technique and microstructures of all
samples were observed using scanning electron microscopy (SEM).

201
Development of translucent silicon nitride ceramics by SPS process
with various additives
Junichi Hojo
Faculty of Engineering, Kyushu University, Fukuoka, 812-8581 Japan;
e-mail: [email protected]
Keywords: silicon nitride, translucency, spark plasma sintering, sintering additives

Polycrystalline translucent Si3N4 ceramics are receiving a great attention in a special opti-
cal application owing to its high mechanical strength and thermal and chemical stability.
However, Si3N4 is poor in sinterability because of its strong covalent bonding. To achieve the
translucency of Si3N4 ceramics, appropriate sintering condition and sintering aid are required.
High density, fine-grained microstructure and a low content of sintering aid are important
to reduce the light scattering by pores, grains and grain boundary phase. The spark plasma
sintering (SPS) is effective to produce highly-densified sintered bodies with fine-grained
microstructure because of the high heating rate and short-time sintering.
Translucent Si3N4 ceramics were tried to fabricate by the SPS process using binary ad-
ditives of AlN-MgO, AlN-Y2O3 and Al2O3-Y2O3 systems and single additives of MgO and
Y2O3 systems. The sintering additives of AlN-MgO and AlN-Y2O3 systems typically form
SiAlON-like composition by reaction with Si3N4. In the present systems, a liquid-phase sin-
tering mechanism is expected in SiO2-Al2O3-MgO and SiO2-Al2O3-Y2O3 systems, in which
Si3N4 includes impurity SiO2 and AlN includes impurity Al2O3. MgO and Y2O3 also form
the oxide liquid phase with SiO2. The translucency of sintered body was evaluated in visible
light region.
Fine α-Si3N4 powder with high purity was useful to achieve the high translucency of sin-
tered bodies. When the content of additive was large, α -SiAlON formed in AlN-MgO and
AlN-Y2O3 systems with a high translucency, and β -SiAlON in Al2O3-Y2O3 system with a low
translucency. On the other hand, β-Si3N4 formed at a small content in AlN-MgO, AlN-Y2O3
and Al2O3-Y2O3 systems, and exhibited a high translucency. This means that the crystalline
phase is not important for optical translucency. Although the rod-like grain growth of β-Si3N4
causes light scattering, the fine-grained β -Si3N4 ceramics achieved the high translucency
even in Al2O3-Y2O3 system. In the single additive systems, all sintered bodies were β-Si3N4.
The high translucency was achieved at a small content of Y2O3 but not in a large content. The
translucency was low in MgO system at any additive content. The factors on translucency
will be discussed on the base of sintered morphology and additive composition.

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References
1. W. Yang, J. Hojo, N. Enomoto, Y. Tanaka and M. Inada, “Near Infrared Transmittance of Translu-
cent Si3N4 Sintered Ceramics”, Materials Letters, 96, pp. 155–157, 2013.
2. W. Yang, J. Hojo, N. Enomoto, Y. Tanaka and M. Inada, “Influence of Sintering Aid on the Translucen-
cy of Spark Plasma-Sintered Silicon Nitride Ceramics”, J. Am. Ceram. Soc., 96, pp. 2556–2561, 2013.

503
Ultra-fast firing: the role of heating rate in flash sintering
W. Ji1,3, B. Parker1, S. Falco2, J.Y. Zhang3, Z.Y. Fu3, R.I. Todd1
1
University of Oxford, Department of Materials, Parks Road, Oxford OX1 3PH, UK
2
University of Oxford, Department of Engineering Science, Oxford OX1 3PJ, UK
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,
3

Wuhan University of Technology, Wuhan 430070, China

It has recently been reported that in “flash sintering”, ceramics can be sintered in a few sec-
onds with the aid of an electric field. It is generally assumed that this dramatic acceleration in
sintering rate is directly related to the presence of the electric field. This presentation consid-
ers the alternative possibility that the accelerated sintering is instead a consequence of the
rapid heating rate involved in flash sintering rather than a direct effect of the electric field on
mass transport. The sintering of 3YSZ powder compacts at temperatures of 1100–1300 °C
and dwell times of 5 s–2 h was compared with heating rates of between 0.08 and ~100 °C/s.
Both flash sintering and alternative heating methods producing rapid heating without the
application of an electric field to the specimen were used. The results show that rapid heat-
ing can accelerate sintering by over 2 orders of magnitude compared with heating to the
same temperature at conventional rates, even without the application of an electric field. It is
concluded that much of the acceleration of densification in flash sintering of 3YSZ is a con-
sequence of the rapid heating involved rather than being a direct effect of the electric field.
Possible explanations are discussed with reference to the observed microstructures.

784
Processing of single phase EuTiO3 bulk ceramics – the effect of
processing conditions
M. Kachlik1*, K. Maca1, S. Kamba2
1
CEITEC BUT, Brno University of Technology, Purkynova 123, 612 00 Brno, Czech Republic;
*
e-mail: [email protected]
2
Institute of Physics ASCR – v.v.i. Na Slovance 2, 182 21 Prague 8, Czech Republic
Keywords: perovskite, bulk ceramics, solid-state reactive sintering

The EuTiO3 is frequently studied rare-earth perovskite system, which exhibits in the bulk
form incipient ferroelectricity; the ferroelectric behaviour was observed only in the epitaxial
thin films under large biaxial compressive strain.1 It also exhibits anti-ferromagnetic ordering

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(G-type) below TN ≈5.3K.2 The research of magnetoelectric properties of this material suffers
due to problems with processing of this advanced ceramic material. Bulk samples had either
phase impurities in the form of pyrochlore (Eu2Ti2O7) or high porosity (around 20% t.d.). The
absence of thermodynamic data is the crucial issue in the field of novel advanced material
processing. In the case of EuTiO3 ceramics, it means that it is not possible to establish the
optimal experimental setup by thermodynamic calculations therefore the role of experiment
is irreplaceable.
The main objective of this research was the preparation of phase-pure bulk dielectric Eu-
TiO3 ceramics with minimum of microstructural defects. The solid-state reactive sintering
experiments were performed with isostatically formed green bodies (300 MPa) at different
temperatures in reduction atmosphere with varied hydrogen partial pressure and flow. Pro-
cessing conditions were optimized with the aim to (i) ensure the chemical reaction of oxide
precursors, (ii) allow the reduction of europium from +3 to the +2 oxidation state and (iii)
prevent secondary phases and/or microstructural defects formation. The single phase EuTiO3
samples with electric resistivity varied from dielectric to conductor level were prepared dur-
ing the experiments and the effect of processing conditions on microstructural and functional
properties was discussed.

References
1. J.H. Lee, L. Fang, et al., “A strong ferroelectric ferromagnet created by means of spin–lattice cou-
pling”, Nature, 466, pp. 954–958, 2010.
2. T. Katsufuji and H. Takagi, “Coupling between magnetism and dielectric properties in quantum
paraelectric EuTiO3”, Phys. Rev. B, 64, 054415, 2001.

184
Spark plasma sintered single phase Ca-α-SiAlON ceramic utilizing
nano-sized precursors at lower temperatures
Raja Muhammad Awais Khan1*, Moath Mohammad Al Malki2, Abbas Saeed Hakeem3,
Muhammad Ali Ehsan3, Tahar Laoui2
College of Aeronautical Engineering, National University of Sciences & Technology, Islamabad,
1

Pakistan; *e-mail: [email protected]

Center of Excellence in Nanotechnology, King Fahad University of Petroleum & Minerals, Dhahran
2

31261, Saudi Arabia

Department Mechanical Engineering Department, King Fahad University of Petroleum & Minerals,
3

Dhahran 31261, Saudi Arabia

Keywords: nano-ceramics, SiAlON, silicon nitride, spark plasma sintering

The present work aimed to the development of nitrogen rich single phase alpha(α)-SiAlON
by spark plasma sintering (SPS) technique, utilizing nanosized starting powders and incor-
porating calcium oxide (CaO) as a densification additive. A decrease in sintering temperature
along with enhancement of mechanical properties was anticipated.

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Spark plasma sintering was used to process single phase Ca-α-SiAlON employing nano-
sized precursors at relatively lower temperatures of 1500 °C and 1600 °C for three different
holding times (10, 20 & 30 min) at respective sintering temperatures. The chemical composi-
tion of nitrogen rich Ca-α-SiAlON was fixed to be Ca0.8Si9.2Al2.8O1.2N14.8 for all the samples,
corresponding to m and n values of 1.6 and 1.4 respectively in the general formula of Ca-α-
SiAlON. The densification and mechanical properties of the sintered ceramics were exam-
ined to investigate the effect of sintering temperature and holding time on the properties. All
samples were completely densified at each set of processing parameters.
For either sintering temperatures (at all holding times), a remarkable amalgamation of
properties, namely hardness and toughness, was obtained for all the samples; and the great-
est values for both the properties were attained at 30 min holding time, with Vickers hard-
ness values of 21.6 GPa and 20.5 GPa and fracture toughness values of 7.3 MPa√m and 9.7
MPa√m for sintering temperatures of 1500 °C and 1600 °C, respectively. In order to inspect
the variation in mechanical properties, the phases formed during sintering process were iden-
tified and correlated to the changes in mechanical properties of the samples. Microstructural
analysis of cross-section and fracture surface was carried out for samples sintered at 1500 °C
and 1600 °C at 30 min holding time.
The relative lower hardness (20.5 GPa) for sample sintered at 1600 °C and 30 min holding
time was associated to the larger grain size as compared to sample sintered at 1500 °C and 30
min holding time. With regard to fracture toughness, sintering at either 1500 °C or 1600 °C
for 30 min holding time, the yielded fracture toughness values were consequence of forma-
tion of elongated α-SiAlON grains.

335
Preparation of zero thermal expansion ceramics by sol-gel and hot
pressing
M. Kracker1*, C. Thieme1,2, J. Häßler1, C. Rüssel1
Otto-Schott-Institut, Chair of Glass Chemistry I, Jena University, Fraunhofer Str. 6, 07743 Jena,
1

Germany; *e-mail: [email protected]

Fraunhofer Institute for Microstructure of Materials and Systems, Walter-Hülse-Straße 1, 06120
2

Halle, Germany
Keywords: sol-gel, zero thermal expansion, microstructure

Materials which exhibit zero thermal expansion (ZTE) are of major importance for science
and technology. Recently, a novel class of ZTE materials was discovered in a Sr and Ba
containing zinc-silicate system with the generalized formula Ba1-xSrxZn2-yMySi2-zGezO7 (M =
Mg, Co, Cu, Mn, Ni). Unfortunately, the occurrence of a large anisotropy presents a prob-
lem especially regarding the synthesis of compact ceramic specimens and consequently their
property determination.
Pressure-less sintering procedures to prepare a solid sample were not successful. For this
purpose, a high temperature pressure assisted sintering technique was developed. It is now

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possible for the first time to prepare compact ceramic samples from the as mentioned solid
solution phase, applicable for the determination of the real thermal expansion properties
within a polycrystalline structure1.
Additionally, raw materials prepared by a Sol-Gel route as well as a solid-state reaction
technique has been processed to compact samples in order to compare the resulting morphol-
ogy and their corresponding thermal expansion.
Compact ceramic specimens prepared from powders synthesized by a solid-state reaction
show a cracked and porous microstructure and reveal a strong negative thermal expansion
certainly with a large hysteresis and a permanent dimensional change. In contrast, powders
prepared by a Sol-Gel method show a crack and pore free microstructure. Also, the thermal
expansion is no longer negative. It shows now a very low, near zero thermal expansion with-
out a hysteresis or an irreversible change in length.

Reference
1. M. Kracker, C.Thieme, J. Häßler, C.Rüssel “Sol–gel powder synthesis and preparation of ceramics
with high- and low-temperature polymorphs of BaxSr1-xZn2Si2O7 (x = 1 and 0.5): A novel approach
to obtain zero thermal expansion”, J. Eur. Ceram. Soc., 36, pp. 2097–2107, 2016.

040
Impact of field assisted sintering on porcelain microstructure
Wirat Lerdprom*, William E. Lee
Centre for Advanced Structural Ceramics, Department of Materials, Imperial College London,
South Kensington Campus, London, SW7 2AZ, UK; *e-mail: [email protected]
Keywords: porcelain, mullite, microwave sintering, spark plasma sintering, flash sintering,
field assisted sintering technique

Sintering of porcelains has been studied extensively to understand and improve densifica-
tion and phase evolution which directly control the physical and mechanical properties of
the products. Recently, considerable attention has been drawn to ‘Field Assisted Sintering
Techniques (FAST)’ to ceramics but only a few studies have dealt with porcelains. In this
presentation, we report the effect of rapid heating in spark plasma sintering, flash sintering
and microwave sintering on a porcelain body compared to conventional sintering. The FAST-
densified samples were characterized using XRD, SEM, TEM and microindentation. The ef-
fect of FAST on the densification and phase evolution of mullite, glass formation and quartz
dissolution will be discussed. For example, densification in porcelains using FAST was fast
due to rapid glass formation. Different mullite morphologies were observed. SPS produced
mullite oriented perpendicular to the compressive plane whilst microwaves produced ran-
domly oriented and fibre-like mullite. Flash sintered samples contained large volumes of
glass and dendritic mullite.

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References
1. Y. Iqbal, W.E. Lee, Microstructural evolution in triaxial porcelain. Journal of the American Ceramic
Society, 83(12) (2000) 3121–3127.
2. W. Lerdprom, R.K. Chinnam, D.D. Jayaseelan, W.E. Lee, Porcelain production by direct sintering,
Journal of the European Ceramic Society, 36(16) (2016) 4319–4325.
3. W. Lerdprom, C. Li, D.D Jayaseelan, S. J. Skinner, W.E. Lee, Temperature dependence of electrical
conductivity of a green porcelain mixture, Journal of the European Ceramic Society, 37(1) (2017)
343–349.

799
Theoretical and experimental study of the transition from open to
closed porosity sintering stage
Karel Maca1*, Tomas Spusta1, Jiri Svoboda2, Katarina Drdlikova1
CEITEC BUT, Brno University of Technology, Purkynova 123, 612 00 Brno, Czech Republic;
1

*
e-mail: [email protected]
Institute of Physics of Materials, Academy of Sciences of the Czech Republic, Zizkova 22, 616 62
2

Brno, Czech Republic

Keywords: oxide ceramics, sintering, porosity, hot isostatic pressing, transparent ceramics

Capsule-free hot isostatic pressing (HIP) is advanced sintering technique for processing of
fully dense ceramic materials with variety of high-tech applications.1 For successful HIP treat-
ment the presintered samples have to be gas-tight, which means to be at the stage of closed
porosity. The research in the field of transition from open to closed porosity stage is rarely
published in the relevant literature, therefore the deep experimental study of pore closure has
been carried out for alumina, magnesia-alumina spinel, tetragonal and cubic zirconia. The
results were compared with three theoretical models2–4 and arising differences were analysed
in detail.5 Furthermore two-step presintering,6 as an innovative approach within capsule-free
HIP technique, was utilized as a tool for obtaining Er-doped alumina exhibiting high optical
transparency in combination with visible and infrared luminescence and exceptional hardness.

References
1. H.T. Larker, R. Larker. Hot Isostatic Pressing, in: Mater. Sci. Technol., Wiley-VCH Verlag GmbH
& Co. KGaA, 2006.
2. W. Beere, “Unifying Theory of Stability of Penetrating Liquid-Phases and Sintering Pores”, Acta
Metall., 23, pp. 131–138, 1975.
3. W.C. Carter, A.M. Glaeser, “The morphological stability of continuous intergranular phases: Ther-
modynamic considerations”, Acta Metall., 35, pp. 237–245, 1987.
4. J. Svoboda, H. Riedel, H. Zipse, “Equilibrium Pore Surfaces, Sintering Stresses and Constitutive-
Equations for the Intermediate and Late Stages of Sintering. 1. Computation of Equilibrium Sur-
faces”, Acta Metall. Mater., 42, pp. 435–443, 1994.
5. T. Spusta, J. Svoboda, K. Maca, “Study of pore closure during pressure-less sintering of advanced
oxide ceramics”, Acta Mater., 115, pp. 347–353, 2016.
6. K. Bodisova, R. Klement, D. Galusek, V. Pouchly, D. Drdlik, K. Maca, “Luminescent rare-earth-
doped transparent alumina ceramics”, J. Eur. Ceram. Soc., 36, pp. 2975–2980, 2016.

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493
Solid solution formation and mechanical properties of ZRC ceramics
enhanced by tic particles and graphene
Burak Cagri Ocak, Onuralp Yucel, Filiz Sahin, Gultekin Goller
Istanbul Technical University, Department of Metallurgical and Materials Engineering, 34469 Maslak,
Istanbul, Turkey
Keywords: ZrC based ceramics, solid solution, graphene, spark plasma sintering

ZrC ceramic is characterized by an excellent combination of properties comprising high

melting point, hardness, wear resistance, thermal conductivity, good creep resistance, and
excellent chemical stability. However, consolidation difficulties, poor fracture toughness
generally restrict the extensive applications of monolithic ZrC. Studies in recent years have
indicated that graphene nanoplatelets (GNP) addition can significantly improve the mechani-
cal properties of ceramic matrices. In this study, ZrC–TiC–Graphene composites containing
11–20 vol% TiC and in the range of 1.0–9.0 vol% graphene were prepared by spark plasma
sintering at temperatures of 1700 °C for 300 s under a pressure of 40 MPa. Fully dense ZrC–
TiC–GNP composites with a relative density of more than 98% were obtained. The micro-
structure and mechanical properties of the ceramics have been characterised. It was observed
that TiC additions effectively promoted the densification process by forming (Zr,Ti)C solid
solution. The sintered composites were then characterized with respect to their densification,
microstructure, and mechanical properties change with the combination of TiC and graphene
nanoplatelets. Increasing amount of GNP up to 3.0 vol% improve the fracture toughness, and
leads to decrease the hardness.

References
1. D. Sciti, S. Guicciardi, M. Nygren, “Spark plasma sintering and mechanical behaviour of ZrC-
based composites”, Scr. Mater., 2008, 59, 638–641.
2. B. Niu, F. Zhang, W. Ji, J. Y. Zhang, Z. Y. Fu, W. M. Wang, “Effect of solid solution formation on
densification of spark plasma sintered ZrC ceramics with TiC as sintering aid, Advances in Applied
Ceramics, 2016, 115:1, 55–59.

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737
Spark plasma sintering of silicon nitride with the crystallization and
phase transformation in the absence of sintering additive
Manshi Ohyanagi*, Kenshiro Shirai, Ryunosuke Ozaki
Department of Materials Chemistry, Facuty of Science and Technology, Ryukoku University,
Yokotani 1-5, Seta Ohe-cho, Ohtsu, Shiga-Pref., Japan; *e-mail: [email protected]
Keywords: spark plasma sintering, silicon nitride, mechanical alloying

Silicon nitride (Si3N4) shows high strength, high hardness and high toughness which is the
reason why it can be utilized as mechanical parts. The Si3N4 exhibits two kinds of the crystal
structures of α and β forms with hexagonal. The compact of α form shows high hardness
and the β form shows the characteristics of high toughness. The phase transition from α to β
forms of Si3N4 takes place at about 1400 oC, and it decomposes above1800 oC which often
depends on the bulk density of Si3N4 compact, that is, how loose and/or dense. The Si3N4
powder is also known to be hard to sinter due to the low self-diffusion coefficient because
of nature of strong covalent bond in the Si-N. For this reason, Si3N4 powders are often sin-
tered with a sintering additive such as Al2O3 and Y2O3 through the liquid sintering process in
which the powders densify with the grain growth. Although the sinterability of the powders
can be improved with the additives, they make the high-temperature strength of the compact
decrease. On the other hand, our group found that a stacking-sequence disordered silicon car-
bide (SiC) prepared by high energy ball milling of elementary Si and C can be sintered with
the transformation to the ordered form in the absence of any additives1-3. The high energy ball
milling of Si3N4 also made the crystal forms amorphous. In this work, we describe the effect
of the milling time on the formation of amorphous Si3N4 from the crystal form, and the full
consolidation by spark plasma sintering (SPS) of the amorphous powders with the crystal-
lization and phase transformation in the absence of sintering additive.

References
1. M. Ohyanagi, T. Imai, N. Toyofuku, D. Nakagawa, Z.A. Munir, “Microscopic and Spectroscopic
Characterization of Stacking-Sequence Disordered SiC”, J. Am. Ceram. Soc., vol. 98[1] 50–56
(2015).
2. M. Ohyanagi, T. Yamamoto, H. Kitaura, Y. Kodera, T. Ishii, Z.A. Munir, “Consolidation of Nano-
structured β-SiC with Disorder-Order Transformation”, Scripta Materialia, vol. 50, No. 1, 111–114
(2004).
3. T. Yamamoto, H. Kitaura, Y. Kodera, T. Ishii, M. Ohyanagi, Z.A. Munir, “Consolidation of Nano-
structured β-SiC by Spark Plasma Sintering”, J. Am. Ceram. Soc., vol. 87, No. 8, pp. 1436–1441
(2004).

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142
From wet sponges to optoceramics
Annika Pille1*, Andrei Kanaev1, Daniel Chateigner2, Yassine El Mendili2, Eduard Feldbach3,
Thierry Billeton4, Frédéric Schoenstein1
1
Laboratoire de Sciences des Procédés et des Materiaux, CNRS UPR-3407, Université Paris 13,
Sorbonne Paris Cité, Villetaneuse, France; *e-mail: [email protected]
2
Normandie Université; CRISMAT-ENSICAEN, IUT-Caen, Université de Caen Normandie, Caen,
France
3
Institute of Physics, University of Tartu, Estonia
4
Laboratoire de Physique des Lasers, CNRS UMR-7538, Université Paris 13, Sorbonne Paris Cité,
Villetaneuse, France
Keywords: alumina, ceramics, transparent, spark plasma sintering, doping, texture analysis, lumines-
cence

Fig. 1. Growing alumina monolith in the climate chamber (a), backscattered electron image of the sintered
ceramic (b) and pole figures with crystallite shapes from the XRD texture analysis (c)

Polycrystalline alumina ceramics are abundantly used in industry due to their chemical inert-
ness, good insulating qualities and fascinating mechanical, thermal, and optical properties.
Spinel ceramics have lately been in the limelight because of their promising nanoscale self-
healing properties1, which make them perfect for the pursuit of highly tolerant materials in
the nuclear fusion power plants. The self-healing is only efficient for grain sizes below 100
nm. Thus starting powder with uniformly small crystallite/particle size is of utmost impor-
tance. There are a lot of different commercial alumina powders available but they tend to
have wide particle size distributions. This leads us to revitalize the technique of aluminum
oxidation through liquid mercury-silver layer2 developed in our workgroup some years ago.
This room-temperature synthesis (see Fig. 1a) leads to uniform ultraporous monoliths of
hydrated alumina fibers, which can be easily doped by vapor or liquid. In this communica-
tion we will present the preliminary results of using alumina monoliths to produce alumina
(see Fig. 1b), spinel and mullite ceramics with different grain sizes and optical properties.
Comparison will be made using commercially available alumina powders. Texture study of a

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high-pressure sintered alumina ceramic will be presented (see Fig. 1c). Spark plasma sinter-
ing with two previously established3 heating cycles was used to consolidate the materials.
Optoelectronical properties of received materials were studied via cathodoluminescence.

References
1. Ackland, G. Controlling Radiation Damage. Science 327, 1587–1588 (2010).
2. Vignes, J. L. et al. Ultraporous monoliths of alumina prepared at room temperature by aluminium
oxidation. J. Mater. Sci. 43, 1234–1240 (2008).
3. Tõldsepp, E. et al. Spark plasma sintering of ultra-porous γ-Al2O3. Ceram. Int. 42, 11709–11715
(2016).

626
Optimisation of impregnated SiCf/SiC preforms for microwave
chemical vapour infiltration
Matthew Porter1, Andrea D’Angio1, Jon Binner1, Michael Cinibulk2, Beatriz García Baños3
1
Metallurgy and Materials, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
2
Ceramic Materials & Processes Composites Branch Materials and Manufacturing Directorate,
Air Force Research Laboratory, Wright-Patterson Air Force Base, OH, 45433-7817, USA
3
DIMAS – ITACA Institute, Universidad Politécnica de Valencia, Camino de Vera s/n 46022, Spain
Keywords: microwave, chemical vapour infiltration, ceramic matrix composite, SiC, SiC fibre

To deliver the succeeding generation of aerospace propulsion systems, major modification

to the materials used and their manufacture are required to replace dating in service compo-
nents. High-temperature ceramic fibre reinforced ceramic matrix composites (HT-CMCs),
specifically SiCf/SiC, have been identified as potential candidates to operate in the hostile
aero-thermo-chemical environments experienced in service without compromising on struc-
tural integrity whilst keeping mass at a premium.1 Presently a lack the high-temperature prop-
erties and durability that is essential for long-life at the temperatures envisioned is preventing
widespread utilisation of these properties.2 Current advanced manufacturing techniques are
able to produce HT-CMCs and have been utilised in aerospace applications but none of these
techniques to date have been capable of unlocking SiCf/SiC full potential.
One of these advanced methods, chemical vapour infiltration (CVI) is an effective manu-
facturing route capable of creating near fully dense components with an extremely refined
microstructure with little or no preform degradation and minimal residual stresses3 but its
current material output is microstructurally defective and susceptible to failure in the more
demanding conditions the aerospace industry encounters. CVI’s issues are three fold4; pro-
cessing is incredibly slow using isothermal heating rates so batch production is 2–3 months,
secondly premature closure results in residual porosity, which requires subsequent machining
stages to re-open the closed channels which reduces the efficiency of the process to between
>10%. Lastly, as a consequence of the previous two points, associated costs are very high
and the product expensive. Microwave energy has been proposed to offer a potential solution
to heat the preform for CVI, it produces a favourable inverse temperature profile meaning

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temperature is hottest in the centre of the component, the contrast of conventional CVI. This
inverse profile is more energy efficient and initiates densification at the centre of the sample
thus avoiding surface porosity closure, and hence facilitating reactant gas transport through-
out the entire structure. It is expected that the use of microwave enhanced CVI processing
routes could yield near fully dense products in 72–96 hours.5
Current work has been dedicated to preparation of SiC fibre preforms prior to microwave
processing with regard to decreasing processing times further. This study has been a multi-
disciplinary approach building on previous research has investigated the impregnation of SiC
fibre preform with SiC powder.6 This factor along with other important parameters have also
been considered; dielectric properties of constituent materials, uniformity of powder applica-
tion, pore distribution and size and permeability of the composites to facilitate the production
of optimum preform characteristics for infiltration.

References
1. Cinibulk, M. Constituent development for high-temperature capable ceramic matrix composites.
Materials Science and Technology. 2016. Salt Lake City.
2. Sangsuwan, P., et al., Reactive infiltration of silicon melt through microporous amorphous carbon
preforms. Metallurgical and Materials Transactions B, 1999. 30(5): p. 933–944.
3. Xu, Y.Y., X., Chemical Vapour Infiltration, in Chemical Vapour Deposition: An Integrated Engi-
neering Design for Advanced Materials. 2010, Springer London: London. p. 165–213.
4. Lamon, J., Chemical Vapor Infiltrated SiC/SiC Composites (CVI SiC/SiC), in Handbook of Ce-
ramic Composites, N.P. Bansal, Editor. 2005, Springer US: Boston, MA. p. 55–76.
5. Timms, L.A., et al., Reducing chemical vapour infiltration time for ceramic matrix composites.
Journal of Microscopy-Oxford, 2001. 201: p. 316–323.
6. Binner, J., et al., Use of Electrophoretic Impregnation and Vacuum Bagging to Impregnate SiC
Powder into SiC Fiber Preforms. International Journal of Applied Ceramic Technology, 2015.
12(1): p. 212–222.

766
Insitu study of densification at high heating rates
Vaclav Pouchly, Karel Maca
BrnoUniversity of Technology, CEITEC BUT, Brno, Czech Republic

The fast sintering techniques attract high attention not only due to economic reasons. From
the scientific point of view there are many questions about the mechanisms of rapid sintering
which should be answered. Among fast sintering techniques, Spark Plasma Sintering (SPS) is
fast developing consolidation technique, due to the synergy of fast heating rate, uniaxial pres-
sure and pulsed electrical field. Recently, enhanced densification of tetragonal ZrO2 sintered
by rapid heating rates (hundreds of °C/min), has been reported even during pressure-less
sintering1,2 and the role of electromagnetic field was questioned.3
In this work, ZrO2 ceramics were sintered by SPS with various heating rates, ranging from
units °C/min up to several hundred °C/min. The sample shrinkage was continuously moni-
tored during the whole sintering. The apparent activation energy of densification was evalu-

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ated by means of newly developed Master Shrinkage Curve model designed for anisotropic
shrinkage. The effect of the heating rate on the value of apparent sintering activation energy
is evaluated and discussed.

References
1. Salamon, D., Maca, K., Shen, Z.J. Rapid sintering of crack-free zirconia ceramic by pressure less
spark plasma sintering, Scr. Mater., vol. 66 (2012), 899–902.
2. Salamon, D., Kalousek, R., Zlamal, J., Maca, K. Role of conduction and convection heat transfer
during rapid crack-free sintering of bulk ceramic with low thermal conductivity, J. Eur. Ceram.
Soc., vol. 36 (2015), 2955–2595.
3. Ji, W., Parker, B., Falco, S., Zhang, J.Y., Fu, Z.Y., Todd, R.I. Ultra-fast firing: Effect of heating
rate on sintering of 3YSZ, with and without an electrical field, J. Eur. Ceram. Soc., 2017, in press.

234
Al2O3-Y3Al5O12 composites with submicron microstructure by hot
pressing of yttrium aluminate glass microspheres
Anna Prnová1, Peter Švančárek1, Milan Parchovianský1, Ľubomír Hric2, Dušan Galusek1
1
Joint Glass Centre of the IIC SAS, TnUAD and FChFT STU, Trenčín, Slovakia
2
RHP-Technology GmbH, Forschungs- und Technologiezentrum, Seibersdorf, Austria

Yttrium aluminate glass microspheres with composition of the eutectic in a pseudobinary

system Al2O3-Y3Al5O12 (YAG) were prepared by feeding a polycrystalline powder precursor
into methane-oxygen flame. Kinetics of crystallization of the glass was studied in detail by
differential thermal analysis. The glass crystallized in several stages, with initial formation of
YAG in two steps (937 and 1000 °C), with subsequent crystallization of α-Al2O3 at T > 1300
°C. The obtained information was utilized for preparation of bulk materials by hot pressing
in the temperature range 840–1600 °C and pressures up to 80 MPa, with isothermal dwell
0120 min. Depending on the conditions of hot pressing experiments dense composites with
various microstructures and phased composition were prepared. Hot pressing at 1600 °C
without isothermal dwell yielded dense composite with fine two phase microstructure with
α-Al2O3 and YAG phases percolating at a submicrometre level and Vickers hardness ~ 15
GPa. Extension of the isothermal dwell at 1600 °C resulted in microstructure coarsening and
decrease of Vickers hardness.

Acknowledgments
The financial support of this work by the project SAS-MOST JRP 2015/6, VEGA 1/0631/14, and APVV
0014-15 is gratefully acknowledged. This publication was created in the frame of the project “Centre
of excellence for ceramics, glass, and silicate materials” ITMS code 262 201 20056, based on the Op-
erational Program Research and Development funded from the European Regional Development Fund.

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902
Grain growth transitions in perovskite ceramics: bimodal
microstructures, anisotropy and point defects
Wolfgang Rheinheimer*, Michael Hoffmann
Institute of Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany;
*
e-mail: [email protected]

Perovskite materials are widely used in a variety of electronic devices, e.g. capacitors, oxy-
gen conductors, PTC (positive temperature coefficient) heaters and piezoelectric actuators.
Many macroscopic properties of polycrystalline perovskites are governed by their grain
boundaries and, therefore, depend strongly on microstructure evolution (sintering and grain
growth) during processing.
Several perovskite ceramics are known to show a non-Arrhenius type of grain growth.
Strontium titanate has a grain growth rate transition that has been well documented, with
decreasing growth rates between 1350 °C and 1425 °C. Other materials such as barium tita-
nate, lithium lanthanum titanate and barium strontium titanate show similar grain growth rate
transitions. The growth transitions are coupled to the formation of bimodal microstructures
and are postulated to be caused by grain boundary structural transitions.
This talk reviews our current understanding of the grain growth rate transitions in
perovskite ceramics. A simple mean field approach is often used for quantifying these ef-
fects on a macroscopic scale. However, this approach fails to capture the underlying physics
of bimodal anisotropic grain growth that occurs in ceramic perovskites. Important factors
including anisotropy, atomistic boundary structure, segregation, wetting, faceting, boundary
stoichiometry, space charge and interfacial drag need to be considered explicitly. A discus-
sion of open questions and future directions will be presented.

644
Inverse hall-petch relation in nanostructured oxide ceramics fabricated
by high-pressure SPS
Maxim Sokol*, Barak Ratzker, Sergey Kalabukhov, Nahum Frage
Department of Materials Engineering, Ben-Gurion University of the Negev, Beer-Sheva, Israel;
*
e-mail: [email protected]
Keywords: spinel, YSZ, SPS, inverse hall-patch

High pressure (up to 1 GPa) spark plasma sintering (HPSPS) technique allows to fabricate
nanostructured (20–30 nm) polycrystalline ceramics at relatively low temperatures with short
sintering time. The specimens obtained by HPSPS technique display a unique combination of
optical and mechanical properties, comparable or even better than the best results reported in
literature for a two-stage fabrication process (pressureless sintering followed by hot isostatic
pressing or vacuum sintering).

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Our recent experimental results on densification of polycrystalline transparent magnesium

aluminate spinel (PMAS) and yttria stabilized zirconia (YSZ) has raised some fundamental
questions related to microstructure evolution, densification and grain growth kinetics. Fur-
thermore, for the first time, the minimal grain size (of about 40 nm) where a Hall-Petch rela-
tion is valid was established and an inverse Hall-Petch correlation was clearly observed for
ceramics with grain size less than 30 nm.
The present work focuses on the understanding of sintering behavior during HPSPS pro-
cess and on clarification of the grain growth mechanism. A model explaining the effect of
grain size on the mechanical properties, was developed and will be discussed.

563
Effect of metal doping on heat transfer in Spark Plasma Sintering
process
Hua Tan*, David Salamon
Central European Institute of Technology, Brno University of Technology, Brno, Czech Republic;
*
e-mail: [email protected]
Keywords: Spark Plasma Sintering, metal doping, heat transfer

Spark Plasma Sintering (SPS) is one of the novel sintering processes accompanied with
unique kind of heating – pulsing electrical current. The benefits of the pulsing electric cur-
rent is the oft-repeated claim that electric pulsing creates a plasma which activates surfaces of
powder particles through removal of surface layers.1,2 However, so far convincing evidence
of this conditions is absent.3 In spite of conflicting results, pulsing in SPS is also able to in-
fluence particle movements due to its strong electromagnetic field when doping conductive
metals (e.g., iron) to nonconductive matrix.
In this study, γ-Al2O3 powders doped with various metals (Fe, Cu, and Ni) were sintered
via SPS. Two heating modes–auto and manual mode were applied to observe the role of elec-
tromagnetic field on sintering. Phase transformation of γ to α-Al2O3 serves as direct indica-
tor of internal temperature, independently on measured outside temperature.
Particle movement and altering of heat transfer method were proofed during the SPS pro-
cess of electrically nonconductive materials doped by metals. Shrinkage, density, tempera-
ture and microstructure were investigated to analysis and quantify the impact of metal dop-
ants on heat transfer in SPS process.

References
1. Omori M. Sintering, consolidation, reaction and crystal growth by the spark plasma system (SPS).
Materials Science and Engineering: A 2000;287:183–188.
2. Shen Z, Johnsson M, Zhao Z, Nygren M. Spark plasma sintering of alumina. Journal of the Ameri-
can Ceramic Society 2002;85:1921–1927.
3. Munir ZA, Anselmi-Tamburini U, Ohyanagi M. The effect of electric field and pressure on the
synthesis and consolidation of materials: A review of the spark plasma sintering method. Journal of
Materials Science 2006;41:763–777.

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661
Flash joining of CVD-SiC coated ceramic matrix composites
Peter Tatarko1, Salvatore Grasso2, Theo G. Saunders2, Valentina Casalegno3,
Monica Ferraris3, Michael J. Reece2
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dubravska cesta 9,
1

845 36 Bratislava, Slovakia; e-mail: [email protected]

School of Engineering & Materials Science and Nanoforce Technology Ltd.,
2

Queen Mary University of London, Mile End Road, London E1 4NS, United Kingdom;
e-mails: [email protected], [email protected]
Politecnico di Torino, Applied Science and Technology Department, Corso Duca degli Abruzzi 24,
3

10129 Torino, Italy; e-mail: [email protected]

Keywords: flash joining, diffusion bonding, Spark Plasma Sintering, Cf/SiC composites, Ti interlayer

The purpose of this work was, for the first time, to bring together the flash processing and the
joining of ceramic materials, thus allowing flash joining of ceramics. Flash joining of CVD-
SiC coated Cf/SiC samples with a Ti interlayer was achieved using a Spark Plasma Sintering
machine. The influence of different heating powers and discharge times were investigated.
The sample flash joined at a maximum heating power of 2.2 kW (peak electric current of 370
A) within 7 seconds showed the highest apparent shear strength of 31.4 MPa, which corre-
sponds to the interlaminar shear strength of the composites. A maximum joining temperature
of ~ 1237 °C was reached during the flash joining. An extremely rapid heating rate of 9,600
°C/min combined with a very short processing time hindered any reaction between the CVD-
SiC coating and the Ti interlayer. A defect-free interface was obtained, and no transverse
cracks were observed in the Ti interlayer. The Ti foil did not melt or shrink during joining,
resulted in the limited diffusion of Si and C from the CMCs into the Ti. Therefore, the forma-
tion of Ti3SiC2 was not observed. T a sound joint was obtained by forming a metallic kind
of joint (Ti-based) at the joining temperature, in which the absence of any reaction phases
(titanium silicides, carbides or ternary phases) significantly shortened the time necessary for
the solid-state diffusion bonding. The Ti interlayer also partially filled up the surface cracks
in the CVD coating on the CMCs due to plastic flow. This is believed to strengthen the joint.
The apparent shear strength of the flash joint was higher when compared to the apparent
shear strength of the Cf/SiC joints when joined with Ti (both 30 and 130 μm) using a standard
SPS process at 1700 °C with a heating rate of 100 °C/min and a dwell time of 5 minutes.
This constitutes a significant reduction in a processing time and the maximum temperature
required, which in turn leads to energy savings and potentially higher industrial interest in the
process. The present work clearly demonstrates that, when the right conditions are achieved,
a strong joint can be obtained within 7 seconds using flash joining.

Acknowledgments
The research leading to these results has received funding from the European Community’s 7th Frame-
work Programme FP7 2007-2013 under the grant agreement No.: 609188, within the European project
ADMACOM (Advanced manufacturing routes for metal/composite components for aerospace). P.T.
gratefully acknowledges the contribution of the Slovak Research and Development Agency under the
grant No.: APVV-15-0469 and the Scientific Grant Agency of the Slovak Republic under the grant No.:
VEGA 2/0189/15.

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267
Effects of processing and sintering conditions on density and
microstructure of microinjection molded oxide CMCs
M. Tülümen1, T. Hanemann1,3, M.J. Hoffmann2, R. Oberacker2, V. Piotter1
Karlsruhe Institute of Technology, Institute of Applied Materials (IAM-WK),
1

D-76344 Eggenstein-Leopoldshafen, Germany;

e-mails: [email protected], [email protected], [email protected]
Karlsruhe Institute of Technology, Institute of Applied Materials (IAM-KWT), D-76131 Karlsruhe,
2

Germany; e-mails: [email protected], [email protected]

University of Freiburg, Departments of Microsystems Engineering (IMTEK), D-79110 Freiburg,
3

Germany
Keywords: CMC, fiber orientation, sintering, microstructure, grain growth, density, ceramic injection
molding

Ceramic matrix composites (CMCs) are created by adding fibers with variety of fiber struc-
ture into various ceramic materials to provide condition / task adapted properties. On the oth-
er hand, ceramic injection molding is an automated net shaping process that can produce the
ceramic parts with complex geometry and good surface quality without the requirement for
a post-processing step. In this study, we produced aluminum oxide CMCs (Al2O3 powder:
TMDAR, Taimicron; Al2O3 chopped fibers: 3M Nextel 610) by using ceramic µ-injection
molding process. Each step such as feedstock preparation, molding step, debinding or sinter-
ing, has significant effect on the final properties of the CMCs parts. Measurement of density
as a function of time, temperature, fiber content or -orientation coupled with the examination
of the final microstructure is a useful method to evaluate the ceramic parts. At 1200 °C rela-
tive density decreased at about 35% with increasing amount of oxide chopped fibers. The
reason of such a low sintering temperature for aluminum oxide based material is to prevent
the grain growth in the fibers.1 In addition, the form of the injection mold defines the fiber
orientation that differentiate the density of the sintered parts. The difference between tensile
specimen (higher orientation) and disc form (random orientation) is about from 1 to 10%
depending on temperature and the amount of fiber in the material.

Reference
1. Schmücker, M. and Mechnich, P. (2008), Microstructural Coarsening of Nextel™ 610 Fibers Em-
bedded in Alumina-Based Matrices. Journal of the American Ceramic Society, 91: 1306–1308.

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487
Formation of molybdenum boride layers on TZM alloy by spark
plasma sintering process
Baris Yavas, Onuralp Yucel, Filiz Sahin, Gultekin Goller
Istanbul Technical University, Department of Metallurgical and Materials Engineering, 34469 Maslak,
Istanbul, Turkey
Keywords: TZM alloy, molybdenum boride, boriding, spark plasma sintering

TZM alloy is one of the most important molybdenum (Mo) based alloy which has a nomi-
nal composition containing 0.5–0.8 wt% titanium (Ti), 0.08–0.1 wt% zirconium (Zr) and
0.016–0.02 wt% carbon (C). It is a possible candidate for high temperature applications in a
variety of industries. However, the rapid oxidation of TZM alloys at high temperature in air
and low wear resistance are considered to be the main drawbacks.1–5 In this study molybde-
num boride phase was formed on the surface of TZM alloy by spark plasma sintering (SPS)
process. Boron carbide (B4C) was used as a boron source during the boriding. Both sintering
and boriding process were performed in a single step at constant temperature of 1420 °C in
various pressure (40–60 MPa) and holding time (5–15 min) under vacuum. The effect for-
mation Molybdenum Boride layers and sintering parameters on the microstructure, surface
hardness, wear resistance and oxidation resistance were investigated. The results showed
that boride layers composed of MoB and Mo2B have a thickness in the range of 137–213 µ.
Moreover, increase in pressure and holding time result in increase in density, hardness, wear
and oxidation resistance of the alloy.

References
1. J. Fan, M. Lu, H. Cheng, J. Tian, and B. Huang, “Effect of alloying elements Ti, Zr on the property
and microstructure of molybdenum,” Int J Refract Met H, vol. 27, pp. 78–82, 2009.
2. H. A. Calderon, G. Kostorz, and G. Ullrich, “Microstructure and plasticity of two molybdenum-
base alloys (TZM),” Mater. Sci. Eng., vol. 160, pp. 189–199, 1993.
3. R. Ohser-wiedemann, C. Weck, U. Martin, A. Müller, and H. J. Seifert, “Spark plasma sintering
of TiC particle-reinforced molybdenum composites,” Int J Refract Met H, vol. 32, pp. 1–6, 2012.
4. S. Majumdar, I. G. Sharma, S. Raveendra, I. Samajdar, and P. Bhargava, “In situ chemical vapour
co-deposition of Al and Si to form diffusion coatings on TZM,” Mater. Sci. Eng. A, vol. 492, pp.
211–217, 2008.
5. M. Nagae, T. Yoshio, J. Takada, and Y. Hiraoka, “Improvement in Recrystallization Temperature
and Mechanical Properties of a Commercial TZM Alloy through Microstructure Control by Multi-
Step Internal Nitriding,” Mater. Trans., vol. 46, no. 10, pp. 2129–2134, 2005.

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236
Conversion of MAX phase single crystals in highly porous carbides by
high temperature chlorination
Shiqi Zhang1, Lu Shi1,2, Frédéric Mercier3, Odette Chaix-Pluchery1, Didier Chaussende1,
Isabelle Gélard1, Benoît Hackens2, Thierry Ouisse1
LMGP, Université Grenoble-Alpes/CNRS, 3 parvis Louis Néel - CS 50257 - 38016 Grenoble cedex
1

1, France; e-mails: [email protected], [email protected]

IMCN/NAPS, Université Catholique de Louvain, 2 Chemin du Cyclotron, 1348 Louvain-la-Neuve,
2

Belgium
SIMAP, Université Grenoble-Alpes/CNRS, 1130 rue de la Piscine - BP 75 - F-38402 St-Martin-
3

d’Heres cedex, France

Keywords: MAX phase, chromium carbides, CVD chlorination, porosity, magneto-transport

We apply high temperature chlorination to the exfoliation of the chemically sensitive A-

atom planes of single crystals of nano-lamellar MAX phases1,2,3. This allows us to synthesize
highly porous and electrically conducting refractory carbides. Focusing on the case of po-
rous Cr3C24, we investigate the dependence of the layer morphology, structure and formation
kinetics on processing parameters such as temperature and time. Many properties, such as
porosity and specific surface area, can be controlled and optimised through an appropri-
ate choice of parameters, which may expand the application range already covered by the
previously developed processing techniques. XRD analysis shows that the porous material
exhibits a preferential crystalline orientation.The Raman signature of Cr3C2 and Cr7C3 is de-
termined for the first time, and allows us to follow the creation and elimination of the various
phases as a function of processing time and temperature. Variation of electrical resistivity and
magnetoresistance versus temperature and magnetic field is also investigated.

References
1. M. Barsoum, MAX phases: Properties of Machinable Ternary Carbides and Nitrides, Wiley-VCH,
Weinheim, 2013.
2. T. Ouisse, L. Shi, B.A. Piot, B. Hackens, V. Mauchamp, D. Chaussende, “Magnetotransport proper-
ties of nearly-free electrons in two-dimensional hexagonal metals and application to the Mn+1AXn
phases”, Phys. Rev. B, 92, pp. 045133, 2015.
3. L. Shi, T. Ouisse, E. Sarigiannidou, O. Chaix-Pluchery, H. Roussel, D. Chaussende, B. Hackens,
“Synthesis of single crystals of V2AlC phase by high-temperature solution growth and slow cooling
technique”, Acta Mater., 83, pp. 304–309, 2015.
4. S. Hashimoto, A. Yamaguchi, “Growth of Hollow Cr3C2 Polycrystals with Cr2O3”, J. Am. Ceram.
Soc., 78, pp. 1985–1988, 1995.

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Poster presentations

788
Synthesis of reaction-sintered silicon carbide ceramics by a two-stage
siliconizing method
H.M. Abuhimd1, M.S. Alshahrani1, P.S. Grinchuk2, D.V. Solovei2, M.O. Stepkin2,
A.V. Akulich2, A.A. Khort2
National Nanotechnology Research Center King Abdulaziz City for Science and Technology, Riyadh,
1

11442, P.O. Box 6086, Saudi Arabia; e-mail: [email protected]

A.V. Luikov Heat and Mass Transfer Institute of the National Academy of Sciences of Belarus,
2

Minsk, 220072, P. Brovki 15, Republic of Belarus; e-mail: [email protected]

Keywords: silicon carbide ceramics, siliconizing, reaction-sintered SiC

Since the 20th century silicon carbide ceramics are well known, and thanks to its unique
physical and chemical properties has been widely used in aerospace, aviation, automobile
and semiconductor industries.1 There are many kinds of SiC ceramics are exist and most of
which the reaction sintering siliconizing fabrication process of the carbon filler or skeleton
are used.2 This process is carried out in a vacuum or in an inert atmosphere at a temperature of
1600–1800 °C and provides impregnating of workpiece by silicon forming a reaction-bonded
silicon carbide. However, this method has some limitations on the thickness of the preform,
since silicon penetrates into detail begins to react with carbon, resulting the formation of sili-
con carbide having a higher melting point and which stops the impregnation of liquid silicon
into the deep of the detail. This effect reduces the density of ceramics increasing its porosity,
resulting in degradation of the product technical performance. For neutralization of this ef-
fect, the two-step siliconizing method for oversized substrates with a diameter up to 200 mm
and a thickness of 15 mm was developed and applied.
Essence of the method in the following: onto the surface of C-SiC composite preformed
workpiece placed in a graphite crucible, silicon powder is sprinkled. Crucible is tightly
closed with a graphite lid and placed in a high temperature vacuum furnace chamber. After
vacuum pumping till 2∙10–2 torr pressure the heating of furnace till temperatures of 1500 °C
is produced and followed by aging. This operation is leads to the complete melting of silicon
and impregnated throughout the entire volume of the preform that corresponds to the first
stage of the process. At the second stage of the process the temperature raises to 1800 °C at
which the reactions sintering of carbon constitutes the composite and melt silicon forming
a reaction-sintered silicon carbide is take place. The x-ray studies showed that the resulting
oversized product consists of 6-H and C-3 polytypes of silicon carbide with minor inclusions
of free silicon. The mechanisms of silicon infiltration, including capillary effect and diffusion
of silicon atoms through carbon mesh, are discussed. Obtained results indicate the perspec-
tives of using of this method for fabrication of silicon carbide oversized details.

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References
1. N.P. Bansal, Handbook of Ceramic Composites. Kluwer Academic Publishers, Boston, 2005.
2. Jung-Hye Eom, Young-Wook Kim, Santosh Raju, “Processing and properties of macroporous sili-
con carbide ceramics: A review”, J. of Asian Cer. Soc., 1, pp. 220–242, 2013.

867
Optimization of the thermal insulation of the die during SPS sintering
Youssef Achenani1, Malika Saâdaoui1, Abdelkhalek Cheddadi1, Gilbert Fantozzi2
Mohammed V University in Rabat, Mohammadia School of Engineers, Avenue Ibn Sina, P.O. Box
1

765-Agdal, Rabat, Morocco

Lyon University, National Institute of Applied Sciences of Lyon, MATEIS Laboratory, UMR 5510
2

CNRS, 20 Avenue Albert Einstein, F-69621 Villeurbanne Cedex, France

Keywords: Spark Plasma Sintering, finite element modeling, thermal insulation

Based on the simultaneous application of axial pressure and elevated temperature generated
by a high current flow, Spark Plasma Sintering (SPS) is one of the most attractive consoli-
dation techniques. The sintering is achieved at a lower temperature and a shorter duration
compared to conventional techniques, which allow to enhance the mechanical or physical
properties of the materials.
Finite element modeling has contributed to investigate the influence of several experi-
mental parameters on the temperature distribution, which is of crucial importance to the SPS
processing, since it directly affects the microstructure homogeneity and the final properties
of the sintered materials.
In the present work, the influence of the thermal insulation of the die is investigated us-
ing a finite element model based on the thermoelectric coupling during SPS sintering, that
allowed to simulate the temperature distribution in the sample. It is sown that in the case of
alumina, chosen as a model for non-conductive materials, a partial thermal insulation of the
die is more effective to reduce the radial temperature gradients within the sample, than the
commonly used total insulation. The model is used to determine the optimized height of the
thermal felt necessary to minimize the radial gradient and to discuss the effect of the sample
dimensions.

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292
Effect of ceramic addition on structural and mechanical properties of
steel alloys
Haroune Rachid Ben Zine1,2, Ákos Horvath2, Filiz Cinar Sahin3, Zsolt Czigany2,
Katalin Balazsi2, Csaba Balazsi2
1
Óbuda University, Bécsi út 96/B, 1034 Budapest, Hungary;
e-mails: [email protected], [email protected]
2
HAS-Centre for Energy Research, Konkoly-Thege M. str. 29-33, 1121 Budapest, Hungary
3
Istanbul Technical University, Maslak, Istanbul 34469, Turkey
Keywords: attrition milling, Spark Plasma Sintering (SPS), Nano-size ceramic powders, submicron
sized structure, mechanical and structural properties

The powder metallurgy technology provides more controlled microstructure, a homogeneous

dispersion of nano-sized oxide particles in the metal matrix and tailored properties in terms
of strength and radiation resistance.1 Oxide-dispersion strengthened (ODS) steels are good
candidates for use in nuclear reactors generation IV and the first fusion power plants because
of its neutron resistant property.2 The application of ODS steels strongly depends on the
availability of large batches of materials.3 The Höganäs 316L stainless steel powder and four
nano-sized ceramic powders: Y2O3, Al2O3, Si3N4 and SiC have been used to study the effect
of ceramic addition on the structural and mechanical properties of steel alloys. Eight alloys
have been prepared during this work. Homogenous dispersion of the nano-size ceramic par-
ticles on the surface of the stainless steel grains has been achieved by high efficient attrition
milling for five hours. A good coverage of steel grains by ceramic particles has been ob-
served. The morphological changes of the stainless steel grains, the covering and the disper-
sion of the ceramic particles have been observed by Scanning Electron Microscopy (SEM)
and verified by Energy-dispersive X-ray spectroscopy (EDS). A fast sintering of powder
mixtures has been performed by Spark Plasma Sintering (SPS) in order to obtain submicron
sized structure. The mechanical properties of the solid samples have been presented and
tested using tensile, three and four points bending, tribology and hardness tests. The effect of
ceramic addition on the structural and mechanical properties of the 316L Höganäs Stainless
steel has been clearly observed by SEM, EDS, X-ray Diffraction (XRD) and Transmission
Electron Microscopy TEM.

References
1. Cs. Balazsi, F. Gillemot, M. Horvath, F. Weber, K. Balazsi, F. Cinar Sahin, Y. Onuralp, A. Horvath.
Preparation and structural investigation of nanostructured oxide dispersed strengthened steels. J.
Mat. Sci. 46 (2011) 4598–4605.
2. Hongtao Zhang et al. Processing and microstructure characterization of oxide dispersion strength-
ened Fe–14Cr–0.4Ti–0.25Y2O3 ferritic steels fabricated by spark plasma sintering. J. Nuclear Mat.
464 (2015) 61–68.
3. Haroune Rachid Ben Zine, Ákos Horváth, Katalin Balázsi, Csaba Balázsi. Submicron sized sin-
tered ODS steels prepared by high efficient attritor milling and spark plasma sintering. Courier du
Savoir. 2017 (submitted).

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003
Ca-doped Magnesium Aluminate (Spinel) synthesized by precipitation
route in alcoholic medium
L.B. Caliman1, D. Hotza2, R.H. de Castro3, D. Gouvêa1
1
University of Sao Paulo, Sao Paulo, Brazil
2
UFSC
3
UC Davis
Keywords: magnesium aluminate, precipitation, nanomaterials

Magnesium aluminate (MgAl2O4), also called Spinel, presents excellent refractory and me-
chanical properties, low density and high optical transmission in visible and mid-wavelength
infrared spectra. Many dopants are used in order to obtain nanometric particle distribution
and properties improvement. Magnesium aluminate particle size is also affected by the syn-
thesis route. Samples of Ca-doped magnesium aluminate were prepared using a precipitation
route with NH4OH, aluminum and magnesium nitrates, calcium carbonate as dopant and
ethanol as solvent. Ethanol is used to avoid the problem of the hydroxides different solubility
depending on pH in aqueous solution. The hydroxides precipitate was calcined at 900 °C to
obtain magnesium aluminate oxide and then milled. Samples were characterized by XRD,
Infrared, Surface Area Analysis (BET), Dilatometry and SEM. Resulting powders presented
particle size range between 3–10 nm and the only identified crystalline phase, despite the
amount of dopant, was MgAl2O4. Conventional sinter tests were carried out in different con-
ditions and the obtained sintered pellets were translucent and highly dense. The increase in
the dopant’s concentration favors the particle size decrease and also densification and sinter-
ability. SPS sinter tests and mechanical properties determination of the sintered pellets are
being carried out.

199
Crystal structure and piezoelectric properties of (LiCeNd)-multidoped
CaBi2Nb2O9 Aurivillius type ceramics
Feng Cao, Xiangxiong Zeng, Zhihang Peng
Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of
Aerospace and Materials Engineering, National University of Defense Technology, China;
e-mail: [email protected]
Keywords: Rietveld-refinement, structure properties, piezoelectric properties, CaBi2Nb2O9

(LiCeNd)-mutlidoped CaBi2Nb2O9 Aurivillius phase ceramics were prepared via a conven-

tional solid state sintering route. The crystal structure, micro-structure, dielectric and piezo-
electric properties were systematically investigated. XRD patterns showed a single crystal
structure, indicated (LiCeNd) dopants entered into lattice point and formed solid solutions.

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The Rietveld-refinement showed a gradual change in crystal structure from orthorhombic

to tetragonal with increasing (LiCeNd) doping concentration. The Ca0.85(Li0.5Ce0.25Nd0.25)0.
15Bi2Nb2O9 (CBN-LCNd15) ceramics possess the optimum properties, and the d33 and Tc
values were found to be ~13.1 pC/N and ~900 oC, respectively. The thermal depoling behav-
ior also demonstrated that the CBN-LCNd15 ceramics possess outstanding thermal stability
of piezoelectric properties (d33~11.3 pC/N, T= 850 oC for 2h). This demonstrates that the
(LiCeNd)-mutlidoped CBN-based ceramics are a promising candidate for ultrahigh tempera-
ture applications.

088
In-situ X-ray diffraction study of alumina α-Al2O3 behavior
Houria Chikh-Afir
USTHB, Faculté de chimie, BP 32 El-Alia, Bab-Ezzouar, Alger, Algerie;
e-mail: [email protected]

We determined the crystalline characteristics of the hexagonal α-alumina phase by X-ray

diffraction at high temperatures between 293 and 2308K under dynamic vacuum. Our ex-
perimental values allow us to deduce an anisotropy of the ‘c’ direction compared to the ‘a’
direction of approximately 12% in the range of 293K–1760K: Such an anisotropy is related
to internal constraints in the alumina structure which may cause plastic deformation. There
is quite a difference in the range 1760K–2308K: no further anisotropy remains. The perfect
isotropic expansion of the alumina cell leads us to conclude the absence of any internal con-
straint above 1760K. As the anisotropy which characterizes the alumina structure is a direct
consequence of the fact that the aluminum atoms occupy two thirds of the octahedral sites in
the compact hexagonal subnetwork formed by the oxygen atoms, we believe that the isotropy
in question must surely translate an equal occupation for all octahedral sites so that the site
contains statistically 2/3 Aluminium atom.

255
Nitrogen and fluorine effect on the crosslink density of some
aluminosilicate glasses
Carolina Clausell-Terol, Antonio Barba-Juan, Juan C. Jarque-Fonfría,
Àngel R. Garcia-Bellés
Instituto Universitario de Tecnología Cerámica, Departamento de Ingeniería Química,
Universitat Jaume I, 12071 Castellón, Spain
Keywords: glasses, oxynitrides, oxifluoronitrides, crosslink density, nitrogen, fluorine

The effects of fluorine and nitrogen substitution for oxygen in calcium–(magnesium)–(yt-

trium) aluminosilicate glass have been examined. Forty-two glasses in the Ca–(Mg)–(Y)–
Si–Al–O–(N)–(F) system have been prepared and characterized with respect to Density (ρ),

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molar volume (MV), compactness (C), free volume (FV), DTA glass transition temperature
(Tg,DTA), dilatometric glass transition temperature (Tg,dil), dilatometric softening point (TDS)
microhardness (µHv) and Young’s modulus (E).
This paper reviews factors affecting the physical, thermal and mechanical properties of
three different oxyfluoronitride glass systems, showing how composition variables can be
used in additive equations to understand important predictors of property values. A modi-
fied method for calculating glass crosslink densities has been used, which takes into account
increased partitioning of aluminium from the network to a modifier role as fluorine content
increase. This method allows to explain changes in thermal properties with composition (as
glass transition temperature) but not changes in mechanical properties (as Young’s modulus
or microhardness), which are controlled by glass compactness (packing density).

516
Oxyacetylene and Oxypropane torch flame characterisation for UHTC
and UHTCMC screening tests
Lorna Cormack, Virtudes Rubio*, Jon Binner
School of Metallurgy and Materials, University of Birmingham, UK; *e-mail: [email protected]
Keywords: UHTC, UHTCMC, torch testing

The development of material systems suitable for ultra high temperature application is cur-
rently of great scientific interest. Ultra high temperature ceramics (UHTCs), which have high
melting temperature around 3000 °C1, and ultra high temperature ceramic matrix composites
(UHTCMCs) based on carbon or silicon carbide fibre reinforcement, have been extensively
investigated for aerospace applications as sharp leading edge components and thermal pro-
tection system which require resistance to these temperatures2. To enable this investigation
the development of characterisation methods to examine how materials behave at these tem-
peratures is vital3. A number of methods can be used to heat materials to these temperatures,
some cannot recreate hypersonic flight conditions such as static furnace oxidation testing and
other such as plasma wind tunnel testing and arc-jet testing are very expensive. The use of
gas torches currently offers a comparatively simple and low cost technique of characterising
and initial screening of potential UHTC materials4. They have this potential because they
can easily achieve the temperatures required and offer high heating rates, however to allow
the results to be compared with those from other techniques the velocity and heat flux of
the flame gas must be known. The current work has been focus on characterisation of the
oxyacetylene and oxypropane torch flame gas velocity and heat flux measurements of oxy-
propane torch. After that, different UHTCMCs were tested at different distance from the tip
nozzle using both torches.

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References
1. A. Paul, S. Venugopal, J.G.P. Binner, B. Vidhyanathan, A.C.J. Heaton, P.M. Brown, “UHTC–car-
bon fibre composites: Preparation, oxyacetylene torch testing and characterization”, J. Eur. Ceram.
Soc., 33(2), pp. 423–432, 2013.
2. S. Tang, J. Deng, S. Wang, W. Liu, K. Yang, “Ablation behaviors of ultra-high temperature ceramic
composites”, Mater. Sci. Eng. A, 465(1), pp. 1–7, 2007.
3. E.L. Corral, L.S. Walker, “Improved ablation resistance of C-C composites using zirconium
­diboride and boron carbide”, J. Eur. Ceram. Soc., 30(11), pp. 2357–2364, 2010.
4. Y. Wang, Z. Chen, S. Yu, “Ablation behavior and mechanism analysis of C/SiC composites”, J.
Mater. Res. Technol., 5(2), pp. 170–182, 2016.

407
Friction and wear of Al2O3-GO/RGO composites
Tomasz Cygan1*, Jaroslaw Wozniak1, Marek Kostecki1, Agnieszka Jastrzebska1,
Mateusz Petrus1, Piotr Klimczyk2, Piotr Putyra2, Lucyna Jaworska2, Andrzej Olszyna1
Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141,
1

02-507 Warsaw, Poland; *e-mail: [email protected]

The Institute of Advanced Manufacturing Technologies, ul. Wrocławska 37 A, 30-011 Cracow,
2

Poland
Keywords: Alumina, ceramic matrix composites, graphene oxide, wear resistance, friction behaviour

This paper presents the results of the study of the properties of alumina ceramics-GO/RGO
composites during the friction and wear studies. Based on the previous experiments, two
types of the Al2O3 matrix composites were produced: reinforced with graphene oxide (GO)
synthesized by a modified Hummer's method1 and reinforced with modified graphene oxide
nanoplatelets (RGO-Al2O3).2 All samples were prepared by powder metallurgy and consoli-
dated by Spark Plasma Sintering (SPS). Friction tests using the ball-on-disc method and wear
tests as dry machining on C45 steel were executed. Coefficients of friction, wear rate of disc
and ball as well as cutting tool life and roughness parameter Ra of machined steel surface
were analyzed. Scanning Electron Microscopy (SEM) observations for samples after tests
were also carried out, to reveal the types of wear. The work compares also cutting and fric-
tion performance of produced composites with those of commercial ceramic cutting tools.

References
1. J. Wozniak, A. Jastrzebska, T. Cygan, A. Olszyna, “Surface modification of graphene oxide nano-
platelets and its influence on mechanical properties of alumina matrix composites”, J. Eur. Ceram.
Soc., Volume 37, Issue 4, pp. 1587–1592, 2017.
2. T. Cygan, J. Wozniak, M. Kostecki, M. Petrus, A. Jastrzębska, W. Ziemkowska, A. Olszyna, Me-
chanical properties of graphene oxide reinforced alumina matrix composites, Ceram. Int., ISSN
0272-8842, http://dx.doi.org/10.1016/j.ceramint.2017.02.015. Article in press.

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765
Ni catalysts derived from hydrotalcite for the dry reforming reaction of
methane. Effect of the addition of Si
B. Djebarri1,2, F. Touahra2,3, N. Aider2, F. Bali2, V.M. Gonzalez-Delacruz4, K. Bacharri3,
J.P. Holgado4, A. Caballero4, D. Halliche2
1
Department of Chemistry, Faculty of sciences, University of M’hamed Bougara, Independence
Avenue, 35000 Boumerdes, Algeria
2
Laboratoire de Chimie du Gaz naturel, Faculté de Chimie,USTHB,Bp32, El-Alia, Alger, Algérie
3
Centre de Recherches Scientifiques (CRAPC), BP 248, Alger, 16004, Algérie
4
Instituto de Ciencia de Materiales de Sevilla and Departamento de Quimica Inorganica, (CSIC-
University of Seville), Avda. Americo Vespucio, 49, 41092 Seville, Spain
Keywords: CH4, CO2, hydrotalcite, sintering

CO2 reforming of methane shows a growing interest from the both industrial and environ-
mental point of view. CO2 and CH4 are undesirable greenhouse gases and both are consumed
by the proposed reaction. NiMgAl, NiAl, NiAlSi, NiMgAlSi were prepared by coprecipita-
tion at constant basic pH and calcined at 800 °C. The non-calcined compounds exhibit the
characteristic diffractions of hydrotalcite-like layered double hydroxide materials confirmed
by infrared spectroscopy. Samples containing sillicium show a poor cristallinity. Neverthe-
less, after calcination the hydroltacite-like structure is completely destroyed. The BET sur-
face area results, after calcination at 800 °C, showed some differences among the catalysts.
The results of H2-TPR measurements of the calcined samples indicated that NiAl and NiAlSi
present reduction profiles at lower temperature. NiMgAl and NiMgAlSi present reduction
profiles at high temperature. The dry reforming of methane by carbon dioxide in presence of
various catalysts is studied at 750 oC. For NiAl and NiAlSi catalysts CH4 conversions were
close to 70.0%, with a H2/CO ratio close to 0.9. In the NiMgAlSi sample the CH4 conversion
decrease to 50%, and the H2/CO ratio reaches values lower than unity. The NiMgAl sample
exhibit a higher conversion 95.0% close to stoichiometric values and a H2/CO ratio of almost
1, which can explained by the high stability of the support and the resistance to sintering of
particles, maintaining a very high specific surface (ca. 100 m2/g), after the reducing treat-
ment.1 Overall, it appears that the catalytic performances of the catalysts decreased as a func-
tion of sintering, in the following sequence NiMgAl> NiAlSi> NiAl> NiMgAlSi.

Reference
1. B. Djebarri, V.M. Gonzalez-Delacruz, D. Halliche et al. Reac. Kinet. Mecha. And, Cata. 111(2014)
259.

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866
To sinter water and oxygen sensitive materials using Spark Plasma
Sintering
Mirva Eriksson*, Zhijian Shen
Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University
S-106 91 Stockholm, Sweden; *e-mail: [email protected]

The state of the art Spark plasma sintering unit with capacity of sintering samples up to 20
mm diameter placed in the argon atmosphere glove box. This makes it possible to limit the
input of oxygen and water in the materials. The entire process can be done in a protective
atmosphere from the powder handling and loading the mold to the sintering without breaking
the protective chain. In that way air sensitive materials can be sintered and also the effect of
water and oxygen on sintering process can be investigated. The effect of water on sintering
of zirconia has been investigated by calcinating powder in vacuum at different temperatures
prior sintering. The sintering was done without exposion to the air as well the comparison has
been done with calcination in air and sintering at the same conditions. The sintering behav-
iour and microstuctures has been investigated and compared.

509
Spark Plasma Sintering: an advanced processing route for spring
magnet fabrication
Nancy Flores1*, Giulia Franceschin1, Souad Ammar1, Raul Valenzuela1,2
ITODYS, Paris Diderot University, 15 rue Jean Antoine de Baif, Paris, France;
1

*
e-mail: [email protected]
IIM, Universidad Nacional Autónoma de Mexico, Circuito Exterior, Ciudad Universitaria, Coyoacán,
2

04510, Ciudad de México, México

Keywords: permanent magnets, spring magnet, spark plasma sintering, nano-structured ceramics

Spark Plasma Sintering (SPS) is a non-conventional sintering technique that allows densifying
materials reducing sintering time, preventing grain growth and even preserving an epitaxial
arrangement at interface in composite materials1. To the best of our knowledge, SPS was sel-
dom used to produce spring magnetic composites. In most of the cases hard and soft oxides
nanoparticles (NPs) are co-sintered1,2. Unfortunately, the reached maximal magnetic energy
(BH)max of resulting nanostructures, remains small compared to that of their bulk counterparts.
In this work we proposed to prepare cobalt ferrite (CFO) and iron metallic (F) nanocomposites
presenting spring magnet effect; using SPS and starting from polyol–made CFO and F NPs.
Our main aim is to obtain permanent magnets with as high as possible (BH)max values varying
material processing conditions: size of CFO NPs, CFO/F nominal atomic ratio, SPS pres-
sure and temperature. The microstructure and the magnetic properties of the produced CFO-F
nanocomposites are investigated and compared.

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References
1. C. Fei, et al. J. Magn. Magn. Mater., 323, 1811–1816 (2011).
2. P. Jenuš, et al. J. Am. Ceram. Soc., 99: 1927–1934 (2016).

396
Parameters and sinterability of Al2O3-SiO2-Zro2 (y2o3) nanoparticles
Jānis Grabis*, Dzidra Jankoviča, Ints Šteins, Inta Sīpola, Māra Lubāne
Institute of Inorganic Chemistry Faculty of Material Science and Applied Chemistry Riga Technical
University, 3/7 Paula Valdena Street, Riga, Latvia, LV-1048; *e-mail: [email protected]
Keywords: sol-gel synthesis, thermal plasma synthesis, nanopowders, spark plasma sintering, nano­
structural mullite

Mullite-zirconia ceramics due to high refractivity, thermal shock resistance, good chemical
stability and improved mechanical resistance are promising material for structural and func-
tional application. However, the parameters of ceramic are determined by sintering method,
raw materials, their purity, particle size and activity. The objective of this work was to com-
pare parameters and sinterability of nanosized powders, prepared in Al2O3-SiO2-ZrO2(Y2O3)
system by synthesis in thermal plasma flow (PL) and by well-known sol-gel combustion syn-
thesis (SG). Thermal plasma synthesis was based on evaporation of coarse-grained (10–40
µm) Al2O3, SiO2, ZrO2, and Y2O3 powders in radio frequency air plasma. Formation of the
products via vapour phase led to obtaining homogeneous composites with spherical shape
and relatively wide particle size distribution in the range of 20–100 nm. This could be ex-
plained by different growth conditions of particles due to temperature distribution of plasma
flow and by the collisions of the liquid particles. The sol-gel combustion synthesis was per-
formed by mixing water solutions of Al, Zr and Y nitrates with TEOS ethanol solution at
100 oC for 1 h. Molar ratio of Al and Si was 3:2. Additive of zirconia with 3 mol% of yttria
was 5; 10 or 20 wt.%. Glycine water solution was added to the solution of precursors and
temperature was increased up to 120 oC. The formed gel was calcinated at 500 oC for 2 h and
after this the temperature was increased to 1000 oC. The as-prepared by both methods pow-
ders contained t-, m-ZrO2 and X-ray amorphous phases. Additional calcination of SG and PL
prepared samples led to formation of mullite at 1250–1300 oC and 940–990 oC respectively
depending on the content of zirconia. Densification of as-prepared partially X-ray amorphous
SG particles with specific surface area of 20–28 m2/g started at 10150–1150 oC depending on
the content of zirconia. Final relative density of the samples was reached at 1500 oC during 3
min. Densification of PL powders with specific surface area of 32-41 m2/g started at 900 oC
and final relative density (99.3%) was reached at 1400 oC during 3 min due to regular shape
of the particles. All sintered bodies contained mullite, t-ZrO2 and m-ZrO2 phases. SEM stud-
ies showed grain size mainly in the range of 0.8–1.5 µm. SG samples contained also rod-like
mullite crystals with diameter of 1.2 µm. Hardness of the bulk materials was in the range

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of 13.20–13.85 GPa. Spark plasma sintering of the partially X-ray amorphous Al2O3-SiO2-
ZrO2(Y2O3) nanosized powders allowed to decrease sintering temperature and to obtaine
materials with fine-grained microstructure.

Acknowledgments
Financial support to this project was provided by National Research Programme (IMIS2).

601
Microstructural and magnetic properties of SPS and hot-magnetic press
consolidated Sr-ferrite ceramics
Petra Jenuš1*, Andraž Kocjan2,1, Spomenka Kobe1
1
Department for Nanostructured Materials, Jožef Stefan Institute, Ljubljana, Slovenia;
*
e-mail: [email protected]
2
Jožef Stefan International Postgraduate School, Ljubljana, Slovenia
Keywords: Sr-ferrite, spark plasma sintering, hot-pressing

In the last years, much effort has been again devoted to the research of ferrite-based per-
manent magnets, due to the so called “rare-earth crisis.”1,2 In particular, a quest to enhance
maximum energy product (BHmax), which is a figure of merit in permanent magnets, is still
underway. Large BHmax values are found in magnets combining substantial magnetization at
remanence with high coercivity. Both parameters are influenced by materials properties, such
as crystalline and shape anisotropy (remanence), particle’ size (coercivity). In this study, we
will present how initial particle size, shape and sintering conditions influence microstructure
and consequently magnetic properties of sintered Sr-ferrite ceramics.
Two sets of powders and sintering conditions are being used. Namely, commercial Sr-
ferrite (SFO) with a particle size in the micron range and isotropic shape, and hydrothermally
synthesized Sr-ferrite with hexagonally shaped platelets with a diameter up to 500 nm and
thickness up to 50 nm. Both powders are being sintered with two different sintering set-ups;
spark plasma sintering (SPS) and consolidation with a hot-magnetic press. Sintering with
SPS promotes the alignment of hydrothermally synthesized SFO particles in the direction
of the applied pressure, which is also the direction of materials’ easy axis and thus the en-
hancement in remanence is perceived. Moreover, no grain growth was observed, which is
beneficial for maintaining particle’ size at the nanoscale and thus exploiting advantages of
nanosized induced phenomena. On the other hand, consolidation in the hot-magnetic press,
due to the applied external magnetic field, results in orienting spins in the shape-wise, iso-
tropic material (commercial SFO), which leads to the enhancement of BHmax of commercial
SFO powders.
Starting powders were examined by transmission (TEM) and scanning electron micros-
copy (SEM), while the microstructural characterization of consolidated magnets was done
with SEM. Magnetic properties of starting powders and consolidated SFO ceramic magnets
were evaluated with vibrating sample magnetometer and permeameter.

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References
1. R. Skomski and J.M.D. Coey, “Magnetic anisotropy — How much is enough for a permanent mag-
net?”, Scripta Materialia, 112, pp. 3–8, 2016.
2. https://ec.europa.eu/growth/sites/growth/files/critical-importance-risk.jpg, 2014.

925
Preparation of transparent ALON ceramics by using spark plasma
sintering
V.N. Kazakova*, E.G. Grigoryev
National Research Nuclear University “MEPhI”, Kashirskoe sh. 31, Moscow, Russia, 115409;
*
e-mail: [email protected]
Keywords: current activated pressure assisted sintering, AC electric field-assisted sintering, nano-
crystalline boron carbide

Boron carbide (B4C) with its high hardness, wear resistance and rather low density is quite
a promising material for lightweight armor, blasting nozzles, grinding wheels and other in-
dustrial applications. Ceramics based on boron carbide can be obtained by various meth-
ods.1–3 Field assisted sintering technique is a modern technique of sintering under pressure
and it is widely used for the manufacture of refractory ceramics in nowadays. We studied two
methods for sintering of boron carbide: spark-plasma sintering and (SPS) and high-voltage
consolidation (HVC). The effect of spark-plasma sintering regimes and high-voltage consoli-
dation regimes on the microstructure and mechanical properties boron carbide ceramics was
investigated. It is established that the achievement of high density of compacts from boron
carbide is possible for solid-phase sintering / consolidation by both methods. It is shown that
for the investigated SPS regimes the maximum level of boron carbide sample density is ob-
served at a sintering temperature of 1850–1950 °C. Also, high-voltage consolidation of boron
carbide powders was carried out. The high-voltage consolidation consists in the affect of a
discharge with a high current density (≈100 kA*cm–2) and a short pulse duration (less than
300 μs) on the powder compact. The increase in the density of the material, its microhardness
with increasing voltage of a high-voltage discharge is shown.

Acknowledgements
The work was carried out with the financial support of the Russian Science Foundation (grant № 16-
19-10213). The Interdepartmental laboratory of perspective technologies of creation of new materials
at the National Research Nuclear University MEPhI was established under the program of mega-grants
of the Russian Government (grant № 11.G34.31.0051).

References
1. Clark Н.К. The crystal structure of boron carbide / Н.К. Clark, J.L. Hoard // J. Am Chem. Soc.-
1943.-V. 65.- P. 2115–2119.
2. Swinkels F.B., Ashby M.F. Nonconventional pressure-assisted powder consolidation methods. Acta
Metallurgica, 29. – 1981. - P. 259–281.

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3. Moshtaghiouna B.M. Effect of spark plasma sintering parameters on microstructure and room-tem-
perature hardness and toughness of fine-grained boron carbide (B4C) / B.M. Moshtaghiouna, F.L.
Cumbrera-Hernándeza, D. Gómez-Garcíaa, S. de Bernardi-Martína, A. Domínguez-Rodrígueza, A.
Monshib, M.H. Abbasib // J. of the Eur. Cer. Soc. – 2013. – V. 33.– I 2. – P. 361–369.

945
Flash sintering of a three-phase alumina, spinel, and yttria-stabilized
zirconia composite
David Kok1, Shikhar Krishn Jha2, Emanuele Sortino2, Devinder Yadav2, Rishi Raj2,
Scott J. McCormack3, Kuo-Pin Tseng3, Waltraud M. Kriven3, Martha L. Mecartney1
1
Department of Chemical Engineering and Material Science, University of California, Irvine, CA,
USA
2
Department of Mechanical Engineering, University of Colorado at Boulder, CO, USA
3
Department of Material Science and Engineering, University of Illinois at Urbana-Champaign, IL,
USA

Three-phase ceramic composites constituted from equal volume fractions of α-Al2O3,

­MgAl2O4 spinel and cubic 8 mol% Y2O3-stabilized ZrO2 (8YSZ) were flash-sintered under
the influence of DC electric fields from 50 to 500 V/cm. Experiments were conducted either
by using a constant heating rate with a set voltage or isothermal experiments with increasing
voltage. Higher electric fields inhibited grain growth due to the lowering of the flash tem-
perature and an accelerated sintering rate. During flash sintering, alumina reacted with the
spinel phase to form a high-alumina spinel solid solution, identified by electron dispersive
spectroscopy and from a decrease in the spinel lattice parameter as measured by X-ray dif-
fraction. Synchrotron in-situ X-ray diffraction experiments demonstrate that the formation
of high-alumina spinel occurs in less than 3 seconds along with the formation of a transient
phase. The influence of 8YSZ content on flash behavior of the composite is reported.

495
The SPS sintering of different size and morphological forms of silicon
carbide powders
Marek Kostecki*, Jaroslaw Wozniak, Tomasz Cygan, Mateusz Petrus, Andrzej Olszyna
Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141,
02-507 Warsaw, Poland; *e-mail: [email protected]
Keywords: silicon carbide, SPS, ceramic, microstructure, liquid phase sintering

Several sintering experiments of different SiC powders were performed using SPS method.
The studies involved different geometry and size of powder particles: equiaxed micro par-
ticles, nanopowder and whiskers. There were significant differences in the microstructure

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and the basic mechanical properties (hardness, Young’s modulus) arising from the morphol-
ogy of the used powders. One of the greatest drawbacks in the manufacturing of SiC is the
difficulty to sinter dense samples without the use of additives. For the purpose of comparison
the sintering additives Al2O3 and Y2O3 were used. It has been found that obtaining dense sin-
ters is possible due to the presence of phases activating mechanisms of mass transport, thus
facilitating densification process during sintering. The use of yttria and alumina as sintering
additives cause a liquid phase presence during the sintering and intensifying process. Particu-
larly interesting microstructure characterized by open porosity was obtained using powder
with whisker morphology. This type of microstructure is suitable for production of filters
operating at high temperatures.

505
An original concept for the rapid elaboration of C/C composites:
the film boiling chemical infiltration
Amandine Lorriaux1, Laurence Maillé1, Arnaud Delehouzé2, Patrick David3
1
University of Bordeaux, LCTS, UMR 5801, 3 allée de la Boétie 33600 Pessac, France;
e-mails: [email protected], [email protected]
2
Safran Ceramics, rue du touban 33185 Le Haillan, France;
e-mail: [email protected]
3
CEA Le Ripault, 37260 Monts, France; e-mails: [email protected], [email protected]
Keywords: kalamazoo, pyrocarbone (PyC), chemical vapour deposition (CVD), Chemical Vapour
Infiltration (CVI)

A work based on the development of an original process for the fabrication of a C/C compos-
ite for aeronautic and nuclear industries is presented: the “film boiling” densification.
Nowadays C/C composite are mostly elaborated by CVI (Chemical Vapour Infiltration).
This process is long and restrictive, indeed the elaboration takes several weeks. Using “film
boiling process” for the densification of a carbon fiber preform allows a large reducing of the
processing time with respect to CVI (50 to 100 faster).1,2
The carbon preform is immersed into a carbon precursor and heated up above the precur-
sor decomposition temperature. The precursor in contact with hot surfaces will vaporize and
form a “vapour film boiling” at the interface. The preform, heated up above the precursor
decomposition temperature, the vapours will decomposed leading to the deposition of C
inside the preform. The immersion in a liquid allows the precursor high concentration thus
the process is not limited by the diffusion of the species, leading to a rapid densification. Ex-
periments were first carry out with hydrocarbure precursors. Several experiments parameters
were tuned, such as deposition temperature, time or pressure, to estimate their influence on
the deposition kinetics and the obtained matrix.
The presented work will focus on the PyC deposition from cyclohexane in order to better
understand the deposition mechanisms. Indeed several types of PyC can be observed in the
literature: Dark laminar PyC (DL), Smooth laminar PyC (SL), Rough laminar PyC (RL) and

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Regenerative Laminar (ReL). Understanding all the deposition mechanisms will help the
chemists to tune experimental set up to obtain the suitable PyC.
Microstructural, liquid phase and gas phase analysis were carried by polarized light optical
microscopy (PLOM), Fourier transform infra-red (FTIR) and gas chromatography coupled to
mass spectroscopy (GC-MS) to answer this question.

References
1. P. Delhaès, “Chemical vapour deposition and infiltration processes of carbon materials”, Carbon,
40, pp. 641–657, 20022.
2. D. Rovillain, M. Trinquecoste, E. Bruneton, A. Derre, P. David, P. Delhaès, “Film boiling chemi-
cal vapor infiltration: An experimental study on carbon/carbon composite materials”, Carbon, 39,
1355–1365, 2001.

728
Mixed electronic and ionic conductivity and stability of 8YSZ/graphene
bulk composites
Daniel Marinha1*, Manuel Belmonte2
1
LSFC, UMR 3080 Saint-Gobain CREE/CNRS, 550 Avenue Alphonse Jauffret, 84306 Cavaillon,
France; *e-mail: [email protected]
2
Institute of Ceramics and Glass (ICV-CSIC), Campus Cantoblanco, 28049 Madrid, Spain
Keywords: YSZ, graphene, CMC, SPS, sintering

Graphene is added to structural oxide and non-oxide ceramics to improve the mechanical,
electrical and tribological properties. Examples include Al2O3, SiC and Si3N4, among oth-
ers.1 Similar improvements have been reported in Yttria-stabilized Zirconia, YSZ-graphene
composites.2 YSZ is a well-known oxygen-ion conductor and is used as solid oxide fuel cell
electrolytes in past decades. YSZ-graphene composites should therefore display mixed ionic
and electronic conductivity, exploited for several electrochemical high-temperature devices
and processes. Perovskites with mixed-valence transition metals in the B-site are typically
used, but these materials are prone to thermo-chemical and mechanical degradation.
This study will characterize the mixed electronic and ionic conductivity of YSZ/graphene
composites prepared by spark plasma sintering (SPS), as a function of graphene loading,
and compare them to alternative sintering methods. Starting from a 8YSZ suspension with
graphene nanoplatelets (GNPs) powders, we establish a protocol to obtain dense and homo-
geneous composites, as confirmed by SEM and Raman performed on fractured surfaces. As
expected the GNPs concentrate along the grain boundaries and tend to align perpendicularly
to the pressure during SPS. Impedance spectroscopy with increasing GNP loading estab-
lished a percolation limit between 2.5 and 3.75 wt.% and an increase of total conductivity by
105, with activation energy of 0.4 eV.
The stability of composites was established at isothermal conditions and varying the oxy-
gen partial pressure (pO2). Composites are stable in reducing conditions pO2<10–4 atm) up
to 600 °C for several hours. However, Nyquist plots at 350 °C and 0.21 atm show an irre-

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versible transition from electron to ion conductor behaviour, and increased grain boundaries
resistance by 20 fold, compared to simple YSZ with identical grain size. We conclude that
graphene blocks ion diffusion at the grain boundaries and establish a stability domain of
operation conditions for YSZ-graphene composites. Results are compared with samples sin-
tered at different atmospheres and heating rates.

References
1. Markandan, K., Chin, J.K. and Tan, M.T.T. Recent progress in graphene based ceramic composites:
a review (2017) Journal of Materials Research, 32(1), pp. 84–106.
2. Shin, J.-H., Hong, S.-H. Fabrication and properties of reduced graphene oxide reinforced yttria-
stabilized zirconia composite ceramics (2014) Journal of the European Ceramic Society, 34 (5),
pp. 1297–1302.

674
Influence of niobium on silicate glasses for nuclear waste
immobilization
S.R.H. Mello-Castanho*, D.L. Costa e Silva, A.C. Silva, M.A. Silva
Nuclear and Energy Research Institute - IPEN, São Paulo, Brazil; *e-mail: [email protected]
Keywords: nuclear waste, niobium, vitrification

Nuclear waste immobilization by vitrification process is a potential route because it allows

many elements to be incorporated into the glass and consequently the final waste volume is
reduced up to 80% its initial volume.1 The effect of Nb addition into silicate glasses modified
by B2O3 and Al2O3 additions was studied. In this work, compositions of the system CaO-
Na2O-SiO2-RxOy2 were studied, where RxOy represent modifications with additions of B2O3
and Al2O3. In these compositions, the B2O3 was gradually substituted by Nb2O5 and the effects
of this substitution were evaluated. The gasses, obtained by traditional quenching method,
were characterized by X-ray diffraction (XRD), Fourier Transformed Infrared Spectroscopy
(FTIR), Raman Spectroscopy and Differential Thermal Analysis (DTA). The XRD diffrac-
tion patterns confirmed that the materials are completely amorphous and the DTA analysis
revealed that the glass-transition-temperature (Tg) slightly increases by increasing the Nb
content, which suggests that the Nb might be participating in the glass structure. Similar ten-
dency was verified by determination of the Hrubÿ parameter,3 which is related to the stability
of the glasses against devitrification. The formation of metaborate rings and boroxol goups
was apparently stimulated by the addition of less than 1.0 mol% of Nb, indicating a compe-
tition between borum and niobium for positions in the glass network. It was also observed
that Nb induces the glass network to the predominance of SiO4 Q3 units, which is directly
associated to an increase in the chemical stability of the glasses. Such results are indicative
that the chemical durability of the studied glasses might be improved by the Nb addition. This
compositional system might be a promising alternative to the production of a new family of
glasses suitable for the immobilization of nuclear wastes.

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References
1. M.I. Ojovan, W.E. Lee, Elsevier 2nd. Ed. 2015.
2. A.C. Silva, S.C. Santos, S.R.H. Mello-Castanho, Mat. Sci. Forum. 727–728, pp. 1496–1501, 2012.
3. A.A. Cabral Jr., C. Fredericci, E.D. Zanotto, J. Non Crys. Sol. 219, pp. 182–186, 1997.

911
Microstructure and strength composites beta-sialon – boron nitride
obtained by spark-plasma sintering
Evgenia Nefedova1, Vladimir Goltsev1, Evgeny Grigoryev1*, Dmitry Fokin1,
Konstantin Smirnov2
1
National Research Nuclear University “MEPhI”, Kashirskoe sh. 31, Moscow, 115409 Russia;
*
e-mail: [email protected]
Institute of Structural Macrokinetics and Materials Science, Russian Academy of Sciences,
2

Chernogolovka, Moscow, 142432 Russia

Keywords: combustion synthesis, spark plasma sintering, beta-sialon, boron nitride

Composites β-SIALON – BN are highly promising for metallurgical applications such as

tubes for metal pouring, pipe heaters, nozzles, dozer units, annular breakers, buckets, cru-
cibles, lining plates, thermocouple casing, etc.1 Combustion synthesis (CS) is a convenient
technique for production of SIALON powders with desired composition, particle size, and
morphology.2 Spark plasma sintering (SPS) is a newly developed process that allows pulsed
direct current to pass through the die and sample to heat them. Compared with conventional
hot pressing, SPS allows higher heating rates and a very short holding time.3 The spark plasma
sintering of β-SiAlON/0–30 wt % BN ceramic composites was investigated. It was studied
the microstructure and the strength of the samples (β-SIALON – BN) consolidated by SPS.
The raw materials (β-Si5AlON7 and BN powders) were prepared by infiltration-mediated
combustion synthesis. Experimentally established were the following process parameters for
SPS of composites with high relative density (>95%) and flexural strength of 250–300 MPa:
(a) heating rate 50 deg/min, (b) maximum temperature 1650–1750 °C, (c) and holding time
5 min. High-density β-SiAlON–BN ceramic composites with improved strength properties
were prepared by spark plasma sintering of combustion synthesis-produced β-Si5AlON7 and
BN powders. Thus obtained machinable ceramics seem promising for fabrication of machine
parts and items operating in severe conditions of strong thermal shock and corrosion-active
media.

Acknowledgement
This work was financially supported by the Russian Science Foundation (grant no. 16-19-10213).

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References
1. L. Gao, X. Jin, J. Li, Y. Li and J. Sun, “BN/Si3N4 nanocomposite with high strength and good
machinability”, Mater. Sci. Eng. A, vol. 415, # 1–2, pp. 145–148, 2006.
2. Y.S. Zhao, Y. Yang, J.T. Li, I.P. Borovinskaya and K.L. Smirnov, “Temperature factor in tailoring
the morphology of Y-α-SiAlON microcrystals fabricated by combustion synthesis”, Int. J. Self-
Propag. High-Temp. Synth., vol. 18, # 2, pp. 87–91, 2009.
3. Z.A. Munir, U. Anselmi-Tamburini, and M. Ohyanagi, “The effect of electric field and pressure on
the synthesis and consolidation of materials: A review of the spark plasma sintering method”, J.
Mater. Sci., vol. 41, # 3, pp 763–777, 2006.

351
Oxidation behavior of stainless steel and polymer derived ceramic
coatings with passive fillers
Milan Parchovianský1*, Ivana Petríková1, Gilvan S. Barroso2, Peter Švančárek1,
GünterMotz2, Dagmar Galusková1, Dušan Galusek1
1
Vitrum Laugaricio – Joint Glass Center of the IIC SAS, TnU AD, and FCHFT STU, Študentská 2,
911 50 Trenčín, Slovakia; *e-mail: [email protected]
2
University of Bayreuth, Ceramic Materials Engineering, D-95440 Bayreuth, Germany
Keywords: PDC ceramics, glass microspheres, hydrothermal corrosion, high temperature oxidation

Polymer-derived ceramics (PDCs) have been investigated in the past few decades for several
applications, such as bulk materials, ceramic fibers and porous ceramics. Additionally, the
PDC approach has proven to be a suitable alternative for the processing of functional coating
systems with protective properties against oxidation and corrosion, high optical emissivity,
and many others.1,2 In this work, the development of a novel thermal barrier coating sys-
tem based on polymer-derived ceramics, applied by simple lacquer methods is reported. The
system consists of a polysilazane (PHPS) bond-coat and an insulating layer formed by the
combination of passive yttria-stabilized zirconia (YSZ), commercial barium silicate glasses
(G018-311 and G018-385), glass microspheres and an (organo)silazane (Durazane 1800).
The aim of this study is to investigate the oxidation resistance of a AISI441 stainless steel
with and without the coating. The high temperature oxidation behaviour of these materials
in a flow-through oxygen atmosphere and water vapour was investigated at the temperatures
of 900 °C, 950 °C and 1100 °C and the exposure times in the range of 1–48 hours. Uncoated
substrate (ferritic steel grade AISI 441) was used as a reference. The rate of oxidation in pure
flow-through oxygen atmosphere and water vapour were determined, and the oxide scales
formed after different exposures times and temperatures on coated and uncoated samples
were characterized by SEM/EDS and XRD, including detailed microstructural and phase
analysis of the oxide scales formed in the atmosphere of oxygen. X-ray diffraction confirmed
extensive corrosion of the uncoated AISI441 stainless steel accompanied by formation of a
Cr2O3, TiO2 and a (Mn, Cr)3O4 spinel containing layer of corrosion products. Beneficial effect
of the PDC coating was observed at the temperature of 900 °C, demonstrated by marked re-

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duction of the weight gain of coated steel after 48 h of exposure to flowing oxygen. At higher
temperatures the protective action of the PDC coating was observed moderately, and a thick
layer of oxidation products was formed at the steel/coating interface.

References
1. P. Colombo, G. Mera, R. Riedel, G.D. Sorarù, “Polymer-derived ceramics: 40 Years of research and
innovation in advanced ceramics”, J. Am. Ceram. Soc., 93, pp.1805–1837, 2010.
2. M. Günthner, A. Schütz, U. Glatzel, K. Wang, R.K. Bordia, O. Greißl, W. Krenkel, G. Motz, “High
performance environmental barrier coatings, Part I: Passive filler loaded SiCN system for steel”, J.
Eur. Ceram. Soc., 31, pp. 3003–3010, 2011.

203
Preparation of SiC/SiCf and SiC/Cf nanocomposites
Krzysztof Perkowski*, Izabela Kobus, Magdalena Gizowska, Milena Zalewska,
Marcin Osuchowski, Gustaw Konopka, Agnieszka Jaworska, Irena Witosławska
Institute of Ceramics and Building Materials, Nanotechnology Department;
*
e-mail: [email protected]
Keywords: nanocomposites, SiC/SiC composites, carbon nanofibers, sintering

Type SiC/SiC and SiC/C composites made by addition of SiC and C nanofibers to the SiC
matrix were fabricated by two kinds of sintering process: with liquid phase of silicon and by
solid state reaction with boron and boron carbide as sintering additives.
In this work ceramic slurries were used to prepare granulates by freeze granulation meth-
od, which provided a uniform arrangement of all components in the whole volume of the
specimen. As a result lamellas like structured SiC/SiC composites were obtained after sinter-
ing. Changes in thermal and mechanical properties caused by addition of SiC and C nano-
fibers were the subject of further researches. It was observed that additives such as SiC and
C nanofibers to SiC matrix has significant influence on the flexural strength and thermal
diffusivity of SiC/SiC and SiC/C composites.

References
1. S.P. Lee, M.H. Lee, J.K. Lee, J.H. Byun, A. Kohyama, “Fabrication and characterization of SiCf/
SiC composites produced by the slurry infiltration process”, Journal of Nuclear Materials, 417, pp.
344–347, 2011.
2. T. Taguchi, Y. Hasegawa, S. Shamoto, “Effect of carbon nanofiber dispersion on the properties of
PIP-SiC/SiC composites”, Journal of Nuclear Materials, 417, pp. 348–352, 2011.
3. K. Yoshida, S. Kajikawa, T. Yano, “Microstructure design and control for improvement of thermal
conductivity of SiCf/SiC composites”, Journal of Nuclear Materials, 440, pp. 539–545, 2013.

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499
Influence of carbon form on sinterability of silicon carbide
Mateusz Petrus1*, Jarosław Woźniak, Tomasz Cygan, Marek Kostecki,
Agnieszka Jastrzębska, Andrzej Olszyna
Faculty of Materials Science and Engineering, Warsaw University of Technology,
1

Woloska 141 Warsaw, Poland; *e-mail: [email protected]

Keywords: carbon, silicon carbide, sintering, SPS, ceramic, ceramic matrix composites

Strong covalent bonds occurring in silicon carbide (SiC) or silicon nitride (Si3N4) cause to
retard solid-phase sintering, because of the slow bulk occurring in this group of materials.1
As was shown by Prochazka dense SiC can be sintered by using carbon and boron sintering
aids.2 Moreover, in work3 it was reported that the morphology of used carbon has a strong
influence on phase structure and relative density.
In this work the mechanical properties and the microstructure changes of samples sintered
with different additions (0.5, 1, 1.5, 2, 2.5, 3 wt%) of six forms of carbon were examined. The
following sources of carbon were used: 1. Multilayer graphene (MLG); 2. Highly oriented
pyrolytic graphite (HOPG); 3. Graphite, 4. Amorphous Carbon, 5. Active Carbon and 6. Car-
bon Black. In order to determine the morphology of used carbon the specific surface area, to-
tal porosity, shape of pores and Raman spectra were measured. The sinters were consolidated
at 1900 oC using the Spark Plasma Sintering method (SPS). The influence of morphology of
carbon on density, hardness, fracture toughness and phase structure of the sintered samples
was investigated.
A high rate of densification was observed for samples with varied amounts of carbon,
depending on the used form. Moreover, samples with the highest relative density show the
highest value of hardness, an almost single-phase structure and equiaxed grains.

References
1. W. van Rijswijk, D.J. Shanefield, Effects of Carbon as a Sintering Aid in Silicon Carbide, J. Am.
Ceram. Soc. 73 (1) pp.148–149, 1990.
2. S. Prochazka, R.M. Scanlan, Effect of Boron and Carbon on Sintering of SiC, J. Am. Ceram. Soc.
58 (1–2) pp. 72, 1975.
3. M. Petrus, J. Wozniak, T. Cygan, B. Adamczyk-Cieślak, M. Kostecki, A. Olszyna, Sintering behav-
iour of silicon carbide matrix composites reinforced with multilayer graphene, Ceram. Int. 43 , pp.
5007–5013, 2017.

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378
Development of silicon nitride based CNT/graphene composite using
hot isostatic pressing (HIP) technique
Awais Qadir1*, Katalin Balazsi2, Csaba Balazsi2
1
Óbuda University, Bécsi út 96/B, 1034 Budapest, Hungary; *e-mail: [email protected]
2
Centre for Energy Research, Hungarian Academy of Sciences, Konkoly-Thege Miklós út 29-33,
1121, Budapest, Hungary
Keywords: hot pressing, Si3N4 composites, SIALON, oxynitrides, CNT, graphene

Different weight percent of CNTs and multilayer graphene (MLG) reinforced silicon nitride
based composites were prepared by hot iso-static pressing (HIP) to investigate the effect of
the CNTs and graphene on mechanical properties of composite. Composite material was in-
vestigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy disper-
sive spectroscopy (EDS) for structural analysis, morphology and incorporation of CNT and
graphene into matrix. Mechanical testing and sliding wear tests were carried out to observe
the effect of CNTs and graphene on mechanical and tribological properties. Significant im-
provement in the micro-harness, tensile strength but slightly improvement in wear resistance
was observed through addition of CNTs and multi layered graphene in Si3N4 ceramic ma-
trix. The improvement in the mechanical properties is mainly attributed to grain refinement,
uniform dispersion and pinning effect caused by the addition of CNTs and graphene. Si3N4
particles were observed at the bottom of the dimples at the fracture site, more likely voids
ignition occurred at the Si3N4/CNTs, graphene interfaces regions. The mechanical proper-
ties, electrical and thermal properties of Si3N4 can be enhanced by the addition of CNT and
graphene in optimum conditions.

References
1. B Fényi, N. Hegman, F. Wéber, P. Arató, C. Balázsi, DC Conductivity of Silicon Nitride Based
Carbon-Ceramic Composites, Processing and Application of Ceramics 1:(1–2) pp. 57–61 (2007).
2. C. Balazsi, Silicon nitride composites with different nanocarbon additives, Journal of the Korean
Ceramic Society 49:(4) pp. 352–362 (2012).
3. C. Balázsi, K. Sedláčková (K. Balazsi), Z. Czigány, Structural characterization of Si3N4-carbon na-
notube interfaces by transmission electron microscopy, Composites Science and Technology 68:(6)
pp. 1596–1599 (2008).

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769
Preparation of transparent AlON ceramics by using spark plasma
sintering
N.A. Rubinkovskiy1, A.G. Zholnin1, E.G. Grigoryev1, M.G. Isaenkova1, A.G. Astashov2,
I.O. Pahilo-Daryal2
National Research Nuclear University “MEPhI”, Kashirskoe sh. 31, Moscow, Russia, 115409;
1

e-mail: [email protected]
A. Baikov Institute of Metallurgy and Materials Science, Russian Academy of Sciences Leninskii
2

prospekt, 49 Russia, 119991

Keywords: AlON, aluminium oxynitride, spark plasma sintering, transparent, powder solid state
reaction

Polycrystalline aluminum oxynitride (AlON, Al(64 + x)/3O(32 − x)Nx, 0≤x≤8) is an ideal material
for transparent armor owing to its high strength and high hardness, highly resistant to rain
and sand damage, and excellent optical properties.1,2 Al2O3 and AlN powder mixtures were
used to synthesise AlON ceramics using the reactive spark plasma sintering (SPS) method
at temperature 1700 °C for 30 min at 40 MPa and a heating rate of 100 °C/min under nitro-
gen. The starting components were taken by the following proportion: 64.3 at.% of Al2O3
and 35.7 at.%. of AlN.3 The powders were mixed by specified proportion in alcohol in an
ultrasonic disperser in alcohol for 40 minutes, and then air dried. The solid-phase synthesis
of ALON with the spark-plasma sintering yielded positive results. The densification, micro-
structure and mechanical properties of the produced ceramics were analysed. The highest
hardness value was recorded to be 18.8 GPa, and the tensile strength of the sample with the
highest AlON ratio was measured to be 187 MPa.

Acknowledgements
The work was carried out with the financial support of the Russian Science Foundation (grant № 16-
19-10213). The Interdepartmental laboratory of perspective technologies of creation of new materials
at the National Research Nuclear University MEPhI was established under the program of mega-grants
of the Russian Government (grant № 11.G34.31.0051).

References
1. Li X, Luo J, Zhou Y. Spark plasma sintering behavior of AlON ceramics doped with different con-
centrations of Y2O3 J. Ceramics International 2015; 35: Journal of the European Ceramic Society
2027–2032.
2. Tabary P, Servant C, Alary JA. Microstructure and phase transformations in the AlN-Al2O3 pseudo-
binary system. J Eur Ceram Soc 2000; 20:913–926.
3. Sahin FC, Kanbur HE, Apak B. Preparation of ALON ceramics via reactive spark plasma sintering.
Journal of European Ceramic Society; 2012; 32 (4):925–929.

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580
Role of particle–particle contacts in the thermophysical behaviour of
green ceramic bodies during drying and firing
David S. Smith*, Siham Oummadi, Delphine Nouguier, Arnaud Alzina, Benoit Naït-Ali
SPCTS, University of Limoges, 12 rue Atlantis 87068 Limoges, France;
*
e-mail: [email protected]
Keywords: ceramic green body, thermal conductivity, particle–particle contacts, drying, firing

After the forming step, a green body is constituted of a compacted powder associated with
typically 40–60% pore volume fraction. Further processing than involves thermal treatments
to remove excess water with a drying step, if needed, and to consolidate the ceramic body
into its final shape during firing. A key aspect, controlling heat and mass transfers in the green
body, is the nature and area of the particle–particle contacts in the compacted powder. The
work presented in this report examines the relation between particle–particle contact area and
thermal conductivity of green ceramic bodies (alumina, zirconia, tin oxide, kaolin clay...).
A model system of metal beads has been studied with flowmeter thermal resistance mea-
surements to illustrate the role of interface planes in the overall thermal conductivity of a
granular assembly. This leads to a simplified model based on a series of interface planes
across the sample to describe the thermal conductivity of the green body.

As a first example, the approach is used to explain the strong decrease of thermal conduc-
tivity of alumina green bodies during the last stage of drying. In particular a marked increase
in the thermal resistance of equivalent interface planes occurs as water is removed from the
neck regions of the grain assembly, i.e. just next to the particle–particle contacts. In a second
example with a nanometric tin oxide powder, BET measurements are used to evaluate the
evolution of the particle–particle contact area compared to the particle–pore surface area.
A significant increase in thermal conductivity can be attributed to an increase of particle–
particle contact area from 5% in the green body to 33% after thermal treatment at 600 °C.
Similar behaviour is observed in zirconia ceramics.
It is concluded that the thermal response time of the green body, controlling the tempera-
ture distribution within the ceramic body during firing, is strongly sensitive to the state of the
particle–particle contacts in the microstructure.

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895
Production of functionally graded silicon carbide-titanium
diboride-aluminium composites by spark plasma sintering technique
and their characterization
Merve Taner, Gürsoy Arslan
Department of Material Science and Engineering, Anadolu University, İki Eylül Campus 26555
Tepebası, Eskişehir, Turkey; e-mails: [email protected], [email protected]
Keywords: functionally graded materials, ceramic-metal composites, spark plasma sintering, silicon
carbide, titanium diboride, mechanical properties

In this study, production of functionally graded silicon carbide-titanium diboride-aluminium

composites by spark plasma sintering technique was investigated. Silicon carbide-titanium
diboride-aluminium powder mixtures containing 70–90 weight % silicon carbide-titanium
diboride and 10–30 weight % aluminium were sintered at 1600–1900 ºC for 5 minutes by
spark plasma sintering.
SiC-TiB2-Al composites were sintered in a single step by using the spark plasma sintering
method. Furthermore, the produced SiC-TiB2-Al composites were designed as functionally
graded composite material (FGM) layers having different compositions and/or residual po-
rosity levels. Phase analysis of the functionally graded composites layers were characterized
by x-ray diffraction, and their microstructure was investigated by using a scanning electron
microscope attached with an energy dispersive x-ray spectrometer. Hardness, compressive
strength values, and densities of the functionally graded composite layer were measured.
Results obtained show that produced composite FGM’s have a microstructure character-
ized by a co-continuous ceramic-metal network. Furthermore, it was determined that the bulk
density of the produced functionally graded composite layers was always above 99.5%, the
hardness gradually decreased from the front layer to the back layer, while the compressive
strength decreased in just the opposite manner.

513
Cutting performance of alumina matrix composites reinforced with
nickel-coated graphene
Jarosław Woźniak*, Tomasz Cygan, Mateusz Petrus, Marek Kostecki, Andrzej Olszyna
Faculty of Material Science and Engineering, Warsaw University of Technology, Woloska 141
Warsaw, Poland; *e-mail: [email protected]
Keywords: cutting tool, machining, SPS sintering, ceramic, ceramic matrix composites

Despite many advantages of graphene, preparation of composites reinforced with Gn still

causes many problems.1 One of the most imported is ceramic matrix – reinforcing phase
interface.2 Lack of bonding between graphene and the matrix create voids on the interface.

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It will act as a stress concentrator and reduce fracture toughness (which is critical for cutting
tool materials) of the composite. The problem can be solved by modification of graphene
surface by application of the nickel layer.3
This paper discusses the influence of nickel-coated graphene addition to alumina matrix
and its impact on mechanical and cutting performance of obtained composites. The com-
posites were prepared via powder metallurgy processing using the SPS method to consoli-
date powder mixtures. Applied method due to lowering the sintering temperature and time
(in comparison to conventional sintering methods) leads to limiting the grain growth of alu-
mina matrix. It has great impact on physical properties of produced sinters. Basic physical
properties of obtained composites such as density, fracture toughness were analysed and
compared with composites reinforced with unmodified graphene. Moreover, machining test
and tribotest of sinters were made and compared with commercially available cutting tool.
The results show that produced cutting tools are characterized with good cutting performance
comparable with commercial cutting tool.

References
1. H. Porwal, P. Tatarko, S. Grasso, J. Khaliq, I. Dlouhy, M. J. Reece, Graphene reinforced alumina
nano-composites, Carbon. 64 (2013) 359–369.
2. J. Liu, H. Yan, M. J. Reece, K. Jiang, Toughening of zirconia/alumina composites by the addition
of graphene platelets, J. Eur. Ceram. Soc. 32 (2012) 4185–4193S.
3. Prochazka, R. M. Scanlan, Effect of Boron and Carbon on Sintering of SiC, J. Am. Ceram. Soc. 58
(1–2) pp. 72, 1975.
4. J. Wozniak, M. Trzaska, G. Cieślak, T. Cygan, M. Kostecki, A. Olszyna, Preparation and mechani-
cal properties of alumina composites reinforced with nickel-coated graphene, Cer. Int. 42 (2016)
8597–8603.

491
Effect of the initial stress on the densification behavior of
nanostructured tetragonal zirconia by sinter-forging below 1000 °C
Michiyuki Yoshida1*, Mitsuki Hada1, Yutaka Shinoda2, Seizo Obata3, Osamu Sakurada1,
Takashi Akatsu4, Fumihiro Wakai2
1
Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan;
*
e-mail: [email protected]
2
Laboratory for Materials and Structures, Tokyo Institute of Technology, Yokohama, Japan
3
Gifu Prefectural Ceramics Research Institute, Tajimi, Japan
4
Faculty of Art and Regional Design, Saga University, Saga, Japan
Keywords: zirconia, gelcasting, sinter-forging, nanoceramics

Since the discovery of transformation toughening, partially stabilized tetragonal ZrO2 has
become one of the major high-performance ceramic materials, while comparatively little at-
tention has been payed to its optical properties. For noncubic ceramics, the optical anisotropy
causes diffuse scattering due to birefringence at grain boundaries. Thus, the transparency of

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tetragonal ZrO2 polycrystal (TZP) basically increases as reducing the grain size at extremely
low porosities.
Recently, our group successfully fabricated the densely packed green body by gelcasting
of zirconia nano-slurry with the solids loading of 7.0 vol%.1 The initial compact prepared by
the gelcasting in our study had the densely packed structure with a narrow pore-size distri-
bution and high connectivity in the particle network. It was found that the coarsening of the
pores, which is thought to be the important obstacle of the densification in nanoceramics, was
not remarkable in the sintering of the densely packed compact. The suppression of the pore
coarsening resulted in the lowering the sintering temperature. Almost fully dense sample
with 99.5% of theoretical density was successfully obtained by the pressureless sintering at
1100 °C for 2 h. The sample sintered at 1100 °C maintained the nanometric structure with the
grain size of 79 nm. The accordingly sintered sample with nanoceramic structure exhibited
the optical translucency, not to say transparency.
It is well known that the application of an external pressure enhances densification kinetic,
and results in the reduction of the sintering temperature. The optical transparency is supposed
to be improved by lowering the sintering temperature. In this study, the sinter-forging char-
acteristic of densely packed compacts of ultrafine TZP particles was investigated below the
temperature of 1000 °C.

Reference
1. M. Yoshida, S. Takeno and O. Sakurada, “Fabrication of translucent tetragonal zirconia by gelcast-
ing of thin zirconia nano-slurry”, J. Ceram. Soc. Japan, 124, pp. 500–505, 2016.

352
Thermal decomposition of gallium nitride crystal growth on different
conditions
Milena Zalewska*, Marcin Osuchowski, Magdalena Gizowska, Krzysztof Perkowski,
Izabela Kobus, Gustaw Konopka, Irena Witosławska
Nanotechnology Department, Institute of Ceramics and Building Materials, 9 Postępu Str., 02-676
Warsaw, Poland; *e-mail: [email protected]
Keywords: thermal decomposition, gallium nitride, hot isostatic pressing

Gallium nitride is characterized by unique properties, which determine its use in many elec-
tronic devices. The most important features are as follow: high chemical resistance, piezo-
and pyroelectric properties, energy gap about 3.45 eV, high thermal conductivity. Properties
listed above give clear evidence that gallium nitride is a perfect material for advanced elec-
tronic applications.
The aim of the work was to determine the decomposition temperature of synthesised gal-
lium nitride single crystals. The single crystals were growing from GaN nanopowder and a
powder mixture: GaN and GaOOH in presence of metallic gallium in conditions of elevated
pressure and temperature in hot isostic pressing.

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The obtained results showed influence of hold time of gallium nitride single crystal at
maximum temperature in the conditions of high nitrogen pressure on temperatures of their
decomposition. Therefore decomosition temperature of gallium nitride depends on the size
of their single crystal formed in hot isostatic press.

References
1. D. Ehrentraut, E. Meissner, M. Bockowski, Technology of Gallium Nitride Crystal Growth, Spring-
er Verlag. Dordrecht, 2010.
2. H. Morkoc. Handbook of Nitride Semiconductors and Devices: GaN-based Optical and Electronic
Devices, Vol. 3, Wiley-VCH, Weinheim, 2008.
3. K.-W. Liua, S.-J. Youngb, S.-J. Changa, T.-H. Hsueha, H. Hungc, S.-X. Chenc, Y.-Z. Chen, Growth
of gallium nitride on silicon by molecular beam epitaxy incorporating a chromium nitride inter-
layer, Journal of Alloys and Compounds, 511, pp. 1–4, 2012.
4. H. Maa, D. Hea, L. Leib, S. Wanga, Y. Chena, H. Wanga, GaN crystals prepared through solid-state
metathesis reaction from NaGaO2 and BN under high pressure and high temperature, Journal of
Alloys and Compounds, 509, pp. 124–127, 2011.
5. R.F. Xiang, Y.-Y. Fang, J.N. Dai, L. Zhang, C.Y. Su, Z.H. Wu, C.H. Yu, H. Xiong, C.Q. Chen, Y.
Hao, High quality GaN epilayers grown on Si (1 1 1) with thin nonlinearly composition-graded
AlxGa1−xN interlayers via metal-organic chemical vapor deposition, Journal of Alloys and Com-
pounds, 509, pp. 2227–2231, 2011.

092
Flash sintering of difficult-to-densify ceramics from soft die and hard
green body
Ji Zou1*, Salvatore Grasso2, Mike Reece2, Jon Binner1
School of Metallurgy and Materials, University of Birmingham, B15 2TT, Birmingham, UK;
1

*
e-mail: [email protected]
School of Engineering and Materials Science, Queen Mary, University of London, London E1 4NS, UK
2

Keywords: flash sintering, UHTCs, colloidal processing, microstructure

Ceramics could be sintered in a spark plasma sintering (SPS) furnace in a flash way, the
highlight of this process is densification could be completed in less than 1 min; therefore,
a huge energy was saved by this approach compared to the one taken at normal SPS condi-
tions. However, due to the designs on the heating system of SPS, the ceramic bodies for flash
SPS (FSPS) have to be partially sintered in a separate run in order to achieve an enough high
compressive strength, which can afford the initial loading (~5–6 kN) and thermal shock later
applied during FSPS. In this presentation, two novel approaches to avoid the pre-sintering
stage of ceramic bodies for FSPS will be demonstrated. Texture free HfB2 based ceramics
with relative density over 95% were achieved in 40 s by optimizing the power and loading
during FSPS. A combination of microscopy analyses including SEM, TEM and EBSD were
used to explore the microstructure features in the as-flashed body, its mechanical property in
terms of hardness and strength will also be reported.

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957
Multiscale mechanical testing and characterization
of SiC/SiC composites for accident tolerant nuclear fuel
David E.J. Armstrong*, Eugene Zayachuk, Steve G. Roberts
Department of Material Science, Universty of Oxford, United Kingdom;
*
e-mail: [email protected]
Keywords: silicon carbide, composites

Silicon carbide ceramics are a candidate material for the use in nuclear power generation
and are suggested to be used in novel accident tolerant fuel (ATF) cladding designs due to
its favorable properties, in particular reduced (compared to Zircaloy) oxidation under acci-
dent conditions, good neutronic performance, high temperature strength and stability under
irradiation. Due to its inherent brittleness, it is suggested to be used in the form of SiC-fiber
reinforced SiC-matrix composite. In order to reliably model behavior of highly non-uniform
and anisotropic composite materials the knowledge of the individual properties of fiber and
matrix, and, crucially, the fiber-matrix interfaces, is required. In addition, nuclear fuel clad-
ding materials are exposed to elevated temperatures during their operation, and therefore the
understanding of the temperature dependences of the relevant properties is essential. Micro-
mechanical testing techniques, such as nanoindentation and microcantilever beam fracture,
allow determination of such localized properties, and can be implemented in the wide range
of temperatures.
In this contribution we present the results of the nanoindentation hardness measurements
and microcantilever fracture tests performed on SiC-SiC fiber composite grown by chemical
vapor infiltration (CVI) method (General Atomic, US), with tests performed both at room and
at different elevated temperatures (up to 600 ºC) in vacuum. In the measurements performed
at room temperature it was found that there is a significant difference in the values of hard-
ness between the matrix and the fiber materials, with fiber being significantly softer and radi-
ally non-uniform in hardness (~17 GPa in the center, ~40 GPa at the periphery, comparable to
the matrix). Matrix hardness is seen to drop from ~45GPa at room temperature to ~35GPa at
500 °C. This can be correlated with the results of elemental mapping using energy-dispersive
X-ray spectroscopy (EDX), which indicate that within the fiber material the grain boundaries
are decorated with excess carbon, abundant in the center and almost absent on the periphery
of the fibers.
Using focused ion beam (FIB) milling, microcantilevers were manufactured at the inter-
phases, within individual fibers and in the bulk matrix. The local microstructure has been
investigated using transmission electron microscopy (TEM), using FIB-machined lift-out

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samples, so that the local preferred direction of the grain growth could have been directly
observed and cantilevers in the matrix could have been oriented differently with regard to it.
It was found that interphases are weak spots (fracture stress ~2.5 GPa), matrix is the strongest
(~20 GPa) and fiber intermediate (~7.5 GPa). TEM was also used on fractured cantilevers
in order to determine the character of crack propagation. It was found that within the matrix
fracture is transgranular, and observed fracture stress is independent on the orientation of the
cantilever axis relative to the direction of the elongated grains in the matrix, within the fiber
it can be both trans- and intergranular, depending on the amount of excess carbon decorating
the grain boundaries, and at the interfaces it follows the interlayer-fiber boundary.
Presented results suggest a methodology enabling to better understand and predict the
properties of SiC fiber composite, in advanced fission and fusion designs, as well as in non-
nuclear applications.

512
Toughened, wear resistant and damage tolerant silicon carbide ceramics
by adding graphene-based fillers
Manuel Belmonte*, Javier Llorente, Pilar Miranzo, M. Isabel Osendi
Institute of Ceramics and Glass (ICV-CSIC), Campus Cantoblanco, 28049 Madrid, Spain;
*
e-mail: [email protected]
Keywords: toughness, strength, wear, damage, graphene, ceramic composites

Silicon carbide (SiC) ceramics are one of the most demanded engineering ceramics due to the
combination of their outstanding tribological and thermal properties jointly with a good me-
chanical response at high temperature. However, the Achilles' heel of these materials is still
their relatively low toughness and limited machinability. To overcome these difficulties, we
have manufactured SiC composites containing graphene-based fillers, in particular, graphene
nanoplatelets (GNPs) or graphene oxide sheets (GOs), which were further reduced to gra-
phene (rGOs) during the spark plasma sintering process. The macro- and micro-mechanical
response of SiC/graphene composites as a function of the filler source and content has been
analysed, the mechanical performance being closely linked to the wear properties.
Fracture toughness (KIC) and strength (σf) measurements evidenced that composites con-
taining just 5 vol.% of rGOs exhibited an outstanding mechanical performance,1 increasing
both KIC and σf by ~162% and ~60%, respectively, when compared to monolithic SiC. In the
case of GNPs composites, filler contents up to 10 vol.% are required to promote a larger oc-
currence of crack shielding mechanisms, with KIC increments of 86%. Furthermore, the con-
tact damage resistance of SiC was clearly enhanced when adding graphene fillers, as Hertzian
contact damage tests using the bonding-interface technique demonstrated. Graphene fillers,
especially rGOs, promoted the formation of a quasi-plastic damage zone beneath the contact,
redistributing the stress field and limiting the subsurface Hertzian cone cracks growth. That
improved damage resistance enhanced the machinability of the composites. Finally, the wear

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resistance of SiC materials under dry sliding conditions significantly enhanced with the addi-
tion of graphene fillers,2 with maximum improvements of ~70% for 20 vol.% GNPs compos-
ites, mainly due to the formation of a wear protecting graphene-based tribofilm.

References
1. M. Belmonte, A. Nistal, P. Boutbien, B. Román-Manso, M.I. Osendi, P. Miranzo, “Toughened and
strengthened silicon carbide ceramics by adding graphene-based fillers”, Scripta Mater., 113, pp.
127–130, 2016.
2. J. Llorente, B. Román-Manso, P. Miranzo, M. Belmonte, “Tribological performance under dry slid-
ing conditions of graphene/silicon carbide composites”, J. Eur. Ceram. Soc., 36, pp. 429-435, 2016.

379
Progress in manufacturing ultra-high temperature ceramic matrix
composites (UHTCMCs)
Jon Binner, Virtudes Rubio, Andrea D’Angio, Matt Porter, William Hillman
School of Metallurgy and Materials, University of Birmingham, UK; e-mail: [email protected]
Keyword: UHTCMC

There is an increasing demand for advanced materials, for aerospace and other applications,
with temperature capability ranging from 1500 oC to well over 2000 °C and able to survive
highly corrosive environments whilst subject to intense heat fluxes and mechanical stresses.
The interaction of environmental conditions together with the requirement that dimensional
stability is maintained makes the selection of suitable materials extremely challenging. This
paper discusses the design, development, manufacture and testing of a new class of ceramic
matrix composites based on C fibre and SiC preforms enriched with ultra-high temperature
ceramic (UHTC) powders and with a matrix infiltrated by either RF- or microwave-heated
chemical vapour infiltration (CVI). These composites will form of suite of materials suitable
for application in severe aerospace environments.

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731
Mechanical behavior of zirconia-based composites with transformation-
induced plasticity
Jérôme Chevalier1, Helen Reveron1, Alethea Liens1, Marta Fornabaio2, Paola Palmero2,
Laura Montanaro2, Tobias Füderer3, Erik Adolfsson4, Vanni Lughi5, Alois Bonifacio5,
Valter Sergo5, Nicolas Courtois6
1
Université de Lyon-INSA de Lyon, MATEIS CNRS UMR 5510, 20 Avenue Albert Einstein, F-69621
Villeurbanne Cedex, France
2
Department of Applied Science and Technology, INSTM R.U. PoliTO, LINCE Lab., Politecnico di
Torino, Corso Duca degli Abruzzi, 24, 10129 Torino, Italy
3
DOCERAM, MOESCHTER GROUP Holding GmbH & Co. KG, Hesslingsweg 65–67, 44309
Dortmund, Germany
4
Ceramic Materials, Swerea IVF AB, 431 53 Mölndal, Sweden
5
Department of Engineering and Architecture, University of Trieste, Via Valerio 6a-34127–Trieste
(TS), Italy
6
ANTHOGYR, 2237 Avenue André Lasquin, 74700 Sallanches, France
Keywords: zirconia, tetragonal to monoclinic transformation, toughness, Weibull analysis

Yttria-stabilized (Y-TZP) zirconia ceramics are increasingly used for developing metal-free
restorations and are now considered as promising alternatives to titanium as dental implants.
Zirconia indeed possesses high strength and good toughness for a ceramic, together with
excellent bio-integration and biocompatibility. However, Y-TZP ceramics are still consid-
ered as brittle ceramics, since transformation induced toughening occurs after cracks start
to propagate. Also, in some circumstances, Y-TZP may be prone to aging. Our current re-
search is focusing on strategies to improve the LTD resistance of Y-TZP but also to develop
alternative composites with better stability in vivo and higher degree of ductility. In this
work the mechanical characterization of a new type of very-stable zirconia-based composites
is presented. These materials are composed of ceria-stabilized zirconia (84 vol%Ce-TZP)
containing two second-phases (alumina and strontium hexa-aluminate) and exhibit excep-
tional strength, toughness and ductility. In other words, in these composites, quite extensive
transformation-induced plastic deformation occurs before failure, which leads to mechanical
behavior laws similar to metallic alloys.

Acknowledgements
The research leading up to these results was undertaken in the framework of the LONGLIFE (FP7/2007-
2013, grant n. 280741) and SISCERA (H2020-FTIPilot-2016, grant n. 737954) European projects.

References
1. H. Reveron et al. Towards long lasting zirconia-based composites for dental implants: Transforma-
tion induced plasticity and its consequence on ceramic reliability (2017) Acta Biomaterialia, 48,
pp. 423–432.
2. Towards long lasting zirconia-based composites for dental implants: Part I: Innovative synthesis,
microstructural characterization and in vitro stability (2015) Biomaterials, 50 (1), pp. 38–46.

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034
Nano-mechanical testing of advanced ceramics
Ján Dusza
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, Košice,
Slovak Republic; e-mail: [email protected]

The deformation and damage characteristics of differently oriented WC grains/crystals in

WC – Co, Si3N4 grains/crystals in reaction bonded Si3N4 system and ZrB2 grains/crystals
in ZrB2 polycrystal were investigated. Depth-sensing nano-indentation and scratch tests of
grains and micro-compression tests of micropillars prepared by focused ion beam from ori-
ented facets of grains were studied. Electron backscatter diffraction (EBSD), atomic force
microscopy (AFM) and scanning electron microscopy (SEM) investigations were performed
to determine the grain orientation and to study the surface morphology and the resulting de-
formation and damage mechanisms around the indents and in micropillars.
The hardness and scratch resistance of the differently orientated grains showed significant
angle dependence from the basal towards the prismatic directions. A strong influence of the
grains orientation on compressive yield stress and rupture stress values was found during the
micropillar test, too. The active slip systems for individual ceramics have been recognized.
The different properties of the basal and prismatic planes was found to be connected with the
different deformation mechanisms – slip and dislocation activities.

Fig. 1. Hardness anisotropy in WC grains and micropillar deformation of ZrB2 micropillar

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084
Ultra-high temperature mechanical behavior of ZrB2-based laminates
William G. Fahrenholtz*, G.E. Hilmas
Missouri University of Science and Technology, Rolla, Missouri, USA; *e-mail: [email protected]

A combined experimental and computational approach has been used to study the elevated
temperature fracture behavior of ZrB2-based ceramics. Experimentally, laminate structures
consisting of alternating layers of ZrB2 and graphite/ZrB2 were produced. After densifica-
tion, the strength of the laminates was tested at temperatures up to 2000 °C. The inelastic
work of fracture was estimated from load deflection curves, which showed that the lami-
nates consumed significantly more energy during fracture than conventional ZrB2 ceram-
ics. Analysis revealed extensive crack deflection due to the laminate structure. In parallel,
multi-phase-field (MPF) models based on the regularized formulation of energy functionals
in Griffith theory were developed to study crack initiation, propagation, and branching in two
dimensions. Models were built by first simulating fracture behavior in single crystal ZrB2 for
comparison to predictions from classic fracture mechanics. Then, propagation of intergranu-
lar and transgranular cracks was simulated by considering the effects of grain boundary en-
ergy anisotropy and crack surface energy in polycrystalline ZrB2 and ZrB2-based laminates.
Simulations were able to reproduce crack deflection/branching behavior in laminates using
realistic properties for the constituent phases. The presentation will discuss new insight into
fracture behavior at elevated temperatures from the combined experimental and computa-
tional approach.

050
New sintering process for high density and limited grain growth with
plastic deformation as dominating mechanism
Zhengyi Fu
Wuhan University of Technology, Wuhan, 430070, China; e-mail: [email protected]
Keywords: sintering, sintering process, plastic deformation, densification mechanism

Traditionally, sintering is the densification process of powder compacts, in which interpar-

ticle pores are eliminated by atomic diffusion driven by thermal energy. The atomic diffusion
may cause also grain growth, besides contributes to densification. For polycrystalline materi-
als, higher density generally results in improvement of properties like strength and tough-
ness, while the undesirable grain growth results in degradation. Attempts have been made to
gain full density, while keep the grains with limited growth.
A new method was proposed to sinter ceramic powders at a lower temperature close to the
onset point of grain growth, at the same time apply a higher pressure to the compact. Fully
dense micro-sized or nano-sized ceramics with limited grain growth were made by the new

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route. The sample shows excellent mechanical properties. The plastic deformation under
high pressure and at high temperature is proved to be the dominating mechanism for the
densification process.

704
Chemical vapor deposition of SiC environmental coating for SiC/SiC
composite
Takashi Goto*, Hirokazu Katsui, Daiki Hori
Institute for Materials Research, Tohoku University, 2-1-1 Katahira Aoba-ku Sendai Miyagi, Japan;
*
e-mail: [email protected]
Keywords: laser chemical vapor deposition, SiC/SiC composite, SiC coating

SiC fiber-reinforced SiC matrix composite (SiC/SiC composite) is an excellent structural

ceramic material because of its high strength, high ductility and light weight. Although MI
(Metal Infiltration) and PIP (Polymer Impregnation Pyrolysis) have been studied to fabricate
SiC/SiC composite, CVD (Chemical Vapor Deposition) could be the most promising because
high corrosion resistant SiC can be prepared. CVD SiC coating has been usually prepared by
using halide precursors such as MTS (Methyltrichlorosilane) and SiCl4 (halide CVD). The
deposition rate of halide CVD is low and by-product HCl would degrade SiC fibers. In the
present study, laser enhanced CVD (LCVD) was applied by using non-corrosive metalor-
ganic precursors, hexamethyldisilane, polycarbosilane and SiH((NCH3)2)3 precursors. CO2,
Nd:YAG and semiconductor (InGaAs) lasers (~250 W) were employed. The laser beam was
expanded to around 20 mm in diameter enabling a wide-scale deposition with scanning laser.
LCVD can prepare highly crystallized β-SiC film at deposition rate of several 100 times
higher and at deposition temperature several 100 K lower than conventional MOCVD. β-SiC
film was prepared at 2200 μm/h at 1500 K by using CO2 laser. α-SiC (2H) film was prepared
at 70–195 μm/h using SiH((NCH3)2)3 precursor at ~1000 K. Plasma can also enhance the
deposition of films in CVD. By combining microwave (2.45 GHz, 0–1.5 kW) and magnetic
field (0.0875 T), much active electron-cyclotron-resonance (ECR) plasma can be formed.
The ECR plasma is highly stable even at a higher pressure, and ionizes gases more than ra-
dio-frequency and micro-wave plasma. We have applied both laser and ECR plasma in CVD
(laser-plasma CVD). The deposition temperature was further decreased in the laser-plasma
CVD. Highly crystallized β-SiC film was prepared by laser-plasma CVD at a significantly
low temperature 1123 K, 150–400 K lower than that of halide CVD, at a deposition rate of
138 μm/h, 10 to 100 times higher than that of MOCVD. Laser CVD was also used to prepare
Yb2Si2O7 and SiAlON bonding layer between SiC fiber and SiC matrix in SiC/SiC composite.

References
1. A. Ito, H. Kanno, T. Goto, J. Euro. Ceram. Soc., 35, pp. 4611–4615, 2015.
2. R. Tu et al., J. Euro. Ceram. Soc., 37, pp. 1217–1223, 2017.
3. H. Cheng et al., J. Euro. Ceram. Soc., 37, pp. 509–515, 2017.

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128
Van der Waals interactions in refractive index matched nanoparticle
dispersions
Thomas Graule1,2*, Katja A. Fröhlich1,3, Eleni Mitrentsis1,2, Frank Clemens1,
Véronique Michaud3
Empa, Swiss Laboratories for Materials Science and Technology, Laboratory for High Performance
1

Ceramics, Überlandstrasse 129, CH-8600 Dübendorf, Switzerland; *e-mail: [email protected]

Technische Universität Bergakademie Freiberg, Institute of Ceramic, Glass and Construction
2

Materials, Agricolastraße 17, Freiberg, Germany

École Polytechnique Fédérale de Lausanne, Laboratory of Polymer and Composite Technology
3

(LTC); EPFL-IMX – LTC, CH-1015 Lausanne, Switzerland

Van der Waals forces have a strong influence on the dispersion quality of ceramic slurries and
finally affect the resulting properties of ceramic parts, filled polymers, hybrid materials and
nanocomposites in general. Reducing the van der Waals forces and therefore, matching the
refractive index between the filler and the matrix should improve dispersion in hybrid materi-
als, as already experimentally shown by Wozniak et al.1 As an alternative, steric stabilization
offers a tool to improve the stability and to modify the rheological behaviour.2,3
However, the dispersion quality of refractive index matched dispersion cannot be assessed
by SLS or DLS based particle size measurement techniques. We present here the rheology
based results of a study applying model dispersions containing silica nanoparticles and as
a solvent mixture a matched 1-butanol and benzyl alcohol system. The refractive index of
the solvent was changed by varying the mixing ratio, and the effect of index difference on
the filler-matrix interaction being investigated. In agreement with the theory, a stronger gel
network was observed when the refractive index of filler and solvent were matched. If the
difference in refractive index of the two materials became too large, particles and solvent in-
teraction was reduced, and agglomerates were formed. This resulted in a weaker gel network.

References
1. M. Wozniak, Y. de Hazan, T. Graule, D. Kata, Rhoelogy of UV curable colloidal silica dispersions
for rapid prototyping applications, J. Eur. Cer. Soc. 2011, 31, 2221–2229.
2. V. Klimkevicius, R. Makuska, T. Graule, Effect of Structure of Cationic Comb Copolymers on their
Adsorption and Stabilization of Titania Nanoparticles, Langmuir 2015, 31, 2074–2083.
3. V. Klimkevicius, R. Makuska, T. Graule, Rheology of Titania Based Ceramic Nanodispersions
Stabilized by Cationic Comb Copolymers; Applied Rheology 26 (2016) 15199–15207.
4. J. Fröhlich, E. Mitrentsis, B. Hoffmann, V. Michaud, T. Graule, Assessment of the Dispersion Qual-
ity of refractive index-matched nanodispersions, J. Applied Rheology, accepted October 2016.

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417
Diamond reinforced ceramic materials:
potential wear resistant components
M. Herrmann, B. Matthey, S. Kunze
Fraunhofer IKTS, Fraunhofer Institute for Ceramic Technologies and Systems, Dresden Germany

Materials with enhanced wear resistance are of great interest for modern industry. In many
cases, advanced ceramics show high wear resistance at room and high temperatures. Never-
theless, there is a demand of a further improvement of the wear and tribological behavior of
these materials. The reinforcement of ceramic materials with super hard particles like cubic
BN (cBN) or diamond is one possibility to overcome the rising requirements. At normal sin-
tering conditions of ceramic materials, diamond and cubic boron nitride are metastable modi-
fications and transform into the soft hexagonal modifications. Therefore, special approaches
have to be applied to obtain dense materials with high hardness, wear resistance and thermal
properties. The possibilities and constraints of diamond-ceramic composites are reviewed.
The most promising way for the production of diamond/SiC components was found to be the
reaction bonding of diamond by silicon infiltration. During this process a three dimensional
skeleton of SiC is formed. Due to the epitaxial growth of the SiC on diamond, a strong inter-
face between diamond and SiC is formed resulting in super-hard wear resistant components
with high thermal conductivity and low thermal expansion coefficients. Such materials can
be produced as bulk materials or as SiSiC ceramic components with a silicon carbide bonded
diamond layer. The layer thickness can be between several 100 µm up to several millimetres.
This allows a cost effective production of large wear parts with complex shapes.
Correlations between preparation, microstructure and wear resistance, mechanical and
thermal properties are given. The results show the great potential of these materials for a
wide range of applications.

209
Temperature dependence of thermal properties for high thermal
conductive silicon nitride ceramics
K. Hirao*, H. Miyazaki, S. Fukuda, Y. Zhou, H. Hyuga
Structural Materials Research Institute, National Institute of Advanced Industrial Science and
Technology (AIST), Moriyama-ku, Nagoya 463-8560, Japan; *e-mail: [email protected]
Keywords: silicon nitride, thermal conductivity, thermal expansion coefficient, metalized substrate

Silicon nitride has attracted much attention as advanced insulating substrates for power mod-
ule because of its excellent mechanical properties with intrinsic high thermal conductivity.
So far extensive research works have been carried out for increasing thermal conductivity
without degrading the mechanical properties. Our group has succeeded in fabricating high

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thermal conductive silicon nitrides by nitrideing Si powder compacts with sintering addi-
tives, followed by post sintering process1. When applying the developed silicon nitride as
metalized substrates in power modules, it is very essential to understand temperature depen-
dence of thermal properties such as thermal conductivity, and coefficient of thermal expan-
sion, CTE for designing structures of power modules. Because it is well known that these
thermal properties exhibit strong temperature dependence around room temperature. In this
investigation thermal properties of silicon nitrides possessing different thermal conductivi-
ties was examined in the temperature range between –50 to 400 ºC. It was revealed that varia-
tion of thermal conductivity with temperature was significant in higher thermal conductive
Si3N4. In addition the material with the highest thermal conductivity (180 W/(m·K) at RT)
kept about 100 W/(m·K) even at 250 ºC. On the contrary, there was little difference between
CTEs of Si3N4 with different thermal conductivities.
In general ceramic substrates are used in the form of metalized substrates in order to
ensure heat conduction from device to heat sink as well as to keep mechanical reliability.
Cu metalized silicon nitride substrates start to be used in high-power modules. Large differ-
ence of CTE between Cu and Si3N4 might affect thermal expansion behaviour of Cu /Si3N4
substrates. The thermal expansion of metalized substrates was examined in the temperature
range between –40 to 250 ºC. It was revealed that the thermal expansion and contraction
curves exhibited hysteresis due to plastic deformation of Cu. In addition transition points
corresponding to elastic to plastic deformation of Cu were observed. CTE of the substrate in
the elastic region substantially matched the estimated value based on the Turner model2 using
measured CTE values.

References
1. Y. Zhou et al., Adv. Mater. 23, 4563–4567(2011).
2. P.S. Turner, Journal of Research of the National Bureau of Standards, 37, 239–250 (1946).

837
SiAlON based ceramics for cutting tool applications
Ferhat Kara1*, Servet Turan1, Alpagut Kara1, Ufuk Akkasoglu2, Ali Celik3, Hasan Mandal4
1
Department of Materials Science and Engineering, Anadolu University, 26555 Eskisehir, Turkey;
*
e-mail: [email protected]
2
MDA Advanced Ceramics Ltd., Teknoloji Gelistirme Bolgesi, Organize Sanayi, 26140 Eskisehir,
Turkey
3
Department of Metallurgy and Materials Science Engineering, Bilecik Seyh Edebali University,
11230 Bilecik, Turkey
4
Faculty of Engineering and Natural Sciences, Sabanci University, 34956 Tuzla, Istanbul, Turkey
Keywords: α/β-SiAlON, intergranular phase chemistry, machining, cast iron, superalloy

SiAlONs are ceramic materials with a range of technically important applications, from cut-
ting tools to wear parts and the properties of SiAlONs can be tailored for specific applica-
tions. Although there many ongoing studies on new materials development for cutting tool

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applications, α/β -SiAlONs have been widely used for machining of cast irons and superal-
loys. Wear performance of the cutting tools are governed by material properties which are
affected by microstructure. Microstructure of α/β -SiAlONs can be controlled by types and
amount of liquid phase sintering additives, which affect the distribution and crystallinity of
intergranular phase, remnant of the additives after sintering. In this presentation, the effect of
various types of sintering additives on the intergranular phase chemistry and microstructures
will be reported for α/β -SiAlONs that are developed to be used in cast iron turning and in
high speed superalloy milling. It will be shown that additive types play an important role
in intergranular phase crystallinity and its wetting behaviour of grain boundaries and hence
the cutting performance in cast iron machining. However, for high speed superalloy mill-
ing, chemical interactions between the superalloy and SiAlON cutting tool material is more
important.

077
High thermal conductivity of liquid-phase sintered silicon carbide
ceramics
Young-Wook Kim*, Yu-Kwang Seo
Department of Materials Science and Engineering, University of Seoul, 163 Seoulsiripdae-ro,
Dongadaemun-gu, Seoul 02504, Korea; *e-mail: [email protected]
Keywords: SiC, thermal conductivity

In this paper, factors affecting the thermal conductivity of LPS-SiC will be presented. The
results suggest that (1) the oxygen impurity in SiC lattice was detrimental in increasing the
thermal conductivity of LPS-SiC; (2) the Al-containing additive compositions should be
avoided for improving the thermal conductivity of LPS-SiC; (3) the N-doping has little ef-
fect on thermal conductivity of LPS-SiC; (4) the occurrence of β→α phase transformation
was detrimental in increasing the thermal conductivity of LPS-SiC; and (5) the selection of
additive compositions which could pick-up oxygen from SiC lattice was important in im-
proving the thermal conductivity of LPS-SiC ceramics. Based on the above understanding, a
fully dense SiC ceramic with a room temperature thermal conductivity of 262 W(m·K)–1 was
obtained via spark plasma sintering β-SiC powder containing Y2O3-Sc2O3. The high thermal
conductivity of the SiC ceramic could be attributed to (1) oxygen content reductions in the
SiC lattice from 6700 ppm to 1770 ppm during SPS processing, (2) the presence of clean
SiC-SiC boundaries, which increased contiguity between SiC grains, and (3) the lack of Y
solubility within the SiC lattice due to large ionic size differences of the elements.

References
1. Y.-W. Kim, K.Y. Lim, W.S. Seo, “Microstructure and Thermal Conductivity of Silicon Carbide with
Yttria and Scandia,” J. Am. Ceram. Soc., 97, pp. 923–928, 2014.
2. T.Y. Cho, Y.-W. Kim, K.J. Kim, “Thermal, Electrical, and Mechanical Properties of Pressureless
Sintered Silicon Carbide Ceramics with Yttria-Scandia-Aluminum Nitride,” J. Eur. Ceram. Soc.,
36, pp. 2659–2665, 2016.

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3. S.H. Jang, Y.-W. Kim, K.J. Kim, S.J. Lee, K.Y. Lim, “Effects of Y2O3–RE2O3 (RE = Sm, Gd, Lu)
Additives on Electrical and Thermal Properties of Silicon Carbide Ceramics,” J. Am. Ceram. Soc.,
99, pp. 265–272, 2016.
4. Y.K. Seo, Y.-W. Kim, T. Nishimura, W.S. Seo, “High Thermal Conductivity of Spark Plasma Sin-
tered Silicon Carbide Ceramics with Yttria and Scandia” J. Am. Ceram. Soc., in press.

309
Engineering design and processing of silicon nitride ceramics for
industrial applications
Hua-Tay Lin
School of Electromechanical Engineering, Guangdong University of Technology,
N0.100 Waihuan Xi Road, Guangzhou 510006, China; e-mail: [email protected]
Keywords: silicon nitride ceramics, ceramic substrate, power electronics

Silicon nitride (Si3N4) ceramics, so-called self-reinforced ceramic materials, exhibit a very
unique microstructure containing whisker-like elongated grains plus fine matrix grains. The
class of Si3N4 ceramics in general shows very good mechanical properties combined with
good resistance to wear, corrosion, and oxidation. Therefore, many government funded ce-
ramic turbine related programs were initialed globally in 1990 to design and implement them
as high temperature structural components such as hot section vane, blade, and turbo rotor
for gas turbine and microturbine engine. These integrated global research efforts conducted
by academia, research institution, industrial sectors, and government during the last four
decades allow the ceramic community to gain a much better understanding on how to control
such a microstructure and the interfaces and continuous intergranular films as they relate
to mechanisms for enhanced toughness in a self-reinforced ceramic. In addition, it is also
now known that the oxide additives could influence the alpha-beta Si3N4 phase transforma-
tion, microstructural evolution, microstructural and chemical bonding of interfacial thin film
during the processing and sintering procedures. Recently, great attentions on Si3N4 ceramic
have been on its application as an insulator substrate for power electronic components; i.e.,
IGBT and LED due to its excellent performance in mechanical properties and reliability to
overcome the increased thermal stress generated during application condition. This presen-
tation will focus on engineering design and processing of chemical compositions and also
microstructure of Si3N4 ceramics to achieve a combined physical and mechanical property
targeted for a specific component application. The implications and challenges to achieve the
aimed properties and performances learned through the course of these studies would also be
presented and discussed in the paper.

Acknowledgement
Research supported by Guangdong Innovative and Entrepreneurial Research Team Program (NO.
2013G061).

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570
Dual scale composite architectures for high temperature structural
applications
F. Monteverde, C. Melandri, S. Failla
ISTEC-CNR, 48018, Faenza, Italy

Dual composite (DC) architectures have been shown to increase wear resistance while main-
taining or increasing fracture toughness in WC-Co composites for room-temperature applica-
tions by the use of multiple, discretely segregated engineered microstructures.
Composites of zirconium diboride (ZrB2) and molybdenum disilicide (MoSi2) are candi-
dates for similar dual composite architectures for high-temperature structural use in corrosive
environments, due to the high-temperature ductility and oxidation resistance of MoSi2.
Multiple DC architectures were prepared by hot-pressing dispersing pre-sintered granules
of known volumetric amount, size and composition in a continuous matrix made of different
loose powder mixtures. Granules were produced by the freeze-spray granulation. Conven-
tional composites of the only compositions representative of granules and matrices were hot
pressed for comparison.
Microstructures were investigated and correlated to mechanical properties including elas-
tic modulus, thermal expansion, flexure strength and fracture toughness at room temperature
up to 1500 °C in air, and compared to corresponding traditional particulate sub-composites.
Shared themes of T03: novel processing, microstructure-property relationships, ceramics
for extreme conditions, oxide and non-oxide structural ceramics, testing and characterisation
of advanced ceramics.

280
A short review on the mechanical properties of pure fully-dense boron
carbide fine ceramics
Bibi Malmal Moshtaghioun, Diego Gómez-García, Arturo Domínguez Rodríguez
Department of Condensed Matter Physics, University of Seville, P.O. 1065, 41080 Seville, Spain
Institute of Material Science, ICMSE CSIC-US, Av. Americo Vespucio 49, 41092 Seville, Spain

Boron carbide is the third hardest material in Nature after diamond and the cubic phase of
boron nitride. This fact, together with its light weight, high corrosion resistance and chemical
stability makes this material a promising candidate for structural application under extreme
environments. Unfortunately, applicability has been restricted by the severe difficulty for
sintering pure dense specimens at moderate temperatures. This drawback has been partially
overcome recently: fine-grained, (average grain size as low as 150 nm) pure near-fully dense
specimens can be prepared by spark plasma sintering under optimized conditions.

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This presentation will outline the room temperature fracture and wear properties as a func-
tion of the grain size as well as the high-temperature creep plasticity. The main features mak-
ing this material a unique material will be emphasized as well as the parts requiring further
investigation.

440
Ceramic-based composites with complex architectures
Eduardo Saiz
Imperial College, London, UK; e-mail: [email protected]

The advance of many technological fields, from healthcare to aeronautics, demands new ma-
terials with unconventional combinations of mechanical and functional properties. Among
these, ceramics are of great interest due to their corrosion and wear resistance, enhanced
chemical and thermal stability, high flexural strength and hardness that make them suitable for
demanding applications. However, the performance of ceramics is often limited by their low
fracture resistance. Significant advances have been achieved in the development of tougher
ceramics-based composites and one of the themes that recurrently appears is the need to
control the materials architecture at multiple length scales from the nano-level and up. In this
respect natural materials such as bone or nacre provide blueprints for the use highly complex,
hierarchical microstructures to enhance fracture resistance. Mineralized natural materials are
composites where the inorganic phase is cleverly interlayered with an organic component
that acts as compliant phase. These composites exhibit characteristic structural features on
multiple length scales from molecular to macroscopic dimension resulting in strong, damage
tolerant materials. In this presentation we will review some advances on the use of top down
methods such as freeze casting or robotic assisted deposition for the fabrication of damage-
tolerant composites whose design takes hints from Nature. These composites combine tech-
nical ceramics with a “soft” phase (metals, polymer or carbon) in complex architectures.
The parameters that determine the material structure and its influence on the mechanical and
functional response will be reviewed. The objective is to discuss the difficulties associated
with the design and fabrication of synthetic structures that mimic the structural and mechani-
cal characteristics of natural counterparts and to point out possible directions of research.

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819
Electrically conductive ceramics – processing and properties
Pavol Šajgalík
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 84536 Bratislava,
Slovakia, e-mail: [email protected]
Keywords: alumina, silicon nitride, silicon carbide, electrical conductivity

Si3N4 and Al2O3 ceramics are insulating materials, SiC is a semiconductor. All of this type of
ceramics are widely used for the engineering applications because of their excellent mechani-
cal and chemical properties. Hardness is one of those which belong to the most important.
This brings also a problem with final machining of these materials. Introduction of the elec-
trically conductive elements without substantial decreasing of the other properties of ceram-
ics is a way how to apply the electrical discharging machining also for this class of materials.
Present paper deals with the processing of three types of ceramics with increased electrical
conductivity. NbTiC electrically conductive phase was used for SiC ceramics, carbon nano-
fibres were used for Si3N4 ceramics and carbon nanotubes were used for Al2O3 ceramics. In
all types the increased electrical conductivity was observed, 2700 S/m for SiC ceramics,
1300 S/m for Si3N4 ceramics and 1800 S/m for Al2O3 ceramics. The way of conductive phase
introduction and its influence on the mechanical properties will be discussed. For the process-
ing was used hot-pressing as well as rapid hot-pressing.

301
Texturing and mechanical properties of MAX phase ceramics and
Zr(Hf)B2-base ultra-high temperature ceramics
Yoshio Sakka1*, Tohru S. Suzuki1, Toshiyuki Nishimura1, Guo-Jun Zhang2
1
National Institute for Materials Science, Tsukuba, Ibaraki, Japan;
*
e-mail: [email protected]
2
Donghua University, 2999 North Renmin Road 201620, Shanghai, China
Keywords: MAX phase, high temperature ceramics, textured ceramics

The controlled development of texture is one of the ways for effectively improving properties
of ceramics. We have demonstrated a new processing of textured ceramics with a feeble mag-
netic susceptibility by colloidal processing in a high magnetic field and subsequent heating1.
The principle of the process is that a crystal with an anisotropic magnetic susceptibility will
rotate to an angle minimizing the system energy when placed in a magnetic field. This pro-
cessing can be applied to fabricate many kinds of textured ceramics with non-cubic structure.
Here, processing of textured MAX phase ceramics and Zr(Hf)B2-base ultra-high temperature
ceramics is demonstrated.

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MAX phases are the layered ternary ceramics with the general formula Mn+1AXn (where
M is an early transition metal, A is an A group element in the periodic table, X is a C or N, and
n = 1, 2, 3). They show unique combination of metallic and ceramic properties, which were
derived from their layered hexagonal structure and the anisotropy of the bonding strength.
There are strong M-X bonds and weak M-A bonds in the nano-laminate. As examples of
MAX phase ceramics improved mechanical properties of textured Nb3AlC2, Ti2AlN and
Ti3SiC2 ceramics are demonstrated2. Textured Nb4AlC3 with plate-like grains shows a high
flexural strength (about 1200 MPa) and the fracture toughness (about 18 MPa•m1/2).
Also some anisotropic properties of textured Zr(Hf)B2-base ultra-high temperature ceram-
ics are demonstrated3.

Acknowledgement
Financial supports partially from the Kakenhi (B) of JSPS and the bilateral project of NSFC-JSPS are
gratefully acknowledged.

References
1. Y. Sakka and T.S. Suzuki, J. Ceram. Soc. Jpn., 113 (2005) 26–36.
2. C.F. Hu, Y. Sakka, et al., J. Am. Ceram. Soc., 94, 410–415 (2011); J. Am. Ceram. Soc., 94, 742–748
(2011); Scripta. Mater., 64, 765–768 (2011); Sci. Technol. Adv. Mater., 12, 044603 (2011); H.B.
Zhang, et al., J. European Ceram. Soc. 35[1] (2015) 393–397.
3. D. W. Ni, G. J. Zhang, et al. Scripta Mater., 60[8] 615–618 (2009); 60[10] 913–916 (2009); W. W.
Wu et al., Inter. J. Appl. Ceram. Tech., 11 (2014) 218–227; Sci. Tech. Adv. Mat. 15 (2014) 014202.

286
Local mechanical properties of advanced structural ceramics measured
using microcantilever beam specimens
Junichi Tatami1*, Saho Fujita1, Yumi Imoto1, Tsukaho Yahagi2, Takuma Takahashi2,
Motoyuki Iijima1
1
Graduate School of Environment and Information Sciences, Yokohama National University,
Yokohama, Japan; *e-mail: [email protected]
2
Kanagawa Academy of Science and Technology, Kawasaki, Japan
Keywords: Microcantilever beam specimen, strength, toughness, Si3N4, SiC, ion-exchange glass

Local mechanical properties are important to understand the nature of the mechanical prop-
erties of bulk ceramics and glass. In this study, the local mechanical properties of several
kinds of ceramics and glass were measured using microcantilever beam specimens prepared
by focused ion beam technique. The size of the sample was about 2.5 × 2 × 15 μm and their
section profile was pentagonal. A sharp single notch was also machined along a target to
measure the fracture toughness. After bending test, the bending strength was calculated by
the fracture load and the second moment of area, and the fracture toughness was estimated by
displacement extrapolation method based on finite element analysis. Although Si3N4 ceram-
ics are often utilized as structural components in the Al casting industry and they occasion-

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ally suffer breakage after long-term use, degradation mechanism has not been clarified, yet.
The degradation behaviour of Si3N4 ceramic surfaces soaked in molten Al in short periods
of time was evaluated using microcantilever beam specimens. The bending strength of the
ceramic surface before and after contact with molten Al was 5.89 ± 1.33and 3.03 ± 0.28 GPa,
respectively. The fracture toughness of the corroded layer in Si3N4 ceramics also decreased
compared to that of the polished surface. Using fractography by observation with scanning
electron microscopy, it was shown that changes in the grain boundary glassy phase resulted
in the degradation of strength and fracture toughness. From this mechanism, the Lu2O3 ad-
ditive was proposed to make highly durable Si3N4 ceramics. In the ion-exchange glass, an
improvement in the strength resulted from compressive stress by replacement of Na+ with
K+. Such ion-exchange should cause structure change, which means that the ion-exchange
possibly results in change in the mechanical properties in the compressive layer. The bending
strength of compressive layer in ion-exchanged glass measured using microcantilever speci-
mens is about 40% higher than that of as-polished glass. There is no significant variation with
the fracture toughness before and after ion-exchange. Young’s modulus of ion-exchanged
glass was higher than that as-polished glass. Consequently, it was shown that the strengthen-
ing of the ion-exchanged glass resulted from the improvement of Young’s modulus. Further-
more, the strength of a neck region of porous SiC ceramics measured using microcantilever
beam specimens was 18.8 GPa. It was found that the strength of bulk porous SiC ceramics
was quantitatively explained by maximum pore size, neck radius and neck strength.

150
Micro-mechanical test method for searching toughening mechanisms
operating at nano-scale
Fumihiro Wakai*, Kimiko Yoshida, Masato Sone, Norimasa Nishiyama
Laboratory for Materials and Structures, Institute of Innovative Research,
Tokyo Institute of Technology, R3-23-4259 Nagatsuta, Midori, Yokohama 226-8503, Japan;
*
e-mail: [email protected]
Keywords: fracture toughness, R-curve, stishovite, silica, transformation toughening

The development of strong, tough, and damage-tolerant ceramics requires nano/microstruc-

ture design to utilize toughening mechanisms operating at different length scales. The tough-
ening mechanisms so far known are effective in micro-scale. Here, we developed a micro-
mechanical test method using micro-cantilever beam specimens to determine the very early
part of resistance-curve. This testing method is a powerful tool to search for toughening
mechanisms that may operate at nanoscale for attaining both reliability and strength of struc-
tural materials. A case study is presented here.
Silica (silicon dioxide, SiO2) is a common mineral found in many rocks and sands. How-
ever, quartz and glass are brittle and easily broken. Recently, Nishiyama1 found that the
brittle glass is transformed to nanocrystalline SiO2 stishovite, which is tough (13 MPa m1/2)
and very hard (33 GPa), by high-pressure synthesis. Stishovite is a high-pressure polymorph

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of silica stable at pressures above 9 GPa. The finding of “fracture-induced amorphization”

in stishovite lead to a proposal of a new type of transformation toughening by the direct
transition from crystal to amorphous state2, which is different from the classical martensitic
transformation of zirconia. We investigated strength and toughness of nanocrystalline stisho-
vite by using micro-cantilever beam specimens. The crack growth resistance curve (R-curve)
rose steeply with crack extension of only a few µm3, and reached to a plateau value of 10.9
MPa m1/2. The sharply rising R-curve is the result of very narrow transformation zone width
of nanocrystalline stishovite. We discussed the effects of grain size,and microstrain on the
critical stress, the transformation zone width, and thereby, the fracture toughness4.

References
1. Nishiyama et al., “Synthesis of nanocrystalline bulk SiO2 stishovite with very high toughness”, Scr.
Mater., 67, pp. 955–958, 2012.
2. N. Nishiyama et al., “Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential
platform for toughening in ceramics”, Sci. Rep., 4, 6558, 2014.
3. K. Yoshida et. al., “Large increase in fracture resistance of stishovite with crack extension less than
one micrometer”, Sci. Rep., 5, 10993, 2015.
4. K. Yoshida, N. Nishiyama, M. Sone, F. Wakai, “Strength and toughness of nanocrystalline SiO2
stishovite toughened by fracture-induced amorphization”, Acta Mater., 124, pp. 316–324, 2017.

117
Thermal insulation ceramics initiative:
from crystal structure modification to morphology design
Jingyang Wang
High-performance Ceramics Division, Shenyang National Laboratory for Materials Science, Institute
of Metal Research, Chinese Academy of Sciences, Shenyang, China; e-mail: [email protected]
Keywords: thermal insulation materials, E/TBC, porous materials

High efficiency engine and propulsion system strictly challenge extensive thermal insulator
candidates by pushing them to their critical property limits in extreme conditions. A critical
demand has been addressed to the simultaneous optimizations on high temperature ther-
mal/chemical stability and extremely low thermal conductivity. How do we discover new
thermal insulation materials through adoption of novel concept or mechanism in order to
achieve giant thermal resistance? This presentation includes our recently progresses on crys-
tal chemistry modification of rare-earth silicates as E/TBC candidates1–3 and morphology
design of highly porous silicates4,5 and nano-carbides6,7 as super thermal insulation materi-
als. Our works showed the strategic engineering of phonon behaviours and nano-scale heat
conduction may initiate and fasten breakthroughs of advanced thermal insulation ceramics
in extreme environments.

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References
1. Y.X. Luo, J.M. Wang, Y. R. Li, and J.Y. Wang, “Giant Phonon Anharmonicity and Anomalous
Pressure Dependence of Lattice Thermal Conductivity in Y2Si2O7 silicate”, Scientific Reports 6,
29801, 2016.
2. Z.L. Tian, L.Y. Zheng, J.M. Wang, P. Wan, J.L. Li, and J.Y. Wang, “Theoretical and experimental
determination of the major thermo-mechanical properties of RE2SiO5(RE = Tb, Dy, Ho, Er, Tm,
Yb, Lu, and Y) for environmental and thermal barrier coating applications”, J. Eur. Ceram. Soc.,
36, pp. 189–202, 2016.
3. Z.L. Tian, L.Y. Zheng, Z.J. Li, J.L. Li, and J.Y. Wang, “Exploration of the low thermal conductivi-
ties of γ-Y2Si2O7, β-Y2Si2O7, β-Yb2Si2O7, and β-Lu2Si2O7 as novel environmental barrier coating
candidates”, J. Eur. Ceram. Soc., 36, pp. 2813–2823, 2016.
4. Z. Wu, L.C. Sun, and J.Y. Wang, “Synthesis and characterization of porous Y2SiO5 with low linear
shrinkage, high porosity and high strength”, Ceramics Inter., 42, pp. 4894–14902, 2016.
5. Z. Wu, L.C. Sun, P. Wan, J.N. Li, Z.J. Hu, and J.Y. Wang*, “In situ foam-gelcasting fabrication and
properties of highly porous γ-Y2Si2O7 ceramic with multiple pore structures”, Scripta Mater., 103,
pp. 6–9, 2015.
6. P. Wan, L.Y. Gao, and J.Y. Wang, “Approaching ultra-low thermal conductivity in β-SiC nanoparti-
cle packed beds through multiple heat blocking mechanisms”, Scripta Mater., 128, pp. 1–-5, 2017.
7. P. Wan, Z. Wu, H. Zhang, L.Y. Gao, and J.Y. Wang, “Porous nano-SiC as thermal insulator: wisdom
on balancing high strength and low thermal conductivity”, Mater. Res. Lett., 4, pp. 104-111, 2016.

154
Making ceramics tolerant to damage by forming nanolaminated
structures: from MAX phases to MAB phases
Yanchun Zhou
Science and Technology on Advanced Functional Composite Laboratory, Aerospace Research
Institute of Materials & Processing Technology, No.1 South Dahongmen Road, Beijing 100076,
China; e-mail: [email protected]
Keywords: non-oxide ceramics, nanolaminated structures, MAX phases, MAB phases,
structure-property relationships

Non-oxide ceramics are potential materials for extreme environment applications such as
scramjet engine components, leading edges and thermal protection systems for hypersonic
vehicles, and cladding materials in generation IV nuclear reactors. However, the defect sen-
sitivity and poor thermal shock resistance are the main obstacles to impede their near-term
applications. The origin of brittleness is the nature of strong covalent bonding, which makes
the activation of slip systems extremely difficult. Formation of nanolaminated structures like
MAX phases (Mn+1AXn, where M is an earlier transition metal, A is a group-A element, X is
carbon or nitrogen, n = 1–6), has been proven an effective approach to overcome the brittle-
ness of transition metal carbides and nitrides. Inspired by the success in development of
MAX phases, nanolaminated ternary borides called MAB phases (where M is a transition
metal, A is a group-IIIA or IVA element, B is boron) were recently proposed. In this presenta-
tion, the structure and properties of MAX phases will be introduced first. These materials are
characterized by a transition metal carbide or nitride layer (Mn+1Xn) interleaved by a close

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packed A-group element layer, which exhibit a unique combination of the merits of both
metals and ceramics. The chemical bondings in these materials are anisotropic with strong
covalent M-X bond and weak M-A bond. The origin of damage tolerance is the presence of
weak τ-type bond between A atom and the adjacent M-X bond chain, which results in low
shear deformation resistance. Similar to MAX phases, MAB phases also exhibit anisotropic
electrical and mechanical properties, low shear deformation resistance and are tolerant to
damage. The high stiffness is originated from the strong covalent B-B or M-B bonds, while
the low shear deformation resistance and easy slip are due to the presence of metallic M-B or
A-A bonds. Slip systems of the new MAB phases will be given and their correlations to the
electronic structure and chemical bonding will be discussed.

References
1. J.Y. Wang, Y.C. Zhou, Recent progress in theoretical prediction, preparation and characterization of
layered ternary transition metal carbides, Ann. Rev. Mater. Res., 39, 10.1–10.29, 2009.
2. M. Ade, H. Hillebrecht, Ternary borides Cr2AlB2, Cr3AlB4 and Cr4AlB6: the first members of the
series (CrB2)CrAl with n = 1, 2, 3 and a unifying concept for ternary borides as MAB-phases, Inorg.
Chem., 54, pp. 6122–6135, 2015.

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Oral presentations

043
Processing and oxidation behavior of ZrB2-SiC-AlN composites
Mufit Akinc
Department of Materials Science and Engineering, Iowa State University, Ames, Iowa, USA;
e-mail: [email protected]

The effects of AlN substitution on sintering, oxidation and thermal properties of ZrB2-SiC
were investigated. Up to 10 vol% AlN was substituted into ZrB2-SiC by replacing ZrB2 or
SiC. Samples were all sintered to nearly full density (93.5%~99.4% depending on composi-
tions) by pressureless sintering. AlN substitutions limited the grain growth of ZrB2. Oxida-
tion resistance of the composites were tested at several temperatures up to 2000 °C using both
static and cyclic oxidation tests. AlN substitutions affected the oxidation behavior by forma-
tion of Al2O3 and/or aluminosilicates. X-ray photoelectron spectroscopy (XPS) showed the
presence of Al2O3 and SiO2 on the surface. Presence of Al2O3 could possibly lead to a modifi-
cation in the viscosity of the glassy oxide scale as well as decrease the viscosity of SiO2 scale
at a higher temperature (1600 °C). Replacement of ZrB2 by AlN resulted in a more protective
scale both at 1000 °C and 1600 °C. Substitution of SiC by AlN resulted in a compromise of
the oxidation behavior at 1600 °C due to devitrification of the scale. Several samples were
also cycled between 2000 °C with plasma heating in a 100 torr air pressure (21% oxygen).
Volatility diagrams were constructed to assess the thermal stability of the oxides formed.
A delicate balance in ZrB2, SiC and AlN is required for optimal performance.

018
Environmental barrier coatings (EBC) for silicon-based ceramic
composites
N. Al Nasiri
Centre for Advanced Structural Ceramics, Department of Materials, Imperial College London,
Royal School of Mines, Prince consort Road, London SW7 2BP, United Kingdom;
e-mail: [email protected]

The need to increase the cycle efficiency and reduce noise and NOx emissions from jet engine
turbine has promoted the development of ceramic matrix composites (CMC) such as silicon
carbide fibre-reinforced silicon carbide (SiC-SiC). Use of CMCs will lead to a significant
improvement in fuel consumption and thrust-to-weight ratio compared to metal alloys. In ad-
dition, the low density of CMCs allows weight savings of up to 30% compared to Ni-based
super alloys equating to about 1000 kg/engine thus leading to vastly improved fuel consump-
tion. However, silicon (Si)-based ceramics such as SiC-SiC have poor environmental dura-

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bility in high velocity combustion environments. Si-based ceramics have excellent oxidation
resistance due to formation of a protective silica layer on reacting with dry air making them
stable at temperatures up to 1200 °C for long-term application. On the other hand, the same
silica layer will react with water vapour to form gaseous silicon hydroxide, leading to high
recession and component failure. To avoid this behaviour, a prophylactic environmental bar-
rier coating (EBC) is required. A variety of EBCs have been developed in the past, which
consists of a minimum of 4 layers requiring a costly application method such as plasma
spraying. In this work, five rare earth monosilicates are being examined as potential EBCs:
Y2SiO5, Yb2SiO5, Lu2SiO5, Gd2SiO5 and Er2SiO5. Their performance in steam environments
is being studied at 1200–1350 °C for different times as a first step to determine which EBC
candidate is most promising for protecting SiC-SiC CMCs in the jet engine environment. The
main aim of this study is to develop a reliable single layer of EBC instead of multilayers and
to develop a low cost method of applying the EBC.

065
Influence of composition on optical properties of Y-α-SiAlONs
Suna Avcioglu1, Semra Kurama2*
Ondokuz Mayıs University, Faculty of Engineering, Department of Materials Science and
1

Engineering, Kurupelit Campus, 55139 Atakum / Samsun, Turkey

Anadolu University, Faculty of Engineering, Department of Materials Science and Engineering,
2

Iki Eylul Campus, 26555, Eskisehir, Turkey; *e-mail: [email protected]

Keywords: SiAlON, phase composition, SPS, microstructure, optical properties

Traditional transparent materials are not suitable for many applications such as; transparent
armors, night vision vehicles, high-speed infrared guided missiles on transparent materials
field focused on development of new materials those have superior mechanical and thermal
properties as well as good optic and IR transmission. SiAlON ceramics generally designed
for use in structural applications under extremely harsh conditions because of their high
strength, good thermal shock resistance and chemical stability. In recent years, serious atten-
tion was taken to improve SiAlON ceramics optical properties.
In this study, translucent Y-α-SiAlON ceramics with different compositions were pro-
duced by using spark plasma sintering (SPS) technique. The IR transmittance, microstructure
and phase assemblages of the sintered samples characterized by using FTIR, SEM and XRD
techniques, respectively. According to the results, the m and n values in the α-SiAlON gen-
eral formula influenced the densification behavior, grain morphology (size, size distribution
and shape), phase assemblages of α-SiAlON and also the composition and distribution of
intergranular glassy phase, therefore, affecting the optical and IR transmission.

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042
High-porosity foamed geopolymers by the frothing/peroxide route for
water purification and thermal insulation
Chengying Bai1, Giorgia Franchin1, Hamada Elsayed1,2, Alessandro Zaggia1, Lino Conte1,
Hongqiang Li3, Paolo Colombo1,4
1
Department of Industrial Engineering, University of Padova, via Marzolo, 9, Padova, Italy
2
Ceramics Department, National Research Centre, El-Bohous Str., 12622 Cairo, Egypt
3
College of Civil Engineering, Hunan University, 410082 Changsha, China
4
Department of Materials Science and Engineering, The Pennsylvania State University,
University Park, PA 16802, USA
Keywords: geopolymer foams, water purification, thermal insulation, porosity

High-porosity metakaolin-based geopolymer foams were fabricated by a gelcasting tech-

nique using hydrogen peroxide (foaming agent) in combination with Tween 80 (surfactant).
Slurries processed in optimized conditions enabled to fabricate potassium based geopolymer
foams with a total porosity in the range of ~67 to ~86 vol% (~62 to ~84 vol% open), thermal
conductivity from ~0.289 to ~ 0.091 W/mK, and possessing a compressive strength from
~0.3 to ~9.4 MPa. Moreover, parameters influencing the compressive strength, the porosity,
the thermal conductivity, and the cell size distribution were investigated. The results showed
that the cell size and size distribution can be controlled by adding different content of sur-
factant and foaming agent. The foamed geopoymer can also be used as adsorbents for the
removal of copper and ammonium ions from wastewater. The foams, due to their low thermal
conductivity, could also be used for thermal insulation.
It was also possible to produce geopolymer formulations that could be printed using addi-
tive manufacturing technology (Direct Ink writing), which enabled to produce components
with non-stochastic porosity.

746
Anisotropic mechanical, thermal and electrical properties of SPSed
aluminum nitride-graphene platelets composites
Sinem Baskut, Alper Cınar, Servet Turan
Department of Materials Science and Engineering, Anadolu University, 26480, Eskisehir, Turkey;
e-mail: [email protected]
Keywords: graphene platelets, AlN, fracture toughness, thermal properties, electrical conductivity

Graphene as an allotrope of carbon consisting of a single layer of sp2 bonded carbon atoms
has high thermal conductivity, superior charge carrier mobility, large specific surface area
and outstanding mechanical properties such as high Young’s modulus (1 TPa) and fracture
strength. This unique set of properties makes graphene promising candidate as a second phase

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for ceramic matrix composite to increase application areas by improving their mechanical,
thermal and electrical properties. Additionally, the uniaxial load applied during production
in the SPS resulted in the preferential orientation of graphene in the microstructure of com-
posites.1,2
Therefore, the motivation of this study was to investigate the effects of graphene platelets
(GPLs) addition in different amounts on mechanical, thermal, electrical properties and mi-
crostructures of SPSed aluminium nitride (AlN) matrix composites as a function of anisot-
ropy. For these purposes, 1, 2, 4 and 8 wt % GPLs added to the AlN and sintered in the SPS
furnace at 1825 °C for 15 minutes. All the mechanical, thermal and electrical measurements
were made in parallel and perpendicular directions to the SPS pressing axis.
The microstructure investigations indicated that the basal planes of the GPLs oriented
perpendicular to the SPS axis in the composite, leads to anisotropic microstructures. The
fracture toughness increased by ~30% in parallel direction and by ~33% in perpendicular
direction with the addition of 1 wt % GPLs into the AlN. The mean toughening mechanisms
are crack deflection and crack bridging in parallel and perpendicular directions, respectively.
The addition of 1 wt % GPLs into AlN resulted the ~37% decrease in both parallel and per-
pendicular directions thermal conductivities. As the GPLs addition increased from 1 to 8 wt
%, the thermal conductivity tended to decrease in the parallel direction whereas it increased
in the perpendicular direction. The perpendicular direction conductivity higher by 2.4% than
parallel direction conductivity in the 1 wt % GPLs added AlN and this value increased up to
90.2% when the added GPLs amount was increased to 8 wt % at room temperature, thereby
indicating the anisotropic effects increased as the added GPLs increased in the composites.
The electrical conductivity values of all composites in perpendicular direction were higher
than in parallel direction. Furthermore, the composites became an electrically conductive
with the addition of 1 wt % GPLs in both directions.

References
1. A.K. Geim and K.S. Novoselov, “The rise of graphene”, Nat. Mater., 6, 183–191, 2007.
2. E. Bodis, O. Tapaszto, K. Zoltan, P. Fazekas, S. Klebert, A.M. Keszler, et al., “Spark plasma sinter-
ing of Si3N4/multilayer graphene composites”, Open Chem., 13, 484–489, 2015.

802
SiC based materials for next generation nuclear power plants
Rajendra Bordia1, Shelly Arreguin, Quan Li
1
Materials Science and Engineering, Clemson University, Clemson, SC 29634 USA

Next generation nuclear reactors are expected to operate with increased efficiency, safety,
proliferation resistance and accident damage tolerance. The feasibility of Generation IV nu-
clear reactor designs is highly dependent upon the development of advanced materials that
can withstand the designed operating conditions. Silicon carbide possesses many of the ideal
material properties necessary and is therefore being explored for various applications in these

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reactors. In this presentation, the challenge and opportunities of using SiC based materials in
nuclear power plants will be presented.
Following the broad overview, the feasibility of using the polymer derived ceramics
(PDC) processing route for nuclear SiC will be discussed. Results will be presented to show
the versatility of the PDC route, to tailor the composition, nanostructure and the resultant
polytypes of SiC to enhance radiation stability. It is also an attractive approach to make a
variety of needed shapes and forms including porous materials, and matrices for composites.
Finally, results will be presented on the use of the PDC approach to make coatings and joints
for SiC based materials. Results on the use of continuum mechanics to process reliable and
crack free coatings and joints and their mechanical properties will be presented.

182
Sintering resistance of advanced plasma-sprayed thermal barrier
coatings with vertical cracks and columnar structures
Lu Bowen1,2, Robert Mücke1, Robert Vaßen1, Xueling Fan2, T.J. Wang2
Materials Synthesis and Processing (IEK-1), Institute of Energy and Climate Research,
1

Forschungszentrum Jülich GmbH, 52425 Jülich, Germany

State Key Laboratory for Strength and Vibration of Mechanical Structures, School of Aerospace
2

Engineering, Xi’an Jiaotong University, Xi’an 710049, China

Thermal barrier coatings (TBCs) are required for enhanced performance of advanced indus-
trial and aero gas-turbines, as one of the key technologies of thermal protection. Air-plasma
spraying (APS) is widely employed to prepare coatings due to its cost-efficiency. Excellent
thermal insulation, and also a certain amount of strain tolerance in thermal cyclic loading,
can be provided by the lamellar microstructure of APS coatings. In order to further improve
the thermal shock resistance, dense vertical cracks have been implemented in conventional
APS coatings. Based on APS technology, suspension plasma spraying (SPS) has been devel-
oped recently. By using suspension feedstock, advanced coatings, with vertical cracks and
columnar structures, can be fabricated. These microstructural features significantly improve
the strain tolerance. However, during high temperature service, TBCs go through a degrada-
tion process called sintering, in which Young’s modulus and viscosity increase irreversibly.
Sintering induced mechanical degradation is one of the main causes of premature failure.
In this study, the effects of strain tolerant microstructures (e.g. vertically cracked and
columnar structured) on the sintering resistance of APS and SPS TBCs are investigated ex-
perimentally and numerically. In-situ bending tests are conducted on free-standing coatings
in the thermomechanical analysis device, which integrates conventional three-point bend-
ing test in a furnace. Evolution of Young’s modulus and viscosity are measured by periodic
loading, during annealing treatment at 1200 ˚C. Based on experimental observation, finite
element models are constructed for both APS and SPS coatings. The effect of sintering on
the mechanical properties is depicted by a constitutive relation, which is developed following
the variational principle. The mechanisms of hardening, induced by sintering, are elucidated

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by comparisons between experimental and numerical results. Additionally, this study lays
foundation to the optimized design of structurally graded TBCs, for further improvement of
sintering resistance.

482
Chemical interaction of CMAS with yttrium silicate environmental
barrier coatings materials in combustion environments
R. Cabezas-Rodríguez1,2, J. Ramírez-Rico1,2, J. Martínez-Fernández1,2, M.T. Johnson3,
K.T. Faber3
1
Dpto. Física de la Materia Condensada, Universidad de Sevilla, Avda. Reina Mercedes SN, 41012
Sevilla, Spain
2
Instituto de Ciencia de Materiales de Sevilla, CSIC-Univ. Sevilla, Avda. Américo Vespucio 49,
41092 Sevilla, Spain
3
California Institute of Technology, Pasadena, CA 91125, USA

Rare earth silicates, such as yttrium silicates, are potential materials for improved oxidation
and erosion protection due to their high melting point, low volatilization rate, low thermal
expansion coefficient, and low oxygen permeation constant. Thus, yttrium silicates have po-
tential applications as a high-temperature ceramic and environmental/thermal barrier coat-
ings for structural Si-based ceramic materials such as SiC or Si3N4.
However, these rare earth silicates tend to induce chemical reactions between different
underlying layers in an EBC multilayer system and they are susceptible to attack by vitre-
ous melts, such as molten deposits. These molten deposits are based on calcium-magnesium
alumino-silicates (CMAS) that, originating from siliceous debris ingested with the intake
air, react with the Y2SiO5 topcoat and cause degradation and cracking. Therefore represents
a fundamental threat to progress in gas turbine technology by limiting lifetime of yttrium
silicate as environmental barrier coatings.
The objective of this work is to study the chemical interaction of yttrium silicate environ-
mental barrier coating, Y2SiO5, synthesized by different methods with CMAS at combustion
environment conditions.
The phase transformation and the microstructural evolution due to this exposure were
studied by X-ray diffraction (XRD), quantitative phase analysis reference intensity ratio
(RIR), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy
(EDS), respectively.

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747
Heat treatment effect on the microstructural changes in the vicinity of
fibre matrix interfaces of SiOC based composites
Zdeněk Chlup1*, Martin Černý2, Jana Schweigstillová2, Adam Strachota3,
Martina Halasová1, Ivo Kuběna1
1
Institute of Physics of Materials, v.v.i., ASCR, Brno, Czech Republic; *e-mail: [email protected]
2
Institute of Macromolecular Chemistry, v.v.i., ASCR, Prague, Czech Republic
3
Institute of Rock Structure and Mechanics, v.v.i., ASCR, Prague, Czech Republic
Keywords: CMSs, SiOC, pyrolysis, interface, microstructure, TEM

The interface properties between matrix and reinforcement in the composites play important
role and influence resulting mechanical properties significantly. The quality of the interface
predetermines overall behaviour of the composite. Composite behaviour is given by the ef-
ficiency of the load transfer from matrix to the reinforcement. Weak interfaces lead to the
reliable tough composite material but with low strength. Contrary, strong interfaces result
in high strength accompanied by low fracture resistance.1 Composite materials applicable
at high temperatures usually use ceramic fibres as reinforcement. Therefore microstructural
changes at the interface and its vicinity is crucial aspect for the long term application at high
temperatures.2
The aim of this work is to describe in detail microstructural changes with various thermal
treatment of SiOC based unidirectionally reinforced composite materials prepared via py-
rolysis of polysiloxane preforms reinforced by ceramic fibres. The standard mechanical test
were used to determine basic mechanical properties of the composites as elastic modulus,
strength and fracture toughness.3–5 These properties were further correlated with the micro-
structural changes found in the vicinity of interfaces. The transmission electron microscopy
was employed to determine microstructural changes of the interfaces of selectively prepared
TEM lamellae. The lamellae were prepared from neighbouring fibres selected on the pol-
ished cross-section of the composite using a focused ion beam build in SEM. Both the EDS
analyses and the selected area diffraction analyses in TEM were employed to obtain both the
chemical and the crystallographic information, respectively. It was found that with increasing
temperature of heat treatment the microstructure of matrix was changed only slightly con-
trary the fibre microstructure which significantly developed and formation of new crystalline
phases was observed.

References
1. I.M. Low, Ceramic Matrix Composites: Microstructure, Properties and Applications, Woodhead
Pub. and Maney Pub. 2006.
2. K.K. Chawla, Jom 47(12) (1995) 19–21.
3. M. Cerny, P. Glogar, Z. Sucharda, Z. Chlup, J. Kotek, Composites Part a-Applied Science and
Manufacturing 40(10) (2009) 1650–1659.
4. M. Halasova, M. Cerny, A. Strachota, Z. Chlup, I. Dlouhy, Journal of Composite Materials 50(11)
(2016) 1547–1554.
5. Z. Chlup, M. Cerny, A. Strachota, Z. Sucharda, M. Halasova, I. Dlouhy, Journal of the European
Ceramic Society 34(14) (2014) 3389–3398.

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589
Elastic constants of carbon fibres derived from nanoindentation of
a 2D-C/SiC composite system
Tamás Csanádi1*, Dušan Németh1, Chengyu Zhang2, Ján Dusza1,3
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 04353 Košice,
1

Slovak Republic; *e-mail: [email protected]

Science and Technology on Thermostructural Composite Materials Laboratory, Northwestern
2

Polytechnical University, Xi’an, China

Donát Bánki Faculty of Mechanical and Safety Engineering, Óbuda University, Népszínház utca 8,
3

1081 Budapest, Hungary

Keywords: elastic constants, carbon fibre, nanoindentation, micromechanical model

Elastic constants of single carbon fibres were estimated by a novel nanoindentation based
method and subsequently predicted by a modified micromechanical model. The method was
proposed for carbon fibres but can be applied generally to any transversely isotropic material.
This case study was carried out on a T-300 PAN-based carbon fibre reinforced SiC compos-
ite material (2D-C/SiC) at room temperature. Transversal and longitudinal cross-sections of
individual fibres were indented by a sharp Berkovich tip up to the maximum depth of 150
nm. Assuming transverse isotropy of the fibres, their five elastic constants were deduced
from the measured indentation moduli using numerical and analytical models (Vlassak and
Nix1, Delafargue and Ulm2) and finite element method simulation. The elastic constants were
estimated to c11 = 30.9, c12 = 9.7, c13 = 12.2, c33 = 237.3 and c44 = 10.9 GPa. The complete
set of measured elastic constants were analyzed and then predicted by a modified two- and
three-phase Eshelby-Mori-Tanaka (EMT) micromechanical model. The analysis revealed
that an anisotropic ‘amorphous’ matrix should be assumed to achieve an appropriate fit with
experimental results.

References
1. J.J. Vlassak, W.D. Nix, “Measuring the elastic properties of anisotropic materials by means of in-
dentation experiments”, J. Mech. Phys. Solids., 42, pp. 1223–1245, 1994.
2. A. Delafargue, F-J. Ulm, “Explicit approximations of the indentation modulus of elastically ortho-
tropic solids for conical indenters”, Int. J. Solid. Struct. 41, pp. 7351–7360, 2004.

722
On the fracture toughness testing of ceramics
R. Danzer, T. Lube
Institut für Struktur- und Funktionskeramik, Montanuniversität Leoben, Leoben, Austria

Ceramics are very brittle materials. Fracture toughness, which characterizes the resistance
against crack propagation, is therefore extremely significant for them. But – compared to the
situation of metals – fracture toughness testing is not routinely measured in ceramics charac-
terization and fracture toughness is rarely used for design.
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This is mainly caused by two reasons. First, specimens with geometries like those used for
metals fracture toughness testing are much too large, complicated and expensive to be ma-
chined from ceramics. Second, fracture toughness testing requires a well-defined and sharp
pre-crack in the specimen. In metallic materials such cracks can be obtained by fatigue pre-
cracking. This is not practicable in ceramics, because they are not highly susceptible to cyclic
fatigue. Some alternative methods for the generation of the pre-crack have been developed
in the past. They lead to controversial discussions about the validity of fracture toughness
testing results.
The state of the art of fracture toughness measurement techniques for ceramics will be
critically discussed. Furthermore, examples for new methods, that are especially applicable
to small specimens (a need in material’s development), will be presented.

183
Influence of HIP post-treatment on microstructure and density of
silicon carbide sintered by SPS
Florimond Delobel1,2*, Sébastien Lemonnier1, Elodie Barraud1, Julien Cambedouzou2,3
1
ISL, 68301 Saint-Louis Cedex, France; *e-mail: [email protected]
2
ENSCM, 34000 Montpellier, France
3
ICSM, UMR 5257 CEA/CNRS/ENSCM/Université de Montpellier, 30207 Bagnols sur Cèze Cedex,
France
Keywords: silicon carbide, Spark Plasma Sintering, Hot Isostatic Pressing

To prevent damages caused by impact of a small-calibre projectile on a structure or human,

dual hardness armour is generally used. It is composed by a ceramic layer in front pressed
on a bottom face, called “backing”, in metal or composite material. The aim of this ceramics
is to break up the projectile and to distribute loading on the backing. The backing is used to
support ceramic layer and to take over fragments.
Silicon carbide is the ceramic which presents the best cost/efficiency ratio for ballistic ap-
plications, especially in dual hardness armour because of its high compressive strength, high
hardness and low density. The use of this ceramic would permit to offer better mobility and
autonomy to the armoured vehicles with equivalent protection. In this view, studies are cur-
rently performed to increase ballistic performances of materials used, in other words improve
and optimize their mechanical properties and thus their microstructure.
The development of highly dense ceramics is essential for ballistic applications. Indeed,
the presence of porosity involves defects in the pellet which could initiate the brittle failure
of the latter. Sintering of silicon carbide is particularly difficult because of the high covalent
character of its chemical bonds and the important effects of interface energy in grain bound-
aries. A fine control of initial powder characteristics (particles size, morphology, purity …)
would permit to improve green body compactness and to favour densifying mechanisms.
These two aspects are favourable to obtain dense materials with fine and homogeneous mi-

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crostructure and high mechanical resistance. The choice of sintering process is essential to
control the evolution of microstructure and reach the expected properties.
The aim of this PhD work is to develop dense ceramics in silicon carbide by Spark Plasma
Sintering combined with Hot Isostatic Pressing post-treatment from a powder synthesized by
laser pyrolysis. The effects of structural characteristics and purity of powders on sintering be-
haviour will be particularly controlled, as well as mechanical properties of obtained material.

696
Bio-inspired CNT reinforced ceramic composite materials
Koen Evers1*, Nicole Grobert1, Richard Todd1, Claudio Ferraro2, Eduardo Saiz2,
Harshit Porwal3, Mike Reece3
1
Department of Materials, Oxford University, Oxford, UK; *e-mail: [email protected]
2
Centre for Advanced Structural Ceramics, Imperial College London, London, UK
3
Nanoforce, Queen Mary University of London, London, UK
Keywords: biomimetic, CNT, composite, freeze casting, alumina

Carbon nanomaterials such as carbon nanotubes (CNTs) are often considered to be the ulti-
mate reinforcement material for strong and light organic and inorganic composite materials.
However, research on CNT composites has been hindered by the fact that commercially
available CNTs are often tightly agglomerated and hence require sophisticated dispersion
techniques to detangle them before they can be employed as fillers or reinforcements. Recent
developments in the production and up scaling of nanotubes in the nanomaterials by design
group at Oxford have paved the way towards the successful exploitation of CNT properties
for the generation of multifunctional composite materials. Combining this with biomimetic
ceramic microstructure architectures which are manufactured using new developments in
freeze-casting, this promises to deliver a novel material that improves current ceramic mate-
rials significantly.

References
1. André Meyers, M. & Chen, P.-Y. Biological Materials Science: Biological Materials, Bioinspired
Materials, and Biomaterials. (Cambridge University Press, 2014).
2. Deville, S., Saiz, E. & Tomsia, A.P. Ice-templated porous alumina structures. Acta Mater. 55, 1965–
1974 (2007).

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049
Advanced oxide ceramic composites based on graphene
Yuchi Fan1, Wan Jiang1, Akira Kawasaki2
1
Institute of Functional Materials, Donghua University, Shanghai, 201620, China
2
Department of Materials Processing, Graduate School of Engineering, Tohoku University, Sendai,
980-8579, Japan

Graphene is a 2D carbonaceous material with extraordinary mechanical and electrical prop-

erties which is very suitable to be exploited as reinforcement in ceramic matrix composites
(CMC) for achieving superior performance. Different from previous intensively studied car-
bon based reinforcement such as carbon fiber and carbon nanotube, the extremely thin 2D
feature of graphene can profoundly change the properties of CMC especially in the case of
oxides. In alumina composite, a percolation threshold as low as 0.38 vol.% is achieved and
the electrical conductivity surpasses 103 Sm −1 when graphene content is only 2.35 vol.%.
More interestingly, it is found that the charge carrier type changes from p- to n-type as gra-
phene content becomes higher, as a result of synergistic doping effect between graphene
and oxide matrix. Further study reveals that the doping level can be manipulated by tun-
ing the concentration of oxygen vacancy of matrix, which is realized in yttria stabilized
zirconia composite as a proof of concept. In addition, the graphene based oxide CMC also
shows outstanding mechanical properties, as exemplified by alumina composite in which an
unprecedented increase of strain tolerance by ~40%, completely retained fracture strength
(417MPa) and enhanced fracture toughness (5.3MPam1/2) are simultaneously realized at
merely 2.18vol.% of filler loading. Therefore, it is believed that the graphene based oxide
ceramic composites are very promising material for the application requiring both advanced
functional and mechanical properties.

564
Effect of graphene content on the tribological behaviour of 3YTZP
reinforced with graphene nanoplatelets
F. Gutiérrez-Mora1,2, A. Gallardo-López1,2, A. Morales-Rodríguez1,2, R. Poyato2
Departamento de Física de la Materia Condensada, Universidad de Sevilla-ICMSE (CSIC), Apdo.
1

1065, 41080 Sevilla, Spain

Instituto de Ciencia de Materiales de Sevilla ICMSE, CSIC-Universidad de Sevilla, Avda. Américo
2

Vespucio 49, 41092 Sevilla, Spain

Keywords: 3YTZP, GNP, friction, wear, tribofilm

Zirconia-based ceramics have a wide range of structural and functional applications in in-
dustry, including cutting tools, bearing parts, solid oxide fuel cells, oxygen sensors, ceramic
membranes and medical prostheses owing to their excellent mechanical properties, good
ionic conductivity and high temperature stability. Although the inherent brittleness of these

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materials prevents their use in applications where tribological aspects are involved, the use
carbon-based reinforcements, such as CNTs or graphene, has a positive impact in fracture
behaviour. Besides, these carbon-based materials are prone to exhibit good lubricating prop-
erties due to the well-known behaviour of graphite as a solid lubricant1.
Tribological studies using graphene as reinforcement in ceramic bodies have revealed
that, in general, incorporation of graphene to the composites improves their wear resistance
and reduces their friction coefficient. Different mechanisms have been proposed to explain
this behaviour, such as formation of a graphene-rich lubricating tribolayer due to exfoliation
of embedded graphene platelets or graphene-induced fracture toughness improvement that
positively affects the wear resistance.
In this work, the tribological behaviour of yttria tetragonal zirconia reinforced with dif-
ferent GNP amounts (2.5, 5, 10 and 20 vol%) is described. Friction and wear results are
compared to monolithic 3YTZP used as a reference material. In tests performed at normal
loads above 10 N, the presence of wear debris at the tracks influenced the friction coefficient
and wear rates, being these parameters lower for higher GNPs content. Electron microscopy
studies and an extensive Raman analysis were performed to determine the nature of a transfer
layer deposited on the composites wear track during tribological tests.

Reference
1. W. Bollmann, J. Spreadborough. “Action of graphite as a lubricant”. Nature, 186, pp. 29–30, 1960.

416
Anisotropy of properties of silicon carbide – graphene composites
Ondrej Hanzel1, Richard Sedlák2, Jaroslav Sedláček1, Alexandra Kovalčíková2,
Martin Fides2, Ján Dusza2, Pavol Šajgalík1
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dubravska cesta 9, 845 36 Bratislava,
1

Slovakia
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 040 01 Košice,
2

Slovakia
Keywords: silicon carbide, graphene nanoplatelets, graphene oxide, in-situ graphene, anisotropy

Graphene as a single layer of sp2 bonded carbon atoms has excellent mechanical, thermal
and electrical properties1–6 and due to that fact is widely used as a filler in various polymer,
metal and ceramic matrix composites. This work focuses on SiC based composites with ad-
dition of 1, 3 and 5 wt. % of graphene nanoplatelets (GNP) or as synthesized graphene oxide
(GO). Rapid hot pressing (RHP) was used for sintering at 1800 °C (heating rate 100 °C/min)
and load of 50 MPa for 5 minutes in vacuum. Dense silicon carbide/graphene nanoplatelets
(GNPs) and silicon carbide/graphene oxide (GO) with yttrium oxide and aluminium oxide as
a sintering additives were prepared by this technique. Functional properties (electrical con-
ductivity and thermal diffusivity) and mechanical properties (hardness, fracture toughness
and elastic modulus) of such sintered composites were studied in parallel and perpendicular
direction to the RHP pressing axis. In reference sample SiC-Y2O3-Al2O3, without any arti-

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ficial addition of graphene, sintered by electrically assisted sintering technique – rapid hot
press formation of graphene domains were observed. Comparative sintering of reference
powders in conventional hot press was performed. For confirmation of presence graphene
domains in RHP reference sample Raman spectroscopy, SEM and TEM were used. Also
anisotropy of functional and mechanical properties of reference samples prepared by conven-
tional hot press and rapid hot press was studied and compared.

References
1. K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V. Grigorieva,
A.A. Firsov, Electric Field Effect in Atomically Thin Carbon Films, Science 306 (2004) 666–669.
2. C. Lee, X. Wei, J.W. Kysar, J. Hone, Measurement of the Elastic Properties and Intrinsic Strength
of Monolayer Graphene, Science 321 (2008) 385–388.
3. R. Prasher, Graphene Spreads the Heat, Science 328 (2010) 185–186.
4. A.A. Balandin, Thermal properties of graphene and nanostructured carbon materials, Nat. Mater.
10 (2011) 569–581.
5. S. Ghosh, I. Calizo, D. Teweldebrhan, E.P. Pokatilov, D.L. Nika, A.A. Balandin, W. Bao, F. Miao,
C.N. Lau, Extremely high thermal conductivity of graphene: Prospects for thermal management
applications in nanoelectronic circuits, Appl. Phys. Lett. 92 (2008) 151911-1-3.
6. S.V. Morozov, K.S. Novoselov, M.I. Katsnelson, F. Schedin, D.C. Elias, J.A. Jaszczak, A.K. Geim,
Giant intrinsic carrier mobilities in graphene and its bilayer, Phys. Rev. Lett. 100 (2008) 016602-
1-4.

181
Characterisation of anisotropic thermal conductivity of ceramic/metal
composites using freeze casted ceramic preform
D. Hautcoeur1, Y. Lorgouilloux2, A. Leriche2, M. Gonon3, B. Nait-Ali4, D. S. Smith4,
V. Lardot1, F. Cambier1
1
Belgian Ceramic Research Centre (BCRC), Avenue Gouverneur Cornez, 4 B-7000 Mons, Belgique
2
Laboratoire des Matériaux Céramiques et Procédés Associés (LMCPA) UVHC, 59600 Maubeuge,
France
3
UMONS-FPMs- Pôle Matériaux – Service Science des matériaux, 7000 Mons, Belgique
4
Centre Européen de la Céramique – École Nationale Supérieure de Céramique Industrielle Groupe
d’Études des Matériaux Hétérogènes 87068 Limoges, France
Keywords: freeze casting, ice templating, ceramic/metal composite, anisotropy, thermal conductivity

Freeze casting by ice templating was used for processing ceramic preforms. The porosity was
then filled by metal using a low-pressure infiltration technique and ceramic/metal composites
were obtained. Two ceramic materials were studied, alumina and zirconia, and the preforms
exhibit an anisotropic lamellar structure with ellipsoidal pores ranging from 35 µm to 40 µm
and porosity from 64 to 67%. This processing route leads the anisotropic morphology to be
conserved after metal infiltration. The aim of the present work was to study the anisotropic
thermal conductivity of such composite with different ceramic materials. Thermal conduc-
tivities were ranging from about 13 W.m–1.K–1 to 80 W.m–1. K–1 perpendicular and parallel to
the freezing direction respectively, for zirconia/metal composite. The thermal diffusivity of

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the composites was determined by Flash measurements on flat disk in order to calculate the
thermal conductivity as a function of structure orientation. A simple model based on Max-
well equation was used in order to evaluate the influence of residual porosity and to predict
thermal conductivity.

Acknowledgements
We acknowledge the FSE and the SPW – DGO6 for their financial support (grant number ECV320600F-
DOO7F/1017208/ECOPOR, subvention FIRST DOCTORAT Centre Agréé International).

120
Wear damage and fracture of SiC based composites with graphene and
carbon nanotubes
Pavol Hvizdoš1*, Martin Fides1, Richard Sedlák1, Róbert Džunda1, Alexandra Kovalčíková1,
Miroslav Hnatko2, Paweł Rutkowski3
1
Institute of Materials Research (SAS), Watsonova 47, 04001 Košice, Slovakia;
*
e-mail: [email protected]
2
Institute of Inorganic Chemistry (SAS), Dúbravská c. 9, 845 36 Bratislava 45, Slovakia
3
AGH University of Science and Technology, Mickiewicza 30, 30-059 Krakow, Poland
Keywords: SiC, CNT, graphene, TiNbC, mechanical properties, electrical conductivity

SiC based ceramic materials with nano carbon additives, namely with in-situ grown carbon
nanotubes (CNT) and multilayered graphene platelets (GPL) were prepared and studied. The
materials were compacted by hot pressing.
As a reference material a single phase SiC was prepared by the same way, too. The mi-
crostructure and chemical composition of the resulting materials were studied by SEM/EDX.
Hardness and fracture toughness of prepared materials were evaluated and propagation of
indentation cracks was analyzed. The electric conductivity as function of fraction of additives
was determined. Self-mated friction and wear was measured by ball-on-disc technique in dry
conditions under load of 5 N.
Six materials with 0–6 wt. % GPL were prepared. GPL had preferential orientation given
by the hot pressing direction and often remained in stacks. With increasing amount of GPL
hardness (21 GPa -> 15 GPa) and elasticity (440 GPa -> 380 GPa) decreased. Toughness and
strength improved as mechanisms of crack bridging and deflection by GPLs acted as tough-
ening mechanisms. Coefficient of friction in all materials was between 0.4 and 0.6, GPL did
not affect it. Wear rate was improved by higher amounts of GPLs 10–6 – 10–5 mm3/Nm. Wear
mechanisms were similar in all materials, mostly governed by cracking and oxidation.
Electrical conductivity was very low, far insufficient for electric discharge machining
(EDM). Higher amounts and better distribution of carbon phases is required for EDM to be
considered possible.
In the systems SiC-CNT a novel way to prepare the CNTs with high quality and excel-
lent distribution grown in-situ by CCVD on iron nanoparticle pre-cursor was designed. The
prepared mixtures were subsequently compacted by hot pressing. Three SiC-CNT compos-

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ites together with reference SiC-(Fe) were prepared by CCVD and HP. Microstructure stud-
ies proved excellent quality and distribution of CNT. However, full densification is still a
challenge and residual porosity remains. Hardness was good considering the porosity. With
presence of CNT moderate decrease, from 24 GPa for down to 17–19 GPa, was observed.
Indentation fracture toughness behaved similarly, i.e. decreased from ~7 MPa.m1/2 for the
monolith down to ~4 MPa.m1/2 for highest amount of CNT. Electric conductivity increased
with amount of CNT and for higher amounts (5 and 10% CNT) exceeded 1000 S/m (1448
S/m and 2873 S/m, resp.) which shows a potential for sufficient values. Preliminary friction
studies found COF ~ 0.4 and showed weak effect of CNTs. Main wear mechanisms were
again cracking and oxidation.

284
Thermo-chemical properties of re-silicate environmental barrier
coatings
Byung-Koog Jang1*, Nobuo Nagashima1, Kee-.Sung Lee2, Eugenio Garcia3,
Seongwon Kim4, Yoon-Suk Oh4, Hyung-Tae Kim4
1
Research Center for Structural Materials, NIMS, Tsukuba 305-0047, Japan;
*
e-mail: [email protected]
2
School of Mechanical Systems Engineering, Kookmin University, Seoul 136-702, Korea
3
Institute of Ceramics and Glass, ICV–CSIC, Kelsen 5, 28049 Madrid, Spain
4
Korea Institute of Ceramic Engineering and Technology, Icheon 467-843, Korea
Keywords: environmental barrier coatings, Y2SiO5, SiC, oxidation, corrosion

The improvement of the gas turbine inlet temperature is a key factor involved in increasing
the fuel efficiency and reducing the carbon emissions of a gas turbine. Due to the high limit
point of temperature capability, non-oxide silicon-based ceramics, such as SiC/SiCf, Si3N4
and SiC,1 have been investigated extensively as potential structural material for hot gas parts
for next-generation gas turbines. Owing to the presence of oxygen and high-temperature wa-
ter vapor in the combustion environment, SiC based ceramics was degraded by recession due
to chemical reaction under steam environment. In order to solve this problem, the protecting
layer, called EBC (environmental barrier coatings), is necessary.2 In the present study, the
influence of isothermal heat treatment on thermo-chemical properties of Y2SiO5 coatings on
SiC was investigated.
Y2SiO5 coatings have been deposited by flame spray technique as protection layer of SiC
substrate from oxidation and steam corrosion. In this work, Y2SiO5 coatings are heat treated
by different temperature and different exposed times in air environment condition. The ther-
mal behaviors such as phase transformation, microstructure change and TGO growth has
been examined by XRD, SEM, and EDS analysis. The hot corrosion between Y2SiO5 coat-
ings and CMAS was examined by isothermal heating at 1400 °C in air during 1~50 hrs.
In addition, the mechanical properties are evaluated by nano-indentation test. The thick-
ness of corrosive region at top surface of Y2SiO5 by the reaction between Y2SiO5 coating and
CMAS was increased with increasing the heat treatment time.

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References
1. B.K. Jang and Y. Sakka, “Thermophysical Properties of Porous SiC Ceramics Fabricated by Pres-
sureless Sintering”, Sci. Tech. Adv. Mater., 8. pp. 655–659, 2007.
2. K.N. Lee, “Current status of environmental barrier coatings for Si-based ceramics”, Sur. Coat.
Tech., 1, pp. 133–134, 2000.

096
Investigation of the mechanical behavior of MAX phases by acoustic
emission technique
K. Kozak1,2, C.Tiffoche1, G. Antou1, T. Chotard1
Université de Limoges, SPCTS, UMR 7315, 12 rue Atlantis F-87000 Limoges, France;
1

e-mails: [email protected], [email protected], [email protected]

AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Kraków,
2

Poland
Keywords: carbides, acoustic emission, mechanical properties, high temperature

Since the last two decades, MAX phases have attracted researcher’s attention. Due to their
chemical composition and structure, they provide a unique combination of metal-like and
ceramics-like properties.1 Their name, Mn+1AXn phases with n = 1, 2 or 3, refers to their
chemical composition, where M is an early transition metal, A is an A-group element (Si, Al,
etc.) and X is carbon or nitrogen.
Mechanical properties of two ternary carbides, Ti3SiC2 and Ti2AlC, were investigated
under cyclic bending tests with simultaneous acoustic emission monitoring (AE) at room
temperature. Results show significant differences between both of them in terms of observed
microstructural changes associated with acoustic emission response. Thanks to this technique
coupled with an accurate SEM investigation, mechanisms such as debonding of layers in
MAX phases grains or damage occurrence in secondary intermetallic phases (microcrack-
ing) were identified and their specific acoustic signatures separated populations of AE signals
were distinguished.
In addition, ultrasonic pulse echography in “long bar mode” (US) and acoustic emission
(AE) techniques were applied for high-temperature investigations. Results for both materi-
als show a decrease of the Young’s modulus with increasing temperature which is more
marked around maximal temperature of the thermal cycle for Ti2AlC material. Additionally,
AE activity during heating (up to 1473 K and 1632 K) and cooling stages was recorded.
The increase of the maximal temperature of the thermal cycle influences the number of re-
corded cumulated hits. This difference in acoustic response might indicate the beginning of
microstructural changes or activation of other deformation mechanisms. Both measurements
(US+AE) highlights the role of the plastic deformation mechanism activated over the brittle-
to-plastic transition temperature.

Reference
1. M.W. Barsoum and M. Radovic, “Elastic and mechanical properties of the MAX phases,” Annu.
Rev. Mater. Res., 41, pp. 195–227, 2011.

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036
Material development, processing and testing of a silicon nitride turbine
rotor
Willy Kunz
Fraunhofer Institute for Ceramic Technologies and Systems IKTS, Dresden, Germany;
e-mail: [email protected]

Micro gas turbines with cogeneration of heat and power are very suitable for peripheral en-
ergy supply. To increase efficiency and decrease pollutant emissions, higher operating tem-
peratures or lower cooling efforts of the turbine stage are aspired. Subsequently, this leads
to thermal loads at the turbine components that cannot be suffered by superalloys for long
term applications. High performance ceramics promise a higher temperature capability and
strength. This makes them candidates for being the future generation turbine material. Silicon
nitride (Si3N4) is one of the most refractory ceramics, providing a good balance of thermal
stability and mechanical properties.
For this reason a silicon nitride rotor for a radial flow micro gas turbine with 30 kWel was
developed. The illustration of a realistic profile of operational demands via simulative cou-
pling of thermal and (fluid-) mechanical loads was the groundwork for material development.
A further verification of the materials suitability was performed via stress considerations,
non-destructive testing and burst testing. A field test verified the suitability of silicon nitride
for the highest loaded components of gas turbines.

098
The investigation of zirconia based precursors and ceramics via
thermodynamic approaches
Olga Kurapova1,2*, Sergey Shugurov1, Sergey Lopatin1, Alexander Shorokhov1,
EvgeniaVasil’eva1, Vladimir Konakov1,2
1
Institute of Chemistry, St Petersburg State University, Universitetskiypr 26, 198504, Russia;
*
e-mail: [email protected]
2
Peter the Great St Petersburg Polytechnic University, St. Petersburg 195251, Russia
Keywords: stabilized zirconia ceramics, sol-gel synthesis, STA, EMF, high temperature mass spec-
troscopy

Due to their exceptional anion conductivity at high temperatures cubic zirconia solid so-
lutions are widely used as solid electrolyte (SE) materials in different electrochemical de-
vices. However the search of the optimal ceramic compositions for their long-term use in
the aggressive atmosphere of industrial processes remains a great challenge for science and
technology. The precise knowledge of the thermochemical data on thermal prehistory, tem-
perature and concentration dependence of the electromotive force (EMF) on ambient oxygen,

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ion transfer number of SE as well as the evaporation features in ZrO2 based systems at high
temperatures makes it possible to develop high-performance zirconia based SE for in-situ
measurements at extremely high temperatures in aggressive ambiance. Thus the goal of the
present work was the detailed investigation of thermochemical behaviour of MxOy-ZrO2 sys-
tems (M = Ca2+, Y3+, Ce4+, La4+) via the systematic thermochemical approach that includes
simultaneous thermal analysis (STA), EMF measurement and high-temperature mass spec-
troscopy. The synthesis of precursors powders was performed by reversed co-precipitation
from aqueous solutions under the optimal conditions and by conventional solid state syn-
thesis including milling into a planetary mill. The phase transitions, so as possible exo- and
endo-effects were investigated by STA. Then the precursors was cold pressed into the pellets
and hydrostatically pressed. The pellets were annealed at 1600 °С for 2 hours. Following
galvanic cell О2 (РО2(1)), Pt | SE | Pt, (РО2(2) = 0.21 atm) was used for SE sensor properties
investigation. The evaporation experiments were carried out using Knudsen effusion tech-
nique combined with mass spectrometric analysis of vapor composition. It was show that the
value of crystallization enthalpy up on the phase transition “amorphous precursor → crystal-
line solid solution” can serve the criteria for crystallization completeness of metastable cubic
solid solutions in СаO-ZrO2 system. Phase stabilization of the metastable crystalline solid
solution at 400–1000 °C is due to kinetic factors. YSZ ceramics manufactured from powders
with the mean particle size 40–140 nm shows the highest values of oxygen ion transfer num-
ber i.e. 0.97–0.98 at 600–800 °C. SE manufactured from precursors with the mean particle
size 40–140 nm shows higher sensor characteristic i.e. temperature and oxygen concentra-
tion EMF dependencies, EMF (ENernst - Ereal), tion, response time, then ceramics, manufac-
tured by conventional solid state synthesis. The components of La2O3-ZrO2 system evaporate
separately: there is no temperature range where lanthanum and zirconium gaseous species
are present together. It was found that the activities of lantania in all concentration range of
condensed phase have low negative deviation from ideal case whereas zirconia activities has
strong negative deviation from ideal case.

Acknowledgement
This research work was supported in part by the special President’s scholarship for young scientists
(research project CP-1967.2016.1).

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508
UHTC based matrix as a protection for C/C composites for very high
temperature use: original manufacturing and oxidation resistance
Caroline Liégaut1,3, Pierre Bertrand2, Laurence Maillé3, Francis Rebillat3
Safran Ceramics, Rue de Touban – Les 5 chemins, 33185 Le Haillan, France;
1

e-mail: [email protected]
Université de technologie Belfort-Montbéliard, Laboratoire d’Etudes et de Recherches sur les
2

Matériaux, les Procédés et les Surfaces, IRTES-EA7274, 90010 Belfort, France;

e-mail: [email protected]
Université de Bordeaux, Laboratoire des Composites ThermoStructuraux, UMR-5801, 3 allée de la
3

Boétie, 33600 Pessac, France; e-mails: [email protected], [email protected]

Keywords: aerospace, propulsion, UHTC, RMI, oxidation, oxy-acetylene torch testing

Propulsion applications in aerospace require materials that can withstand extreme conditions:
temperatures rising above 2000 °C in oxidizing and corrosive atmospheres. In a constant
need to improve the protection of carbon/carbon composites, the SiC-based protective coat-
ings are not efficient enough. Ultra High Temperature Ceramics (UHTCs) such as borides,
carbides and nitrides present high melting points, high hardness, chemical inertness and rela-
tively good resistance to oxidation in severe environments. More specifically, diboride-based
compounds such as ZrB2 and HfB2 are of special interest.1 During oxidation, the growth of a
multi-oxide scales composed of a skeleton of a refractory oxide filled with a glass makes their
oxidation resistance better.2,3 The addition of SiC has shown better oxidation resistance than
single phase material, 20%vol. SiC seemed optimal for hypersonic applications.
The aim of this work is to prepare a protective matrix, instead of usual coatings, based
on this reference composition. A two-step manufacturing process is carried out to obtain
Cf/C-UHTC composites. By varying the powder mixtures introduced by slurry impregnation
and metal compositions during reactive melt infiltration (RMI), a wide range of matrix’ com-
positions are generated. The reactive systems involved during manufacturing lead to matrices
composed of ZrB2 and SiC phases, and may contain ZrC or residual metal compounds.
The oxidation resistance evaluation is done under oxy-acetylene torch. Tests are per-
formed in presence of oxygen and water in the flame during at least 3 minutes at maximum
temperature around 2000 °C. Samples characterisation allows determining weight change,
scale thickness and scale compositions. Oxidation kinetics is determined and allows compar-
ing the protection ability of each composition.

References
1. M.M. Opeka et al., “Oxidation-based materials selection for 2000°C+hypersonic aerosurfaces:
Theoretical considerations and historical experience”, J. Mat. Sci., 39, pp. 5887–5904, 2004.
2. S.R. Levine et al., “Evaluation of ultra-high temperature ceramics for aeropropulsion use”, J. Eur.
Ceram. Soc., 22, pp. 2757–2767, 2002.
3. E. Opila et al., “Oxidation of ZrB2- and HfB2-based ultra-high temperature ceramics: Effect of Ta
additions”, J. Mat. Sci., 39, pp. 5969–5977, 2004.

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276
Measuring fracture toughness of Y-TZP
Tanja Lube1, Marco Deluca2
1
Institut für Struktur- und Funktionskeramik, Montanuniversität Leoben, A-8700 Leoben Austria;
e-mail: [email protected]
2
Materials Center Leoben Forschungs-GmbH, A-8700 Leoben, Austria; e-mail: [email protected]
Keywords: fracture toughness, transformation

Yttria-stabilized tetragonal zirconia ceramics (Y-TZPs) are not only used for engineering ap-
plications but also – to an increasing extent – for medical and dental restorations. While the
knowledge of materials properties like strength and toughness is necessary for a safe design
of structural parts in the first case, these properties are material specifications with standard-
ized lower bounds in the other case. Robust test methods are thus a need for all fields of ap-
plication regarding Y-TZPs.
For the determination of fracture toughness of ceramics a number of test methods has been
standardized so far. Generally these methods require a pre-crack (or a suitable substitute)
to be introduced into a bar-shaped specimen, which is then fractured in bending. Not all
methods are equally suited for all kinds of ceramics. Especially fine grained Y-TZPs seem to
be a material class that is particularly difficult to test. Indentation pre-cracking for the SCF
method can usually not be achieved with a Knoop indenter, instead the more complicated
cracks associated with Vickers indenters have to be used. Bridge pre-cracking for the SEPB
test requires extremely high loads due to the high toughness of the material. The robust and
easy to use SEVNB method requires a notch with a tip radius that is comparable in size to the
grain size of the material. Even though fine notches with radii down to a few micrometers can
be produced, it seems to be impossible to fulfil this criterion for materials with typical grain
sizes of just a few hundred nanometers.
Some of these problems may arise from the fact that Y-TZPs are metastable materials
where the tetragonal zirconia grains transform to the monoclinic phase under externally ap-
plied load or during machining. This transformation toughening causes compressive stresses
to appear in the transformed regions. Apparently, such compressive stresses in the vicinity of
a honed notch in a SEVNB fracture toughness specimen will lead to incorrect results.
In this study we investigate the SEVNB fracture toughness of Y-TZP. Notches with dif-
ferent radii are produced and tested. Two groups of specimens are compared: specimens in
the as-notched state and specimens after a heat treatment that re-transformed the m-ZrO2
to the tetragonal polymorph and removed the residual stresses. The amount of m-ZrO2 and
residual stresses are measured in the vicinity of the notch roots using Raman spectroscopy.
The measured fracture toughness values are compared to values obtained with alternative
methods that use sharp pre-cracks. It is shown that below a critical notch root radius the frac-
ture toughness can be correctly measured with the SEVNB method if annealed specimens
are used.

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347
Silica membranes for selective separation of small gasses under
hydrothermal conditions
Mieke W.J. Luiten-Olieman1*, Marcel ten Hove1, Hessel L.Castricum2, Hammad F.Qureshi1,
Cindy Huiskes1, Arian Nijmeijer1, Louis Winnubst1
1
Inorganic Membranes, MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217,
7500 AE Enschede, Netherlands; *e-mail: [email protected]
2
Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam, Netherlands
Keywords: hydrothermal stability, hybrid silica, gas separation, microporous membrane, MAP coat-
ing

The hydrothermal stability of microporous ceramic membranes is of high importance for im-
plementation of these membranes in industry, as a lot of industrial processes include steam.
Often the hydrothermal stability of these ceramic membranes is only tested for either the
mesoporous intermediate membrane layer or the microporous separation layer of the ceramic
membrane.
Here, we present the results of a study on the hydrothermal stability of a ceramic membrane
system consisting of an intermediate γ-alumina layer and a hybrid, ethylene-bridged, silica
separation layer. Also, the influence is investigated of the addition of a monoaluminumphos-
phate (MAP) coating between the α-alumina support and the γ-alumina layer on the mem-
brane stability. The results show that the hybrid silica on γ-alumina retains its gas separation
performance after a hydrothermal treatment albeit with a lower mechanical adhesion between
the hybrid silica and the γ-alumina layer, while a bare γ-alumina layer is degraded during a
hydrothermal treatment. On the other hand, the hybrid silica on a MAP-modified γ-alumina
membrane did not show any signs of delamination after hydrothermal testing. Moreover, a
hydrothermal treatment of the hybrid silica on a MAP modified γ-alumina membrane results
in a significant increase in the H2/N2 (perm)selectivity of a factor 3.
Also by tuning the sol-gel chemistry, the influence of the amount of water on the dip-
coating/gelation process was examined. First, membranes were coated on a support with a
controlled low water content (RH < 0.5%) and no detectable permeation of N2 and CH4 was
observed. Second, the system was pretreated at 90% RH while applying the coating, result-
ing a significantly higher N2 permeation. The formation of larger pores can be understood by
a higher condensation rate and longer drying times when more water is present. This results
in a stronger network that better withstands the compressive forces during drying. By limit-
ing both the water and acid contents in the dip sol, a more dense pore structure is obtained
that gives the highest H2/N2 and CO2/CH4 (perm)selectivity’s found to date for hybrid silica
membranes.
 
References
1. Ten Hove, Metal doped hybrid silica for hydrothermally stable hydrogen separation membranes,
PhD thesis, University of Twente (2016) http://doc.utwente.nl/101915/
2. Castricum, H.L., et al., Hybrid silica membranes with enhanced hydrogen and CO2 separation
properties. Journal of Membrane Science, 2015. 488: p. 121–128.

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385
Near zero thermal expansion ZrW2O8/ZrO2 composites
Bora Maviş1*, İrem Vural2, Güngör Gündüz2, Üner Çolak3, Ali Çelik4
1
Department of Mechanical Engineering, Hacettepe University, Ankara, Turkey;
*
e-mail: [email protected]
2
Department of Chemical Engineering, Middle East Technical University, Ankara, Turkey
3
Energy Institute, İstanbul Technical University, İstanbul, Turkey
4
Bilecik Şeyh Edebali University, Bilecik, Turkey
Keywords: zirconium tungstate, zirconia, spark plasma sintering, thermal expansion coefficient

A zirconium tungstate (ZrW2O8) precursor was synthesized by a novel sol-gel method with zir-
conium oxychloride and tungstic acid as the zirconium and tungsten sources, respectively. This
precursor could readily be crystallized at 600 oC, which in turn provided the desired nanopar-
ticle sizes for the composite production. For synthesis of ZrW2O8/ZrO2 composite system, both
conventional and spark plasma sintering methods were experimented and respective results
were compared and composition ranges that provide composites with almost zero thermal ex-
pansion coefficient’s (CTE’s) were determined. The composites that were conventionally sin-
tered at 1200 oC for 24 hours with Al2O3 as the sintering aid, showed a CTE of 0.20 × 10–6/K
for the compositions fixed at 35% ZrW2O8 and 65% ZrO2. On the other hand, with the spark
plasma sintering method, which was conducted at 1000 oC for 5 minutes without a sintering aid,
a composition of 55% ZrW2O8 and 45% ZrO2 showed a CTE of 0.94 × 10–6/K. For character-
ization of the products X-ray diffraction (XRD), scanning electron microscopy (SEM), photon
correlation spectroscopy (PCS), and thermal and dilatometer analyses (DTA/TGA/DMA) were
used. The observed differences in the obedience to rule of mixtures in the two sintering methods
and identified pressure induced phase transitions in the interparticle regions will be discussed.

671
Synthesis and characterization of a new [Ti1-εCuε]3[Al(1-x)Cux]C2 max
phase solid solution with adjustable substitution rates
Mustapha Nechiche1, Véronique Gauthier-Brunet1, Thierry Cabioc’h1, Anne Joulain1,
Vincent Mauchamp1, Oleg Rivin2, Elad Caspi3, Sylvain Dubois1
1
Institut PPRIME, CNRS/Université de Poitiers/ENSMA, UPR 3346, 86962 Chasseneuil du Poitou-
Futuroscope Cedex, France
2
Physics Department, Nuclear Research Center of the Negev, Beer-Sheva, Israel
3
Department of High-Field Magnet, Helmholtz-Zentrum Berlin, Germany
Keywords: MAX phase, solid solution, powder metallurgy, microstructural characterization.

Ti3AlC2 is a member of the MAX phase compounds having the general formula Mn+1AXn
(n = 1-3), where M is an early transition metal, A is an A group element (from IIIA to VIA),
and X is either carbon or nitrogen. In these materials, the Mn+1Xn layers, characterized by
strong covalent M-X bonds, are interleaved with A layers through weak M-A bonds. This
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inherent nanolayered structure provides a unique combination of metal-like and ceramic-like

properties.
In this work, Ti3AlC2 MAX phase powders were first prepared at 1450 °C for 2 hours from
1.9TiC:1.05Al:1.0Ti reactant mixture. High-energy milling of Ti3AlC2 and Cu (40vol.%)
powders was then performed to form large aggregates containing alternative lamellas of both
compounds. Finally, a new [Ti1-εCuε]3[Al(1-x)Cux]C2-Cu Metal Matrix Composite has been
produced by sintering Ti3AlC2 and Cu co-milled powders. Using XRD and TEM-EDXS, it
has been demonstrated that Cu can enter the crystallographic structure of the Ti3AlC2 MAX
phase, whereas a Cu(Al) solid solution is formed during thermal treatment. TEM-EELS
analyses have demonstrated that Cu is mainly located on the A site of the MAX phase. The
composition of the MAX phase solid solution, determined after selective chemical etching
of the Cu(Al) matrix, by analyzing the filtrate and the solid phase using ICP-OES end EDXS
methods respectively, is Ti3(Al0.5Cu0.5)C2. Thus, Al atoms are substituted preferentially com-
pared to Ti atoms. Using X-ray diffraction and neutron diffraction, it is demonstrated that the
Cu mixing into the Al site is accompanied by lattice distortion that lead to symmetry reduc-
tion into the monoclinic structure.
Moreover, by varying the Cu content in the range 10-50 vol. % in the initial Ti3AlC2-Cu re-
actant mixture, it is demonstrated that the substitution rate of Al by Cu atoms can be adjusted
in the [Ti1-εCuε]3[Al(1-x)Cux]C2 solid solution. Finally, Rietveld refinement allows demonstrat-
ing that the lattice parameters of the monoclinic MAX phase vary linearly with Cu content
on the A site implying that the Vegard’s law is obeyed.

431
Towards sandphobic thermal barrier coatings (TBCs) – characterization
of YSZ-based TBCs exposed to sand laden combustion flows
Andy Nieto1, Michael Walock1, Blake D. Barnett2, Anindya Ghoshal1, Muthuvel Murugan1,
Marc S. Pepi2, Dongming Zhu3, Robert T. Pegg4, Chris R. Rowe4, William R. Gamble2,
Jeffrey J. Swab2, Kevin A. Kerner5
Vehicle Technology Directorate, US Army Research Laboratory, Aberdeen Proving Ground, MD,
1

21005, USA
Weapons and Materials Research Directorate, US Army Research Laboratory, Aberdeen Proving
2

Ground, MD, 21005, USA

Durability & Protective Coatings Branch, NASA Glenn Research Center, Cleveland, OH, 44135,
3

USA
Power & Propulsion, US Navy Naval Air Systems Command, Patuxent River, MD, 20670, USA
4

Aviation Development Directorate, US Army Aviation and Missile Research, Development, and
5

Engineering Center, Ft. Eustis, VA, 23604, USA

Keywords: YSZ, TBCs, CMAS, microstructural evolution, thermal cycling

The increasing operating temperatures of gas-turbine engines has led to the deterioration of
protective thermal barrier coatings by deposition and infiltration of solidified molten sand,
salt, and volcanic ash particulates, typically composed of calcia-magnesia-alumina-silicates

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(CMAS). Future thermal and environmental barrier coatings (TBC/EBCs) will operate at
increasingly higher temperatures and must simultaneously provide improved thermo-me-
chanical performance and resistance to CMAS-induced damage. This work presents ongoing
efforts on the development of ‘sandphobic’ tailored YSZ based coatings deposited onto Ni
superalloy substrates. Tailoring of YSZ coating microstructures is performed by using vari-
ous coating techniques including air plasma spray (APS), solution precursor plasma spray
(SPPS), and electron beam physical vapor deposition (EB-PVD). Coatings are further tai-
lored for CMAS resistance by incorporating Gd2O3 and Gd2Zr2O7 topcoat layers and blended
YSZ/Gd2O3 compositions. A sand ingestion gas turbine engine rig was utilized in order to
evaluate the coatings under realistic operating conditions. The coatings are exposed to a sand
laden combustion environment with air flow temperatures of ~1400 °C. Exposed coatings
are evaluated using confocal microscopy, scanning acoustic microscopy (SAM), scanning
electron microscopy (SEM), energy dispersive spectroscopy (EDS), electron backscattered
diffraction (EBSD), and focus ion beam (FIB) cross-sectioning in order to characterize the
effectiveness of the coatings in preventing CMAS infiltration, CMAS induced spallation, and
build-up of CMAS deposits.

952
Microstructure and mechanical properties of NbB2/SiC-GNP composites
Burak Cagri Ocak, Filiz Sahin, Gultekin Goller, Ipek Akin
Istanbul Technical University, Department of Metallurgical and Materials Engineering, 34469 Maslak,
Istanbul, Turkey
Keywords: NbB2 based ceramics, ultra high temperature ceramics, graphene, spark plasma sintering

Niobium diboride (NbB2), as a typical ultra high temperature ceramic, has a good combina-
tion of properties, such as high melting point (~3040 °C), high hardness (~21 GPa), high
thermal conductivity (~17 W/m·K) and good thermal shock resistance. However, difficulties
in densification, low fracture toughness and poor oxidation resistance of NbB2 limit the use of
these materials. A number of studies have shown that addition of SiC improves the oxidation
resistance by forming a protective SiO2-rich layer and improve fracture toughness of transi-
tion borides. Moreover, recent studies have demonstrated that graphene nanoplatelets (GNP)
addition can significantly enhance the mechanical properties of ceramic matrices. In this
study, GNPs were incorporated into (20-x)SiC-80NbB2 (vol.%) composite powder with x =
0, 0.5, 3, 5, 7 and 10 vol.% contents. The resulting powder mixtures were sintered by spark
plasma sintering (SPS) at 1750 °C under 50 MPa with a 5 min holding time. The prepared
composites were then characterized in terms of their densification, microstructure, oxida-
tion behavior and mechanical properties. Improvement in oxidation resistance as a result of
formation of protective layers and fracture mode change with the incorporation of SiC and
GNPs will be discussed in this presentation.

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References
1. T. Yao, Y. Wang, H. Li, J. Lian, J. Zhang, H. Gou A universal trend of structural, mechanical and
electronic properties in transition metal (M = V, Nb, and Ta) borides: First-principle calculations,
Comp. Mater. Sci., 65 (2012), pp. 302–308.
2. T. Takahashi, S. Kawamata, S. Noguchi, T. Ishida, Superconductivity and crystal growth of NbB2,
Phys. C, 426–431 (2005), pp. 478–481.

257
Microstructural characterization of commercial ceramic materials for
ballistic applications
Daniela Olevano*, Stefano Lionetti
Centro Sviluppo Materiali S.p.A. Via di Castel Romano, 100 - 00128 Rome, Italy;
*
e-mail: [email protected]
Keywords: ceramic, microstructure, Vickers hardness, Weibull modulus, indentation toughness, aver-
age grain size, grain size distribution, EBSD, XRD, TEM, Raman spectroscopy, armour

Room temperature microstructural properties of near fully-dense Al2O3 (Corbit 997), B4C
(Bocadur) and SiC (Sicadur) commercial ceramics for ballistic applications were studied.
Residual porosities were estimated by image analysing of polished surfaces both on cross
section and on impact surface. The results demonstrate anisotropic properties: the grains
pull-out phenomenon is more pronounced on the impact surface in respect to its cross sec-
tion. Results of image analyses and other technical methods for porosity determinations were
compared.
Vickers indentation hardness were measured at different loads. The results confirm the
typical ceramic behaviour already known as indentation size effect1. Furthermore the hard-
ness results were statistically evaluated on the basis of Weibull analysis. Weibull’s approach
to flaw statistics is based on “weakest link statistics” so that failure of one element of a body
leads to failure of the whole body. Weibull moduli were compared between ceramic materi-
als with comparable hardness which corresponds to comparable investigated volume. The
results allow to establish a ranking of material reliability.
In order to quantify the material resistance to brittle fracture, indentation toughness was
determined on the basis of both Niihara2 and Anstis3 equations.
To characterize the microstructure, average grain size and grain size distribution were
measured by the linear intercept method4 on Electron Channeling Contrast Images (ECCI)
and by Electron BackScattered Diffraction (EBSD), respectively.
For a further characterization of the crystallographic phases, X-Ray Diffraction (XRD)
spectra were acquired on all commercial materials. To verify at microscopic scale, the results
have been compared with data acquired by Transmission Electron Microscopy.
Raman spectra were acquired on the same commercial materials in normal and confocal
mode in order to confirm the crystallographic phases already identified by XRD and TEM.
In comparison to TEM, results of Raman spectroscopy are more statistically representative
of the macroscopic material.

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Acknowledgement
This research activity is part of the Ceramball Project-N°: B 1091 GEM1 GP supported by the European
Defence Agency.

References
1. R.C. Bradt, et al. “Fracture Mechanics of Ceramics” Springer, 8 November 2005
2. Niihara et al. J. Mater. Sci. Lett., 1982, 1, 13–16.
3. Anstis et al. J. Am. Ceram. Soc., 1981, 64, 533–538.
4. ASTM E112 – 13 “Standard Test Methods for Determining Average Grain Size”

160
Mechanical and electrical properties of liquid phase sintered porous
SiC using Al2O3-Y2O3-SiO2 as sintering additives
Sang Whan Park1, Sung Il Yun1, Mi Rae Youm1, Sahn Nahm2, Seong-Jai Cho3
1
Materials Architecturing Research Center, Korea Institute of Science and Technology, Seoul, Korea
2
Electro Ceramics Laboratory, Korea University College of Engineering, Korea University, Seoul,
Korea
3
Division of Industrial Metrology, Korea Research Institue of Standards and Science, Seoul, Korea
Keywords: porous SiC, flexural strength, apparent porosity, electrical resistivity

The porous SiC ceramics with specific pore characteristics has been widely used because of
its attractive thermo-mechanical properties as well as chemical resistivity in various environ-
mentally related industries. In this study, porous SiC ceramics with various pore characteris-
tics were fabricated by a liquid phase sintering using SiO2-Al2O3-Y2O3 sintering additives at
the temperature below 1600 °C under argon atmosphere. The average pore size and porosity
of fabricated porous SiC were varied depending on the starting SiC particle size as well as
the amount of sintering additives used. It was found that the fracture strengths of liquid phase
sintered porous SiC with the same porosity were decreased with increasing the pore size.
With increasing the amount of sintering aid from 15 to 25%, the porosity and pore size of
SiC porous body was decreased, but the fracture strength of porous SiC was increased. The
electrical resistivity of liquid phase sintered porous SiC using Al2O3-Y2O3-SiO2 was as high
as 107 Ωcm, which was not closely dependent on the pore size as well as the porosity of the
porous SiC.

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549
Graphene nanoplatelet/3 mol% yttria doped zirconia composites with
high electrical conductivity
R. Poyato1, J. Osuna1,2, A. Morales-Rodríguez1,2, A. Gallardo-López1,2
1
Instituto de Ciencia de Materiales de Sevilla, ICMSE, CSIC-Universidad de Sevilla, Avda. Américo
Vespucio 49. 41092 Sevilla, Spain
2
Departamento de Física de la Materia Condensada, Universidad de Sevilla-ICMSE (CSIC), Apdo.
1065, 41080 Sevilla, Spain
Keywords: graphene nanoplatelets, 3YTZP, microstructure, electrical conductivity

The exceptional electrical properties of carbon nanostructures, such as carbon nanotubes

(CNT) or graphene, have motivated a great interest in incorporating these nanostructures as
second phase in a ceramic matrix, in order to enhance the functionalities of the final com-
posite. An alternative cost-effective option in comparison with CNT or monolayer graphene
is the use of other 2D carbon nanomaterials, such as graphene nanoplatelets (GNP) or gra-
phene nanosheets (GNS). Although remarkable electrical conductivities have been reported
for GNP/ceramic composites, just a few works approaching the electrical characterization of
these materials have been published1,2.
In this work, the microstructure and the electrical properties of 3 mol% yttria-doped zir-
conia (3YTZP) processed with up to 20 vol.% graphene nanoplatelets (GNPs) have been
studied. Wet powder processing in isopropanol and electric pulsed discharge sintering were
used to prepare the composites. The structural integrity of the GNPs was not damaged during
the process, as confirmed by Raman spectroscopy. As a consequence of the uniaxial applied
pressure during sintering, a preferential orientation of the GNPs in the direction perpendicu-
lar to the pressing axis was observed. This microstructural anisotropy resulted in an electrical
anisotropy, since the electrical conductivity measured along the direction perpendicular to
the pressing axis was significantly higher than the one measured along the parallel direc-
tion. Electrical conductivity of the composites along both directions was obtained in a wide
temperature range. The relationships between GNP content, GNP dimensions, microstructure
and electrical conductivity, as well as the conduction mechanisms of the composites, have
been analysed and discussed.

References
1. C. Ramirez, F.M. Figueiredo, P. Miranzo, P. Poza and M. I. Osendi, “Graphene nanoplatelet/silicon
nitride composites with high electrical conductivity”, Carbon, 50, pp. 3607–3615, 2012.
2. B. Román-Manso, E. Domingues, F.M. Figueiredo, M. Belmonte and P. Miranzo, “Enhanced elec-
trical conductivity of silicon carbide ceramics by addition ofgraphene nanoplatelets”, J. Eur. Cer-
am. Soc., 35, pp. 2723–2731, 2015.

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662
Structure, mechanical characteristics and stability of (Ti,Nb)-Al-C
MAX-phases-based composites in hydrogen and oxidizing atmosphere
Tatiana Prikhna1*, Orest Ostash2, Vladimir Sverdun1, Andriy Ivasyshyn2,
Viktoriya Podhurska2, Myroslav Karpets1, Thierry Cabioch3, Lucyna Javorska4,
Pavel Figel4, Patrick Chartier3, Viktor Moshchil1, Jolanta Cyboroń4, Anjey Kalinka4,
Tetiana Zimych1, Alexandra Starostina1, Ludmila Chirko5, Yuriy Chaykovskyi5
1
Institute for Superhard Materials of the National Academy of Sciences of Ukraine, Kiev, Ukraine;
*
e-mail: [email protected]
2
Physico-Mechanical Institute of the National Academy of Sciences of Ukraine, Lviv, Ukraine
3
Universite de Poitiers, CNRS/ Laboratoire PHYMAT, Chasseneuil Futuroscope Cedex, France
4
The Institute of Advanced Manufacturing Technology, Krakow, Poland
5
Institute for Nuclear Research of the National Academy of Sciences of Ukraine, Kiev, Ukraine
Keywords: structure, mechanical characteristics and stability of (Ti,Nb)-Al-C MAX-phases-based
composites in hydrogen and oxidizing atmosphere

The developed materials are promising for interconnects of hydrogen fuel cells, damping
material in machine building, in nuclear industry, for pantographs or sliding bearings, etc.
The dense MAX-phases-based materials of Ti,Nb–Al–C systems prepared by hot pressing at
30 MPa are stable in hydrogen and oxidizing environments at 600 °C, are about twice lighter
(ρ = 4.27 g/cm3) and more stable in air (for 1000 h) than Cr-containing “Crofer” steels. The
addition of Nb leads to the formation of about 10 times thinner surface oxidized layer and
thus to the material stability increase. The most resistant among the studied materials in air at
600 °C for 1000 h turned out to be Ti2AlC-based (73 wt.% of Ti2AlC according to Rietveld
refinement). The SEM study of it matrix revealed the near Ti2,3AlCO0,2 composition and the
presence of elongated near Ti3,6AlC1.9O0,6 grains. Somewhat less stable was preliminarily
oxidized at 1200 oC (for 2 h) Ti3AlC2 (89 wt%). The Ti3AlC2-based materials at room tem-
perature demonstrated 4.6–5.8 GPa microhardness at 5 N load, 500–570 MPa bending and
700–1300 MPa compression strengths, 10.2±0.4 MPa·√m fracture toughness and 2.7·106
Sm/m electrical conductivity at 20 °C. The bending strength of Ti3AlC2-based material in air
at 20 °С was 535 MPa, after keeping at 600 °С in air and hydrogen it decreased to 490 and
500 MPa, respectively. For (Ti,Nb)3AlC2 –based materials the bending strength at 20 °C in
air was 480 MPa and increased by 10% after heating at 600 °С both in air and in hydrogen.
The estimated damping coefficient and stability to radiation of the MAX-phases were as well
high.

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700
Mechanical properties of mixtures of 12Ce-ZrO2 and 3Y-ZrO2
and atom probe tomography of solute distribution
J.J. Roa1,2, H. Aboulfadl3,4, J. Barrirero3,4, M. Turon-Vinas1,2, F. Mücklich3,4, M. Anglada1,2*
1
Universitat Politècnica de Catalunya, CIEFMA, Campus Diagonal Besòs - Edif. DBI, Av. d'Eduard
Maristany, 10-14, 08019 Barcelona, Spain; *e-mail: [email protected]
2
Universitat Politècnica de Catalunya, Research Center in Multiscale Science and Engineering,
Campus Diagonal Besòs – Edif. DBC, Av. d’Eduard Maristany, 10-14, 08019 Barcelona, Spain
3
Chair of Functional Materials, Saarland University, Campus D3-3, D-66123, Saarbrücken, Germany
4
Materials Engineering Center Saarland, Steinbeis Research Center, Campus D3-3, D-66123,
Saarbrücken, Germany
Keywords: 12Ce-ZrO2, 3Y-ZrO2, atom probe tomography, mechanical properties, KIC, LDT

3Y-ZrO2 has attracted much attention in restorative dentistry because of its biocompatibility,
aesthetical appearance, and excellent mechanical properties such as hardness, strength, and
fracture toughness. However, it suffers of low temperature degradation (LTD), which con-
sists in the spontaneous surface tetragonal-monoclinic transformation under the presence
of moisture, which is detrimental since it induces surface microcracking and grain pullout.
There is then interest in using ceria as a dopant for stabilizing the tetragonal phase of zirconia
in concentrations higher than about 10% molar since it makes zirconia much more resistant
to LTD and tougher than 3Y-ZrO2, but Ce-ZrO2 ceramics have lower hardness and strength
than 3Y-ZrO2. In this work mixtures of powders of 12Ce-ZrO2 and 3Y-ZrO2 in different
proportions have been studied with the objective to find out a suitable combination of hard-
ness and indentation fracture toughness for the mixture. The best compromise in mechanical
properties and resistance to LTD were obtained in the mixture with 85 wt% 12Ce-ZrO2-15
wt.% 3Y-ZrO2, which was analysed by atom probe tomography after sintering at 1450 and
1600 °C. It is shown that the solid solution inside the grains is not homogenous and that there
is strong segregation of Al, Ce and Y to the grain boundaries. Segregation to grain boundar-
ies is quantified for all these elements, being stronger in the specimens sintered at 1600 °C.
The mechanical properties and resistance to LTD have also been studied in more detail in the
85/15 mixture. In particular, the strength has been determined and analysed under the pres-
ence of surface micro-notches induced by pulsed laser ablation.

Acknowledgements
Authors greatly acknowledge the MAT2014-60720-R and the European project CREATe-Network
(RISE Project Nº 644013), supported by the Spanish “Ministerio de Economía y Competividad” and
by the European Commission within the RISE Program, respectively. We are grateful to “Secretaria
d’Universitats i Recerca de la Generalitat de Catalunya” for financial support (2014-SGR-130). The
atom probe instrument was financed by the Deutsche Forschungsgemeinschaft (DFG) and the Federal
State Government of Saarland (INST256/298-1 FUGG).S

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290
Fatigue of three advanced SiC/SiC ceramic matrix composites
at 1200 °C in air and in steam*
Marina Ruggles-Wrenn, Nicholas Boucher
Department of Aeronautics & Astronautics, Air Force Institute of Technology, Wright-Patterson Air
Force Base, Ohio 45433-7765, USA
Keywords: ceramic-matrix composites (CMCs), fatigue, high-temperature properties, mechanical
properties, fractography

Silicon carbide/silicon carbide ceramic matrix composites (CMCs) are among leading candi-
date materials for use in advanced aeronautics and space applications, such as turbine engine
components, hypersonic flight vehicles, and spacecraft re-entry thermal protection systems.
In these applications the composites will be subjected to cyclic loadings under high tem-
perature and varying environmental factors. Therefore a thorough understanding of fatigue
performance of SiC/SiC composites in service environments is critical to design and life
prediction for these materials. High-temperature mechanical properties and tension-tension
fatigue behaviour of three advanced SiC/SiC composites are discussed. The effects of steam
on high-temperature fatigue performance of the CMCs are evaluated. The three composites
consist of a SiC matrix reinforced with laminated, woven SiC (Hi-Nicalon™) fibres. Com-
posite 1 was processed by chemical vapour infiltration (CVI) of SiC into the Hi-Nicalon™
fibre preforms. Before the infiltration, the preforms were coated with boron nitride fibre coat-
ing (~0.25 μm thick) to decrease bonding between the fibres and the matrix. Composite
2 had an oxidation inhibited matrix consisting of alternating layers of silicon carbide and
boron carbide and was also processed by CVI. Prior to infiltration, the fibre preforms had
pyrolytic carbon fibre coating (~0.40 μm thick) with boron carbide overlay (~1.0 μm thick)
applied. Composite 3 had a melt-infiltrated (MI) matrix consolidated by combining CVI-SiC
with SiC particulate slurry and molten silicon (Si) infiltration. The fibre preforms were first
coated with BN by CVI. Then a CVI SiC coating of initial matrix was applied to rigidize the
preforms. This step was followed by slurry infiltration of SiC particulates and infiltration of
molten Si to fill in the remaining porosity. The tensile stress-strain behaviour of the three
CMCs was investigated and the tensile properties measured at 1200 °C. The tension-tension
fatigue behaviour of the three SiC/SiC CMCs was investigated at 1200 °C in laboratory air
and in steam. The tests were performed at 1.0 Hz with a stress ratio of minimum to maximum
stress of R = 0.05. Maximum stress ranged from 80 to 160 MPa in air and from 60 to 140
MPa in steam. Fatigue run-out was defined as 2 × 105 cycles. Presence of steam significantly
degraded the fatigue performance of the CVI SiC/SiC composite 1 and of the MI SiC/SiC
composite 3, but had little influence on the fatigue performance of the SiC/SiC composite 2
with the oxidation inhibited matrix. All specimens that achieved fatigue run-out were tested
in tension to failure to characterize the retained tensile properties. Composite microstructure,
as well as damage and failure mechanisms were investigated.

The views expressed are those of the authors and do not reflect the official policy or position of the
*

United States Air Force, Department of Defense or the U.S. Government.

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110
Development of environmental barrier coatings for SiC/SiC ceramic
matrix composites
K. Schönfeld*, H. Klemm, W. Kunz
FhG IKTS Dresden, Germany; *e-mail: [email protected]
Keywords: EBC; CMC; SiC/SiC, corrosion stability

Advanced ceramic matric composites (CMCs), in particular silicon carbide fiber reinforced
silicon carbide matrix composites (SiC/SiC), are increasingly used in the aerospace industry
for manufacturing of hot components due to their excellent properties compared to super
alloys. In the aero engine, a part of the combustion gas is water vapor resulting from the
burning of hydrocarbon fuels in air. The water vapor will corrode the CMC components,
resulting in their final failure. To protect the SiC/SiC components from corrosion, environ-
mental barrier coatings (EBC) have been developed to increase their durability in combustion
environments.
Based on detailed understanding, several multilayer coating systems with high corrosion
stability were fabricated and tested successfully. For the deposition process the atmosphere
plasma spray process (APS) was used.
In this study the oxidation and corrosion behavior of the SiC/ SiC material with differ-
ent EBC systems were investigated. Diffusion processes or reaction at the CMC / coating
interface led to microstructural or chemical change with consequence of crack formation and
failure of the EBC what is discussed in this presentation.

227
Influence of humidity and temperature on the fatigue behavior of
silicon nitride and zirconia ceramics
Christian Schröder1*, Christof Koplin1, Andreas Kailer1, Jens Stockmann2, Wieland Beckert2
Fraunhofer Institute for Mechanics of Materials IWM, Woehlerstrasse 11, 79104 Freiburg, Germany;
1

*
e-mail: [email protected]
Fraunhofer Institute for Ceramic Technologies and Systems IKTS, Winterbergstrasse 28, 01277
2

Dresden, Germany
Keywords: fatigue, corrosion, contact damage, silicon nitride, zirconia

In power engineering applications and chemical facilities there is a high demand for compo-
nents e.g. springs which are resistant against high temperatures as well as corrosion. They
also have to provide a reliable and maintenance-free usage without change of their technical
properties. In this regard, ceramic materials may expand the application range of springs in
comparison to metals, as they are furthermore electrically isolating and nonmagnetic. How-
ever, the time-dependent mechanical strength at static or cyclic loading in corrosive media

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and high temperatures has to be taken into consideration to evaluate the system reliability.
Addressing this aspect, it is focused on the fatigue behavior of silicon nitride and zirconia
ceramics. Both materials are characterized by high strength and fracture toughness and are
therefore the first choice for manufacturing of ceramic springs. Although ceramic springs
have been processed for many years already, there are low experiences with the corrosive, fa-
tigue and relaxation behaviors at high temperatures. Hence, experimental investigations and
numerical simulations have been applied in this study to determine characteristic mechanical
values and to describe the microstructural responses which depend on dynamic loading and
environmental conditions.
The results after cyclic 4-point-bending tests show that the resistance against fatigue clear-
ly diminishes in water. Increasing the temperature to 1000 °C furthermore enables to empha-
size on the influence of high temperatures on the change of strength. Against the background
to use silicon nitride and zirconia for springs, the uniaxial state of stress at cyclic 4-point-
bending was also varied to a torsional loading for particular samples with bone-shaped geom-
etry. Of special interest is additionally the wear resistance of the ceramics surfaces at cyclic
contact loading with spherical shape. The analyses of fractured surfaces after cyclic bending,
torsion and frictionally induced wear were conducted via SEM to investigate the activated
damage mechanisms. Also, the transformation of the metastable tetragonal to stable mono-
clinic phase of zirconia ceramics was investigated via Raman-spectroscopy.
Eventually, material laws have been established on the basis of the experimental data to
numerically calculate the stress distribution of given spring geometries. This approach is
purposeful to reliably predict the live time and to adjust the design of ceramic springs to the
specific loading conditions.

403
CaZrO3-MgO multiphase ceramics obtained from natural and pure raw
materials
Abílio P. Silva1,3*, Fernando Booth2,3, Pilar Pena3, Carmen Baudín3
1
Centre of Mechanics and Aerospace Science and Technologies (C-MAST-UBI), Universidade da
Beira Interior, Rua Marquês d’Ávila e Bolama, 6201-001, Covilhã, Portugal; *e-mail: [email protected]
2
CETMIC (Centro de Tecnología de Recursos Minerales y Cerámica, CIC-CONICET La Plata),
Camino Centenario y 506, C.C.49 (B1897ZCA) M.B. Gonnet, Buenos Aires, Argentina
3
Instituto de Cerámica y Vidrio, CSIC, Kelsen 5, Madrid 28049, Spain
Keywords: multiphase ceramics, CaZrO3-MgO based ceramics, reaction sintering, structural ceram-
ics

Recent trends in materials engineering favour composite materials as opposed to single phase
ones. The most known multiphase ceramics for severe environments are refractories, which
are responsible for the success of essential industries connected to high temperature pro-
cessing, such as glass and cement production, thermoelectric power stations and foundries.
Complex compositions in ternary or quaternary systems such as ZrO2-MgO-CaO, Al2O3-
SiO2-MgO-CaO or Al2O3-SiO2-MgO-ZrO2 are usual.

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The successful design of multiphase ceramics requires an integrated approach which takes
into account the equilibrium phase constitution and how the properties of the constituent
phases affect the global behaviour of the material.
This work is a part of a wider project focused to the development of new multiphase ox-
ide ceramics for structural applications of high responsibility with compositions inspired by
those of refractories. The ternary system ZrO2-MgO-CaO has been chosen due to the high
temperature of its eutectic point, 1982 ºC. Fine grained and dense ZrO2-CaZrO3-MgO ma-
terials of high purity and with different levels and nature of impurities have been developed
and characterise in order to evaluate the capability of multiphase materials in this system
for advanced structural applications. The influence of composition and temperature on the
microstructural and mechanical characterisation is described. In addition, the wear resistance
of the materials is analysed.

Acknowledgements
This work was performed in the frame of the CYTED network HOREF (312RT0453). The authors ap-
preciate the financial support of JECS Trust through mobility, Contract 2015 97.

References
1. S. Serena, M.A. Sainz, A. Caballero, Experimental determination and thermodynamic calculation of
the ZrO2-CaO-MgO system at 1600, 1700, and 1750ºC, J. Am. Ceram. Soc. 87 (2004) 2268–2274.
2. F. Booth, L. Garrido, E. Aglietti, A. Silva, P. Pena, C. Baudín, CaZrO3-MgO structural ceram-
ics obtained by reaction sintering of dolomite-zirconia mixtures, J. Eur. Ceram. Soc. 36 (2016)
2611–2626.
3. Silva, F. Booth, L. Garrido, E. Aglietti, P. Pena, C. Baudín, Sliding wear of CaZrO3-MgO compos-
ites against ZrO2 and steel, J. Eur. Ceram. Soc. 37 (2017) 297–303.
4. Silva, F. Booth, L. Garrido, E. Aglietti, P. Pena, C. Baudín, Influence of phase composition on the
sliding wear of composites in the system CaZrO3-MgO-ZrO2 against ZrO2 and steel, Theor. Appl.
Fract. Mech. 85, Part A (2016) 125–133.

701
Microstructures and properties of bulk Al2O3/Y3Al5O12 eutectic ceramics
prepared by different methods
Luchao Sun*, Jingyang Wang
Institute of Metal Research, Chinese Academy of Sciences, Shenyang, China;
*
e-mail: [email protected]

Directionally solidified Al2O3/Y3Al5O12 ceramic has been received extensive attentions as a

promising candidate for high or ultra-high temperature structural material due to its excel-
lent performances from room temperature to near its melting point. Its outstanding proper-
ties are mainly originated from the unique “Chinese script” microstructure, consisting of
three-dimensionally and continuously entangled single crystal phases without either grain
boundaries or amorphous interfacial phases. However, there is a crucial challenge to fabricate

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large-size bulk eutectic ceramics with fine eutectic microstructure due to the limitations of
their typical preparation methods.
In this work, large-size highly-dense Al2O3/Y3Al5O12 bulk eutectic ceramics were prepared
by both traditional hot pressed sintering and rapid sintering methods such as induction heat-
ing and spark plasma sintering methods. Starting powders were the pulverized eutectic par-
ticles prepared by optical floating zone method. The sintering densification and microstruc-
ture evolution of the Al2O3/Y3Al5O12 eutectics were studied. Moreover, the mechanical and
thermal properties of as-prepared bulk materials are characterized and discussed. The results
show that the initial eutectic particle size and the sintering methods impressively affect the
sintering behavior and the eutectic structures of Al2O3/Y3Al5O12 bulk materials. And most
important of all, the sintered bulk samples show analogous mechanical properties compared
with directionally solidified eutectic material. Therefore, this work provides feasible ways to
process large bulk eutectic ceramics for its potential applications.

283
Surface and volume crystallization in glasses from the system
BaO-SrO-ZnO-SiO2
Christian Thieme1,2*, Michael Kracker2, Liliya Vladislavova2, Christian Patzig1,
Katrin Thieme2, Christian Rüssel2, Thomas Höche1
Fraunhofer Institute for Microstructure of Materials and Systems, Walter-Huelse-Straße 1,
1

06120 Halle, Germany; *e-mail: [email protected]

Otto-Schott-Institut, Chair of Glass Chemistry I, Jena University, Fraunhoferstr. 6,
2

07743 Jena, Germany

Keywords: crystallization, thermal expansion, nucleation, transmission electron microscopy

Glasses and glass-ceramics containing high concentrations of alkaline earth oxides are
widely known as high thermal expansion materials for sealing applications. However, in
the system BaO-SrO-ZnO-SiO2, a recently found phase with the formula Ba1-xSrxZn2Si2O7
exhibits very low or even negative thermal expansion. This phase can be precipitated in
high concentrations from suitable glasses. Unfortunately, such glasses show solely surface
crystallization, which makes it impossible to prepare large sized samples. For this purpose,
volume crystallization has to be achieved. In order to trigger the formation of volume crys-
tals, different additives such as ZrO2, SnO2, Au, and Pt are introduced, and their performance
as nucleation agents is analyzed within the scope of this study. To examine the crystallization
behavior, various methods are combined, which are differential scanning calorimetry, X-ray
diffraction, UV-vis-spectroscopy, scanning electron microscopy, and analytical high resolu-
tion scanning transmission electron microscopy.
It will be shown that the used additives affect the crystallization behavior in different
ways, which is, amongst others, caused by the different size of the particles acting as nucle-
ation centers, ranging from above 1 µm to below 10 nm, depending on the used additive and
the applied heat treatment.

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139
Aligned porosity SiOC ceramics
Cekdar Vakifahmetoglu
Department of Mechanical Engineering, Istanbul Kemerburgaz University, 34217, Istanbul, Turkey;
e-mail: [email protected]
Keywords: porous ceramics, aligned porosity

A simple and inexpensive technique was developed to form porous SiOC monoliths having
aligned but also gradient porosity. Preceramic polymer blends were mixed with a catalyst,
followed by curing via directional heating the molds, and pyrolysis. SEM, tomography (CT),
BET and water immersion porosimetry were used to characterize the structural properties of
the porous materials. The resulting bodies have axially oriented channels (average diameter
in between 0.59–1.25 mm) and open porosity up to 85 vol% with high specific surface area
(121.9 m2/g).

Fig. 1. Aligned porosity samples, (left image) cured thermoset, and (right image)
tomography image of the pyrolyzed sample

235
Effect of SiC on the oxidation resistance of carbon fibre reinforced
ZrB2/SiC composites
A. Vinci, L. Zoli, D. Sciti
CNR-ISTEC, Institute of Science and Technology for Ceramics, Via Granarolo 64, I-48018 Faenza,
Italy

Ultra-High-Temperature-Ceramics (UHTCs) are a novel class of refractory materials charac-

terized by melting points exceeding 3000 °C and very good thermo-mechanical properties.1
Among UHTCs, ZrB2/SiC composites have been investigated as potential candidates for the
fabrication of reusable Thermal Protection Systems (TPS) for aerospace applications due to

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their good oxidation resistance.2 However, their low fracture toughness and thermal shock
resistance remain major obstacles to their implementation.3,4
For this purpose, continuous carbon fibres (~45 vol.%) were used as reinforcement in or-
der to increase their damage tolerance and thermal shock resistance.5 The resulting materials
were labeled “UHTCMCs” (Ultra High Temperature Ceramic Matrix Composites).
In this work, the oxidation resistance of carbon fibre reinforced ZrB2/SiC composites was
investigated. Composites with SiC amounts ranging from 5–20 vol.% were fabricated by
slurry infiltration and hot pressing at 1900 °C and 40 MPa. Oxidation tests were carried out
on cut specimen (2 × 2.5 × 12 mm3) in a bottom-up loading furnace at 1500 °C and 1650 °C.
The resulting microstructures were analysed by SEM-EDS and X-ray diffraction analysis.
Results show that the formation of a viscous borosilicate glass phase is essential for the
protection of carbon fibres from oxidation; low amounts of SiC do not provide enough pro-
tection against fibre degradation, while excessive formation of SiO2 is not beneficial for
oxidation resistance. The best compromise was found for the composition with 15% of SiC
which was characterized by the lowest degree of oxidation and weight loss.

References
1. W.G. Fahrenholtz, G.E. Hilmas, I.G. Talmy, J.A. Zaykoski, Refractory diborides of zirconium and
hafnium, J. Am. Ceram. Soc. 90 (2007) 1347–1364. doi:10.1111/j.1551-2916.2007.01583.x.
2. L. Zoli, D. Sciti, Efficacy of a ZrB2–SiC matrix in protecting C fibres from oxidation in novel
UHTCMC materials, Mater. Des. 113 (2017) 207–213. doi:10.1016/j.matdes.2016.09.104.
3. R. Zhang, X. Cheng, D. Fang, L. Ke, Y. Wang, Ultra-high-temperature tensile properties and fracture
behavior of ZrB2-based ceramics in air above 1500°C, Mater. Des. 52 (2013) 17–22. doi:10.1016/j.
matdes.2013.05.045.
4. E. Zapata-Solvas, D.D. Jayaseelan, H.T. Lin, P. Brown, W.E. Lee, Mechanical properties of ZrB2-
and HfB2-based ultra-high temperature ceramics fabricated by spark plasma sintering, J. Eur.
­Ceram. Soc. 33 (2013) 1373–1386. doi:10.1016/j.jeurceramsoc.2012.12.009.
5. D. Sciti, A. Natali Murri, V. Medri, L. Zoli, Continuous C fibre composites with a porous
ZrB<inf>2</inf> Matrix, Mater. Des. 85 (2015) 127–134. doi:10.1016/j.matdes.2015.06.136.

428
Fabrication and characterization of nacre-inspired metal infused
ceramics
Amy Wat1,3*, Jein Lee2, Bernd Gludovatz3, Eun Soo Park2, Robert O. Ritchie1,3
1
Department of Materials Sciences & Engineering, University of California, Berkeley, 210 Hearst
Mining Building, Berkeley, CA 94720, USA; *e-mail: [email protected]
2
Department of Materials Sciences & Engineering, Seoul National University, South Korea
3
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA
Keywords: brick-and-mortar, alumina, BMG, structural materials, bioinspired, freeze casting,
presureless infiltration

The goal of this work is to increase the strength and toughness of bioinspired ceramic mate-
rials, modelled on the brick-and-mortar structure of nacre. Past theoretical studies (Begley,
et al. 2012) have suggested that a metallic mortar, as opposed to a polymer, would lead to

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significantly improved properties in a nacre-like material as long as the strength of the mortar
does not exceed the ceramic bricks. Based on these results, a freeze-cast ceramic scaffold
was infiltrated with a metal. This work used freeze casting because it is a relatively simple
technique to replicate the hierarchical structure of nacre. One challenge for producing a ce-
ramic/metal composite is that metals typically do not wet ceramics. This introduces the need
for high pressure to overcome capillary forces during infiltration. To resolve this issue, a Zr-
based bulk metallic glass (BMG) (Zr46Cu30.14Ag8.36Al8Be7.5) was used as the metallic mortar
because it reacts with the surface of the alumina to create an interfacial layer the metal readily
wets. This study focuses on how the mechanical properties of the hybrid ceramic materi-
als changes with respect to the infiltration temperature and ceramic content in order to find
the optimal processing conditions to create an effective brick-and-mortar architecture. The
results illustrate a trade-off between the fracture toughness and the flexural strength of the
resulting materials. Samples with higher ceramic content and higher infiltration temperature
have lower flexural strength, but higher fracture toughness. One cause of this behaviour is the
increasing infiltration temperature decreases the glassiness of the BMG phase, which leads to
an increase of thickness of the brittle intermetallic phase.

Reference
1. Begley, M.R., N.R. Philips, B.G. Compton, D.V. Wilbrink, R.O. Ritchie, and M. Utz. “Microme-
chanical models to guide the development of synthetic ‘brick and mortar’ composites.” J. Mech.
Phys. Solids, 60, pp. 1545–1560, 2012.

279
Fly ash based-cordierite containing mullite geopolymer composite
Darunee Wattanasiriwech1*, Faisal Arif Nurgesang1, Suthee Wattanasiriwech1,
Patthamaporn Timakul2
1
Materials for Energy and Environment Research Group, School of Science, Mae Fah Luang
University, Thailand 57100; *e-mail: [email protected]
2
National Metal and Materials Technology Centre, Thailand 12120
Keywords: geopolymer composite, compressive strength, modulus of rupture, thermal property

Attempt to improve thermal properties of the fly ash based-geopolymer was performed
by compositing with cordierite containing mullite in the 20–60 wt% replacement range. A
number of characterization and property testing were carefully executed. The XRD showed
existence of cordierite, mullite, quartz, cancrinite and lazurite in all the geopolymer com-
posites. Upon heating the geopolymer composite, lazurite phase became more intensed and
at 800 °C, cordierite had reacted and changed to diopside. Derivative thermal gravimetric
analysis (DTG) and dilatometer test results showed that the geopolymer composite (60%
cordeirite replacement) had a much smaller weight loss, and thus a smaller shrinkage, than
the based geopomer (control), producing a less internal stress. Improvement of the compres-
sive strength and the superior strength retention ability after the thermal exposure at 400 °C
was found in the geopolymer composite especailly those with 20–40 wt%. Further heating

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to 600 °C, all geopolymers showed insignificant difference in the compressive strength. Fire
resistance was improved with increasing the cordierite contents. This research showed that
compressive strength and thermal properties of fly ash based geopolymer could be improved
by compositing with cordierite containing mullite in the selected amounts.

515
Tuning ceramic microstructures using capillary suspensions with
incorporated nanoparticles
Moritz Weiß1,2*, Erin Koos1,2
Soft Matter, Rheology and Technology, Department of Chemical Engineering, KU Leuven,
1

Celestijnenlaan 200F, 3001 Leuven, Belgium; *e-mail: [email protected]

Institute for Mechanical Process Engineering and Mechanics, Karlsruhe Institute of Technology,
2

Gotthard-Franz-Strasse 3, Germany
Keywords: porous materials, open porosity, structure formation, hierarchical structure, mechani-
cal strength, nanoparticles, sintering, capillary suspensions, high temperature applications, filtration,
catalysis

Capillary suspensions can be used as stable precursors to create porous ceramics with a high
open-porosity. Capillary suspensions are solid-liquid-liquid systems with a small amount of
an immiscible secondary fluid added to a suspension. A strong particle network forms due
to capillary forces, which changes the material strength from fluid-like or weakly elastic to
strong gel-like behavior.1 The particle network connected through capillary bridges is much
stronger than those created by van der Waals forces; it does not collapse during debinding or
sintering, and therefore can serve as precursor for sintered materials with high open-porosity.2
We utilize the secondary fluid to deposit ceramic nanoparticles specifically in the contact
regions of the microparticles. Therefore, we have advanced control over the resulting micro-
structure. We show an increased mechanical stability and a lower sintering temperature for
the sintered bodies by adding 2–40 vol% nanoparticles to the secondary phase. Moreover,
the resulting pores are smoother and give rise to a higher permeability. Thus, we are able to
control the sintering of the neck regions and pore shape, which allows us to specifically tune
the final ceramic properties. These nanoparticles can also be from a dissimilar material.
Through this approach, we can use nanoparticle-laden secondary liquids as a temperature
stable “bonding agent” for catalytically active particles, e.g. zeolites, to generate hierarchi-
cally structured porous bodies. The capillary-induced particle network creates macroporosity
and microporosity is supplied by the coarse particles. The sintering activated neck formation
of the ceramic nanoparticles “glues” the coarse particles together and supplies mechanical
stability while preserving the inherent porosity in the catalytic particles. The strength and
porosity can be controlled by combining the particle size dependency with nanoparticle type
and sintering temperature. Hence, we can create hierarchically structured porous bodies with
high specific surface area for high-temperature catalysis applications.

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References
1. E. Koos, N. Willenbacher, “Capillary Forces in Suspension Rheology”, Science, 331, pp. 897–900,
2011.
2. J. Dittmann, E. Koos, N. Willenbacher, “Ceramic Capillary Suspensions: Novel Processing Route
for Macroporous Ceramic Materials”, J. Am. Ceram. Soc., 96, pp. 391–397, 2013.

218
A study on the feasibility of Zrn+1AlCn and Zrn+1SiCn MAX phases
for future fission environments
E. Zapata Solvas1, N. Ni2, William E. Lee1
Centre for Nuclear Engineering, Department of Materials, Imperial College London, London SW7
1

2AZ, UK
Centre for Advanced Structural Ceramics, Department of Materials, Imperial College London,
2

London SW7 2AZ, UK

After Fukushima’s nuclear disaster there has been a growing interest in introducing new
safety concepts for future fission reactors. One approach is to develop Accident Tolerant
Fuels (ATF) that can withstand the harsh environment within a fission reactor for at least 10
hours in a Loss-of-Coolant-Accident (LOCA). MAX phases are potential candidates for use
in ATF as cladding. The system that has been targeted is Zrn+1AlCn. Zr offers compatibility
with the zircaloy cladding, Al offers resistance to corrosion and oxidation, while C limits
nuclear transmutation. In addition, ZrSi2 has been recently proposed as another candidate for
ATF, which suggests that Zrn+1SiCn MAX phases could be potentially used in ATF. However,
there are some concerns about corrosion resistance due to the presence of Si and SiO2 solubil-
ity under normal pressurized water reactor (PWR) operating conditions as well as accident
scenarios.
This work examines stabilization of Zrn+1AlCn MAX phases by partial substitutions in the
quaternary systems (Zr,M´)n+1ACn and Zrn+1(A, A´)Cn where A = Al, Si. Synthesis and sinter-
ing of MAX phases will be discussed as well as oxidation resistance, corrosion resistance in
PWR conditions and thermal properties.

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158
Design and characterization of substoichiometric zirconium carbides
for Gen-IV Very High Temperature Reactors (VHTRs)
Jie Zhang*, Lina Chen, Yiming Lei, Jingyang Wang
Shenyang National Laboratory for Materials Science, Institute of Metal Research,
Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016, China;
*
e-mail: [email protected]

Zirconium carbide is considered as an attractive structural material for new generation reac-
tors operating at high temperature, due to its promising properties, including high melting
point, high hardness, good wear and corrosion resistance, high thermal conductivity at high
temperature, high thermal-chemical stability, as well as low cross section capture for neutrons
and superior resistance to radiation damage. Besides, zirconium carbide is a typical non-
stoichiometric compound with a high carbon vacancy concentration. Using First-principle
calculations, the structural characteristics and stability of non-stoichiometric zirconium car-
bide have been identified. Accordingly, advanced zirconium carbides have been designed by
tuning the carbon vacancy characteristics. Then non-stoichiometric ZrC0.86, ZrC0.78, ZrC0.55,
and ZrC0.49 were synthesized by PVD method. The microstructure, and mechanical properties
of the as-synthesized coatings were investigated. Finally, the irradiation damage tolerance
against Au ions were performed to evaluate the feasibility of the advanced zirconium car-
bides in Very High Temperature Reactors.

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Poster presentations

653
Effects of additive amount and mechanical alloying duration
on the microstructural and mechanical properties of ZrB2 ceramics
prepared via pressureless sintering
Duygu Ağaoğulları1*, Hasan Gökçe2, M. Lütfi Öveçoğlu1
Department of Metallurgical and Materials Engineering Department, Istanbul Technical University,
1

34469 Maslak, Istanbul, Turkey; *e-mail: [email protected]

Prof. Dr. Adnan Tekin Materials Science and Production Technologies Applied Research Center
2

(ATARC), 34469 Maslak, Istanbul, Turkey

Keywords: zirconium diboride, mechanical alloying, co sintering aid, pressureless sintering

Amongst various transition metal borides, zirconium diboride (ZrB2) has attracted consider-
able interest due to its superior properties such as high melting point, low density, high hard-
ness, high elastic modulus, low thermal expansion coefficient, high electrical and thermal
conductivity, high wear, corrosion and thermal shock resistance, good oxidation resistance,
excellent chemical inertness and durability.1 ZrB2 has been used in cutting tools, crucibles
and dies for molten metals, thermocouple sheaths, ballistic armours, wear resistant coatings,
electrodischarge machining electrodes, particulate reinforced composites, integrated circuits,
leading edges and nosecaps for hypersonic atmospheric re-entry, rocket nozzle inserts and
high temperature nuclear reactors.1,2 However, consolidation problems, weak fracture tough-
ness, flexural strength and intrinsic brittle character of ZrB2 usually restrict its extensive ap-
plications as a structural material. The densification of ZrB2 requires extremely high sintering
temperatures and long dwell times because of a rather-low self-diffusion coefficient caused
by the predominant covalent bonding. Such extreme processing conditions induce excessive
grain growth, internal stresses and microcracks which are detrimental to mechanical proper-
ties. Besides, densification of ZrB2 is feasible at lower temperatures with the use of sinter
additives such as Fe, Ni, Cr, Co, Mo and Cu or some silicides, oxides, etc.2
On the basis of the reported literature, pressureless sintering of ZrB2 with Co metallic ad-
ditive is not a well-discussed topic. This study presents the microstructural and mechanical
properties of ZrB2 ceramics prepared by using a combined method of mechanical alloying
(MA), cold pressing and pressureless sintering. The effects of Co addition (0, 5, 10 and 20
wt.%) and mechanical alloying duration (0, 3, 6 and 9 h) on the properties of ZrB2 ceram-
ics were investigated. MA experiments were carried out in a SpexTM 8000D Mixer/Mill and
milled powders were subsequently compacted to cylindrical preforms by uniaxial pressing
at 400 MPa. The green compacts were sintered in a controlled atmosphere at 1550 ºC for
1 h. Phase and microstructural characterizations of the mechanically alloyed (MA’d) and
sintered samples were performed by X-ray diffractometer (XRD), optical microscope (OM)
and scanning electron microscope/energy dispersive spectrometer (SEM/EDS). Density
measurements were conducted using Archimedes method. Vickers hardness, elastic modulus
and fracture toughness of the sintered samples were measured using Indentation technique.

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References
1. A.W. Weimer. Carbide, Nitride and Boride Materials Synthesis and Processing, Chapman & Hall,
Cambridge, Great Britain, 1997.
2. J. Rodríguez-Sánchez, E. Sánchez-González, F. Guiberteau, A.L. Ortiz, “Contact-mechanical prop-
erties at intermediate temperatures of ZrB2 ultra-high-temperature ceramics pressureless sintered
with Mo, Ta, or Zr disilicides”, J. Eur. Ceram. Soc., 35, pp. 3179–3185, 2015.

660
Study of microstructure and functional properties of layered BaTiO3–
ferrite–BaTiO3 magnetoelectric composites obtained by SPS method
Mirela Airimioaei1, Cristina E. Ciomaga2*, Alexandra Guzu1, Nadejda Horchidan1,
Lavinia P. Curecheriu1, Nicoleta Lupu3, Florin M. Tufescu1,4, Liliana Mitoseriu1
1
Dielectrics, Ferroelectrics & Multiferroics Group, Department of Physics, Al. I. Cuza Univ. of Iasi,
11 Carol I Bv., 700506, Iasi, Romania
2
Research Department, Faculty of Physics, Dielectrics, Ferroelectrics & Multiferroics Group,
Al. I. Cuza Univ. of Iasi, 11 Carol I Bv., 700506, Iasi, Romania; *e-mail: [email protected]
3
National Institute of Research and Development for Technical Physics, Iasi 700050, Romania
4
GRADIENT Srl., Street Codrescu no. 17, Iasi 700495, Romania

Multiferroic trilayer BaTiO3–Co0.8Zn0.2Fe2O4–BaTiO3 (BT–CZF–BT) and BaTiO3–CoFe2O4–

BaTiO3 (BT–CF–BT) composites are synthesized by Spark Plasma Sintering method. The
investigation of the cross-sectional view of the trilayer composites using scanning electron
microscopy shows a clear interface between the different layers. Microstructural SEM analy-
sis (fracture) of the layered composites consolidated by SPS indicates the presence of two
distinct phases: grey area corresponding to the ferroelectric phase (BT), while dark regions
correspond to the magnetic phase (CF/CZF). It can be observed that by SPS consolidation
was obtained good quality dense composite ceramics with (2–2) interconnectivity and a good
separation of the two phases, with neat and clean interface without porosity and limited
interdiffusion at interface. Furthermore, the dependence of dielectric properties on the fre-
quency and temperature has been examined. In the dielectric constant versus temperature
plots, a dielectric anomaly is observed near the ferroelectric to paraelectric phase transition
of the BT, which shifts towards high temperature side as frequency increases for all the
samples, demonstrating relaxor like behavior. In addition, broad peaks are also noticed in the
loss tangent versus temperature plots in the same temperature range. Study of ferroelectric
(P(E), dc-tunability and pyroelectric effect) properties have been investigated and discussed
in details. The evolution of temperature and of the pyroelectric current for the layer BT-CZF/
CF-BT ceramic samples for determination of pyroelectric coefficient on heating and cooling
rate, respectively was described. The influence of the magnetic layer (CZF/CF) thickness and
dc magnetic field on the magnetoelectric coefficient (αE) of the layer composites is studied.

Acknowledgments
This work was supported by MEN-UEFISCDI project no. PN-II-PT-PCCA-2013-4-1119.

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936
Preparation and characterization of aligned alumina scaffolds using
Bi-directional freeze casting
Sana Algharaibeh and BoSu
Biomaterials Engineering Group (bioMEG), School of Oral & Dental Sciences, University of Bristol,
UK; e-mail: [email protected]
Keywords: freeze casting, alumina, highly aligned structure, dual tempreture gradients

Freeze casting or ice templating, is a novel method to fabricate highly porous ceramic materi-
als. Despite its well-documented advantages, the lack of a precise way to control the hierar-
chical structure of the porous network is considered a major limitation1. Understanding the
freezing mechanism to fabricate reproducible highly aligned structure materials using freeze
casting is important to apply these porous materials to biological and industrial applications2.
In this work, alumina ceramic slurries were freeze casted under dual temperature gradients.
A special mould using a polymer wedge with different slope angles was used to modulate the
temperature field. The effects of different processing parameters (cooling rate, mould slope
angle, solid loading and binder concentration) on lamellar orientation were studied. The re-
sults showed that freezing under dual temperature gradients produced highly aligned ceramic
scaffolds. Increasing both the cooling rate and the mould slope angle increase the size of the
highly aligned ordered ceramic domain. Using different alumina solid loadings in the initial
suspension had a minimum effect on the aligned lamellar structure. Increasing the binder

Fig. 1. Light microscope images show the alignment of lamellar structure of ceramic samples produced at
different cooling rates (1, 5 and 10 °C/min) and using different copper moulds with various slope angles
(α = 0°, 5°, 10° and 20°). The colour gradient represents different angles of lamellar alignment, the colour
bar at the right side of the images

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concentration affected ice crystal’s growth in an aligned direction. Therefore, freeze casting
technique under dual temperature gradients could be used as a viable method to fabricate
highly aligned porous materials. By controlling the microstructural features, it is possible to
produce biomimetic materials with potentially superior mechanical properties.

Acknowledgments
The authors wish to thank the Wolfson Bioimaging EM department and the Elizabeth Blackwell Insti-
tute, through its Wellcome Trust ISSF Award.

References
1. Bai H, Chen Y, Delattre B, Tomsia AP, Ritchie RO. Bioinspired large-scale aligned porous materials
assembled with dual temperature gradients. Science advances. 2015;1(11):e1500849.
2. Deville S. Freeze-casting of porous ceramics: A review of current achievements and issues.
­Advanced Engineering Materials. 2008;10(3):155–169.

504
Yttrium silicate used as environmental barrier coating:
relation between microstructure and protection efficiency
Simon Arnal1, Fabrice Mauvy2, Francis Rebillat1
Laboratoire des Composites Thermostructuraux, 3 allée de la Boetie 33600 Pessac, France;
1

e-mail: [email protected]
Institut de Chimie de la Matière Condensée de Bordeaux, 87 Avenue du Dr Schweitzer,
2

33600 Pessac, France; e-mail: [email protected]

Future generations of parts of turbines will be replaced by Ceramic Matrix Composites

(CMCs). Generally these CMCs consist of ceramic matrices reinforced fibers, both in silicon
carbide. However, at elevated temperatures and under severe atmospheres, the silica protec-
tive scale over silicon carbide volatilize as hydroxides species and the resulting recession of
silicon carbide may cause the loss of the composite’s mechanical properties.
To protect CMCs, EBCs are put in place. The most stable EBCs are often rare-earth sili-
cates.1 This investigation is focused on yttrium silicate EBCs. To deposit EBCs, each process
generates a different microstructure, by varying the duration of sintering, for example, or by
varying the particle size distribution of the powder. These differences in microstructure will
have an important influence on the ionic conductivity inside the coating as well as the reces-
sion rate of EBCs.2 The challenge of this investigation is to measure the ionic conductivity
of yttrium silicates (mono and di) and to quantify their rate of recession. Ionic conductivity
has been revealed by employing complex impedance spectroscopy. The use of this technique
allows determining the ionic conductivity of the ceramic at different temperatures in various
environments dry or wet. Moreover, the contribution of the bulk and the grain boundaries can
be separated. For different microstructures (nanostructured or micron), the grain surface and
grain boundaries surface will be different therefore, inducing changes in the ionic conductiv-
ity also. A similar issue occurs in the case of volatilization at the EBC surface. For example,
reactions of volatilization should take place in the less crystallized zones as grains boundar-

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ies. Further, model layered composite (EBC/Si/EBC) are made and submitted to moist air at
high temperature, to compare the efficiency of the EBC to limit the diffusion of oxidizing
species with the previous measured ionic conductivity. More than the role of microstructure,
its efficiency is related with the grain growth rate in function of ageing.

References
1. K.N. Lee, D.S. Fox, N.P. Bansal, Rare earth silicate environmental barrier coatings for SiC/SiC
composites and Si3N4 ceramics. J. Eur. Ceram. Soc., 25, pp. 1705–1715, 2005.
2. E. Courcot., F. Rebillat, F. Teyssandier, C. Louchet-Pouillerie, “Stability of rare earth oxides in a
moist environment at high temperatures-Experimental and thermodynamic studies. Part I: The way
to assess thermodynamic parameters from volatilization rates”, J. Eur. Ceram. Soc., 30 (9), pp.
1903–1909, 2010.

582
Wear behavior and mechanical properties of SiC/GPLs composites with
different counterparts
Ján Balko1*, Richard Sedlák1, Alexandra Kovalčíková1, Pawel Rutkowski2,
Aleksandra Dubiel2, Ján Dusza1
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 04001 Košice,
1

Slovak Republic; *e-mail: [email protected]

AGH University of Science and Technology in Krakow, Faculty of Material Science and Ceramics,
2

Department of Ceramics and Refractories, al. A. Mickiewicza 30, Krakow, Poland

Keywords: wear, friction coefficient, hardness, toughness

Wear behavior and mechanical properties of composites with silicon carbide matrix with ad-
dition from 0.5 to 6 wt.% of GPLs filler were investigated and compared to the monolithic
silicon carbide material. All experimental materials, containing 0.5 wt.% of boron and 3.5
wt.% GPLs as sintering additive plus 0 wt.% (reference sample) – 6 wt.% GPLs as reinforc-
ing phase, were hot pressed at 2100 °C for 1 h under 25 MPa in argon flow. The wear behav-
ior was observed by means of the ball-on-flat technique with a both silicon carbide and tung-
sten carbide – cobalt balls used as the tribological counterpart at room temperature ~25 °C,
in dry sliding at different loads (5, 30 and 50N). Addition of such amounts of GPLs did not
lower the coefficient of friction. Wear rates values showed strong dependence on the applied
load, at both tribological pairs. Tenfold increase of normal load (from 5 to 50 N), results wear
rate increase of two orders of magnitude. Friction coefficients decrease with an increase of
the applied load. The influence of the GPLs addition on bending strength, fracture toughness
and related fracture characteristics was investigated. Both the bending strength and fracture
toughness increased with increasing of GPLs additives. The fracture toughness was enhanced
due to the activated toughening mechanisms mainly in the form of crack bridging and crack
branching, while the crack deflection was limited.

Acknowledgement
The authors gratefully acknowledge for the financial support from projects: VEGA 2/0163/16, VEGA
2/0189/15, VEGA 2/0130/14, APVV-15-0496 and MVTS 7RP ERA.NET-GRACE.

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581
Novel ceramic composites reinforced with ZrO2 nanofibers
Eszter Bódis1*, Kolos Molnár2, Anna Mária Keszler1, Szilvia Klébert1, Péter Fazekas1,
Zoltán Károly1, János Szépvölgyi1
Plasma Chemistry Research Group, Institute of Materials and Environmental Chemistry,
1

Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar tudósok körútja 2.,
1117, Budapest, Hungary; *e-mail: [email protected]
Department of Polymer Engineering, Faculty of Mechanical Engineering Budapest,
2

University of Technology and Economics, Műegyetem rkp. 3, 1111 Budapest, Hungary

Keywords: Si3N4, ZrO2 nanofibers, electrospinning, SPS, mechanical properties

Silicon nitride (Si3N4) based ceramics exhibit a remarkable combination of mechanical prop-
erties: good wear, oxidation and corrosive resistance, excellent thermal shock resistance and
not at least high hardness, however, currently their poor fracture toughness is a significant
disadvantage which is a limitation factor for its widespread application. In case of Si3N4
many reinforcing phases have been studied successfully, for example, it was reinforced with
various ceramics particles and carbon structures, such as nanotubes and graphene. The dif-
ferent carbon structures could show very good opportunity to improve the fracture tough-
ness1; however, the main drawback of these non–oxide secondary phases is their mechanical
properties degradation at elevated temperatures under air. To avoid this degradation, one
of the potential reinforcing phase is the ZrO2. Therefore, in this work we are investigating
an alternative route to develop a SPS sintered Si3N4 ceramic composites with high fracture
toughness and strength reinforced by self-made electrospun 3 mol% Y2O3 partially stabilized
ZrO2 nanofibers, which could be suitable to use the composites at high temperature beside in
air atmosphere, as well.
We obtained significant fracture toughness and flexural strengths improvements in ZrO2
fiber reinforced Si3N4 composites. The sample loaded by 15 wt% ZrO2 fibers had 10.05±
0.7 MPa m1/2 fracture toughness and 543±19 MPa flexural strength, which means 105% and
115% improvements respectively, regarding to the reference sample. Thus, the incorpora-
tion of fiber into the Si3N4 composite is effective way to increase the fracture resistance and
avoided the catastrophic fracture behaviour since ZrO2 fiber is able to improved mechanical
properties of the composites in a complex way, such as phase transformation toughening and
fiber toughening mechanisms.

Reference
1. E. Bódis, O. Tapasztó, Z. Károly, P. Fazekas, Sz. Klébert, A.M. Keszler, K. Balázsi, J. Szépvölgyi,
Spark plasma sintering of Si3N4/ multilayer graphene composites, Open Chem., 13 484–489, 2015.

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140
Spark plasma sintering of alumina ceramics
M.S. Boldin*, А.А. Popov, E.A. Lantsev, А.V. Nokhrin, V.N. Chuvil’deev
Lobachevsky State University of Nizhny Novgorod (National Research University), Research and
Development Institute of Physics and Technology, Gagarin Ave. 23, Nizhny Novgorod, Russia;
*
e-mail: [email protected]
Keywords: spark plasma sintering, ceramics, alumina

In recent decades, the high-speed compaction technology known as Spark Plasma Sintering
(SPS) has become a frequent practice in powder engineering.1 One of the key features of
SPS technology that distinguishes it from other consolidation technologies is its high control
precision of sintering parameters. Optimization of SPS modes allows to obtain almost any
oxide ceramics with density close to 100% and grain growth factor below 2.2 At the same
time, ultrafine-grained structure of sinter materials ensures high strength properties. On the
other hand nano powders, surfactants, and ultrasonic-mixing processing allow to obtain even
distribution of the dispersed particles in the base material and therefore reduce their volume
fraction without decreasing of the mechanical strength. From this perspective, it looks very
promising to combine innovative approaches to obtaining powder composite systems and
SPS technology to produce Al2O3-based ceramics, which is the goal of the present work.
It is crucial to note that unless a continuous net of grain boundaries is formed, coarsening
of grain is impeded. A net of grain boundaries is considered to be formed at relative density
of ρ ~ 90%. From this point an intense grain growth is observed.3 In this context, in order to
obtain materials with maximum density and minimum grain size it is required to optimize
temperature and isothermal time after the material passes through ρ ~ 90%. At high sinter-
ing temperature, boundary migration speed is generally high, boundaries may «come off the
pores» leaving them in the grain volume. In this case, pores dissolution rate as well as con-
traction will be controlled by volume diffusion rather than grain boundary diffusion. Dense
materials are therefore hard to obtain. To eliminate the come-off effect, boundary migration
speed shall be slowed down. It can be achieved through reducing the sintering tempera-
ture after reaching the 90%-density point. This approach is known as «Two Step Sintering»,
«Multi Step Sintering», «Rate Control Sintering».
Lowering the temperature at the second sintering stage helps to reduce grain growth rate
while maintaining pores dissolution rate at a reasonable level. materials in order to obtain
lightweight ceramics Al2O3/ZrO2 with enhanced strength properties. Optimization of SPS
modes helps to produce ceramics with grain size of less than 400 nm, microhardness HV = 24
GPa, and crack resistance KIC = 4.2 MPa·m1/2.

References
1. Munir Z.A. and Quach D.V. 2011 J. Am. Ceram. Soc. 94 (1) 1.
2. Orru R., Licheri R., Locci A.M., Cincotti A., and Cao G. 2009 Materials Science and Engineering
R 63 127.
3. Fang Z.Z. Sintering of advanced materials fundamentals and processes. Woodhead Publishing Lim-
ited, 2010.

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047
Alumina/zirconia composites toughened by the addition of graphene
flakes
Marek Boniecki
Institute of Electronic Materials Technology, Warsaw, Poland; e-mail: [email protected]

The effect of graphene flakes on the mechanical properties of the composite containing 20
wt. % Al2O3 and 80 wt. % ZrO2 (stab. 3 mol% Y2O3) was studied. To obtain samples a com-
mercial ceramic powder produced by Tosoh (Japan) and graphene oxide (GO) made in Insti-
tute of Electronic Materials Technology (Poland) were used. The obtained composites based
on an aqueous (GO) mixtures of both components. After drying, they were sintered under a
uniaxial pressure (HP furnace). The composites contained by weight from 0 to 3% of GO.
It was found that as a function of the GO: fracture toughness has a maximum for 0.02% GO
(42% increase compared to GO free matrix), strength decreases, the Young’s modulus and
Vickers hardness remain constant up to 0.5% GO, and then decrease.

783
Electrical and magnetic properties of SiC ceramics with addition
of Ti and NbC
Roman Bystrický1, Jaroslav Sedláček1, Martin Škrátek2, Milan Tapajna3, Pavol Šajgalík1
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, Bratislava,
1

Slovakia; *e-mail: [email protected]

Institute of Measurement Science, Slovak Academy of Sciences, Dúbravská cesta 9, Bratislava,
2

Slovakia
Institute of Electrical Engineering, Slovak Academy of Sciences, Dúbravská cesta 9, Bratislava,
3

Slovakia
Keywords: silicon carbide, hot-press, electrical conductivity

In this work silicon carbide based composites were prepared by hot-press method. 30, 40 and
50 mass% of of Ti and NbC were used as sintering additives. Their molar ratio was kept at
1:1.8 (Ti:NbC). Samples were sintered by two step sintering to avoid the squeezing out the
melted titanium above 1668 °C. Composites were sintered at 1650 °C for 3 h and subsequent-
ly at 1850 °C for 1 h under mechanical pressure of 30 MPa in Ar atmosphere. Composite
with 50% of Ti-NbC phase showed the electrical conductivity of 240 S·mm–1, which is three
times order higher than in reference SiC. SEM analysis showed that there are agglomerates
of SiC grain and agglomerates of (Ti, Nb)C solid solution in the sample. Only a thin layer of
secondary phase is located between SiC grains. XRD pattern confirmed the formation of (Ti,
Nb)C solid solution in the SiC matrix. Magnetic measurements showed that the sample with
50 mass% Ti-NbC is clearly ferromagnetic at 2K while the behavior of samples with 30 and

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40 mass% of Ti-NbC is changing from ferromagnetic to diamagnetic at higher fields (up to

7T). At room temperature samples with 30 and 40 mass% of Ti-NbC are diamagnetic and the
sample with 50 mass% of Ti-NbC is paramagnetic.

597
Characterization of thermal barriers coatings of Y-TZP/AL2O3/SiC
composite obtained by suspension plasma spraying
V. Carnicer1, E. Cañas1, M.J. Orts1, R. Moreno2, M.D. Salvador3, P. Carpio3, L. Navarro3,
E. Sánchez1*
Instituto de Tecnología Cerámica (ITC), Universitat Jaume I (UJI), Av. Sos Baynat s/n, 12006
1

Castellón, Spain; *e-mail: [email protected]

Instituto de Cerámica y Vidrio (ICV), Consejo Superior de Investigaciones Científicas (CSIC),
2

Kelsen 5, E-28049, Madrid, Spain

Instituto de Tecnología de Materiales (ITM), Universitat Politècnica de València (UPV),
3

Camino de Vera, s/n, 46022 Valencia, Spain

Keywords: thermal barrier coatings, suspension plasma spraying, composite, self-healing

Thermal barrier coatings (TBCs) are used for protection of metals and ceramic components
against corrosion, erosion and high temperature. The most common composition is based in
yttria-stabilised zirconia (Y-TZP) because this material exhibits excellent mechanical and
thermal properties. Nevertheless, continued use in extreme temperatures and aggressive con-
ditions favours the appearance of cracks and the quick wear of the zircona layer. Hence,
these TBCs must be improved in order to increase their lifetime under aggressive conditions.
For that reason, the design of new TBCs with a self-healing functionality, which allows to
increase the TBCs lifetime, could be an alternative challenge.
There are few ceramic materials with this ability, being silicon carbide (SiC) the most
studied one. Nevertheless, SiC particles tend to decompose and oxidise inside a plasma torch
losing their healing ability. The preservation of this ability is essential, thus, a new strategy
has been followed in the present work in order to avoid the decomposition of the SiC. This
strategy consists of employing a suspension as feedstock instead of powders. In this way, the
solid material receives less energy during deposition due to solvent evaporation. Further-
more, the addition of a third compound (Al2O3), which helps to melt the matrix mixture, can
make a further contribution to the protection of the SiC particles in the plasma torch.
In accordance with the proposed strategy, an aqueous-based suspension of SiC, Y-TZP and
Al2O3 was prepared and deposited by suspension plasma spraying (SPS). The deposition was
performed onto substrates of stainless steel, employing different solid contents and stand-off
distances with the purpose of assessing coatings microstructure. The obtained coatings were
microstructurally analysed by scanning electron microscopy (SEM) and energy dispersive
X-ray (EDX), while the different crystalline phases were determined by X-ray diffraction
(XRD). The characterisation reveals the presence of unmelted SiC particles dispersed in a

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partially melted matrix of Al2O3/Y-TZP, confirming that the SiC particles have not been oxi-
dised during plasma spraying, preserving its potential self-healing ability. Besides, the effect
of stand-of distances on the coatings porosity and adherence was also assessed.

Acknowledgements
This work has been supported by the Spanish Ministry of Economy and Competitiveness (ref.
MAT2015-67586-C3-R).

506
Adhesion assessment of bioactive coatings deposited by atmospheric
plasma spraying
Eugeni Cañas*, Mónica Vicent, Mª José Orts, Enrique Sánchez
Instituto de Tecnología Cerámica (ITC), Asociación de Investigación de las Industrias Cerámicas
(AICE), Universitat Jaume I (UJI), Avenida Vicente Sos Baynat s/n, Castellón, Spain;
*
e-mail: [email protected]
Keywords: bioactive powders, atmospheric plasma spraying, bioactive coatings, coatings adhesion

Bioactive coatings are used in the field of medicine as coatings for orthopaedic implants
made of bio-inert materials such as stainless steel, chromium/cobalt or titanium alloys with
the aim of conferring biocompatibility and protecting them against the corrosion and the deg-
radation promoted by biological fluids. Usually, these coatings can be deposited by different
techniques such as enamelling, sol-gel or dipping. However, atmospheric plasma spraying
(APS) is one of the most studied and used method for obtaining these coatings. While bio-
active coatings have to accomplish several requirements (biocompatibility, porosity, rough
surface, etc.), a good adhesion to the implant surface represents one of the most important
challenges which is hardly reached.
Therefore, the aim of the present work is to prepare bioactive coatings by APS employing
different spraying parameters and substrates in order to model the adhesion of the coatings
and to determine the best parameters that allow to prepare coatings with good adhesion to the
substrate. For that purpose, a statistical analysis was performed evaluating the adhesion in
function of different variables, each one at two different levels, and correlating the adhesion
with them. The variables chosen are the argon flow and the feedstock feed rates, the type
of substrate and the presence of a bond coat. Furthermore, coatings were microstructurally
characterised by scanning electron microscopy and their nature (amorphous or crystalline)
was determined by X-ray diffraction.
The obtained results show significant differences in coatings adhesion in function of the
variables tested, varying this mechanical property from 0.6 to 10 MPa. Moreover, the model
and the correlations between variables obtained from the statistical analysis, confirm that the
adhesion is strongly influenced by the presence of a bond coat as well as the plasma gases
flow rate and the type of substrate. Besides, it can be appreciated that coatings with higher
adhesion values show better microstructures.

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Acknowledgements
This work has been supported by Research Promotion Plan of the Universitat Jaume I (ref. PRED-
OC/2015/50).

438
Creep behaviour of alumina reinforced composites sintered by spark
plasma sintering
Rafael Cano-Crespo1*, Bibi Malmal-Moshtaghioun1, Diego Gómez-García1,2,
Arturo Domínguez-Rodríguez1, Rodrigo Moreno-Botella3
1
Departmento de Física de la Materia Condensada, Universidad de Sevilla, Avenida de Reina
Mercedes s/n, 41080 Sevilla, Spain; *e-mail: [email protected]
2
Instituto de Ciencia de Materiales de Sevilla, CSIC-US, Avenida Américo Vespucio 49,
41092 Sevilla, Spain
3
Instituto de Cerámica y Vidrio (ICV- CSIC), E-28049, Madrid, Spain
Keywords: graphene-oxide, carbon nanofiber, alumina composites, creep resistance

Alumina (Al2O3) ceramic composites reinforced with either graphene oxide (GO) or carbon
nanofibers (CNFs) were prepared using Spark Plasma Sintering. The effects of GO and CNFs
on the microstructure and in consequence, on their mechanical properties, were investigated.
The microstructure of the sintered materials have been characterized quantitatively prior to
and after the creep experiments in order to determine the deformation mechanism.
Carbon materials, such as carbon fibers or carbon nanotubes (CNTs), or graphene, have
been used in the last decades to improve the mechanical properties of a large variety of ma-
terials. Another way to improve the mechanical properties of alumina is by means of fibers
as reinforcement in ceramic composites. Fiber/whiskers usually have diameters ranged from
a micrometer to tens of micrometers and lengths from several micrometers till hundreds of
micrometers, embedded inside a fine-grained ceramic matrix.1
The study of their plasticity can permit to go insight the intrinsic mechanisms of matter
flow and phase arrangement under loading conditions. This basic information is crucial to
feedback and improve the processing conditions for an optimized composite.
High-temperature creep behavior of graphene-oxide reinforced alumina composites and
carbon nanofiber reinforced ones prepared by spark plasma sintering have been studied at
temperatures as high as 1200 ºC and above. The results show that the microstructure is quite
stable during creep and consistent with grain boundary sliding as the deformation mecha-
nism. The graphene-oxide-reinforced alumina composite is systematically more creep resis-
tant than the carbon nanofiber one, although the creep resistance diminishes when tempera-
ture increases. In this context, graphene oxide and carbon nanofibers offer similar advantages
in very high-temperature applications of alumina composites.

Reference
1. B.R. Lawn. Fracture of brittle solids. 2nd ed. Cambridge, Cambridge University Press, 1990.

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112
Low volumetric heat capacity insulation coating by room-temperature
operating spray coating process
Jong-Jin Choi*, Sae-Jung Yoon, Byung-Dong Hahn, Cheol-Woo Ahn
Functional Ceramics Department, Korea Institute of Materials Science, 797 Changwondaero,
Changwon, South Korea; *e-mail: [email protected]
Keywords: insulation, low volumetric heat capacity, spray coating

Insulation coating with both low thermal conductivity and low volumetric specific heat is
useful for heat loss reduction of engine combustion chamber without any sacrifice in other
engine performances.1 In comparison with conventional dense - high volumetric specific
heat insulation coating, the low volumetric specific heat coating can reduce surface tempera-
ture of insulation coat on combustion chamber wall rapidly, according with the fluctuating
temperature of in-cylinder gas. To realize low volumetric specific heat, microstructure of
the coat should be porous. Also, the coat should have high enough durability – adhesion
strength, hardness, and chemical inertness for real operating condition, justly with low ther-
mal conductivity. In this work, we fabricated porous ceramic insulation film with thickness of
~100um, porosity of 35~42%, adhesion strength of 20~28MPa, thermal conductivity of less
than 0.5W/mK without thermal damage of metal substrate by novel ceramic spray coating.
The processing, microstructure, thermal properties, and mechanical properties of the films
were analyzed.

Fig. 1. Microstructure of dense and porous insulation film fabricated by room-temperature operating
­ceramic spray coating process

Reference
1. A. Kawaguchi et al., SAE Technical Paper 2016-01-2333, 2016.

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048
Improvement of densification uniformity in carbon/silicon carbide
composites by chemical vapor infiltration
Kyoon Choi*, Jin-Won Seo, Kyung-Mi Kim
Icheon Branch, Korea Institute of Ceramic Engineering and Technology, Icheon 17303, Korea;
*
e-mail: [email protected]

Ceramic matrix composites (CMCs) have attracted lots of attentions due to their increased
fracture toughness, elongation and thermal shock resistance, which results in wide appli-
cations under extreme environmental conditions. The silicon carbide-based CMCs can be
commercially produced by silicon infiltration, precursor infiltration pyrolysis (PIP), chemi-
cal vapor infiltration (CVI) and their combined (or repeated) processes. The CVI process is
carried out by chemical deposition of reactive gaseous species into porous fiber preforms. As
a carbon fiber preform is exposed to a mixture of hydrogen and methyl-trichlorosilane (MTS)
at elevated temperature around 1000 degree Celsius, silicon carbide is deposited in between
the carbon fibers by decomposition of MTS. After CVI process, pores still exist partially in
the preform. Distribution of the remained pores varies with the infiltration depth of precur-
sor gas that is related to the gas flow and the temperature distribution of the preform. Im-
provement of densification uniformity of the preform is the main purpose of this work. The
optimum condition for densification was predicted with CFD simulation and the resultant
microstructure of CMC was demonstrated.

224
Ceramic materials for high efficiency advanced microturbines
Stefano Concari
RSE – Ricerca Sistema Energetico SpA, Milano, Italy

Gas microturbines are considered as a small size generation technology with a simplified
plant exercise and maintenance and a reduced environmental impact; commercial success
of the technology is however hindered by a limited efficiency compared to other small size
technology as internal combustion generation plants. The increase of electrical and overall
efficiency would allow to extent also the field of application for the microturbines with a pos-
sible application also in residential and tertiary sectors where the electrical and thermal de-
mands change in time and are highly weather conditions dependant. Production of advanced
microturbines, with efficiency comparable to internal combustion engines, is strictly related
to the possibility to manufacture some parts of the machine with materials showing a satis-
factory mechanical and oxidation resistance to more severe exercise conditions; in particular
high temperature resistant materials, as ceramic type, are required.
Preferable materials for high efficiency microturbines are, up to now, silicon nitrides whose
increased resistance can be obtained by sintering with particular additives or by protection

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with coatings in order to improve high temperature corrosion resistance. During recent years
RSE performed a characterisation activity of commercial and under development silicon
nitride materials that can be used for manufacturing advanced microturbines. Four point
bending mechanical strength tests have been performed at ambient and high temperatures
up to 1200 °C for yttrium and rare earth metal added silicon nitrides; results of mechanical
tests and material exposition in burner rig at 1200 °C confirm rare earth metal added silicon
nitride as preferable to yttrium added ones, unless some yttrium silicon nitride later can be
satisfactory for application in rotor and casing of high efficiency microturbines with limited
increase of gas inlet temperature (TIT).
The relevant loss of material observed in burner rig tests, for any tested silicon nitride
suggests that, also the most resistant material requires a protective coating application. Base
on this result a first trial of ceramic materials coated by other ceramics have been prepared
and tested, among tested combinations of materials a promising solution appears to be the ap-
plication of ytterbium disilicates on silicon nitride. A good resistance in exposition to severe
conditions has been observed for it, but further studies for optimisation of coating process
and tests for the characterisation of the overall system are still required before than actual
application on a prototype microrotor component.

381
Development of geopolymer composites reinforced with fiber felts
Alberto Conte1*, Gianluca Passante2, Paolo Colombo3
1
Department of Industrial Engineering, University of Padova, Via Marzolo 9, 35131, Italy;
*
e-mail: [email protected]
2
Trucker Subforniture s.r.l., Italy
3
University of Padova, Italy
Keywords: geopolymer, composite, fibers felt, RTM

Geopolymers are synthetic inorganic alumino-silicate materials generally formed by reaction

of an aluminosilicate with an alkali (Na,K) silicate solution. The reaction occurs at room
temperature, so geopolymer can be considered as a type of bi-component inorganic resin.
Considering their inorganic structure, geopolymer composites have better thermal proper-
ties than organic resins, which typically decompose by oxidation starting from ~400 °C.
In collaboration with Trucker Subforniture s.r.l., geopolymer based composites reinforced
with different kinds of felt, have been developed as alternative to GFRP and CFRP, for ap-
plications where a high thermal resistance is required.
Different kind of fibers were considered as reinforcement; using felts based on recycled fi-
bers it is possible to keep the cost lower than that of virgin fibers, in particular for carbon and
basalt fibers. Geopolymer composites were developed using RTM and infusion technology.
In order to have a good infiltration of the felts, the rheology of a potassium based geopolymer
resin was optimized in terms of water and alkalinity.
Density, mechanical properties and thermal stability of the different composites were
tested.

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References
1. A. Natali, S. Manzi, M.C. Bignozzi, Novel fiber-reinforced composite materials based on sustain-
able geopolymer matrix, Procedia Engineering, 21, pp. 1124–1131, 2011.
2. D. Ribero and W.M. Kriven, “Properties of Geopolymer Composites Reinforced with Basalt
Chopped Strand Mat or Woven Fabric”. J. Am. Ceram. Soc., 99, pp. 1192–1199, 2016.

413
Characterization of slip casting of ceramic Hollow Sphere slurries and
casting properties for ceramic processing applications
János Csizmazia
Engineering Division, Bay Zoltán Nonprofit Ltd. for Applied Research, Kondorfa u. 1.,
HU-1116 Budapest; e-mail: [email protected]
Keywords: Hollow Sphere, ceramic slurry, slip casting, closed cell foams

Light weight ceramic foams and composites are in focused attention in ceramic industries,
due to their high energy absorption, outstanding thermal properties, and light weight. They
have a significant potential for application in a wide range of industries, such as refractories,
light weight structural ceramics, metal casting parts, gas sensors, gas- and molten metal fil-
tration, implants, adsorbing structures, catalyst carriers, heat-insulation materials. The use of
Hollow Spheres (HSs) to build such ceramic foams is advantageous, as the cell sizes can be
easily controlled by the diameters of the HSs.
In the literature, to fabricate such kind of composites, several manufacturing process were
used, for instance sacrificial cores1, high temperature binders2, and dry compressing technol-
ogy3.
The goal of this research is to manufacture HS ceramic composites and coatings with slip
casting method. The slip casting method gives one the ability to increase packing densities
with avoiding the fracture of the HSs during manufacturing. Moreover, slip casting tech-
nique can be automated easily. The main limit of this technique is the size of the used HSs,
as gravitational forces play more significant role in colloidal systems, as the used particles’
size are increased.
In this study, I have chosen fine sized, commercially available mullite HSs, with an aver-
age diameter of 90 µm, the distribution of their sizes was lognormal with the standard devia-
tion value of 0.35. The slurry was built on with the use of various amount of HSs, dispersant,
and distilled water. Flow curves, sedimentation curves were plotted, and it has been proved,
that there exists a technological window, where the slurry is stable enough to use in slip cast-
ing, and in coating technologies. Slip casted specimens with cylindrical shape were prepared,
and fired at different temperatures in the range 1000 to 1400 °C. The shrinkage behaviour
strongly depended on the firing temperature. The output densities were in the range 26 to
47% of mullite’s density. The feasibility of producing ceramic closed cell foams with slip
casting method starting with HSs has been demonstrated.

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References
1. I. Thijs, J. Luyten, S. Mullens, Producing Ceramic Foams with Hollow Spheres, J. Am. Ceram.
Soc., 87, pp. 170–172, 2003.
2. H. Geng, X. Hu, J. Zhou, X. Xu, M. Wang, A. Guo, H. Du, J. Liu, Fabrication and compressive
properties of closed-cell alumina ceramics by binding hollow alumina spheres with high-tempera-
ture binder, Ceram. Int., 42, pp. 16071–16076, 2016.
3. D.J. Green, Fabrication and Mechanical Properties of Lightweight Ceramics Produced by Sintering
of Hollow Spheres, J. Am. Ceram. Soc., 68, pp. 403–409, 1985.

889
Layered functionally graded alumina ceramic composites
Maria Drozdova1, Roman Ivanov1, Miguel Angel Rodríguez2, Irina Hussainova1*
1
Department of Mechanical and Industrial Engineering, Tallinn University of Technology,
Ehitajate tee 5, 19086 Estonia; *e-mail: [email protected]
2
Instituto de Cerámica y Vídrio (CSIC), Campus Cantoblanco, 28049 Madrid, Spain
Keywords: alumina, graphene, functionally graded, composite

Multi-layered ceramic composites with alternation of grain sizes in layers have been pro-
duced by adding thin inter-layers of graphenated alumina nanofibers (GAIN) between lay-
ers of pure alumina. The composite was mounted layer by layer directly in the graphite
mold, using filter to precipitate alumina nanopowder and GAIN layers from corresponding
suspensions. The 20 mm diameter samples were consolidated by Spark Plasma Sintering
(SPS) technology at 1350 °C in nitrogen atmosphere under 50 MPa pressure. The effect of
inter-layers on microstructure and mechanical properties of alumina has been studied. SEM
analysis of microstructure reveals distinct grain size reduction in the areas surrounding GAIN
layers. Vickers hardness, fracture toughness and nanoindentation tests have been performed.

358
Electrophoretic deposition of dispersion of ZrB2 and SiC powders on
woven carbon fibers for the processing of novel UHTCMCs
S. Failla, L. Zoli,C. Baldisserri, D. Sciti
CNR-ISTEC, National Research Council of Italy - Institute of Science and Technology for Ceramics,
Via Granarolo 64, I-48018 Faenza, Italy

In the present work, the deposition of Zirconium diboride (ZrB2) or/and Silicon carbide
(SiC), on carbon fibers via electrophoretic deposition (EPD) is studied. The final purpose is
the fabrication of novel ultra-high-temperature ceramics matrix composites (UHTCMCs) for
aerospace featuring optimized fiber/matrix interfaces. Ceramic coatings are required for the
optimization of the fiber/matrix bonding, oxidation protection, and prevention of fiber-matrix
interfacial degradation at high temperatures. Ethanol –based ceramic suspensions of ZrB2 or/

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and SiC powders have been studied in order to determine the optimal solid concentration and
dispersant amount. Several deposition experiments were carried out to optimize voltage and
deposition time. An incremental approach was adopted, starting from deposition onto indi-
vidual bundles, then unidirectional carbon fabrics, and finally 2D carbon fabrics. The unidi-
rectional coated woven carbon fibers were further infiltrated with a ceramic slurry, overlayed,
and consolidated by hot pressing, to obtain 30 × 30 × 5 mm3 pellets. The microstructure of
the pellet was examined by scanning electron microscopy and optical microscopy. Flex-
ural strength and fracture toughness were measured on machined bars at room temperature,
reaching values of 280 MPa and 14 MPa*m1/2, respectively. The structure obtained by the
combination of these techniques is typical of novel UHTCMC materials that can potentially
couple the high oxidation resistance of UHTCs to the damage-tolerance of CMCs, provided
that a suitably tailored matrix/fiber interface can be obtained.

635
Mechanical properties and wear damage of silicon carbide composites
with carbon nanotubes
Martin Fides1, Pavol Hvizdoš1*, Alexandra Kovalčíková1, Róbert Džunda1,
Miroslav Hnatko2
1
Institute of Materials Research (SAS), Watsonova 47, 04001 Košice, Slovakia;
*
e-mail: [email protected]
2
Institute of Inorganic Chemistry (SAS), Dúbravská c. 9, 845 36 Bratislava 45, Slovakia
Keywords: SiC, CNT, nanoindentation, mechanical properties, tribology, electrical conductivity

Five types of composites based on silicon carbide were prepared and studied. SiC/CNT pow-
der precursors were produced by CCVD method and compacted by hot pressing (1850 °C/
Ar/60 min/40 MPa).
Mechanical properties such a hardness and elastic modulus of the composites were inves-
tigated by nanoindentation using Berkovich indenter tip (applied load 500 mN). Hardness of
the composites as a whole was also evaluated by the macro-indentation method with Vick-
ers diamond tip under the load of 1 kg (9.81 N). Indentation fracture toughness (KIC) was
calculated from the lengths of the radial cracks produced in the material under the load of
10 kg (98.1 N) using the Anstis formula. The microstructure and chemical composition of
the resulting materials were studied by SEM/EDX. The electric conductivity as function of
fraction of additives was determined. Tribological properties have been characterized by the
ball-on-disc method at the ambient temperature and dry wear conditions at the 5 N load, 500
m sliding distance with the static partner made from SiC.
Resulting materials were relatively hard HV1 = 24 GPa and with presence of CNT mod-
erate decrease down to HV1 = 17-19 GPa. Similarly, the fracture toughness decrease with
presence of CNT from 7 MPa.m1/2 down to 4 MPa.m1/2. Nanoindentation shown that hardness
HIT of monolithic sample was around 26 GPa and with increasing amounts of CNT decrease
down to the roughly same value 21GPa. The samples with CNT had similar modulus of

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elasticity (EIT = 337-348 GPa) and for monolith sample EIT = 434 GPa. Electrical conductiv-
ity was determined by the four point probe method and the measured values increases with
amount of CNT (1.76 S/m for monolith, 420.2 S/m for 2.5% CNT, up to 2873.6 S/m for 10%
CNT). Created wear track was observed using scanning electron microscopy and main wear
mechanisms were cracking and oxidation. Area of the wear track cross-section was measured
using 3D optical profiler and the wear loss volume was calculated according to the interna-
tional standard ISO 20808.

007
Influence of post-hip treatment on the optical and microstructural
properties of MgAl2O4 spinel
Caroline Gajdowski1,2*, Judith Böhmler1, Yannick Lorgouilloux2, Sébastien Lemonnier1,
Elodie Barraud1, Anne Leriche2
Institut franco-allemand de recherches de Saint-Louis, 5 rue du Général Cassagnou, Saint-Louis,
1

France; *e-mail: [email protected]

Laboratoire des Matériaux Céramiques et Procédés Associés, boulevard Charles de Gaulle,
2

Maubeuge, France
Keywords: ceramic, transparent, spinel, pressureless, HIP

Magnesium aluminate spinel (MgAl2O4) ceramic exhibits a high potential for application in
which a combination of optical and mechanical properties is needed: an isotropic propaga-
tion of the light due to a cubic structure, a wide range of transmission, low density and high
toughness.1
Conventional transparent armour is commonly a multi-layered system of glass and poly-
mer, which provides ballistic protection and optical transparency. Found in the civil and
military fields as windows of vehicles, face shields or lenses, a transparent armour has to be
thick to face armour piercing bullets and multi-impacts, which implies a substantial increase
of weight, volume and a loss of optical quality.2 With higher mechanical properties than
glass, polycrystalline ceramic could be an alternative as the front face. In addition, its use is
expected to lead to a significant lightweighting since it favours the global efficiency through
the fragmentation of the projectile and the decrease of the penetration at the impact.3
In order to elaborate transparent ceramic, a procedure was established where the introduc-
tion of defects is minimised. Indeed, transparency involves an absence of scattering centres
such as pores and secondary phases, which may cause a loss of optical quality. Therefore,
high purity of the raw powder and full density of the sintered sample are required.
Commercial spinel MgAl2O4 powder was directly poured into a die and compacted. Then,
the obtained samples were pressureless sintered under vacuum without sintering aids. Fi-
nally, a post-treatment by hot isostatic pressing was applied to reach full density and thus to
obtain transparent spinel by the elimination of the residual porosity. The study is focused on
the influence of the post-HIP parameters on the microstructural and optical properties. Prom-
ising result was obtained on spinel ceramic with a thickness of 2 mm and a diameter of 21

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mm, which exhibits an in-line transmission higher than 82% in the visible and near-infrared
wavelengths domains (94% of the theoretical value) and a heterogeneous microstructure with
two populations of grain size (25 ± 8 µm and 130 ± 50 µm).

References
1. Rubat du Merac et al., Fifty years of research and development coming to fruition; Unraveling the
complex interactions during processing of transparent magnesium aluminate (MgAl2O4) spinel, J.
Am. Ceram. Soc., 2013.
2. Grujicic at al., Design and material selection guidelines and strategies for transparent armour sys-
tems, Materials & Design, 2012.
3. Strassburger, Ballistic testing of transparent armour ceramics, J. Eur. Ceram. Soc., 2009.

538
Graphene – ceramic composites with 3YTZP matrix
A. Gallardo-López1,2, C. Muñoz-Ferreiro1,2, A. Morales-Rodríguez1,2, F. Gutiérrez-Mora1,2,
R. Poyato2
Departamento de Física de la Materia Condensada, Universidad de Sevilla-ICMSE (CSIC), Apdo.
1

1065, 41080 Sevilla, Spain

Instituto de Ciencia de Materiales de Sevilla ICMSE, CSIC-Universidad de Sevilla, Avda. Américo
2

Vespucio 49, 41092 Sevilla, Spain

Keywords: 3YTZP, GNP, processing, SPS, electrical conductivity.

Ceramic composites with carbon nanostructures (carbon nanotubes, graphene…) constitute

an interesting research topic due to the expected reinforcement effect of the ceramic ma-
trix and especially due to the fact that significant values of electrical conductivity can be
achieved. Yttria tetragonal zirconia polycrystalline (3YTZP) ceramic makes an interesting
matrix for these composites since it exhibits quite high fracture toughness due to the te-
tragonal to monoclinic transformation toughening effect during crack propagation.1 It can
also conduct electricity at high temperatures by ionic conduction. Graphene has exceptional
electrical, thermal and mechanical properties, including extremely high electron mobility at
room temperature and a very high Young’s modulus.2 However, due to its high surface area,
graphene tends to form agglomerates, so it is very difficult to obtain individual graphene
sheets. For its use in composites, graphene is commonly in the form of graphene nanoplate-
lets (GNP) and thinner graphene nanosheets or few layered graphene (FLG), both composed
by pile up of several graphene sheets.
In this work, processing of graphene/3YTZP composites with different number of gra-
phene sheets (i.e. differing in planar dimension and thickness) has been approached by wet
powder techniques, paying special attention to dispersion of the graphene nanostructures
into the ceramic matrix to minimize or avoid their agglomeration. Uniaxial pressure sintering
with a pulsed electric discharge furnace (spark plasma sintering, SPS) provided composites
with a high degree of microstructural anisotropy. The effect of processing conditions and
graphene dimensions on the microstructure, hardness, crack propagation and electrical con-
ductivity of the composites has been evaluated.

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References
1. R.H.J. Hannink, P.M. Kelly, B.C. Muddle, “Transformation toughening in zirconia containing ce-
ramics”, J. Am. Ceram. Soc., 83, 3, pp. 461–487, 2000.
2. V. Singh, D. Joung, L. Zhai, S. Das, S.I. Khondaker, S. Seal, “Graphene based materials: Past, pre-
sent and future”, Prog. Mater. Sci., 56, 8, pp. 1178–1271, 2011.

568
Effect on the mechanical properties of Ce-YTZP/Al2O3 nanocomposites
for dentistry use
Lorena Gil1, Maria Dolores Salvador1, R. Torrecillas2, S. Rivera2, Amparo Borrell1*
Instituto de Tecnología de Materiales (ITM), Universitat Politècnica de València, Camino de Vera,
1

s/n, 46022 Valencia, Spain; *e-mail: [email protected]

Centro de Investigación en Nanomateriales y Nanotecnología (Consejo Superior de Investigaciones
2

Científicas, Universidad de Oviedo, Principado de Asturias), Avenida de la Vega 4-6, 33940 El

Entrego, Spain
Keywords: dental ceramic materials, microwave sintering, mechanical properties, microstructure

Ceramic materials are commonly used in restorative dentistry, because they have an esthet-
ics closer to the natural tooth and do not produce allergic reactions or rejection. The most
popular ceramic material in this field is zirconia-based materials. Therefore, the purpose of
the present study is to investigate zirconia doped with ceria and toughened with alumina.
This material is less common than zirconia doped with yttria, and it has not already been
researched in detail. Hence, it can be a good topic since is estimated that 240 million people
in the Western World have lost at least one tooth. Most of these patients benefit greatly from
dental implants.
The samples, that have been studied, are Ce-YTZP/Al2O3 nanocomposites and have the
following proportion: 65%vol 10Ce-ZrO2 + 35%vol Al2O3. They were sintered using a non-
conventional method, microwave technology, in order to enhance the mechanical properties
and at the same time to reduce production costs and processing times1.
Both the starting and sintered material have been evaluated. Regarding the raw mate-
rial, grain size, phase constitution and X-ray diffraction have been assessed. The mechanical
properties, final density and microstructure of the sintered sample have also been studied.
Another aim of this investigation is to compare the studied ceramic material with YTZP,
a commercial zirconia currently used in dental reconstructions. Moreover, the effects of the
alumina particles dispersed in the zirconia matrix have also been investigated.

Acknowledgements
This work has been supported by the Spanish Ministry of Economy and Competitiveness MINECO by
MAT2015-67586-C3-R project and Juan de la Cierva-Incorporación contract (IJCI-2014-19839), and
the Generalitat Valenciana by the PROMETEO/2016/040 project.

Reference
1. A. Presenda, M.D. Salvador, F.L. Peñaranda, R. Moreno and A. Borrell, “Effect of microwave
sintering on microstructure and mechanical properties in Y-TZP materials used for dental applica-
tions”, Ceram. Inter., 41, pp. 7125–7132, 2015.

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634
Rheological principles of development hetero-modulus
and hetero-viscous ceramic matrix composites with
extreme dynamic strength
László A. Gömze1,2,3, Ludmila N. Gömze2
1
University of Miskolc, Institute of Ceramics and Polymer Engineering, Miskolc, Hungary;
e-mail: [email protected]
2
IGREX Engineering Service Ltd, Igrici, Hungary; e-mail: [email protected]
3
Tomsk State University, Tomsk, Russia
Keywords: ceramics, composites, diamond-like, elasticity, hetero-modulus, nanostructure, rheology,
strength, viscosity

Materials with different crystalline and morphological compositions have different chemical,
physical, mechanical and rheological properties, including wear protection, melting tempera-
ture, module of elasticity and viscosity.1–4 Examining the material structures and behaviors of
different ceramic bodies and CMCs under high speed collisions in several years the authors
have understood the advantages of hetero-modulus and hetero-viscous complex material
systems to absorb and dissipate the kinetic energy of objects during high speed collisions.
Applying the rheo-mechanical principles the authors successfully developed a new family
of hetero-modulus and hetero-viscous alumina matrix composite materials with extreme
mechanical properties including dynamic strength. These new corundum-matrix compos-
ite materials reinforced with Si2ON2, Si3N4, SiAlON and AlN submicron and nanoparticles
have excellent dynamic strength during collisions with high density metallic bodies with
speeds about 1000 m/sec or more. At the same time in the alumina matrix composites can be
observed a phase transformation of submicron and nanoparticles of alpha and beta silicone-
nitride crystals into cubic c-Si3N4 diamond-like particles can be observed, when the high
speed collision processes are taken place in vacuum or oxygen-free atmosphere.
Using the rheological principles and the energy engorgement by fractures, heating and
melting of components the authors successfully developed several new hetero-modulus,
hetero-viscous and hetero-plastic complex materials. These materials generally are based
on ceramic matrixes and components having different melting temperatures and modules of
elasticity from low values like carbon and light metals (Mg, Al, Ti, Si) up to very high values
like boride, nitride and carbide ceramics. Analytical methods applied in this research were
scanning electron microscopy, X-ray diffractions and energy dispersive spectrometry. Digital
image analysis was applied to microscopy results to enhance the results of transformations.

References
1. S. Kulkov, N. Savchenko, 2008 Wear Behavior of Zircona Based Ceramics Under High-Speed
Dry Sliding on Steel, Építőanyag, v. 60, 3, pp. 62–64, http://dx.doi.org/10.14382/epitoanyag-jsb-
cm.2008.10
2. A. Morikawa, T. Suzuki, K. Kikuta, A. Suda, H. Shinjo, 2009 Improvement of OSC performance
for CeZrO4 solid solution with Al2O3 diffusion barrier, Építőanyag, v. 61, 1, pp. 2–5, http://dx.doi.
org/10.14382/epitoanyag-jsbcm.2009.1

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3. N.I. Ershova, I.Y. Kelina, 2009 High-temperature wear-resistant materials based on silicon nitride,
Építőanyag, v. 61, 2, pp. 34–37, http://dx.doi.org/10.14382/epitoanyag-jsbcm.2009.6
4. L.A. Gömze, L.N. Gömze, 2009 Alumina-based hetero-modulus ceramic composites with extreme
dynamic strength – phase transformation of Si3N4 during high speed collisions with metallic bodies,
Építőanyag, v. 61, 2, pp. 38–42, http://dx.doi.org/10.14382/epitoanyag-jsbcm.2009.7

916
Effect of different steel binders on microstructural and mechanical
properties of NbC-Fe cemented carbides prepared from fine NbC
powder
Amir Hadian1,2*, Cyrus Zamani2, Frank Jörg Clemens1
1
Empa, Swiss Federal Laboratories for Materials Science & Technology, Laboratory for High
Performance Ceramics, 8600, Dübendorf, Switzerland; *e-mail: [email protected]
2
School of Metallurgy and Materials Engineering, University of Tehran, Tehran, Iran
Keywords: fine NbC powder, cemented carbide, binder, tool steel, cubic carbide

WC-Co cemented carbides are materials with wide applications as tools due to their excellent
mechanical properties like hardness and toughness. Due to the proven toxic nature of Co and
WO3 in WC-Co cemented carbide, researches have been taking place during the last decades
to substitute them with non- toxic materials. Reports show that NbC matrix cemented carbide
can be a good candidate due to the non-toxic and not water soluble characteristic of Nb2O5.1
Moreover, studies have shown improved elevated temperature mechanical and tribological
properties of these materials.2,3 The aim of this study was to analyze the effect of binder phase
on the mechanical and microstructural properties of NbC-Fe base cemented carbides. Mean-
while the effect of adding TaC, VC, and Mo2C cubic carbides as particle growth inhibitors
was also studied. For this mean, two grades of 316 L stainless steel and DIN 1.3207 high
speed tool steel were selected as binder. Fine NbC powder (d50 = 0.8 µm) was mixed with 12
wt% of each grade and gas pressure assisted sintered for 1 h at 1460 °C. Microstructural and
elemental mapping of the sintered parts were performed by scanning electron microscope
(SEM) equipped with energy dispersive spectrometer (EDS). Mechanical properties, includ-
ing Vickers hardness and indentation toughness were also assessed.
Results indicated that the binder phase can influence the mechanical and microstructural
properties of the NbC-Fe base cemented carbide. Microstructural investigations showed a
higher NbC particle growth rate with stainless steel as the binder. It was also evident that
the addition of cubic carbides can greatly limit the NbC particle growth rate. Mechanical
properties measurements indicated higher hardness values for the sample with high speed
tool steel as binder. Moreover it could be observed that the addition of cubic carbides can
greatly influence the mechanical properties due to the reduced NbC particle size inside the
sample. A maximum hardness of 15.4 ± 0.8 GPa was measured for the sample with high
speed tool steel as the binder and cubic carbides as particle growth inhibitors. A low fracture

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toughness of 2.6 ± 0.15 MPa.m1/2 was achieved for the same sample. It was evident from
the microstructural investigations that the low fracture toughness is related to high density of
pores inside the sample.

References
1. M. Woydt, H. Mohrbacher, J. Vleugels, and S. Huang. “Niobium carbide for wear protection–tailor-
ing its properties by processing and stoichiometry.” Met. Powder Rep. 71, no. 4, pp. 265–272, 2016.
2. M. Woydt, and H. Mohrbacher. “The tribological and mechanical properties of niobium carbides
(NbC) bonded with cobalt or Fe 3 Al”, Wear, 321, pp. 1–7, 2014.
3. M. Woydt, and H. Mohrbacher. “The use of niobium carbide (NbC) as cutting tools and for wear
resistant tribosystems.” Int. J. Refract. Metals. Hard. Mater., 49, pp. 212–218, 2015.

757
Influence of particle arrangement during electrophoretic deposition
to properties of alumina and zirconia ceramics
Hynek Hadraba1*, Zdeněk Chlup1, Daniel Drdlík2, Jaroslav Cihlář2, Tomáš Zikmund2
1
CEITEC IPM, Institute of Physics of Materials, Czech Academy of Sciences, Zizkova 22,
616 62 Brno, Czech Republic; *e-mail: [email protected]
2
CEITEC BUT, Brno University of Technology, Purkynova 123, 612 00 Brno, Czech Republic
Keywords: electrophoretic deposition, alumina, zirconia

Electrophoretic deposition is shaping method enabling preparation of ceramic material from

stable suspension of ceramic particles by means of direct electric current.1–3 The aim of the
work was to identify an effect of the electric current magnitude on the particle arrangement,
final microstructure and resulting mechanical properties. The alumina and zirconia layers
were prepared by electrophoretic deposition from stable suspensions of alumina and zirconia
ceramic powders having different particle size distribution functions. The stable alumina and
zirconia suspension were prepared by dispersing of powders in isopropanol and stabilized
with monochloracetic acid.4,5 Recently, it was found that the real time dependence of particle
deposition differs from the theoretical prediction for given electrical conditions.6 By precise
measurement of kinetics of the electrophoretic deposition the current electrophoretic mobili-
ty of the particles and corresponding amount of particles taking part in the deposition process
were found. It was found that with decreasing the electrical current the electrophoretic mobil-
ity was increased but in contrast the amount of particles taking part in the deposition process
was decreased. Also the green and fired densities of deposits depend on the electric current
used for the electrophoretic deposition. At lower electric currents just the particles having
high electrophoretic mobility and thus having high radiuses were deposited. The increasing
velocity of particles under higher electrical currents also led to the deterioration of particle
arrangement in the electrode and thus to the increasing of the pore sizes lowering final densi-
ties of deposits. These microstructural changes reflected in the hardness decrease of about

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300HV5 in the case of alumina. The optimized process of the electrophoretic deposition of
alumina and zirconia using isopropanolic suspensions stabilized by monochlor acetic acid al-
lowed preparation of the laminate consisting of strongly bonded layers of certain thicknesses.

References
1. I. Corni, M.P. Ryan, A.R. Boccaccini, Journal of the European Ceramic Society 28(7) (2008) 1353–
1367.
2. A.R. Boccaccini, C.B. Ponton, JOM 47(10) (1995) 34–37.
3. L. Besra, M. Liu, Progress in Materials Science 52(1) (2007) 1–61.
4. K. Maca, H. Hadraba, J. Cihlar, Ceramics International 30(6) (2004) 843–852.
5. H. Hadraba, K. Maca, J. Cihlar, Ceramics International 30(6) (2004) 853–863.
6. H. Hadraba, D. Drdlik, Z. Chlup, K. Maca, I. Dlouhy, A. Boccaccini, O. VanDerBiest, R. Clasen,
J. Dickerson, Electrophoretic Deposition: Fundamentals and Applications Iv 507 (2012) 209–213.

723
Influence of machining and crack healing on the strength of
a commercial silicon carbide ceramic
Walter Harrer, Ruth Prackwieser, Robert Danzer*
Institut für Struktur- und Funktionskeramik, Montanuniversität Leoben, Leoben, Austria;
*
e-mail: [email protected]

Failure of brittle materials starts in general from defects which exist in the volume or on the
surface of the specimens. Surface flaws, which are more dangerous than volume flaws, can
be introduced by machining. They decrease the strength of specimens and components. This
investigation compares two different ways to avoid surface defects and, as a consequence,
increase the strength.
For the investigation disc shaped silicon carbide samples were machined with different
machining conditions. As expected, it could be shown that a better (gentler) machining in-
creases the strength. In order to heal the surface defects a sample of specimens was heat
treated and then tested with the B3B-test. Microstructural investigations (SEM, FIB) reveal
the formation of a thin glassy layer which heals the cracks on the surface if these are not too
large.
It was observed that a better machining as well as annealing (depending on machining
conditions and healing temperature, respectively) leads to a significant increase of strength
(up to 250%) in the same amount.

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928
Safety performance evaluation of silicon carbide ceramics for accident
tolerance fuel in hydrothermal exposure conditions
Seung-Jae Lee1, Kwang-Young Lim1, Young-Wook Kim2
1
Materials Development Section, KEPCO Nuclear Fuel, Daejeon 305-353, Republic of Korea
2
Functional Ceramics Laboratory, Department of Materials Science and Engineering,
The University of Seoul, Seoul 130-743, Republic of Korea
Keywords: SiC, nuclear fuel, PBAT, TRISO, ATF

The recent events at the Fukushima Daiichi nuclear power plant in Japan highlighted the
need for added safeguard, including fuels with enhanced accident tolerance that can delay
or even prevent severe accidents. In this sense, the use of particle-based accident tolerant
(PBAT) fuels is an alternative strategy for overcoming this issue by multiple silicon carbide
(SiC) barriers such as SiC layer in TRISO and the dense SiC matrix of the ceramic capsules.
The performance on high temperature oxidation of PBAT fuel is one of important factors for
plant safety of nuclear reactors. In this work, safety performance evaluation of SiC ceram-
ics for accident tolerance fuel (ATF) in hydrothermal exposure condition was performed
at 1200 and1700 oC for ~25hr. PBAT fuel and monolithic SiC ceramics was fabricated by
hot-pressing and normal pressureless sintering, respectively. After 25hr hydrothermal oxida-
tion, some TRISO kernel in PBAT fuel were exposed and inner surface portion of PBAT fuel
shows pore channel by permeated liquid phase through the grain boundary and junction. The
high temperature oxidation resistance of SiC ceramics was dependent on the chemistry inside
the grain structure, the additive composition and the additive content. More importantly, sup-
pression of liquid phase formation by reaction between SiO2 and junction part is ans essential
factor for oxidation resistance performance of SiC ceramics. Detail data for oxidation behav-
ior of SiC ceramic under hydrothermal exposure conditions will be presented.

287
Measurement of residual stress caused by gallium-ion implantation
from FIBing in alumina
Jiawei Jiang, Richard I. Todd*
Department of Materials, University of Oxford, Parks Road, OX1 3PH, United Kingdom;
*
e-mail: [email protected]
Keywords: focused ion beam, gallium ion implantation, residual stress, alumina, fracture toughness

Toughness measurements of the individual microstructural components of alumina, i.e. grains

and grain boundaries, are indispensable to a full understanding of the mechanical properties
of the bulk material. One method for making such measurements is to test microcantilever
beams manufactured using focused ion beams (FIB) and including a notch at the chosen

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microstructural feature. However, residual stress caused by Ga-ion implantation at the notch
root during FIBing is thought to influence the results in alumina, though to a lesser extent
in some other ceramics.1 To clarify the extent of this effect, the present study measures the
implantation stresses in single crystal alumina and silicon by applying a combination of vari-
ous methods such as beam curvature measurements in a dual-beam FIB. The effect of FIB
accelerating voltage is also investigated. The implications of the results for microcantilever
toughness measurements are described.

Reference
1. Norton, A.D., et al. Microcantilever investigation of fracture toughness and subcritical crack
growth on the scale of the microstructure in Al2O3. Journal of the European Ceramic Society, 35,
p. 4521–4533, 2015.

478
Control of sintering of NiO/GDC porous ceramics by mechanical
treatment of raw materials
Kenji Kajii1, Junichi Tatami1*, Motoyuki Iijima1, Masahiro Asayama2, Toshio Shimizu2
1
Yokohama National University, 240-8501, Japan; *e-mail: [email protected]
2
Toshiba Co., Yokohama, Japan
Keywords: NiO/GDC, mechanical treatment, sintering, control

Solid oxide electrolysis cells (SOEC) have a layered structure of dense solid electrolyte and
porous electrode. Gadrinium doped ceria (GDC) is a typical solid electrolyte having good
ionic conductivity and high relative density. Porous composites of GDC and Ni, which is
converted from NiO, are generally used because the electrode requires ionic and electron
conductivity. In order to fabricate the layered structure, it is necessary to sinter layered pow-
der compacts at the same time. However, difference in the sintering shrinkage behavior of the
powder compact layers resulted in deformation and fracture of the products after sintering.
In this work, sintering shrinkage behavior of NiO/GDC porous ceramics was controlled by
restricting contact between NiO particles using the GDC coated NiO composite particles.
The composite particles were prepared by mechanical treatment technique. A powder mix-
ture prepared by ball-milling was used as a reference. SEM images of the powder mixture
prepared by mechanical treatment showed that smaller GDC particles existed on a larger
NiO particle. In addition, specific surface area of the composite particles was smaller than
that before mechanical treatment, resulting from jointing of GDC particles on NiO particles.
Microstructural observation of powder compacts indicated that NiO particles are success-
fully separated by GDC particles when the NiO/GDC composite particles were used. Sinter-
ing shrinkage of the powder compact of the mixture particles prepared by ball-milling was
started at 800 °C, which is almost the same as that of a powder compact of raw NiO particles.
This indicated that initial sintering of the powder compact using ball-milled powder was
dominated by sintering of NiO. On the other hand, sintering starting temperature and sinter-

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ing shrinkage behavior of the powder compact using the composite particles agreed with
those of raw GDC particles. This result indicated that GDC particles in the powder compact
using the NiO/GDC composite particles restricted contact NiO particles, and they controlled
the sintering behavior of NiO/GDC porous ceramics. Furthermore, the dominant sintering
mechanism was also confirmed by apparent activation energy calculated by Arrhenius plots
based on MSC theory. Consequently, it was shown that mechanical treatment of raw mate-
rials to make use of composite particles was effective in control of sintering of NiO/GDC
porous ceramics.

486
Effect of residual stress in FRP stage on liquid silicon infiltrated
C/C-SiC composites
Seyoung Kim1*, Sangkuk Woo1, Insub Han1, Young-Hoon Seong1, Soo-hyun Kim1,
Jong Seob Song2
1
Energy Material Laboratory, Korea Institute of Energy Research, 152 Gajung-ro Yuseong-gu
Daejeon, South Korea; *e-mail: [email protected]
2
Division of Material Science and Engineering, Chung-nam University, Daejeon, South Korea

Keywords: residual stress, LSI, composites

Fiber reinforced ceramic matrix composite materials are most promising materials in aero-
space and high temperature environmental application because of its high thermal and struc-
tural stability. In this study, LSI (Liquid silicon infiltration) process was applied to fabricate
ceramic matrix composite. Generally, porous C/C preform is prepared from FRP material by
carbonizing and transversal cracks are formed that acts as a path for liquid silicon infiltra-
tion. Various residual stress in FRP material were introduced by fiber volume fraction control
and measured by drilling method. During carbonization step, most of obtained cracks were
transversal segment cracks in low residual stressed FRP specimen. However, not only seg-
ment cracks but also fiber and matrix interfacial cracks were occurred in high residual stress
introduced specimen. The relation between residual stress in FRP material and carbonized
composites was investigated with finite element analysis. Higher residual stress in FRP in-
duced fiber matrix debonding and it caused silicon infiltration into debonded crack during
LSI process that weaken reinforced carbon fiber. For evaluation of residual stress effect in
LSIed composite, density, porosity and mechanical properties were investigated including
SEM observation for microstructure.

References
1. D. Jiang. “Simulating the Initial Stage of Phenolic Resin Carbonization via the ReaxFF Reactive
Force”, J. Phys. Chem. A., 113, pp. 6891–6894, 2009.
2. Y. Yamashita, “A study on carbonization of phenol-formaldehyde resin labelled with deuterium and
13C”, Carbon, 19, pp. 89–94, 1981.

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489
CMAS and hot corrosion resistance behavior of functionally graded
Al2O3/CYSZ thermal barrier coatings
Fatih Kırbıyık, Gultekin Goller
Metallurgy and Materials Engineering Dept. Istanbul Technical University, Istanbul, Turkey
Keywords: hot corrosion, CMAS, Al2O3, CYSZ, thermal barrier coating, functionally graded, thermal
cycling performance

Hot corrosion salts and CMAS powders are main destructive factors in thermal barrier coat-
ings. Low quality fuel that is used as energy producer in combustors releases hot corrosion
molten salts on gas turbine engine parts.1 CMAS powders that are taken from air shorten
maintenance time of TBCs.2
In this study, alumina/CYSZ powders were produced by APS with functionally graded
design as TBC materials. Functionally graded eight layered specimen showed better proper-
ties on thermal cycle, adhesion and thermal shock resistance in the previous study. Therefore,
functionally graded eight layered TBC specimen was chosen to evaluate hot corrosion and
CMAS attack resistance at high temperature conditions. Hot corrosion and CMAS powders
were used together during 1 hr. heating and cooling at the same time, moreover, specimens
were cycled with 1 min. heating and 1 min. air cooling under static heat source CO2 laser.
Microstructure and XRD were evaluated to understand effects of hot corrosion and CMAS
attack on TBCs.

References
1. A. Afrasiai, M. Saremi, A. Kobayashi A comparative study on hot corrosion resistance of three
types of thermal barrier coatings: YSZ, YSZ + Al2O3 and YSZ/Al2O3 Materials Science and Engi-
neering 478, pp. 264–269, 2008.
2. A. K. Rai and R. S. Bhattacharya CMAS Resistant Thermal Barrier Coatings (TBC) International
Journal of Applied Ceramic Tech. 7, pp. 662–674, 2010.

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667
Effect of graphene platelets addition on microstructure and mechanical
properties of boron carbide ceramic composites
Alexandra Kovalčíková1, Richard Sedlák1, Ján Balko1, Paweł Rutkowski2,
Aleksandra Dubiel2, Erika Múdra1, Vladimír Girman3, Ján Dusza1
Institute of Materials Research, Slovak Academy of Sciences, Division of Ceramic and Non-Metallic
1

Systems, Watsonova 47, 040 01 Košice, Slovak Republic

AGH University of Science and Technology in Krakow, Faculty of Materials Science and Ceramics,
2

Department of Ceramics and Refractories, al. A. Mickiewicza 30, 30-059 Krakow, Poland
Pavol Jozef Šafárik University in Košice, Faculty of Science, Institute of Physics, Department of
3

Condensed Matter Physics, Park Angelinum 9, 040 01 Košice, Slovak Republic

Keywords: boron carbide, graphene platelets, microstructure, mechanical properties, wear behaviour

Boron carbide is an interesting material because of its excellent hardness, low density, high
melting point ~2450 °C, and good chemical and wear resistance. For applications of B4C ma-
terials under demanding working conditions, an improvement of reliability, tribological be-
haviour, and mechanical properties is required. The unique structural, electrical, mechanical
and thermal properties of graphene combined with its low density make it an ideal candidate
as reinforcement in ceramic matrix. In this work, the influence of the graphene platelets ad-
dition on the microstructure development, mechanical (hardness, bending strength, fracture
toughness, Elastic modulus), tribological properties (coefficient of friction, wear rate, wear
mechanisms), and electrical conductivity of B4C/ GPLs composites has been investigated.
SEM, TEM, and FIB microscopy have been used for microstructural analyses, character-
ization of fracture origins, fractography, and toughening mechanisms. To analyse the worn
surfaces and wear behaviour after tribological tests, the cross sections using focus ion beam
have been prepared. Almost fully dense boron carbide composites (with grain size in the
range of 2–4.5 µm) with GPLs addition up to 6 wt. % were prepared by hot pressing at 2100
°C/1 h. During the sintering, only GPLs have been used as sintering additives. Multilayer
GPLs were well distributed in B4C matrix, located at the B4C/B4C grain boundaries. The
hardness and Young’s modulus of prepared ceramics significantly decreased from 30.3 to
18.2 GPa and from 411 to 271 GPa with the higher amount of GPLs, respectively. The high-
est fracture toughness of 4.48 MPa.m1/2 was achieved at 6 wt. % of GPLs addition, which
was ~50% higher than the KIC value of reference material. The toughening mechanisms in all
B4C/GPLs composites were similar in the form of crack deflection, crack branching, crack
bridging, and graphene sheet pull-out, only the frequency of their occurrence during crack
propagation and their effectiveness in the toughening process are different. A significant im-
provement of electrical conductivity around two orders of magnitude up to ~1500 S/m was
noticed. The coefficient of friction for composites were similar (0.5–0.6), however the wear

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rate significantly decreased ~77% in the case of B4C+6 wt.% GPLs when compared to refer-
ence material at a load of 5 N, and ~60% at a load of 50 N. The main wear mechanisms were
in the form of abrasion and tribochemical reactions.

Acknowledgements
The authors gratefully acknowledge the financial support from projects VEGA 2/0130/17, VEGA
2/0189/15, and APVV-15-0469.

888
Obtaining of nano composites via alum-thermal and nitrogen processes
in the SiC-Si3N4-ALN-AL2O3-SiO2. system
Z. Kovziridze*, N. Nijaradze, G. Tabatadze, N. Daraxvelidze, Z. Mestvirishvili
Georgian Technical University (GTU), Department of Chemical and Biological Technology,
Technical University of Georgia 69, Kostava str., Tbilisi 0175, Georgia; *e-mail: [email protected]
Keywords: alum-thermal process, nitrogen medium, SiAlON, composites

SiALON-s are solid metal oxide solutions in nitrides. Area of their presence is considered in
four-component system - Si3N4-ALN-AL2O3-SiO2.
In the present paper SiALON-containing nano-composite was obtained through alum-
thermal process on the base of kaolin and aluminum nano-powder in the nitrogen medium,
by the reactive baking method. The advantage of this method is that compounds, which are
newly formed thanks to interaction going on at thermal treatment: Si3N4, Si, AlN are active,
which contributes to SiALON formation at relatively low temperature, at 1250–1300 °C. It is
evident that inculcation of α - Al2O3 and ALN in crystal skeleton of ß-Si3N4 is easier since at
this temperature interval crystal skeleton of Si3N4 is still in the process of formation.
It should also be stated that strength and wear resistance of SiALONs increase in their
presence in silicium carbamide and corundum-containing composites.
The paper offers processes of formation of SiC-SiAlON and Al2O3-SiAlON composites
and their physical and technical properties.
Phase composition of the composites was studied by X-ray diffraction method, while the
structure was studied by the use of optic and electron microscope. Obtained materials are
used in protecting jackets of thermo couples used for melted metal temperature measuring
(18–20 measuring) and for constructions used for placing objects in factory furnaces.

References
1. Zalite I., Zhilinska N., Steins I., Spark plasma sintering of SiAlON nanopowder [Electronic re-
source] IOP Conf. Ser.: Mater. Sci. Eng. Access from IOPscience.2011. Vol. 25. – p. 7.
2. Smirnov K. L. Spark plasma sintering of SiAlON ceramics // Int. J. Self-Propagat. High-Temp.
Syn. – 2007. – Vol. 18, № 2. – p. 92–96.
3. Anya C.C., Hendry A. Hardness - Indentation Fracture Toughness, and Compositional Formula of
X-phase Sialon/ J. of Mat. Sci.-1994. V. 29. p. 527–533.
4. Preparation of composites by Nitro Aluminothermal processes, over B-Sialon Matrix in the Sialon-
Sic-Al2O3 System Journal of Electronics Cooling and Thermal Control, Vol.6,#2, pub. date: June
15, 2016. http://www.scirp.org/journal/jectc, pp. 62–77.

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551
Surface modification of titanium with silicon nitride
Seniz R. Kushan Akin*, Ziya Esen, Ezgi Butev Ocal
Department of Materials Science and Engineering, Cankaya University, Ankara, Turkey;
*
e-mail: [email protected]
Keywords: silicon nitride, titanium, coating, diffusion, hardness

Titanium (Ti) and titanium alloys have been used in biomedical and aerospace industry due to
their combination of properties such as high corrosion resistance, high specific strength and
relativity low density. However, relatively low wear resistance limits the potential applica-
tions of these engineering alloys. Therefore, in this study, the surface of titanium (Grade 2) is
coated with silicon nitride via three different techniques to obtain hard surface coating layer.
Initially, the surface of titanium is coated with a slurry containing Silicon Nitride (Si3N4)
powder using drop casting method and heat treatment for diffusion bonding is conducted
under high purity Argon atmosphere. In the second method, Ti surface is nitrided under high
purity nitrogen gas which is followed by pack siliconization process to obtain in-situ Si3N4
layer. In the last technique, Si3N4 layer is formed by applying pack siliconization and nitrid-
ing as primary and final steps, respectively. The temperature for diffusion bonding, nitriding
and siliconization processes are maintained above α/β transition of titanium. The type and
formation of different phases in the diffusion layer between Ti and Si3N4 is examined by X-
Ray Diffraction (XRD) and Scanning Electron Microscope (SEM). The change in hardness
through thickness is measured by Micro hardness Testing.

429
Effect of carbon content on fluoride adsorption of bone char
Saori Kyogaku1, Masamoto Tafu1*, Miki Inada2, Saori Takamatsu1, Atsushi Manaka1,
Takeshi Toshima1
National Institute of Technology, Toyama College, Hongo-machi 13, Toyama-city, Toyama, Japan,
1

939-8630; *e-mail: [email protected]

Center of Advanced Instrumental Analysis, Kyushu University, 6-1 Kasuga-Koen Kasuga-Shi,
2

Fukuoka, Japan, 816-8580

Keywords: bone char, carbon content, fluoride removal

Bone char is obtained by calcination of bone from food industries under anaerobic condition.
Bone consists of nano-scaled hydroxyapatite (HA) particle and fibrous collagen, and trans-
lates well- crystalline HA and carbonized collagen by calcination. One of the usage of bone
char is as adsorbent of fluoride in polluted water such as ground water. Catching fluoride by
bone char have been considered ion-exchange and/or dissolve-precipitation1,2 of HA in it. In
this study, effect of carbon content in bone char on adsorption property was investigated.

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Bone char was prepared from chicken wing by calcination at 500 °C3 for various peri-
ods. Crystallinity of HA was analysed by powder X-ray diffraction (XRD), and did not ob-
served remarkable change by calcination at this temperature. Carbon content was calculated
by weight change on combustion of carbon content that measured by thermal gravimetric-
differential thermal analyzer (TG-DTA). From result of TG-DTA analysis, carbon amount
did not change by calcination for 6 to 24 hours. Removal (adsorption) amount of fluoride
was estimated by mixing an aqueous solution containing 10 mg/L of fluoride ion and various
amounts of bone char for 24 hours. After treatment, residual content of fluoride in the aque-
ous phase was analyzed by ion selective electrode (ISE). From result of the determination,
removal amount and equilibrium concentration of fluoride was calculated. From results of
fluoride removal, removal amount of fluoride of bone char calcinated for 24 hours was re-
markably decreased. From these results, removal property of bone char seems to affect by not
carbon amount but chemical characteristics of carbon such as crystallinity or polymerization.
Characterization of carbon in the bone char from viewpoint of material science is expected
novel information for improvement of removal property of it.

References
1. V. Sternitzke, R. Kaegi, J-N. Audinot, E. Lewin, J. G. Hering, C.A. Johnson, “Uptake of Fluo-
ride from Aqueous Solution on Nano-Sized Hydroxyapatite: Examination of a Fluoridated Surface
Layer” Environ. Sci. Technol., 46 (2), 802–809, 2012.
2. S. Terasaka, M. Kamitakahara, T. Yokoi, H. Matsubara, “Effects of carbonate inclusion on fluoride
ion removal by hydroxyapatite: A discussion from the viewpoint of hydroxyapatite dissolution” J.
Ceram. Soc. Jpn., 124(12), 1211–1216, 2016.
3. M.J. Larsen, E.I.F. Pearce, G. Ravnholt, “The effectiveness of bone char in the defluoridation of
water in relation to its crystallinity, carbon content and dissolution pattern” Archs. Oral Biol., 39(9),
807–816, 1994.

918
Assembly of transparent polycrystalline ER:YAG ceramics by SPS
M. Lagny1,2, J. Boehmler1, E. Barraud1, S. Lemonnier1, M. Eichhorn1, Y. Lorgouilloux2,
A. Leriche2
Institut franco-allemand de recherches de Saint-Louis - ISL, 5 rue du Général Cassagnou, 68301
1

Saint-Louis Cedex, France

Laboratoire des Matériaux Céramiques et Procédés Associés - LMCPA, Pôle universitaire de
2

Maubeuge, Boulevard Charles de Gaulle, 59600 Maubeuge, France

Keywords: assembling SPS ceramics

Today, transparent polycrystalline ceramics are widely used: they find applications in vari-
ous fields like electronics, biology or optical systems. Our subject is the laser developed at
the ISL is a Solid State Heat-Capacity Laser (SSHCL1): in that case, the gain medium is
an ­Erbium-doped YAG single crystal (Er:YAG) exhibiting an emission at 1.6 μm so-called
­«eye-safe». The main improvements expected for such laser systems concern its maximum
power of solicitation and its lasing time, both limited by an accumulation of heat in the laser

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cavity during use.1 Ways to solve these issues are intensively explored through the replace-
ment of single crystal by polycrystalline ceramics. This approach relies on i) their tunable
fine microstructure allowing to reach better thermomechanical properties than the single
crystals and ii) the possibilities that offers powder metallurgy in terms of controlled doping
profile, which leads to a better distribution of heat in the material, and low production costs
thanks to fast synthesis and low matter waste compared to single crystals synthesis.
In order to integrate the polycrystalline ceramic in a SSHC laser, one must focus on two
aspects: i) make a ceramic with dimensions compatible with ISL SSHCL cavity, and ii) the
development of doping gradient ceramics, allowing a better distribution of heat in the solid
medium.
For satisfying these two conditions, SPS process is considered to be a promising way since
it allows to both to fully densify ceramics and to assemble dense ceramics together. This
approach was considered to produce a large piece of ceramic with a suitable profile doping.
Attention focused on the optimisation of surface preparation and SPS processing parameters
to reach high transmittance and avoid any defect at the interface. Further investigations are
currently carried out by SEM to qualify the interface between the two pieces.

Reference
1. M. Eichhorn, “High-Efficiency Multi-Kilowatt Er3+:YAG Solid-State Heat-Capacity Laser,” 2011.

153
Thermal durability test of suspension precursor plasma sprayed
lanthanum-gadolinium zirconate/YSZ tBC
Kee Sung Lee1*, So Dam Choi1, Yoon Suk Oh2, Seongwon Kim2, Hyung Tae Kim2
School of Mechanical Engineering, Kookmin University, Seoul, South Korea;
1

*
e-mail: [email protected]
Engineering Ceramics Center, Korea Institute of Ceramic & Engineering Technology, Icheon,
2

South Korea
Keywords: thermal barrier coating, plasma spray coating, thermal durability

Heat insulation by ceramic coatings are indispensable for protecting nickel based alloy mate-
rial of hot gas parts in the gas turbine. When fuel is burned with compressed air, temperatures
are known to rise up to 1500 °C, therefore, thermal resistant ceramics such as low thermally
conductible materials are needed to endure severe hot temperature. On the other hand, high
mechanical properties against wear and damages are also required for thermal barrier coat-
ings. Therefore, multi-layers consisting of low thermally conductible material and YSZ lay-
ers are maybe a solution to protect the sub-alloy at both high temperature condition and wear
resistant condition. In this study (La, Gd)2Zr2O7/YSZ thermal barrier coatings are deposited
by suspension precursor plasma spray(SPPS) on the bondcoat/Ni superalloys to insulate high
temperature effectively by pyrochlore-fluorite structure and resist against wear and dam-
age owing to YSZ material. The compositions of multi-layered coatings from La2O3, Gd2O3

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and Y2O3 doped ZrO2 and the thickness of each layer are controlled by processing param-
eters during SPPS. Thermal cycling tests are conducted at 1275 oC for 1hr until interface
delamination occurs during repetitive cycling. Thermal fatigue tests are also conducted to
test thermal durability under 1350 oC of top part and 900 oC or room temperature of bottom
part. The cycles are conducted to 1,100 cycles. Ball indentation tests are conducted before
and after thermal fatigue test. Tungsten carbide ball with a radius of 3.18 mm is used for
obtaining indentation load-displacement curves. Relative hardness and stiffness changes will
be discussed from load-displacement curves. The results indicates that the (La,Gd)2Zr2O7/
YSZ multi-layers have good thermal durability and desirable for high damage resistance than
commercial YSZ material.

References
1. K.S. Lee et al., “Microstructure Controls in Gadolinium Zirconate/YSZ Double Layers and Their
Properties,” J. Ceram. Soc. Jpn., 122, pp. 668–673, 2014.
2. K.S. Lee et al., “Microstructure Design and Mechanical Properties of Thermal Barrier Coatings
with Layered Top and Bond Coats,” Surf. Coat. Technol., 205, pp. 1229–1235, 2010.

314
Reaction-bonded silicon carbide for fusion applications
Alexander J. Leide1,2*, David E.J. Armstrong1, Richard I. Todd1, Steve G. Roberts1,2,
Katsumi Yoshida3, Mike Gorley2
1
Department of Materials, University of Oxford, Parks Road, OX1 3PH, UK;
*
e-mail: [email protected]
2
Culham Centre for Fusion Energy, Abingdon, UK
3
Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, Tokyo, Japan
Keywords: fusion, melt infiltration, silicon carbide, micromechanics

Silicon carbide has potential applications in the breeder blanket of fusion reactors, where
its chemical inertness, low neutron cross-section, radiation tolerance, and low activation are
especially useful. The main challenge currently facing existing forms of “nuclear grade” SiC
is processing them reliably on a large enough scale for making components with minimal
joining. Reaction-bonding is a commercial processing technique capable of making large
components reliably and precisely to near net shapes. Early work suggested that residual
stress between SiC and silicon phases caused by irradiation swelling leads to microcracking
and failure.1
Novel forms of RBSC have been processed with low-activation silicides and fine grain
structure aimed at reducing residual stresses in RBSC caused by radiation-induced swell-
ing. These are investigated using micromechanical techniques, ion implantation, and Raman
microscopy.

Reference
1. R. B. Matthews, “Irradiation damage in reaction-bonded silicon carbide,” J. Nucl. Mater., vol. 51,
no. 2, pp. 203–208, Jun. 1974.

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463
Preparation of reaction-bonded Si-C-N porous ceramics by foaming
Jun Li
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and
Technology, Wuhan, China; e-mail: [email protected]

Preparation of the reaction-bonded Si-C-N porous ceramics was investigated using foaming
and nitriding. Porous Si-C-N ceramics were sintered at 1500–1650 °C under nitrogen atmo-
sphere by silicon carbide and silicon powders as the main raw materials, FS60 as vesicant,
Y2O3 as sintering additive, and HT as foaming agents. The influence of the different sizes Si
powders (d<74μm, 1# and d<9μm, 2# )and sintering temperatures were studied. The phases,
microstructure and mechanical property were characterized by XRD, SEM, TEM and com-
pressive strength tests. The results demonstrated that the porous Si-C-N ceramics were suc-
cessfully obtained with porosity from 47% to 70%, compressive strength from 6.5 MPa to
37.5 MPa, and multi-level vias (pore size from 1 μm to 1000 μm). 1# sample used Si powders
(d<74μm) as porosity ceramics was optimized.

554
Microstructure and properties of pressureless sintered graphene
nanoplatelet/3YTZP zirconia composites
C. López-Pernía1,2, R. Poyato1, A. Morales-Rodríguez1,2, A. Gallardo-López1,2
Instituto de Ciencia de Materiales de Sevilla, ICMSE, CSIC-Univ. de Sevilla, Avda.
1

Américo Vespucio 49. 41092, Sevilla, Spain

Departamento de Física de la Materia Condensada, Universidad de Sevilla-ICMSE (CSIC),
2

Apdo. 1065, 41080 Sevilla, Spain

Keywords: graphenenanoplatelets, 3YTZP, pressureless sintering, microstructure, electrical conduc-
tivity

Incorporation of carbon nanostructures as reinforcement phase for ceramics has been an at-
tractive topic in the recent decades. More recently, two-dimensional nanosized carbon ma-
terials, such as graphene nanoplatelets (GNP), multilayered graphene (MLG) or few layer
graphene (FLG) have emerged as an alternative to carbon nanotubes or carbon nanofibers,
since remarkable properties have been reported for ceramic composites incorporating these
2D nanomaterials1,2. Typically, these composites are prepared by a colloidal or wet powder
mixing procedure and a pressure assisted sintering technique, being the most common used
techniques hot pressing (HP) and spark plasma sintering (SPS). However, despite the poten-
tial interest of the pressureless sintering (PLS) of these composites, the published studies up
to date are scarce.

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The aim of this work is the fabrication and study of 3YTZP composites reinforced with
GNPs. Composite powder was prepared by wet powder mixing and pressureless sintered in
argon flow at temperatures between 1200–1500 ºC.The effects of GNP content and process-
ing conditions on the densification, microstructure, hardness and electrical conductivity of
the composites were analysed and discussed.

References
1. L.S. Walker, V.R. Marotto, M.A. Rafiee, N. Koratkar and E.L. Corral. “Toughening in graphene
ceramic composites”, ACS Nano, 5, pp. 3182–3190, 2011.
2. C. Ramirez, P. Miranzo, M. Belmonte, M.I. Osendi, P. Poza, S.M. Vega-Diaz and M. Terrones.
“Extraordinary toughening enhancement and flexural strength in Si3N4composites using graphene
sheets”, J. Eur. Ceram. Soc., 34, pp. 161–169, 2014.

898
Organically-modified ceramic membranes for solvent nanofiltration
M.W.J. Luiten-Olieman*, C.R. Tanardi, A.F.M. Pinheiro, Renaud M. Merlet, A. Nijmeijer,
L. Winnubst
Inorganic Membranes, MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217,
7500 AE, Enschede, The Netherlands; *e-mail: [email protected]

Highlights
1. An overview of different grafting techniques will be presented.
2. A variety of polymers can be attached onto the pore surface of ceramic membranes.

Separation of solvents by membranes is a potential key enabling technique for many chemi-
cal processes. State-of-the art polymeric or ceramic membranes do not always meet stabil-
ity and/or selectivity demands at process-relevant conditions like separation/purification of
harsh organic solvents and operations at high temperatures or pressures. In order to fulfil
these operational requirements a concept is developed, based on mesoporous (pore size 5–10
nm) ceramic membranes, as a non-swelling and non-compactable, rigid material, acting as
a support, on which polymer materials are immobilized; i.e. covalently or electrostatically
bonded. In this way the pore size and surface chemistry of membranes can be adjusted for
any specific separation application by varying the composition/structure of the polymer.
This functionalization of ceramic membranes is viable through grafting. Grafting is a pro-
cess in which a specific organic substance is chemically bonded to an inorganic substrate.
The OH-groups of the oxide ceramic surface will react with the hydrolysable groups of the
to-be grafted organic moiety to produce a stable bond, resulting in a permanent modification
of ceramic membranes.
An overview will be presented of the different grafting techniques, summarized in Fig. 1.
Some performance results will be given as well.

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Fig. 1. Three ways of grafting

References
1. Tanardi, C.R., Organically-modified ceramic membranes for solvent nanofiltration: Fabrication and
transport studies, in Science and Technology. 2015, University of Twente, Neterlands.
2. Pinheiro, A.F.d.M., Development and Characterization of Polymer-grafted Ceramic Membranes for
Solvent Nanofiltration, in Science and Technolog. 2013, University of Twente, Ede, Netherlands.

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147
Spark plasma sintering of alumina ceramic reinforced with WC-Co
Manku Masemola1, Enoch N. Ogunmuyiwa2*, Oluwagbenga T. Johnson3,
Mxolisi B. Shongwe1, Saliou Diouf1, Peter A. Olubambi4
Department of Chemical, Materials & Metallurgical Engineering,
1

Tshwane University of Technology, Pretoria, South Africa;

e-mails: [email protected], [email protected], [email protected]
Department of Chemical, Materials & Metallurgical Engineering, Botswana International University
2

of Science and Technology, Private Bag 16, Palapye, Botswana; *e-mail: [email protected]
Department of Mining & Metallurgical Engineering, University of Namibia, Ongwediva Campus,
3

Ongwediva, Namibia; e-mail: [email protected]

Department of Chemical Engineering, University of Johannesburg, Johannesburg, South Africa;
4

e-mail: [email protected]
Keywords: alumina, tungsten carbide cobalt, spark plasma sintering, mechanical properties, cutting
tools

Alumina (Al2O3) and cemented tungsten carbide cobalt (WC-Co) are ceramic materials suc-
cessfully used for metal cutting tools because they provide good strength, hardness and dura-
bility. Al2O3 has poor toughness and WC-Co do not allow high speed cutting and can easily
deform due to heat generated while cutting. Hence, the combination of Al2O3 and WC-Co
becomes a matter of interest. However, the combination of Al2O3 and WC-Co has not been
extensively studied and not clearly understood. As a result, the mixture of Al2O3 matrix with
WC-Co reinforcement was sintered and its mechanical properties investigated in this report.
The composites of 85–95 wt% Al2O3 and particle reinforcement containing varying ratios of
WC-Co were prepared by conventional powder processing and the powder mixtures were
sintered using spark plasma sintering between 1400 and 1600 °C in an argon atmosphere.
Physical and mechanical properties of the composites, such as density, hardness and frac-
ture toughness including microstructure were investigated. It was found that the composites
of 98–99.9% relative density were achieved after sintering at 1600 °C for the WC-12Co
composites. The prepared Al2O3/WC-Co composites provided both hardness and fracture
toughness between 17–18 GPa and 5–8 MPa.m0.5 respectively, which are still appropriate for
cutting tool applications.

References
1. W. Acchar, C.A. Cairo, and A.M. Segadães. Effect of tungsten carbide additions on the microstruc-
ture and properties of hot-pressed alumina. Mat. Sci. and Eng. A, 406(1), pp. 74–77, 2005.
2. V. Chaiyacote, W. Buggakupta, and N. Chuankrerkkul. Mechanical Properties and Microstructure
of Al2O3/WC-Co Composites. J. of Met. Mat. and Min., 20(3), pp. 5–8, 2010.
3. W.H. Chen, H.T. Lin, P.K. Nayak, M.P. Chang, and J.L. Huang. Sintering behavior and mechanical
properties of WC–Al2O3 composites prepared by spark plasma sintering (SPS). Int’l. J. of Ref. Met.
and Hard Mat., 48, pp. 414–417, 2015.
4. W.H. Chen, P.K. Nayak, H.T. Lin, A.C. Lee and J.L. Huang. Enhanced mechanical properties of
WC-reinforced Al2O3 ceramics via spark plasma sintering. Cer. Int’l., 41(1), pp. 1317–1321, 2015.

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5. P.K. Nayak, H.T. Lin, M.P. Chang, W.H. Chen and J.L. Huang. Microstructure analysis and me-
chanical properties of a new class of Al2O3–WC nanocomposites fabricated by spark plasma sinter-
ing. J. of the Euro. Cer. Soc., 33(15), pp. 3095–3100, 2013.
6. E.M. Pallone, D.R. Martin, R. Tomasi, and W.J. Botta Filho. Al2O3–WC synthesis by high-energy
reactive milling. Mat. Sci. and Eng. A, 464(1), pp. 47–51, 2007.

965
Novel silicon oxycarbide-carbon nanofiber materials with high
electrical and thermal properties
M. Alejandra Mazo, Aitana Tamayo, Juan Rubio
Instituto de Cerámica y Vidrio (CSIC), C/ Kelsen 5 28049 Madrid, Spain; e-mail: [email protected]
Keywords: silicon oxicarbide, ceramic composite, Spark Plasma Sintering, electrical conductivity,
thermal conductivity

Dense bulk silicon oxycarbide-carbon nanofiber (SiOC-CNF) composites have been ob-
tained by Spark Plasma Sintering (SPS) without the degradation of the carbon reinforcement.
SiOC-CNF mixtures with an increasing CNF content ranging from 0.5% to 10% are used.
The application of this non-conventional sintering route which simultaneously applies high
electric current and uniaxial pressure allows obtaining extremely fast heating rates reducing
both sintering temperature and holding times and as consequence dense composites whit
novel properties are obtained. The density of the SiOC-CNF derived materials is similar
independently of the CNF content and it is near 2.2 g/cm3 in all the cases. The electrical con-
ductivity is increased by five orders of magnitude (up to 1×10+2 S/m) and the thermal conduc-
tivity also increases by 40% (up to 2.0 W/mK) when compared to SiOC. These changes must
be related with the formation nanodomains of β-SiC and carbon within the glassy matrix as
consequence of the sintering conditions and the carbon reinforcement.

908
Transport phenomena through grafted ceramics for OSN
Renaud Merlet, Cheryl Tanardi, Arian Nijmeijer, Louis Winnubst*
University of Twente, Enschede, The Netherlands; *e-mail: [email protected]

Unlike their polymeric counterparts, ceramic membranes benefit from a rigid architecture
which does not swell in the presence of organic solvents. However, their hydrophilic surfaces
makes them ill-suited to organic solvent nanofiltration. Grafting short chains of PDMS not
only shrinks the pore to the desired size but also renders them suitable for organic solvent
nanofiltration (OSN). These membranes exhibit particular transport phenomena due to the
localized swelling of the PDMS. The degree of swelling is solvent-dependent, which impacts
both the permeability and retention of the membrane.1

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We have examined how solvent mixtures permeate and solutes are retained across PDMS-
grafted gamma-alumina selective layers supported on alpha-alumina. Four types of mem-
branes were fabricated: two initial pore sizes of alumina, 5 nm and 9 nm, each grafted with
two sizes of PDMS, either a degree of polymerization n = 10 or n = 20. A range of solvents
and their mixtures were tested, from ethanol to toluene, in a cross-flow setup from pressures
10 to 40 bar. Characterization by permporometry and contact angle, as well as retention and
permeability measurements indicated a membrane well suited to OSN applications. Param-
eters such as the size of the initial pore, swollen pore and solute are inputs to a modified
Spiegler Kedem model to predict the performance of these grafted ceramic membranes for
OSN. By allowing the diffusion (but not convection) of solutes through the swollen graft, we
find that predictions obtained through the Spiegler Kedem model agree with the experimental
data.1

Reference
1. R.B. Merlet, C.R. Tanardi, I.F.J. Vankelecom, A. Nijmeijer, L. Winnubst, Interpreting rejection in
SRNF across grafted ceramic membranes through the Spiegler-Kedem model, J. Membr. Sci. 215
(2017) 359–167.

774
Microstructure and mechanical properties of in-situ (Ti,W)C particles
reinforcing iron
Lionel Michelet, Marta Fornabaio, Goran Zagar, Andreas Mortensen
Laboratory of Mechanical Metallurgy, Institute of Materials, École Polytechnique Fédérale de
Lausanne (EPFL), Station 12, CH-1015 Lausanne, Switzerland
Keywords: transition metal carbides, metal matrix composite, mechanical properties, nanoindentation

MC carbides are well known hard phases that are used to give strength, wear and corrosion
resistance to steels or steel matrix composites. In steel, MC carbides are commonly present
as small (micron-sized) particles. The most important and commercially used MC carbide
particles are WC and TiC. The development of cubic (Ti,W)C solid solutions, possible in
this system with up to 50%W, might further improve the mechanical performance of these
reinforcing particles, potentially overcoming some of the application limits of TiC or Ti(CN)-
based cermets. Recent advances in processing carbides have offered a way of producing such
materials; however, no comprehensive investigation of this system has yet been carried out
and there is still a significant lack of knowledge about their intrinsic mechanical behaviour.
Results will be presented from an investigation of the subject, which comprises two main
thrusts: (i) to synthesize in situ (Ti,W)C particles reinforced iron matrix where the tungsten
exchange in the monocarbide TiC phase can be tailored and (ii) to evaluate the mechanical
properties of hard particles by conducting small scale mechanical tests directly on particles
within the microstructure. In particular, high purity and homogeneous (TixW1-x)C particles
have been grown in-situ during solidification within an iron matrix by arc-melting. Mechani-

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T03: Advanced structural ceramics – Poster presentations

cal properties (elastic modulus and hardness) of (TixW1-x)C particles, exposed on the polished
surface of the iron matrix, are probed by nanoindentation testing. The variation of composite
microstructure and carbide morphology as well as that of the elastic modulus and hardness of
the particles is then quantified as a function of the Ti/W ratio.

Acknowledgements
This research was funded by the European Research Council under the European Union’s Seventh
Framework Programme (FP/2007-2013) / ERC Advanced Grant Agreement No. 291085.

281
Gigantic grain growth in boron carbide ceramics during spark plasma
sintering
Bibi Malmal Moshtaghioun, Diego Gómez-García, Arturo Domínguez Rodríguez
Department of Condensed Matter Physics, University of Seville, P.O. 1065, 41080 Seville, Spain
Institute of Material Science ICMSE, CSIC-US, Av. Americo Vespucio 49, 41092 Seville, Spain

In the ceramic fields, research on ultra-high-temperature ceramics is a hot topic nowadays.

Boron carbide deserves a particular attention since it is one of the hardest material in the
Nature.
Sintering of boron carbide has been an overwhelming task until recently, due to the very
low diffusion coefficients and the extremely high temperatures required to this end. In this
regard, spark plasma sintering has revealed as a crucial technique for fully-dense preparation
of fine-grained boron carbide ceramics.
The study of the mechanical and microstructural properties is now available. This presen-
tation is concentrated on the grain growth kinetics at very high temperatures, typically over
1800 ºC, during SPS sintering. It will be shown that grain growth does not follow the classi-
cal laws because growth kinetics is drastically affected by the presence of the electrical field
as well as singular microstructural evolution of boron carbide grains.

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678
Effect of zirconia surface treatments on friction coefficient and surface
properties
C.G. Moura1*, M. Buciumeanu2, R.S.F. Pereira3, O. Carvalho1, F.S. Silva1, R.M.
Nascimento4
1
CMEMS-UMinho, Universidade do Minho, Campus de Azurém, 4800-058, Guimarães, Portugal;
*
e-mail: [email protected]
2
Cross–Border Faculty of Humanities, Economics and Engineering, University of Galati, Dunarea de
Jos, Domneasca 47, 800008 Galati, Romania
3
Ceramics and Composites Materials Research Center (CERMAT)-UFSC, Campus de Florianópolis,
88040-900, Florianópolis-SC, Brazil
4
Materials Science and Engineering Post-Graduate Program, UFRN, 59078-970 Natal, Brazil
Keywords: zirconia, surface treatment, roughness, friction coefficient

Zirconia is a widely used ceramic material in biomedical field, mainly because of its high
mechanical properties and biocompatibility. However, zirconia is chemically inert and it does
not allow to naturally form a direct bond with bone1. It has been already shown that surface
roughness plays an important role in cell response2. Thus, several treatments such as sand-
blasting, etching and laser irradiation were used to enhance the biological performance of
zirconia surface1. Among these, laser technology has been extensively used as there is no risk
for surface contamination, like in the case of blasting and etching treatments, and also there
is no change in the bulk properties of the material1,3.
The aim of this study was to investigate the surface modification of Yttria-tetragonal zir-
conia polycristals (3Y-TZP) using different treatments, such as sandblasting, etching and
laser irradiation by a Nd:YAG. Sandblasting treatment was performed with 100-µm alumina
particles and etching treatment was accomplished using hydrofluoric acid.
To determine both the static and dynamic coefficient of friction a reciprocating pin-on-
plate tribometer (Bruker-UMT-2, USA) was used. The plates (4×16×x20) were bones that
were cut from a femur of bovine. The pins were the studied materials. The bone plates were
mounted in an acrylic electrochemical cell attached to the tribometer. The bones were always
hydrated with a Phosphate Buffered Saline (PBS) fluid. The tribological parameters were 150
N normal load, at a frequency of 1Hz, and the total stroke length 5 mm.
The surfaces were inspected by Scanning Electron Microscopy/Energy Dispersive Spec-
troscopy (SEM/EDS). Roughness was measured using a surface profilometer (Surftest SJ
201, Mitutoyo, Tokyo, Japan). Wettability characteristics were also evaluated. Results sug-
gest that the investigated surface treatments have a great influence on friction behavior of
zirconia 3Y-TZP. Also, it is shown that the wettability characteristics of the zirconia 3Y-TZP
can be improved by laser surface treatment.

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References
1. Hao L, Lawrence J, Chian KS. Osteoblast cell adhesion on a laser modified zirconia based biocer-
amic. J Mater Sci Mater Med. 2005;16(8):719–726. doi:10.1007/s10856-005-2608-3.
2. Soon G, Pingguan-murphy B, Wee K, Ali S. Review of zirconia-based bioceramic: Surface modifi-
cation and cellular response. 2016;42:12543–12555.
3. Martinez H. Review article. Optimal implant stabilization in low density bone. 1991:423–432.

939
Effect of freezing temperature on microstructure and mechanical
properties of porous Si3N4 ceramics produced by freeze casting
Fatemeh Nahvizadeh, Farhad Golestanifard, Hamidreza Rezaie
Centre of Excellence for Ceramic Materials, School of Metallurgy and Materials Engineering,
Iran University of Science and Technology (IUST), Narmak, Tehran 16846, Iran;
e-mails: [email protected], [email protected], [email protected]
Keywords: freeze casting, freezing temperature, porous silicon nitride, unidirectional porosity

Porous silicon nitride ceramics have been widely used in industrial applications, such as
high-temperature gas filters and separation membranes because of its excellent mechanical
properties at both room and elevated temperatures, good oxidation resistance, good thermal
shock resistance, thermal–chemical corrosion resistance as well as lightweight structural ma-
terials1–4. For practical applications, these properties are related to the pore structure (shape,
morphology, orientation, porosity, etc.). The porous ceramics from freeze casting do not
have ultra-high porosity and have large interconnection and dense ceramic networks that are
necessary to enhance its mechanical properties. In addition, freeze casting is able to easily
control the pore morphology, porosity, microstructure as well as the mechanical properties
of porous ceramics by adjusting the concentration of ceramic slurry, vehicle phase, freezing
rate and freezing temperature3 such as –18, –1983, –10, –60 °C6 and sintering conditions2,7.
However, as we know, the reports on the microstructural control and mechanical properties
of porous silicon nitride ceramics fabricated by freeze casting are very scarce. The purpose
of this study is to illustrate the influence of freezing temperature on the microstructure and
mechanical properties of porous Si3N4 ceramics produced by freeze casting8.
In this research, porous silicon nitride ceramics were fabricated by freeze-casting pro-
cess at different freezing temperatures to obtain different pore morphology. The microstruc-
ture and mechanical strength of porous Si3N4 were investigated3. Slurries were prepared
by mixing distilled water. The suspensions consist of solid loading 35vol%. Slurries were
ball-milled for 24 h and de-aired by stirring in a vacuum desiccator. The resultant slurries
were then poured into molds immersed in liquid nitrogen (–196 °C) and freezer (–5 °C).
Immediately after casting, the ice crystals grow unidirectionally. After the frozen samples
were completely dried under special sublimation cycles for 3 days, the green compacts were
placed in a graphite crucible with a silicon nitride-based powder bed and sintered in a graph-
ite resistance furnace at 1650 °C for 4 h. Samples were kept in furnace to get cool down. The
densities of the samples were calculated from the dimensions and weight of the samples.

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Crystalline phases of the sintered porous Si3N4 ceramics were characterized by X-ray dif-
fraction (XRD). Quantitative analysis of αand β-Si3N4 phase content was determined by
comparing the peak intensity ratios9. The microstructure of the cross section was observed by
scanning electron microscopy (SEM). Flexural strength measured in air at room temperature.
Although both samples have same density and α and β-Si3N4 phase content and porosity
percentage, they have different flexural strength. Freezing samples in freezer contains large
pores interconnected with dendritic microstructure, but freezing samples in liquid nitrogen
has fine pores interconnected with columnal microstructure. Pore shape and size and wall
thickness are effective on flexural Strength, in away that freezing samples in liquid nitrogen
and freezer has strength of 81.74 and 39.92MPa, respectively.

References
1. R. Zhang, D. Fang, Y. Pei, and L. Zhou, “Microstructure, mechanical and dielectric properties of
highly porous silicon nitride ceramics produced by a new water-based freeze casting,” Ceram. Int.,
vol. 38, no. 5, pp. 4373–4377, Jul. 2012.
2. S. Kurama, M. Herrmann, and H. Mandal, “The effect of processing conditions, amount of addi-
tives and composition on the microstructures and mechanical properties of a -SiAlON ceramics,”
vol. 22, pp. 109–119, 2002.
3. Y. Xia, Y.-P. Zeng, and D. Jiang, “Microstructure and mechanical properties of porous Si3N4 ce-
ramics prepared by freeze-casting,” Mater. Des., vol. 33, pp. 98–103, Jan. 2012.
4. F. Ye, J. Zhang, H. Zhang, and L. Liu, “Pore structure and mechanical properties in freeze cast
porous Si3N4 composites using polyacrylamide as an addition agent,” J. Alloys Compd., vol. 506,
no. 1, pp. 423–427, Sep. 2010.
5. K. Araki and J. W. Halloran, “Room-Temperature Freeze Casting for Ceramics with Nonaqueous
Sublimable Vehicles in the Naphthalene – Camphor Eutectic System,” vol. 2019, no. 10706, pp.
2014–2019, 2014.
6. S. W. Sofie, “Fabrication of Functionally Graded and Aligned Porosity in Thin Ceramic Substrates
With the Novel Freeze? Tape-Casting Process,” J. Am. Ceram. Soc., vol. 90, no. 7, pp. 2024–2031,
Jul. 2004.
7. F. Ye, J. Zhang, H. Zhang, and L. Liu, “Effect of sintering temperature on microstructure and me-
chanical properties of highly porous silicon nitride ceramics produced by freeze casting,” Mater.
Sci. Eng. A, vol. 527, no. 24–25, pp. 6501–6504, Sep. 2010.
8. F. Ye, J. Zhang, L. Liu, and H. Zhan, “Effect of solid content on pore structure and mechanical
properties of porous silicon nitride ceramics produced by freeze casting,” Mater. Sci. Eng. A, vol.
528, no. 3, pp. 1421–1424, Jan. 2011.
9. A. Materials, “The a / β silicon nitride phase transformation,” vol. 13, pp. 1199–1205, 1978

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443
Reactivity of dicalcium phosphate dihydrate with various fluoride
compounds
Saki Nakada1, Masamoto Tafu1*, Yoshiaki Hagino2, Saori Takamatsu1, Atsushi Manaka1,
Takeshi Toshima1, Keiichiro Yamamoto3
1
National Institute of Technology, Toyama College (Hongo), Hongo-machi 13, Toyama-city, Toyama,
Japan, 939-8630; *e-mail: [email protected]
2
Fudo Tetra Corp, 7-2, Nihonbashi-koami-chou, Chuou-ku, Tokyo, Japan, 103-0016
3
National Institute of Technology, Toyama College (Imizu), 1-2 Ebie-neriya, Imizu city, Toyama,
Japan, 933-0293
Keywords: calcium phosphate, fluoride, soil pollution

Remediation of soil by fluoride compound is important environmental issue because of fluo-

ride in the polluted soil affect health impact to surrounding ground water for drinking water.
Mineralization and stabilization of fluoride in the polluted soil is one of the candidates. In
previous study, we have appeared that transform reaction of dicalcium phosphate dihydrate
(DCPD) is applicable to stabilization of fluoride in the polluted soil1 for long term over 2
years2. However, stabilization amount of fluoride by addition DCPD was different on vari-
ous sites. We have assumed that this difference of reactivity of DCPD with fluoride in the
polluted soil depend on chemical formation of fluoride such as mobile (soluble), residual
(insoluble) and exchangeable, etc.
In this study, reactivity of DCPD with various fluoride compounds in an aqueous solution.
We selected calcium fluoride as residual fluoride content in the polluted soil. Calcium fluo-
ride used in this study was sludge from wastewater treatment on the assumption of polluted
soil in industrial sites. In previous study, it was appeared that DCPD do not react fluoride ion
directly but form nano-scaled precursor on surface of the DCPD particles. To improve reac-
tivity of the DCPD, DCPD was pre-treated and induced the nano-scaled precursor1 on it. The
DCPD was mixed with the calcium fluoride and ultra-pure water, and reacted for 24 hours
at room temperature. After reaction, fluoride concentration in the solution was analysed by
ion selective electrode and ion meter. By using the DCPD, fluoride release from dissolution
of the calcium fluoride was successfully inhibited. From result of powder X-ray diffraction
analysis of obtained solid phase, it was appeared that the calcium fluoride was transformed
to stable flouraptite (FAp) by reaction of the DCPD with fluoride ion from calcium fluoride
in gradually. From these result, addition of DCPD is applicable to immobilize and transform
stable fluoride residual in the polluted soil to form of stable mineral, FAp.

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References
1. M. Tafu, T. Chohji, I. Morioka, M. Hiwasa, H. Nakano, T. Fujita, “Stabilization of Fluoride in
Waste Gypsum by Using Surface-Modified Calcium Phosphate Particle” Trans. MRS-J, 35(2),
377–380, 2010.
2. M. Tafu, A. Manaka, “Immobilization of Fluoride and Heavy-Metals in Polluted Soil”, Chap.7 in
“Environmental Remediation Technologies for Metal-Contaminated Soils”, Ed. H. Hasegawa et al.,
pp. 147–159, Springer, 2016.

441
High temperature erosion behavior of max phase (Ti3SiC2) reinforced
nickel composites
Andy Nieto1, Matt Fuka2, Maharshi Dey2, Michael Walock1, Anindya Ghoshal1,
Muthuvel Murugan1, Surojit Gupta2
1
Vehicle Technology Directorate, US Army Research Laboratory, Aberdeen Proving Ground, MD,
21005, USA
2
Department of Mechanical Engineering, University of North Dakota, Grand Forks, ND, 58202, USA
Keywords: MAX phases, Ti3SiC2, erosion, oxidation, composites

MAX phases have attracted considerable attention in recent years due to their unique set of
properties that may enable them to bridge the gap between metals and ceramics. Ti3SiC2 is
one of the most promising MAX phases for elevated temperature applications due to its low
density, high temperature strength, and relatively high oxidation resistance below 1100 °C.
These properties, along with the inherent toughness and damage tolerance endowed by the
intrinsic nanolaminate structures present in MAX phases makes Ti3SiC2 an ideal reinforce-
ment for high temperature metals and alloys, such as Ni. In this study, 10 vol. % of Ti3SiC2
MAX phase particulates are used to reinforce a Ni matrix composite (Ni-MAX). The erosion
behavior of Ni-MAX is evaluated at room temperature (RT) and at high temperature (~1000
°C) using 50 µm Al2O3 particles as the erodent media. Particle impingement angles are varied
from 30° to 90°. Erosion scars are analysed using scanning electron microscopy (SEM), ener-
gy dispersive spectroscopy (EDS), x-ray diffraction (XRD), and focused ion beam (FIB) sub-
surface cross-sectioning in order to assess erosion mechanisms, damage modes, and possible
chemical reactions. Erosion performance and behavior of Ni-MAX composites is compared
with that of pure Ni in order to gauge the effectiveness of utilizing MAX phase reinforce-
ments for enhanced erosion resistance at RT and ~1000 °C.

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803
Irradiation of ceramics based on titanium, zirconium,
and hafnium nitrides with high-energy xenon ions
Aleksandr Ogarkov1*, Sergei Shevtsov1, Konstantin Kuznetsov1, Ivan Kovalev1,
Aleksandr Nechaev2, Andrei Chernyavskii1, Valentin Ievlev3, Konstantin Solntsev1
1
Baikov Institute of Metallurgy and Materials Science, Russian Academy of Sciences,
Leninskii pr. 49, 119334 Moscow, Russia; *e-mail: [email protected]
2
Joint Institute for Nuclear Research, Moscow region, Dubna, Russia
3
Lomonosov Moscow State University, Moscow, Russia
Keywords: titanium nitride, zirconium nitride, hafnium nitride, ceramics, oxidative constructing,
irradiation

The purpose of this work is to assess the structural and morphological changes produced in
Ti, Zr, and Hf nitrides by irradiation with high-energy xenon ions. Titanium was nitrided at
1700 °C, and zirconium and hafnium at 2000 °C for 60 min. The starting materials used were
ribbons 60 mm in length and 3.0 × 0.5 mm in cross section. Samples of the Ti, Zr, and Hf
nitrides were irradiated with 167-MeV +24Xe136 ions to a fluence of 5.3 × 1014 cm–2 at a tem-
perature of 20–25 °C for a total of ten days. The use of xenon ions with this energy, which
are not radioactive, makes it possible to simulate the formation of uranium fission fragments.
Irradiation produced no changes in the phase composition and lattice parameter of the
nitrides.
Irradiation of titanium and hafnium nitrides leads to the formation of nano- and micro-
pores in the surface layer of the samples. The surface layer of zirconium nitride samples con-
tains nanopores both before and after irradiation. The presence of pores in the unirradiated
ZrNx samples probably ensures the possibility of structural relaxation without further pore
formation under irradiation. The pore size characteristic of irradiated ZrNx is greater than that
of the unirradiated material. High-resolution TEM of the irradiated ZrNx samples revealed
local crystal structure distortions unrelated to dislocations and attributable to the impact of
high-energy xenon ions.

Acknowledgments
This work was supported by the Russian Science Foundation, project no. 14-13-00925 (federal state
budget funded science institution Baikov Institute of Metallurgy and Materials Science, Russian Acad-
emy of Sciences).

References
1. Kuznetsov, K.B., Solntsev, K.A., and Chernyavskii, A.S., RF Patent 2 337 058, 2008.
2. Kuznetsov, K.B., Shashkeev, K.A., Shevtsov, S.V., Ogarkov, A.I., Tret’yakov, N.N., Saprina, M.P.,
Kostyuchenko, A.V., Chernyavskii, A.S., Ievlev, V.M., and Solntsev, K.A., “Structure and hardness
of ceramics produced through high-temperature nitridation of zirconium foil”, Inorg. Mater., 51,
pp. 820-827, 2015.

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981
Comparison of the properties of un-seeded and seeded alumina powders
Bediha Orbay, Azade Yelten, Suat Yilmaz*
Department of Metallurgical and Materials Engineering, Istanbul University, 34320 Avcilar, Istanbul,
Turkey; *e-mail: [email protected]
Keywords: α-Al2O3, Sol-gel, seeding

Alumina (Al2O3) is a widely used structural ceramic due to its high compression strength,
hardness, chemical stability and wear resistance. Sol-gel is an effective way to obtain alu-
mina powders with high purity at low temperatures.1–4 From our previous studies, it was
found out that sol-gel derived alumina powders used as a component of a composite material
(alumina-hydroxyapatite) did not show sufficient mechanical strength.3 Therefore, in this
study it was aimed to enhance the compression strength of alumina by applying the seeding
approach.1,2,4 α-Al2O3 seeding enables to control the nucleation and growth mechanism of
alumina grains during hydrolysis and peptization process.1,2,4 Aluminium isopropoxide (AIP,
(Al(OC3H7)), Aldrich ≥ 98%), the starting material, was hydrolysed at 90 °C by employ-
ing a heating mantle with magnetic stirrer. At this point, a novel principle was followed;
the seeding agent, α-Al2O3 (Merck, 0.063–0.2 mm), was mixed with the starting precursor
and added together to the distilled water to be hydrolysed. In this way, it was tried to create
protentional nucleation areas in the boehmite (AlOOH) sol. In order to compare the effect
of seeding on the properties of sol-gel derived alumina powders, un-seeded and wt.10% of
AIP seeded samples were prepared. 40 ml HCl (Merck, 37%) was used as peptizer agent to
accelerate the hydrolysis reactions. After hydrolysis and peptization steps, partially opaque
boehmite solution was obtained. Un-seeded and seeded samples were gelated at 110 °C for 6
h and then heat treated at 1600 °C for 2 h with a 10 °C/min heating and cooling rate. Finally,
irregular shaped alumina powders were produced and these powders were ground manually
utilizing a mortar and pestle. Cylindrical pellets were formed from the ground powders by
using a hydraulic press and stainless steel moulds. The pellets were sintered at 1600 °C for
1 h. XRD, FTIR, SEM-EDS analyses were carried out for the powder samples while bulk
density, % apparent porosity and compression strength determinations were performed for
the sintered pellets.

References
1. C.S. Norhdahl and G.L. Messing, “Sintering of α-Al2O3-seeded nanocrystalline γ- Al2O3 powders”,
Journal of the European Ceramic Society, 22, pp. 415–422, 2002.
2. Y. Kobayashi, Y. Mabuchi, M. Hama, K. Inoue, Y. Yasuda and T. Morita, “Seeding technique for
lowering temperature during synthesis of α-alumina”, Journal of Asian Ceramic Societies, 3, pp.
139–143, 2015.
3. A. Yelten, S. Yılmaz, F. N. Oktar, “Sol-Gel Derived Alumina-Hydroxyapatite-Tricalcium Phos-
phate Porous Composite Powders” Ceramic International, 38, pp. 2659–2665, 2012.
4. B. Orbay, “Improvement of Physical and Mechanical Properties of Alumina Produced by Sol-Gel
Method”, M.Sc. Thesis, Istanbul University, continuing.

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903
Characterization of tungsten boride – tungsten disilicide composites
fabricated by mechanical alloying and pressureless sinterıng
Didem Ovalı*, Duygu Ağaoğulları, M. Lütfi Öveçoğlu
Particulate Materials Laboratories, Department of Metallurgical and Materials Engineering, Faculty
of Chemical and Metallurgical Engineering, Istanbul Technical University, 34469 Maslak, Istanbul,
Turkey; *e-mails: [email protected], [email protected]
Keywords: tungsten boride, tungsten silicide, composite, mechanical alloying, pressureless sintering

Tungsten boride (WB) has a potential for industrial applications at extreme environmental
conditions amongst transition metal borides due to exhibiting interesting properties such as
high melting point, high hardness, high abrasion resistance, chemical inertness, magnetic and
electrical properties and good thermal shock resistance.1–3 Tungsten disilicide (WSi2) can be
a good candidate as a reinforcement material thanks to its abrasive/adhesive wear resistance
and oxidation resistance.4,5
In this study, WB composites with various amounts of WSi2 addition were produced by
high energy ball milling, cold pressing and pressureless sintering. Ball milling experiments
were conducted in ethanol and Ar atmosphere using WC-Co vial and balls at different dura-
tions. Phase and microstructural characterizations of the sintered samples were performed
using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. Ar-
chimedes and pycnometer density measurements were carried out. Microhardness and wear
resistance tests of the sintered samples were also conducted. Moreover, oxidation resistance
studies were employed via thermogravimetric analyzer (TGA).

References
1. R. Kiessling, “The Borides Of Some Transition Elements”, Acta Chem Scand., 4, pp. 209–227,
1950.
2. L. Brewer, D.L. Sawyer, D.H. Templeton, C.H. Dauben, “A Study of the Refractory Borides”, J Am
Ceram Soc., 34, pp. 173–179, 1951.
3. Q. Li, D. Zhou, W. Zheng, Y. Ma, C. Chen, “Global structural optimization of tungsten borides”,
Phys Rev Lett., 110, pp. 1–5, 2013.
4. L. Silvestroni, G. Meriggi, D. Sciti, “Oxidation behavior of ZrB2 composites doped with various
transition metal silicides”, Corros Sci., 83, pp. 281–291, 2014.
5. T. Murthy, J. Sonber, C. Subramanian, R. Hubli, A. Suri, “Densification, characterization and oxi-
dation studies of TiB2–WSi2 composite”, Int J Refract Met Hard Mater., 33, pp. 10–21, 2012.

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685
Grain refining in Al2O3-Ni nanocomposites prepared via pressureless or
field assisted sintering
Tomasz Pawlik1, Fotini Petrakli2, Athena Tsetsekou2, Malgorzata Sopicka-Lizer1
1
Silesian University of Technology, Krasinskiego 8, 40-019 Katowice, Poland
2
National Technical University of Athens, 9 Irooon Polytechneiou, Zografos, Athens, Greece
Keywords: nanostructured alumina, Ni inclusions

The aim of the present work is to (get a better knowledge) elaborate on the grain refining
process by incorporation of Ni nanoinclusions into alumina nanoparticles and subsequent
densification employing either pressureless or field-assisted sintering.1 Hybrid Al2O3-Ni
nanoparticles were prepared through an innovative wet-chemical route utilizing a hyper-
branched polymer (poly(ethylene)imine) as template material to synthesize the boehmite
powder and combine it with Ni ions. Various treatments were followed to receive a deag-
glomerated γ-alumina/Ni powder. DTA/Tg and dilatometric studies were carried out. Pres-
sureless sintering was performed in the high temperature range of 1500–1650 °C under vari-
ous atmospheres: air, argon and nitrogen. Field assisted sintering (FAST) was completed
under uniaxial pressure of 50 MPa in the temperature range of 1150–1350 °C for 2–15 min
investigating various heating-up regimes. Density and microscopic studies of the average
grain size were performed. It has been shown that the examined specimens were densified
with varying rate depending on the densification parameters and that the presence of Ni inclu-
sions was effective in preventing densification. Pressureless sintering in argon atmosphere
at 1650 °C led to a relative density of 90% but the mean grain size appeared large with their
distribution lying in the range of 4–20 μm. FAST densification resulted in relative density in
the range of 96–98% after sintering at 1350 °C for 4 min, but the grain size was in the order
of 3–4 μm. Nanometric grains of an average diameter of 500 nm formed as a result of sinter-
ing at 1200 °C for 2 min, but the relative density was about 70%. Consolidation of powders
in the temperature range of 1200–1300 °C caused an abrupt grain size growth but elongation
of the consolidation time did not lead to higher densification. Discussion of the observed
behaviour is provided.

Reference
1. Robert Besler, Marcel Rossetti da Silva, Maksym Dosta, Stefan Heinrich, Rolf Janssen, “Discrete
element simulation of metal ceramic composite materials with varying metal content”, J. Eur. Cer-
am. Soc., 36, pp. 2245–2253, 2016.

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915
Synthesis and characterization of selected Al2O3-YSZ composites for
the application in CMAS resistant thermal barrier coating systems
Paul Prigorodov, Dung Than Tran, Rainer Telle
Institute of Mineral Engineering, RWTH Aachen, Aachen, Germany
Keywords: thermal barrier coating, CMAS, ATZ, alumina toughened zirconia, composite, sol-gel

Today’s state of the art topcoat material in thermal barrier coatings (TBCs) for airplane gas
turbines is 7-8 wt.% yttria stabilized zirconia (7YSZ) which shows two main limitations
regarding the application’s conditions. Firstly the long-term operation temperature is limited
to ~1200 °C. Above that accelerated sintering and destructive phase transformations can be
observed. Specifically spoken the metastable tetragonal t’-phase decomposes into a phase
equilibrium of cubic and tetragonal ZrO2 phases (c + t). During thermal cycles the reversible
phase transformation in between t-ZrO2 and monoclinic ZrO2 (m) leads to stress-induced
spallation of the topcoat. The second limitation arises in dusty environments where molten
silica-rich CMAS particles (amorphous Ca-Mg-Al-Si-slags) infiltrate the 7YSZ topcoat and
decompose the t’-phase by chemical reactions. Moreover rapid densification can be observed
which lowers the thermal conductivity and induces topcoat spallation during thermal cycles.
One possible solution to overcome the given limitations would be the use of Al2O3-YSZ
composites (ATZ). By adding α-Al2O3 to YSZ the t’-phase can be stabilized chemically and
mechanically thus allowing higher operation temperatures. Furthermore an Al2O3 reservoir
switches the chemical CMAS composition to faster crystallisable phases which may hinder a
complete infiltration of the topcoat.
ATZ-composites have been wet-chemically synthesized with 1, 10, 20 and 30 wt.% of
α-Al2O3. The yttria content in YSZ was fixed to 9.7 mol.% which lead to the crystallization of
t’-phase even by slow cooling. Fully-dense specimen have been prepared and essential char-
acterizations regarding their thermo-physical properties, phase stabilities and CMAS corro-
sion have been carried out. The sintering rate of ATZ with higher α-Al2O3 content is lowered
and maximum densification delayed to higher temperatures. At the same time the thermal
conductivity increases and the CTE decreases as expected. Thermal cycling in between 800
°C and 1250 °C shows no measurable volume changes for the ATZ composites but for the
9.7YSZ indicating a higher stability of the t’-phase in ATZ composites. CMAS corrosion
tests show well-crystallized CMAS and anorthite on ATZ surfaces and glassy CMAS on
9.7YSZ surfaces. Moreover XRD results showed less t’-decomposition after CMAS corro-
sion in ATZ composites.

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566
Nano-sized SiC rich composite coatings produced by noble gas ion
mixing
A.S. Racz*, A. Sulyok, G. Vertesy, Z. Kerner, M. Menyhard
Centre for Energy Research, Hungarian Academy of Sciences, Konkoly Thege Miklós út 29–33,
1121 Budapest, Hungary; *e-mail: [email protected]
Keywords: SiC, nano coating, ion mixing, corrosion

Silicon carbide (SiC) is a material that has attracted considerable interest for a long time,
particularly due to its high temperature strength, thermal shock resistance, good thermal con-
ductivity and its inertness to exposure in corrosive environments. In thin film form, SiC is
used for micro/nano-electromechanical system (M/NEMS) operating in harsh-environments
e.g. automotive and aerospace applications such combustion processes or gas turbine con-
trol. Different methods can be used for producing SiC thin films eg.: physical and chemical
vapour deposition. However these methods need elevated temperature which might be disad-
vantageous by certain substrates. Ion bombardment might be also used to overcome the high
activation barrier of the compound formation since it creates far from equilibrium conditions,
where the apparent activation barrier might be much lower.
Recently we have demonstrated that focused ion beam method (FIB) by using Ga+ ions
can be applied to produce some nanometers thick SiC layer at room temperature.1 We have
also presented that the produced layer shows an excellent chemical resistance against poly-
silicon etchants.2 By applying the FIB method the irradiated area is very small, 200*200 µm.
However for suitable protective SiC coatings much larger area is required. Replacing the
expensive and less-efficient FIB method is advisable by other IBM method: e.g. noble gas
ion irradiation.
In the present work a C(20nm)/Si(20nm) multilayer system was irradiated with Ar+ and
Xe+ ions at room temperature applying energy and fluence ranges of 40-120 keV and 1-6x1016
ion/cm2, respectively. The layer thickness and in-depth distribution of SiC was determined by
Auger electron spectroscopy depth profiling. The thickness of the SiC rich region was only
some nanometer and it could be tailored by changing the ion irradiation conditions. The cor-
rosion resistance of the layers was measured by potentiodynamic corrosion test in 4M KOH
solution. The decreasing corrosion exchange currents showed that the corrosion resistance of
the layers was order of magnitude better than that of pure silicon; by selecting the irradiation
parameters carefully the chemical resistance can be tailored.

References
1. A. Barna, S. Gurban, L. Kotis, J. Labar, A. Sulyok, A.L. Toth, M. Menyhard, J. Kovac, P. Panjan,
“Growth of amorphous SiC film on Si by means of ion beam induced mixing”, Appl. Surf. Sci.,
263, pp. 367–372, 2012.
2. S. Gurbán, L. Kotis, A. Pongracz, A. Sulyok, A.L. Tóth, E. Vázsonyi, M. Menyhard, “The chemical
resistance of nano-sized SiC rich composite coating”, Surf. Coat. Technol., 261, pp. 195–200, 2015.

263 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

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771
Erosive wear of slip cast ceramics
Marijana Majić Renjo, Lidija Ćurković*, Irena Žmak
Department of Materials, Faculty of Mechanical Engineering and Naval Architecture,
University of Zagreb, I. Lučića 5, Zagreb, Croatia; *e-mail: [email protected]
Keywords: alumina-zirconia, composite ceramics, solid particle erosion, slip casting, surface rough-
ness

The objective of this investigation was to improve the tribological properties, particularly
the solid particle erosion resistance, of slip cast alumina with the addition of small amount
of zirconia nanoparticles. Two groups of suspensions, with solid loading of 70 wt.%, were
prepared: the first one contained 100% of Al2O3 powder, while the second one contained 99
wt.% of Al2O3 and 1 wt.% of ZrO2 powder. Suspensions were homogenized in a planetary
ball mill and green bodies were formed in prepared plaster moulds. The optimal amount
of used commercial dispersant and homogenization parameters were determined and pre-
viously reported.1 As a result of two different suspensions, two types of green bodies and,
subsequently, sintered samples were produced: monolithic Al2O3 and composite Al2O3-ZrO2
ceramics.
Sintered samples were subjected to the solid particle erosion in order to discover whether
the addition of zirconia nanoparticles improves the erosion resistance of alumina. Solid par-
ticle erosion can be defined as a degradation of material caused by repeated impacts of small
solid particles.2 Silicon carbide was used as an erodent under different impact angles (30° and
90°). According to literature, the lower impact angle (30°) corresponds with abrasive erosion,
while the higher one (90°) correlates to impact erosion.2 Wear mechanisms were analysed by
comparing the surface roughness parameters (Ra, Rz, Rmax) before and after erosion. It is as-
sumed that higher surface roughness after the test indicates lower erosion resistance.3
After the erosion test, all surface roughness parameters increased for both samples. Ob-
tained results confirmed that this type of slip cast ceramics is more sensitive to impact than to
abrasive erosion, because all surface roughness parameters were higher for the higher impact
angle (90°), for both samples. This investigation also confirmed the hypothesis that tribologi-
cal properties of alumina can be improved with the addition of the small amount of zirconia
nanoparticles: all surface roughness parameters were higher for monolithic alumina than for
composite alumina-zirconia, for both impact angles.

References
1. M. Majić Renjo, Z. Šokčević and L. Ćurković, “Rheological properties of concentrated alumina-
zirconia suspensions”, 15th Young Researchers’ Conference, Belgrade, 2016.
2. Friction, Lubrication, and Wear Technology, ASM Handbook, vol. 18, ASM International, Materi-
als Park, 1992.
3. B. Bhushan, Introduction to Tribology, Second edition. John Willey and Sons, New York, 2013.

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572
Influence of yttria stabilized zirconia nanoparticles on the setting time
of submicrometer-sized Portland cement
G.M. Rodríguez T., J. Zarate-M., J.C. Rubio A., M.E. Contreras-G.
Instituto de Investigación en Metalurgia y Materiales, Universidad Michoacana de San Nicolás de
1

Hidalgo, C.U. Edificio U, C.P. 58000, Morelia, Michoacán, México

Facultad de Ingeniería Civil, Universidad Michoacana de San Nicolás de Hidalgo, C.U. Edificio C,
2

C.P. 58000, Morelia, Michoacán, México

Keywords: average particle size, setting time, hydration process, Portland cement

The objective of this research was to determine the effect of the addition of Yttria stabilized
Zirconia in t 'phase nanoparticles, on the setting time of the composite Portland cement paste
(CPC 40) with submicronic average particle size. The CPC 40 was subjected to a milling
process in a planetary ball mill to obtain the submicrometric size, and the Yttria stabilized
Zirconia in its t' tetragonal phase was obtained by sol-gel and spray drying synthesis pro-
cess. After thermal treatment at 600 °C the obtained spherical aggregates were subjected to
a grinding process to obtain a nanometric particle size. Pastes were prepared with different
combinations and the setting time was evaluated using the Vicat apparatus according to the
ASTM C 187-11E1 and ASTM C 191-01 standards, comparing the results with the control
cement and submicronic cement without addition. The decrease in the average particle size
APS of the CPC 40 from 13.6 to 0.83 microns, has a very important effect as an accelerator
in the CPC 40 hydration process, reducing the initial setting time by up to 88% and increas-
ing the requirement of Water up to 49% to obtain the normal consistency (penetration of the
Vicat needle of 10 mm). For the different cement pastes, the temperature evolution during the
setting time process was evaluated, and the hardened pastes were characterized by Scanning
Electron Microscopy SEM. The effect of the nanometric particles of Yttria stabilized Zirco-
nia on the submicron CPC 40 cement, on the one hand, increases the water requirement as it
decreases the penetration of the Vicat needle in the normal consistency test, and on the other,
increases the initial setting time by 300% for an optimal addition of nanoparticles of 0.5%.

References
1. Gerardo Manuel Rodríguez Torres, Juan Zarate Medina, María Eugenia Contreras García, Synthe-
sis and characterization of Zirconia-Yttria nanoparticles in t’ phase by sol-gel and spray drying.
Építőanyag Journal of Silicate Based and Composite Materials 2016/4 Vol. 68, No. 4, pp 120–123.
2. Ali Nazari, Shadi Riahi, Shirin Riahi, Seyedeh Fatemeh Shamekhi and A. Khademno. An inves-
tigation on the Strength and workability of cement based concrete performance by using ZrO2
nanoparticles. Journal of American Science 2010.
3. L. Senff, D. Hotzab, S. Lucas, V.M. Ferreira, J.A. Labrincha. Effect of nano-SiO2 and nano-TiO2
addition on the rheological behavior and the hardened properties of cement mortars. Materials Sci-
ence and Engineering. 532 (2012) 354–361.

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477
Fabrication of oriented h-Bn/epoxy resin composites by applying
a low magnetic field using multi-layered-graphene-coated platelets
Fumika Sakamoto1, Takuma Takahashi2, Junichi Tatami1*, Motoyuki Iijima1
1
YOKOHAMA National University, Yokohama 240-8501, Japan;
*
e-mail: [email protected]
2
Kanagawa Academy of Science and Technology, Kawasaki, Japan
Keywords: h-BN, orientation, mechanical treatment

Hexagonal boron nitride (h-BN) has intrinsically high thermal conductivity and electrical in-
sulation, and the typical shapes of conventional h-BN particles are plate-like because c plane
of h-BN was developed. The h-BN platelets have been dispersed in a resin to improve its
thermal conductivity. Since thermal conductivity of direction perpendicular to c-axis of h-BN
are much higher than that parallel to c-axis, the improvement of thermal conductivity of a res-
in has been reported by orientation of h-BN platelets with a high magnetic field using a super
conducting magnet. In this work, oriented h-BN/epoxy resin composites were successfully
fabricated by applying a low magnetic field using the multilayered-graphene-coated h-BN
composite platelets. Two types of h-BN having different particle size were used as raw ma-
terials. Multilayer-graphene-coated h-BN platelets were prepared through mechanical treat-
ment technique under the same condition. SEM images showed that the original morphology
of the h-BN platelets remained after the mechanical treatment and small irregularities existed
on their surface. Furthermore, signal of carbon appeared on the surface of the composite
platelets in the elemental mapping of EDS, which showed that multilayered-graphene was
successfully coated on the h-BN platelets. After mixing and deforming an epoxy resin, a
curing agent and the composite platelets, they were poured into a mold and cured with and
without the application of a low magnetic field of 0.5T. The XRD peak intensity of (100) of
h-BN epoxy resin composites prepared with a magnetic field was larger than that prepared
without a magnetic field, which indicated that c-axis of the composite particles are oriented
in a direction normal to the applied magnetic field. Such orientation of h-BN resulted from
the large anisotropy of magnetic susceptibility of multilayered-graphene coated on the h-BN
platelets. The peak intensity of (002) with a magnetic field increased with an increase in the
volume fraction of h-BN. Use of coarser h-BN platelets caused the better orientation even
at the same volume fraction compared with use of finer platelets. These mean that lower
viscosity of h-BN/epoxy resin mixtures due to the lower volume fraction and/or the coarser
particle size of the h-BN platelets resulted in the higher the orientation by applying a magnet
field. Microstructural observation also showed that the high orientation of h-BN platelets in
the h-BN/epoxy resin composites prepared in a low magnetic field. Consequently, oriented
h-BN/epoxy resin composites was successfully fabricated by applying a low magnetic field
using the multilayered-graphene-coated h-BN composite platelets, and degree of the orienta-
tion was controlled by the particle size of the composite platelets and the viscosity of h-BN/
resin mixtures.

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445
Mechanical characterization of Y-TZP/Al2O3-NbC nanocomposites
sintered by different techniques
Raphael E.P. Salem1, Fábulo R. Monteiro2, Adriana S.A. Chinelatto2, A.L. Chinelatto2,
Amparo Borrell3, María D. Salvador3, Eliria M.J.A. Pallone1
Department of Biossystems Engineering, Universidade de São Paulo, Av. Duque de Caxias Norte,
1

225 – Pirassununga – São Paulo, Brazil; e-mail: [email protected]

Department of Materials Engineering, Universidade Estadual de Ponta Grossa, Av. Gal. Carlos
2

Cavalcanti, 4748 – Ponta Grossa – Paraná, Brazil; e-mail: [email protected]

Materials Technology Institute, Universitat Politècnica de València, Camí de Vera, s/n, Valencia,
3

Spain; e-mail: [email protected]

Keywords: nanocomposites, zirconia/alumina-niobium carbide, sintering, SPS, mechanical properties

Composites with zirconia matrix and addition of alumina and carbides have been studied for
the improvement of mechanical properties, as fracture toughness and wear strength. How-
ever, carbide-containing materials need non-conventional sintering methods, due to their low
sinterability and high reactivity with oxidizing atmospheres. In this work, there was produced
a 3 mol % yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP) matrix nanocomposite
with 5 vol% of a nanometric Al2O3-NbC powder obtained by high-energy reactive milling.
The incorporation of this powder in the matrix was done by the suspension mixing tech-
nique, in a ball mill. The resulting powder was characterized by X-ray diffraction, to verify
the present phases, and conformed in cylindrical shape. The sintering of the nanocomposites
was performed by two techniques: (a) conventional sintering, at the temperatures of 1400 oC,
1450 oC and 1500 oC for 2 h, using graphite powder as sacrifice material, to prevent carbide
oxidation, and (b) non-conventional sintering, by Spark Plasma Sintering (SPS) technique,
for 15 minutes, at vacuum, under the pressure of 80 MPa, at the temperatures of 1300 oC,
1350 oC and 1400oC. The characterization of the sintered nanocomposites was done by ap-
parent density measurement and X-ray diffraction. The mechanical properties of the sintered
nanocomposites were evaluated by Vickers microhardness measurements, nanohardness and
Young’s modulus determination by nanoindentation and calculation of fracture toughness
using the indentation technique. The results showed that, by the proposed method, there was
possible to produce 3Y-TZP/Al2O3-NbC nanocomposites with high density by both sintering
techniques (>97% TD in conventional sintering and >98% in SPS), with good dispersion of
the Al2O3 and NbC phases on the 3Y-TZP matrix, keeping NbC structure without its decom-
position. The hardness and fracture toughness these nanocomposites were also improved
with relation to 3Y-TZP without addition of Al2O3-NbC, attaining 13.2 GPa and 8.6 MPa.
m1/2, for the samples sintered conventionally, and 12.7 GPa and 8.0 MPa.m1/2, for the samples
sintered by SPS, respectively.

Acknowledgements
This work have been financially supported by project nro 2015/07319-8, São Paulo Research Founda-
tion (FAPESP).

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References
1. E.M.A. Pallone, V. Trombini, W. Botta, R. Tomasi. “Synthesis of Al2O3-NbC by reactive milling
and production of nanocomposite”. J. Mat. Proc. Tech., 143, p. 185–190, 2003.
2. K. Lu. “Sintering of nanoceramics”. Int. Mat. Rev.,53, p. 21–38, 2008.

363
Advanced oxidation of dyes with ceramic-based electrodes
M.J. Sánchez-Rivera1, A. Gozalbo1,2, V. Pérez-Herranz3, S. Mestre1,2*
1
Instituto Universitario de Tecnología Cerámica, Universitat Jaume I, Castellón, Spain;
*
e-mail: [email protected]
2
Departamento de Ingeniería Química, Universitat Jaume I, Castellón, Spain
3
IEC Group, Departament d’Enginyeria Quimica i Nuclear, Universitat Politècnica de València,
Valencia, Spain
Keywords: pollutants, electrooxidation, ceramic electrodes

Traditional treatments are not successful in dealing with emergent contaminants in recycled
industrial wastewaters as recent standards includes a larger number of substances with lower
discharge limits. In consequence, alternative methods are needed to separate or destroy con-
taminants such as dyes, antibiotics, hormones, etc.1
Advanced oxidation allows the mineralization of organic contaminants without addition
of reactants, because it generates hydroxyl radicals by means of electrodes2. These radicals
can degrade the organic molecules to H2O and CO2. However, chemically resistant electrodes
are needed. Expensive metals show good electrochemical behaviour (Ti, Pd), but ceramic
electrodes can balance the cost with the performance.
A cheaper alternative to more expensive ceramics (ITO, BDD) has been tested. Concretely,
a Sb-doped tin oxide electrode which has been optimized for electrooxidation of dyes. Sin-
tering and doping have been done in the same thermal treatment. Dopant level and sintering
conditions have been adjusted to balance low resistivity with enough mechanical resistance
to easily manipulate the electrodes. In addition, sintering temperatures have been maintained
as near as possible to the traditional ceramic firing interval (1050–1250 ºC).
Results showed that a fraction of the dopant is lost during the sintering, being higher at T
> 1150 ºC (up to 20% of initial proportion), and the samples just densify (volumetric contrac-
tion < 1%). However, the resistivity reaches values low enough for the electrode function
(lower than 1 Ω·cm), with little influence of the sintering temperature.
The electrodes were tested in the oxidation of RB5 dye. Results showed that the electrodes
partially degraded the dye, but sintering temperature and current intensity influences their
performance. The oxidation rate was higher for the electrode sintered at intermediate tem-
perature (1200 ºC) and oxidation of the chromophoric groups was achieved because treated
water lost the colour. However, the mineralization of the RB5 was not complete, as organic
groups were detected in the UV absorption spectra of treated water.
In conclusion, the developed electrodes can eliminate the dye, but additional modifica-
tions are in study in order to achieve its full mineralization.

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Acknowledgements
Authors thanks Ministerio de Economía y Competitividad and Fondo Europeo de Desarrollo Regional
for their support (Ref. CTQ2015-65202-C2-2-R MINECO/FEDER).

References
1. Metcalf & Eddy Inc. Wastewater engineering: treatment and reuse 4th ed. McGraw Hill, New York,
2004.
2. M. Panizza, G. Cerisola, Direct and mediated anodic oxidation of organic pollutants, Chem. Rew.,
(2009) 109, 6541–6569.

300
Morphology dependency of powder flowability of dicalcium phosphate
dihydrate
Yuki Sato, Takeshi Toshima*, Jun Umemoto, Saori Takamatsu, Masamoto Tafu
National Institute of Technology, Toyama College, Hongo-13, Toyama-city, Toyama, Japan,
939-8630; *e-mail: [email protected]
Keywords: powder flowability, dicalcium phosphate dihydrate (DCPD), morphology

Controlling the shape of functional material is one of the important themes; their size and
surface condition (such as specific surface area and ratio of the crystal face) change their
chemical reactivity. When one chooses a functional material as an environmental material,
chemical reactivity and responsibility are necessary factors; moreover, some physical prop-
erties are strongly required at field trial. On the other hands, dicalcium phosphate dihydrate
(DCPD; CaHPO4·2H2O) is researched as the environmental treatment material for removing
fluoride ions. DCPD crystals change to stable material fluoroapatite (FAp; Ca10 (PO4)6 F2)
and immobilizing fluoride ions from some fields (waste water management, soil purifica-
tion).1 And the morphology of DCPD crystals is controllable by adding other ions during
aqueous synthesis, changing the initial pH value and concentrations of calcium and phos-
phate ion. The morphology of DCPD crystals is changeable from tabular structure to petaloid
structure by preceding parameters.2
In this study, we compared the powder flowability between tabular and petaloid shaped
DCPD. Preceding chemical reaction from DCPD to FAp, morphology was kept; therefore
evaluation of powder flowability was important not only transit the DCPD powder from plant
to field, during immobilization fluoride ion, but also after treatment (FAp sludge usability).3
Powder flowability test was complied International Organization for Standardization and
Japanese Industrial Standards. Particle size distribution was measured by laser diffraction
particle size analyzer to calculate the uniformity of powder.
The compressibility ratio shows large different between petaloid (20.9) and tabular (40.2).
The angle of repose result shows that petaloid (36.1˚) was lower than tabular (43.5˚). The col-
lapse angle, spatula angle and uniformity of powder were comparable value (petaloid (23.4˚,
35.9˚ and uniformity was 2.8), tabular (26.6˚, 34.8˚ and uniformity was 3.3)). The analysis

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of Carr’s flowability indices, petaloid shaped DCPD shows good fluidity but tabular shaped
DCPD needs to devise a countermeasure against powder bridging. Moreover, analysis of
Carr’s floodability indices, each sample needs rotary sealing.

References
1. M. Tafu, T. Chohji, I. Morioka, M. Hiwasa, H. Nakano, T. Fujita, “Stabilization of Fluoride in
Waste Gypsum by Using Surface-Modified Calcium Phosphate Particle”, Trans. MRS-J, 35(2),
377–380, 2010.
2. T. Toshima, R. Hamai, S. Fujita, Y. Takemura, S. Takamatsu, M. Tafu, “Morphology Changing at
Incipient Crystallization Condition”, J. Phys.; Conf. Ser 596, 012009, 2015.
3. M. Tafu, T. Masutani, Y. Takemura, T. Toshima, T. Chohji, “Effect of Hydroxyapatite on Reaction
of Dicalcium Phosphate Dihydrate (DCPD) and Fluoride Ion”, Bioceram Dev Appl S1: 015. doi:
10.4172/2090-5025.S1-015, 2013.

628
Boron carbide/graphene platelets ceramics with improved fracture
toughness, functional and tribological properties
Richard Sedlák1, Alexandra Kovalčíková1, Ján Balko1, Paweł Rutkowski2,
Aleksandra Dubiel2, Vladimír Girman3, Ján Dusza1
Institute of Materials Research, Slovak Academy of Sciences,
1

Division of Ceramic and Non-Metallic Systems, Watsonova 47, 040 01 Košice, Slovak Republic
AGH University of Science and Technology in Krakow, Faculty of Materials Science and Ceramics,
2

Department of Ceramics and Refractories, al. A. Mickiewicza 30, 30-059 Krakow, Poland
Pavol Jozef Šafárik University in Košice, Faculty of Science, Institute of Physics,
3

Department of Condensed Matter Physics, Park Angelinum 9, 040 01 Košice, Slovak Republic
Keywords: boron carbide, graphene platelets, microstructure, fracture toughness, conductivity,
tribology

Boron carbide/graphene platelet (B4C/GPLs) composites have been prepared with the addi-
tion of different weight percent of GPLs by hot-press processing technology at 2100 °C in ar-
gon. The influence of the GPLs addition on microstructure development, fracture toughness,
electrical conductivity and tribological properties was investigated. The microstructure was
studied by SEM, TEM, HRTEM, XRD and Raman spectroscopy. SEVNB method was used
for fracture toughness and four-point Van der Pauw method for electrical conductivity mea-
surement. Almost fully dense B4C/GPLs composites have been prepared with lower wt.%
of GPLs additives with relatively homogeneously distributed platelets in the matrix. With
increasing amount of GPLs additives, the fracture toughness increased due to the activated
toughening mechanisms in the form of crack deflection, crack bridging, crack branching and
graphene sheet pull-out. The highest fracture toughness of 4.48 MPa.m1/2 was achieved at 6
wt.% of GPLs addition, which was ~50% higher than the KIC value of reference material.
The electrical conductivity increased with GPLs addition with percolation threshold between
2–2.5 wt.% of GPLs and reached the maximum values at 4 wt.% GPLs addition. A signifi-
cant improvement of electrical conductivity around two orders of magnitude up to 1526 S/m

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in the perpendicular direction and to 872 S/m in parallel direction was noticed. The friction
and wear behaviour of B4C/GPLs composites have been investigated using the ball-on-flat
technique with SiC ball under dry sliding conditions at room temperature. The coefficient
of friction for composites were similar, however the wear rate significantly decreased ~77%
in the case of B4C+6 wt.% GPLs when compared to reference material at a load of 5 N, and
~60% at a load of 50 N. Wear resistance increased with increasing GPLs content in regards
to the present graphene platelets, which during the wear test pulled-out from the matrix,
exfoliated and created a wear protecting graphene-silicon based tribofilm. For revealing and
observation of the wear damages under the worn surfaces, focused ion beam (FIB) technique
was used for the preparation of the cross section of wear tracks.

498
3D printed geopolymeric lattices: effect of processing parameters
on the mechanical properties
Paolo Scanferla*, Giorgia Franchin, Luca Zeffiro, Paolo Colombo
Department of Industrial Engineering, University of Padova, Padova 35131, Italy;
*
e-mail: [email protected]
Keywords: geopolymers, direct ink writing, geopolymeric lattices, porous ceramics, robocasting

Geopolymers are iniorganic materials generally obtained through the reaction of alumino-
silicates in highly alkaline solutions. These materials consolidate at low temperature and
possess good mechanical, weather and fire resistance, which make them suitable for a wide
variety of applications, such as structural materials, thermal insulation, and so on. Our group
developed mixtures based on geopolymer for additive manufacturing of porous components
via direct ink writing (DIW). We optimized the rheological properties in order to obtain suit-
able inks for the production of highly porous lattices. It should be noted that, as geopolymer
mixtures are subjected to ongoing poly-condensation reactions, their viscosity changes with
time in what ca be seen as a 4D printing process.
Different parameters can influence the mechanical properties of the printed components.
We produced lattices with different porosities and evaluated their compressive strength. The
influence of different consolidation (curing) and calcination treatments on the mechanical
behaviour and on the microstructure of the components was also investigated.

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325
Corrosion resisting properties of pressureless sintered silicon carbide
for the reactor of PFCs gas scrubber
Young-Hoon Seong*, In-Sub Han, Doo Won Seo, Seyoung Kim, Sang Kuk Woo
Energy Materials Laboratory, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu,
Daejeon, 34129 Republic of Korea; *e-mail: [email protected]
Keywords: SiC, pressureless sintering, corrosion weight loss, flexural strength

The PFCs used in the field of the semiconductor industry have very high GWP in the range of
6,500–23,900 and are being combusted over 1500 oC in scrubber system due to its chemically
non-degradable property. However, the metal reactors in gas scrubber are easily corroded
and damaged by HF gas generated from PFCs with high temperature, and the high cost for
frequent replacement of the reactor is occurring. In this study, we fabricated porous honey-
comb SiC with high strength and corrosion resistance for use in the reactor of gas scrubber
through pressureless sintering process. The SiC dough for extrusion was prepared by mixing
SiC powder with carbon resin, organic binder and DI water in optimum ratio. The prepared
SiC dough was extruded into a honeycomb mould and was sintered at 2150 oC for 2hrs in
flowing argon atmosphere. The sintered honeycomb SiC has channels density up to 500 CPSI
(Channels Per Square Inch). To evaluate this honeycomb SiC, we prepared disc type SiC w/o
sintering additives and sintered at 1950–2150 oC. The microstructure and phase were evalu-
ated through SEM and XRD, respectively. The long-term corrosion resisting properties were
also evaluated to confirm the feasibility for the reactor of gas scrubber using HF solution
(conc. 50%) for 1 year. The corrosion weight loss and flexural strength (3-points) were mea-
sured before/after the long-term corrosion test, and the microstructural study was conducted
through TEM analysis.

References
1. O. Borrero-L´opez et al., “Effect of liquid-phase content on the contact-mechanical properties of
liquid-phase-sintered α-SiC”, J. Eur. Ceram. Soc., 27, pp. 2521–2527, 2007.
2. X. Guo et al., “Preparation and properties of SiC honeycomb ceramics by pressureless sintering
technology”, J. Adv. Ceram., 3(1), pp. 83–88, 2014.

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795
2YSZ as alternative matrix for alumina toughened zirconia composites
S. Sequeira1, M.H. Fernandes2, N. Neves3, J. Macias3, N. Vitorino3, M.M. Almeida1
1
Department of Materials and Ceramic Engineering, CICECO, Aveiro Institute of Materials,
University of Aveiro, 3810-193 Aveiro, Portugal
2
Laboratory for Bone Metabolism and Regeneration, Faculty of Dental Medicine, University of Porto,
4200-393 Porto, Portugal
3
Innovnano, iParque, 3040-570 Coimbra, Portugal
Keywords: alumina toughened zirconia, Y-TZP, mechanical properties, bioceramics, biocompatibility

Zirconia and alumina are well known bioceramics, used in the field of orthopedics,1 since
they show reduced wear rate and excellent biocompatibility. However, these ceramics pre-
sented some limitations: the brittleness of alumina and the ageing sensitivity of zirconia.
Zirconia oxide is characterized by the phase transformation with temperature, being nec-
essary a stabilizer to maintain the desired tetragonal phase, with outstanding mechanical
properties. Yttria is the most used stabilizer, replacing zirconia (Zr+4) and forming oxygen
vacancies.2
Alumina-Toughened Zirconia (ATZ) ceramics combines the hardness and wear resistance
of alumina and the fracture toughness as well as flexural strength of zirconia,3 widely used for
those applications that require high mechanical properties such as hip arthroplasty.
In the present work, different aqueous suspensions of Alumina-Toughened Zirconia (ATZ)
composites (20% Al2O3) with 2 and 3 mol% YSZ (synthesized by Innovnano using Emulsion
detonation process) were prepared and characterized before a spray drying process; subse-
quent powder morphology was analyzed by scanning electron microscopy (SEM), chemical
and crystal phase composition using X-ray fluorescence (XRF) and X-ray diffraction (XRD)
respectively. Samples were prepared by uniaxial and cold isostatic pressing followed by low
temperature (1400 ºC) conventional sintering achieving a densification level above 97%. The
obtained ceramics pieces were subjected to mechanical test as hardness, fracture toughness
and flexural strength resulting in a non-negligible improvement of properties for the compo-
sitions with 2 mol% YSZ, up to 5 MPa.m1/2 and 1400 MPa of fracture toughness and flexural
strength respectively.
In order to confirm an eventually degradation as consequence of ageing effect, more typi-
cally for 2YSZ samples were submitted to an accelerate ageing test in an autoclave (134 ºC,
2 bar) without appreciable loss of mechanical properties even after 96 h.
The biocompatibility of these composites was also tested. MG63 cells were seeded on the
sintered samples and MTT and alkaline phosphatase activity assays were performed. The cell
proliferation increased significantly from day 1 to day 4 in both cases, being remarkable that
lower yttria content (802YSZ20A sample) presents higher cell viability in comparison with
803YSZ20A.
The use of 2YSZ instead of 3YSZ as ATZ composite matrix results in an improvement of
the mechanical properties, as well as of biocompatibility without being strongly affected by
the ageing process.

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References
1. A. De Aza, J.Chevailer, and G. Fantozzi, Biomaterials, vol. 23, pp. 937–945, 2002.
2. A.M. Hassan, S.M. Naga, and M. Awaad, Int. J.Refract. Met. Hard Mater., vol 48 pp. 338–345,
2015.
3. S. Begand, T. Oberbach and W. Glien, Key Eng. Mater., vol. 284–286, pp. 1019–1022, 2005.

578
Fabrication of oxide ceramic fibers by needle-less electrospinning
Ivan Shepa*, Erika Mudra, Magdalena Streckova, Jan Dusza
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 04001 Košice,
Slovak Republic; *e-mail: [email protected]
Keywords: electrospinning, nanospider, electrospun nanofibers, alumina, metal oxide catalysts, oxide
ceramics

Ceramic fibers can be effectively produced by electrospinning and post-electrospinning pro-

cess.1,2 In this study the term “needle-less” electrospinning means the free surface electros-
pinning technique developed by ELMARCO and realized in “NanospiderTM” instrument. It
was used for preparation of fine oxide ceramic fibers on the example of α-Al2O3 fibers with
diameters of 0.5–1.5 µm described in this work.
The fabrication process consists of three basic steps: i) preparation of spinning solu-
tion, ii) electrospinning of the prepared solution and collection of the composite fibers, iii)
calcination of the composite precursor fibers. The electrospun fibers were prepared from
polyacrylonitrile/N,N-dimethylformamide (PAN/DMF) polymer solution and Al(NO3)3.9H2O
in ratio 1/10/1. Thereafter, the precursor fibers were calcined in the furnace at 900, 1100, and
1200 °C with a heating rate of 5 °C/min in air. The formation of crystalline phases, surface
morphology and diameters of metastable and final alumina fibers were characterized using
thermogravimetric analysis, X-ray diffraction analysis, scanning electron microscopy and
transmission electron microscopy. The precursor PAN/Al(NO3)3 fibers were amorphous. The
thermal treatment of precursor fibers leads to the polymer decomposition/oxidation, decom-
position of Al(NO3)3 with next phase transition from γ-Al2O3 to α-Al2O3. The fine porous
microfibers composed of pure α-Al2O3 phase were prepared after calcination at 1200 °C. The
same method can be used for preparing ZnO, SnO2, TiO2, ZrO2, CuO and other oxide ceramic
materials.

References
1. A.-M. Azad, “Fabrication of transparent alumina (Al2O3) nanofibers by electrospinning”, Mater.
Sci. Eng. A, 435–436, pp. 468–473, 2006.
2. H. Wu, W. Pan, D. Lin, H. Li, “Electrospinnig of ceramic nanofibers: fabrication, assembly and
applications”, J. Adv. Ceram., 1, pp. 2–23, 2012.

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460
Characterization of joined single-end type RBSC radiant tube
Hyunick Shin, Bokkyu Yun, Youngseok Kim
Inocera Inc., Yongin, Republic of Korea

The aim of this study is to develop single-end type RBSC tube which was focused on joining
of tube and cap. As it has many merits like high thermal efficiency and low pollutant emis-
sion, RBSC radiant tube will be used gradually for heat treat applications. SiC powders were
mixed with thermo-set polymers in a chamber at low temperature. Pouring it into the casting
mold, tube was formed by centrifugal casting and cap was formed by thermo-set molding
method. The formed bodies were heat treated in order to transform polymers to carbon in Ar
purging atmosphere. After joining the tubes with caps using a SiC bonding material, infil-
trated by molten Si at 1500 °C in vacuum. It was studied effects of joining paste composition
on bonding strength and microstructure of joint layer. The bonding strength were measured,
and the microstructures of joint layer and fracture position were observed using microscopy.

243
Effect of sintering atmosphere on the crystal texture and coefficiant of
thermal expansion in cordierite ceramic honeycomb
M.A. Son1, K.-W. Chae1, J.S Kim1, S.H. Kim2
1
Department of Materials Science and Engineering, Hoseo University, Korea;
e-mail: [email protected]
2
Research and Development Division, Ceracomb Co., Ltd, Korea; e-mail: [email protected]
Keywords: cordierite, honeycomb, crystal structure, texture, CTE

Cordierite (Mg2Al3Si5O18) ceramic have a very low coefficient of thermal expansion (~1ppm/
o
C). Hence its honeycomb ceramics have been used as the substrates in DOC (diesel oxida-
tion catalyst), SCR (selective catalytic reduction), and DPF (diesel particulate filters) for
diesel engines. The CTE of cordierite honeycomb can be lowered further to < 1ppm/oC by
means of enhancing the degree of crystal texture of the cordierite honeycomb and controlling
the proportion of the crystal phases between the low symmetry cordierite (SG Cccm) and the
high symmetry indialite (SG P6/mcc) phases. The extrusion process adopted for shaping the
honeycomb substrate increases the degree of crystal texture. Sintering temperature is one of
the important parameters affecting the texture and the crystal phase proportions between the
cordierite and indialite phases.
In this study the effect of sintering atmosphere on the phase proportions between the low
symmetry (orthorhombic) and high symmetry (hexagonal) phases. The evolution of crystal
textures were investigated in the honeycomb sintered under the two different sintering atmo-

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spheres, highly and weakly oxidizing environments. The textured degree and crystal phase
formation were analyzed by using Rietveld refinement method (Full-prof software) for the
XRD patterns of the sintered sample.

Fig. 1. Extruded cordierite preforms

References
1. D.L. Evans, G.R. Fischer, J.E. Geiger, F.W. Martin, Thermal Expansions and Chemical Modifica-
tions of Cordierite, J. of the Am. Cer. Soc. 63, pp. 629–63, 1980.
2. M.D. Karkhanavala, F.A. Hummel, The Polymorphism of Cordierite, J. of the Am. Cer. Soc. 36,
pp. 389–39, 1953.

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652
Microstructure effects on low and high field dielectric properties of
(Ba,Sr)TiO3 based porous solid solutions
Roxana Stanculescu1, Nadejda Horchidan1, Leontin Padurariu1, Carmen Galassi2,
Mihai Asandulesa3, Cristina E. Ciomaga4*, Liliana Mitoseriu1
1
Dielectrics, Ferroelectrics & Multiferroics Group, Department of Physics, Al. I. Cuza Univ. of Iasi,
11 Carol I Bv., 700506, Iasi, Romania
2
CNR -ISTEC, Via Granarolo no. 64, I-48018 Faenza, Italy
3
Petru Poni Inst Macromol Chem, Grigore Ghica Voda Alley 41-A, Iasi 700487, Romania
4
Research Department, Faculty of Physics, Dielectrics, Ferroelectrics & Multiferroics Group, Al. I.
Cuza Univ. of Iasi, 11 Carol I Bv., 700506, Iasi, Romania; *e-mail: [email protected]

Properties of a ceramic system can be improved using porosity and make the material proper
for being used as high-frequency ultrasonic transducers or for tunable applications. The pur-
pose of this study was to prepare and to discuss the role of porosity on functional properties in
Ba0.60Sr0.40TiO3 (BST) ceramics with different degrees of porosity. Preparation followed the
mixed oxide method by solid-state reaction at a sintering temperature of 1450 °C for 2h. The
BST ceramics with various porosities have been obtained by addition of lamellar graphite in
concentration of 10, 20 and 35vol.%.
The phase purity of BST ceramics was checked by XRD analysis. The SEM investiga-
tions showed that with addition of graphite as pore forming the samples present a fracture
mode transformation from intragranular fracture to an intergranular fracture and a decreasing
of grain size of BST. Furthermore, as BST grain size becomes smaller, the volume of grain
boundary increases and the crack prefers spreading along grain boundary to splitting the
strengthened grain. Modifications of the grain size and of the grain boundaries volume were
also observed and discussed.
The effect of addition of carbon black as pore forming agent on the dielectric response at
low and high electric field was investigated and discussed. Impedance spectroscopy study
was carried out in the frequency range of (101–106) Hz at temperatures between (25–200) °C.
The temperature dependence of permittivity at a fixed frequency f = 100 kHz revealed a trend
corresponding to the paraelectric phase, with a Curie temperature far from room temperature,
irrespective of the porosity volume. The porosity level does not modify the temperature cor-
responding to the permittivity maximum. However, since porosity influences by reducing the
ferroelectric phase volume, a depression with the same value of permittivity is noticed in all
the temperature range.
Microstructural, morphological and dielectric investigations at low and high field have
been performed and data were compared with other literature studies. The experimental re-
sults have been shown that the dielectric permittivity of the BST ceramics with different
degrees of porosity decreases with increasing the porosity, from a few thousands down to a
few hundreds, and present a trend of depression with temperature increasing, as required by
wireless applications, without losing the high tunability.

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A strong nonlinearity was observed for all the ceramics, with a tendency toward saturation
for high fields. The relative tunability in BST porous structures preserved similar values as in
the dense ceramics, irrespective of the porosity level.

Acknowledgement
This work was financially supported by CNCS-UEFISCDI project PN-II-RU-TE-2014-4-1494.

308
Removal of fluoride ion in the environments by using calcium
phosphate-carbonate hybrid
Masamoto Tafu*, Saya Fujita, Shunki Muroyama, Saori Takamatsu, Atsushi Manaka,
Takeshi Toshima
National Institute of Technology, Toyama College, Hongo-machi 13, Toyama-city, Toyama, Japan,
939-8630; *e-mail: [email protected]
Keywords: dicalcium phosphate dihydrate (DCPD), fluoride, calcium carbonate

Dicalcium phosphate dihydrate (DCPD; CaHPO4·2H2O) react with fluoride and transforms
stable mineral fluoroapatite (FAp; Ca10 (PO4)6 F2). This reaction is applicable to immobilize
fluoride ions in the water environments1. However, this reaction release excess phosphate ion
such as eq (1).
10CaHPO4·2H2O + 2F– -> Ca10(PO4)6F2 + 4HPO42– + 6H+ + 20H2O (1)
Previously, we reported that addition of calcium carbonate is effective to inhibit release of
phosphate ion from the reaction by supply calcium ion from dissolve calcium carbonate2.
In this research, we investigated application of the DCPD-calcium carbonate hybrid to
treatment of fluoride in waste water. Various materials have applied for waste water treat-
ment; however, removal amount is remarkably decreased to 2–3 mg/g when concentration of
fluoride is lower value such as a few mg/L after treatment3. Removal amount of fluoride from
reaction of DCPD was analyzed by batch experiment. From result of experiment, removal of
fluoride was around 10–15 mg/g in widely fluoride concentrations. This value was 5 times
of adsorption amount of conventional adsorption material such as bone char, or conventional
precipitation method by using aluminum salts. From addition of chemicals decreased than
conventional process, amounts of resulted sludge waste also decreased conventional method.
This result was effective not only waste amount but also economic efficiency including trans-
port and waste management in landfill.
Hybridization calcium carbonate in DCPD improved removal amounts of fluoride ion.
Suitable condition was addition of calcium carbonate in 25 wt% of DCPD. Usage of DCPD-
calcium carbonate in this ration, payment for chemicals for treatment of waste water was de-
creased to around 0.7 Euro/m3 of waste water. This value was 5% of usage of bone char. From
these results, it was concluded that usage of DCPD-calcium carbonate is quite applicable to
treatment of fluoride in waste water.

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References
1. M. Tafu, T. Chohji, I. Morioka, M. Hiwasa, H. Nakano, T. Fujita, “Stabilization of Fluoride in
Waste Gypsum by Using Surface-Modified Calcium Phosphate Particle” Trans. MRS-J, 35(2),
377–380, 2010.
2. M. Tafu, T. Chohji, T. Korenaga, “Treatment of Fluoride in Wastewater and Waste Gypsum Board
Based on Nano-Surface Reaction of Calcium Phosphate” J. Environ. Safety, 1(2), 33–39, 2010.
3. N.A. Medllin-Castillo, R. Lyeva-Ramos, R. Ocampo-Perez, R.F. Garcia dela Cruz, A. Aragon-Pina,
J.M. Martinez-Rosales, R.M. Guerrero-Coronado, L. Fuentes-Rubio, “Adsorption of fluoride from
water solution on bone char” Ind. Eng. Chem. Res., 46, 9205–9212, 2007.

138
Improving the tribological performance of Si3N4 composites by
a few-layer graphene addition
Orsolya Tapasztó1, Jan Balko2, Viktor Puchy2, Péter Kun1, Jan Dusza2, Levente Tapasztó1
Institute of Technical Physics and Materials Science, Centre for Energy Research, Hungarian
1

Academy of Sciences, Konkoly Thege str. 29-33, 1121 Budapest, Hungary

Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 040 01 Košice,
2

Slovak Republic
Keywords: silicon nitride, composites, graphene, melamine, tribology

Despite the outstanding solid lubricant properties of graphite, so far only a very limited im-
provement in the tribological properties of ceramic composites could be achieved by addi-
tion of graphene nanoplatelets (GNPs) – particularly, concerning the reduction of the friction
coefficient. We propose that the reason for this is the relatively low exfoliation degree of the
GNPs. Several exfoliation methods have been employed for graphite, aiming for large quan-
tities of thin GNPs with their structure kept as intact as possible. One of the simplest, yet
most efficient methods is the exfoliation by mechanical milling. Here, we propose to employ
a novel mechano-chemical method to enhance the exfoliation degree of graphene nanoplate-
lets during mechanical milling, but without chemically modifying the resulting graphene
sheets.
By employing the as-prepared ultra-thin few layer graphene nanoplatelets (FL-GNPs) as
filler material, the wear resistance of Si3N4 composites can be increased by about twenty
times, the friction coefficient reduced do nearly its half, while the other mechanical proper-
ties are also preserved or improved.
Using confocal Raman microscopy, we were able to demonstrate the formation of a con-
tinuous FL- GNP tribo-film, already at 5wt% FL-GNP content, which is at the origin of the
outstanding improvement of the tribological performance.

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011
Fabrication and characterization of novel silk / chitin hydrogel /
nano diopside composite scaffolds for tissue engineering
Abbas Teimouri1, Leila Ghorbanian2
1
Department of Chemistry, Payame Noor University, P. O. Box 19395-3697, Tehran, Iran
2
Materials Engineering Department, Isfahan University of Technology, Isfahan, Iran
Keywords: chitin, nanodiopside, composite scaffold, tissue engineering

Tissue engineering has recently developed a growing field in the regeneration of tissues Bio-
materials are required in tissue engineering techniques for the construction of scaffolds by
which relevant cells can be attached, grown, and proliferated. Silk fibroin (SF) is a natural
polymer produced by a variety of insects. Recently, silk cocoons from Bombyx mori have
been used as an in-access material for tissue regeneration purposes.1
Chitin, which is known to be a biocompatible and biodegradable polysaccharide, is the
most abundant polymer on earth after cellulose. It is fabricated from the shells of shrimp and
squid pens. It has also been found that the chitin hydrogel could be prepared by using this
solvent system. In recent studies, the calcium solvent system has been found to be a suitable
solvent to dissolve the chitin in the mild conditions.2
Diopside (CaMgSi2O6) ceramics possess excellent in vitro apatite-formation ability, in
vivo bioactivity, degradability and improved mechanical strength compared to hydroxyapa-
tite.3
In continuation of our previous studies on the construction of composite scaffolds.4–5 In
this research, novel porous composite scaffolds consisting of silk, chitin, and MCM-41 were
prepared using the freeze-drying method. The prepared nanocomposite scaffolds were char-
acterized by SEM, XRD, BET, TGA and FT-IR techniques. In addition, swelling, degradation
and biomineralization capability, cell viability and cell attachment of the composite scaffolds
were evaluated.

References
1. E. Wenk, H.P. Merkle and L. Meinel, “Silk fibroin as a vehicle for drug delivery applications”,
Journal of Controlled Release, 150, pp. 128–141, 2011.
2. H. Tamura, H. Nagahama and S. Tokura, “Preparation of chitin hydrogel under mild conditions”,
Cellulose, 13, pp. 357–364, 2006.
3. Wu, C.; Zreiqat, H. “Porous bioactive diopside (CaMgSi2O6) ceramic microspheres for drug deliv-
ery”, Acta Biomaterialia, 6, pp. 820–829, 2010.
4. A. Teimouri, R. Ebrahimi, R. Emadi, B. Hashemi Beni and A. Najafi Chermahini, “Nano-composite
of silk fibroin–chitosan/Nano ZrO2 for tissue engineering applications: Fabrication and morphol-
ogy”, Int. J. Biol. Macromol. 76, pp. 292–302, 2015.
5. M. Azadi, A. Teimouri and G. Mehranzadeh, “Preparation, characterization and biocompatible
properties of β-chitin/silk fibroin/nanohydroxyapatite composite scaffolds prepared using a freeze-
drying method”, RSC Adv. 6, pp. 7048–7060, 2016.

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151
Improvement usability of environmental material by morphology
changing
Takeshi Toshima*, Jun Umemoto, Yuki Sato, Saori Takamatsu, Masamoto Tafu
National Institute of Technology, Toyama College, Hongo-13, Toyama-city, Toyama, Japan,
939-8630; *e-mail: [email protected]
Keywords: permeability, calcium phosphate, morphology

Dicalcium phosphate dihydrate (DCPD) has attracted attention as an environmental material

for immobilizing fluoride ions from waste water and/or soil by selectively reaction to form
stable material, fluoroapatite (FAp). In the previous reports, the morphology of DCPD can be
controlled by setting following parameters; initial pH, concentration and coexisting of other
ion under solution synthesis1,2. On the other reports, particle shape is kept during preceding
chemical reaction; it is equal to say, DCPD particles act as a template of FAp particles3. For
these reasons, usability of FAp sludge can be controllable by changing DCPD morphology.
In this study we compared the important physical properties for using as environmental
material under waste water and soil treatment. We used four kinds DCPD particles synthe-
sized under different conditions; two samples were petaloid shaped and the others were tabu-
lar shaped. Density and particle size distribution were measured and used them to evaluate
permeability and sedimentation results; affecting reactivity in soil and operability of sludge
after water treatment.
In the case of bulk density, the petaloid shaped particles stacked higher than the tabular
particles and in the case of tap density, all samples became same value. The petaloid shaped
DCPD was quicker in a sedimentation rate and higher tendency permeability than the tabular
shaped DCPD. The sedimentation value of petaloid shaped DCPD was smaller than that
of tabular shaped DCPD. For these results, petaloid shaped DCPD particles have higher
operability than tabular shaped DCPD particles under waste water treatment due to good
sedimentation rate (short time separation waste water and sludge) and value (low moisture
content is equal to low weight, transit cost of the FAp sludge).

References
1. T. Toshima, R. Hamai, M. Tafu, Y. Takemura, S. Fujita, T. Chohji, S. Tanda, S. Li, G. W. Qin,
“Morphology control of brushite prepared by aqueous solution synthesis”, J. Asian Ceram. Soc.,
2(1), 52–56, 2014.
2. R. Hamai, T. Toshima, M. Tafu, T. Masutani, T. Chohji, “Effect of anions on morphology control of
brushite particles”, Key Engineering Materials, Vol. 529–530, pp. 55–60, 2012.
3. M. Tafu, T. Masutani, Y. Takemura, T. Toshima, T. Chohji, “Effect of Hydroxyapatite on Reaction
of Dicalcium Phosphate Dihydrate (DCPD) and Fluoride Ion”, Bioceram Dev Appl S1: 015. doi:
10.4172/2090-5025.S1-015, 2013.

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442
Determination of arsenic in waste gypsum board by using antidote
reaction
Haruka Tsunekawa, Atsushi Manaka*, Saori Takamatsu, Masamoto Tafu
National Institute of Technology, Toyama College, Hongo-machi 13, Toyama-city, Toyama, Japan,
939-8630; *e-mail: [email protected]
Keywords: gypsum board, arsenic, recycling

Gypsum board is commonly used as a house building material and so presents in large quan-
tities when buildings are demolished. Most waste gypsum board is sent to landfill sites.
Therefore, recycle of then waste gypsum is desired because of a lack of landfill capacity.
Recently, many attempts have been made to use waste gypsum board for ground improve-
ment as a roadbed material, a sludge stabilizer or as fertilizer. However, there are difficulties
in gypsum recycling related to entrained impurities such as arsenic because these impurities
cause soil and groundwater pollution. On-site monitoring of arsenic content is essential for
the recycling process of the waste gypsum. In order to determine impurity in gypsum, com-
plicated pre-treatment using harmful agents requires to dissolve gypsum. We have reported
simple pre-treatment method to dissolve gypsum using ion exchange resins1. However, it
was difficult to estimate arsenic in a solution dissolved gypsum sample, because of strongly
interference of phosphate in gypsum to molybdenum blue method used as conventional de-
termination method for arsenic content.
In this study, we attempted to develop evaluation method for arsenic content in gypsum
with 2,3-Dimercaptopropanol and 5-(3-Carboxy-4-nitrophenyl) disulfanyl-2-nitrobenzoic
acid. 2,3-Dimercaptopropanol which is dithiol compound strongly bond with arsenic ion and
widely used for therapeutic agent for arsenic poisoning. Concentration of 2,3-Dimercapto-
propanol is able to jugged by discolouring by using 5-(3-Carboxy-4-nitrophenyl) disulfanyl-
2-nitrobenzoic acid (DNTB) which is colour reagent for thiol compounds in phosphate buf-
fer2. Under presence of arsenic, the colour reaction is strongly interfered.
Based on these findings, content is able to be determined without phosphate interference
using colour reaction with 2,3-Dimercaptopropanol and DNTB.

References
1. A. Manaka, H. Sawai, M. Tafu, T. Toshima, Y. Serikawa, T. Chohji; A Simple Preprocessing Meth-
od using Ion Exchange Resins for the Analysis of Fluoride Content in Gypsum , Journal of Ecotech-
nology Research, 16[2], 47–50 (2011).
2. G.L. Ellman, Arch. Biochem. Biophys., 82, 70 (1959).

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787
Thermodynamic approach for Si3N4-superalloy joints and microscopic
characterization
O. Tunçkan1*, S. Turan2
TUNCKAN, Faculty of Aeronautics and Astronautics, Anadolu University, İki Eylul Campus, 26470,
1

Eskisehir, Turkey; *e-mail: [email protected]

TURAN, Dep. of Materials Science and Engineering, Anadolu University, İki Eylul Campus, 26470,
2

Eskisehir, Turkey

In this study, silicon nitride ceramics (Si3N4) were joined by using capacitor discharge tech-
nique with Inconel 718 superalloy interlayer and heat treated in order to determine possible
reactions between these two materials. After capacitor discharge joining, some of the samples
were heat treated at 1100 oC under air and the resulting interfacial microstructure was char-
acterized by using transmission electron microscope (TEM) attached with high angle annular
dark field scanning transmission electron microscope (STEM-HAADF) detector (Fishione)
and energy dispersive x-ray spectrometer (EDS). According to STEM images (BSE), all of
the joining samples were well bonded through the interlayer and cracks were not observed
along the interlayer, interface and the ceramics. According to point TEM-EDS analysis, some
of the new spherical phases formation having white-grey contrast was observed along metal
interlayer and small amount of silicon (Si), nitrogen (N) and aluminium (Al) was detected at
the interlayer of as-joined samples. For the heat treated samples at 1100 °C, the symmetrical
reaction layer was observed at both side of the interlayer which is expanding towards the ce-
ramic side. Furthermore, approximately 1 µm thick continuous another reaction layer next to
this was also determined. According to TEM-EDS point-line scan analysis along the metallic
interface and ceramic side, nickel (Ni), iron (Fe) and chromium (Cr) were detected at reac-
tion layer next to the ceramic side, whereas mainly Cr, niobium (Nb), molybdenum (Mo),
titanium (Ti) and Al were concentrated at the 1 µm thick reaction layer.
In order to obtain thermodynamically favorable phases and diffusion paths, the interface
between two Si3N4/Inconel 718 material was analyzed using CALPHAD based simulations.
Possible chemical reactions and the corresponding free energy changes between Si3N4/Inco-
nel718 materials were calculated and their ternary phase diagrams were also evaluated. All
of the CALPHAD based simulations were performed using the Thermo-Calc software taking
all possible phases in the database TCN17 (TCS-Ni based superalloy database) into account.

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066
Fabrication and mechanical properties of textured Ti3SiC2 systems
Yuichi Uchida1,2*, Koji Morita1, Tohru S. Suzuki1, Toshiyuki Nishimura1, Kenjiro Fujimoto2,
Yoshio Sakka1
1
Research Center for Functional Materials, National Institute for Materials Science, Tsukuba, Ibaraki,
Japan; *e-mail: [email protected]
2
Department of Pure and Applied Chemistry, Tokyo University of Science, Noda, Chiba, Japan
Keywords: MAX phase, grain orientation

Ti3SiC2 is a typical Mn+1AXn (MAX) phase ceramics and shows unique metallic-like and
ceramic-like properties, such as good electrical, thermal conductivities and corrosion, oxi-
dation, wear resistance. Recently, Hu et al. fabricated the textured Nb4AlC3 MAX phase
ceramics by slip casting in a strong magnetic field followed by SPS, and indicated textured
Nb4AlC3 show excellent mechanical properties1. In this study, we attempt to fabricate tex-
tured Ti3SiC2 with excellent mechanical properties.
Ti3SiC2 powder (KANTHAL) was dispersed in ethanol with 1.5 wt% Polyethyleneimine
as a dispersant. Textured green body was prepared by slip casting in a rotating magnetic
field of 12T. In addition, non-textured body was also prepared without the magnetic field as
a reference. They were sintered 1350 °C under a pressure of 40 MPa by SPS. These samples
were characterized by X-ray diffraction, scanning electron microscope. Relative density of
samples was measured by Archimedes method. The flexural strength was measured by me-
chanical strength testing equipment using the three point bending test. The fracture toughness
was measured by same equipment using SEVNB method. The dimensions of samples for the
three bending test and fracture toughness were 2 × 1.5 × 18 mm3 and 2 × 4 × 18 mm3 with a
notch of 0.5 mm depth and 0.1 mm width, respectively.
In the non-textured samples, each of grains was randomly oriented in SEM images. In
contrast, oriented plate-like grains were observed in the textured sample. Furthermore, high
dense structures were observed in these pictures. Relative density of samples was nearly
99%. The degrees of orientation were characterized by XRD patterns. In the top surface
perpendicular to the magnetic field, the intensities of (00l) peaks are very high. On the other
hands, the intensities of other Ti3SiC2 peaks are very small. The Lotgering orientation factor
was calculated in order to determine the degree of orientation. The degrees of orientation
were 0.96 and 0.60 in the specimens prepared with and without an applied magnetic field,
respectively. The bending strength of textured sample was 977.6 MPa and the fracture tough-
ness was 7.29 MPa·m1/2. These values of non-textured sample were 843.1 MPa and 6.57
MPa·m1/2, respectively. The mechanical properties of Ti3SiC2 were enhanced by texturing.

Reference
1. C. Hu, Y. Sakka, T. Nishimura, S. Guo, S. Grasso, H. Tanaka, Sci. Technol. Adv. Mater. 12 044603
(2011).

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282
Tribological properties and nanoindentation of refractory carbides
Marek Vojtko1, Ján Balko1, Tamás Csanádi1, Richard Sedlák1, Alexandra Kovalčíková1,
Piotr Wyzga2, Annamária Naughton-Duszová2, Ján Dusza1
1
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 04001 Košice, Slovakia
2
Centre for Materials Research and Sintering Technology, Institute of Advanced Manufacturing
Technology, Krakow 30–011, Poland
Keywords: refractory carbides, coefficient of friction, wear resistance, nanoindentation, fractography

Wear behavior, deformation, and damage of spark plasma sintered VC, NbC and ZrC refrac-
tory carbides have been investigated using nanoindentation, micro/macro – indentation tests,
and tribology. Fractography was used for the characterization of deformation and damage
mechanisms. Considerable indentation load – size effect was found in all systems with hard-
ness values from 30–36 GPa to 13–17 GPa corresponding to the applied loads of 1 mN and
100 N, respectively. During nanoindentation, characteristic stress-drops were observed on
hardness-displacement profiles of NbC and ZrC at depth region of 15–30 nm while this was
not typical in VC. The highest coefficient of friction was measured for NbC with a value of
0.45 and the lowest for ZrC with an average value of 0.3. The specific wear rate of the NbC
and VC was similar, approximately 3.10–6 mm3/Nm, only the wear rate of ZrC was larger,
approximately 2.10–5 mm3/Nm.
According to the fractographic examination the wear of the NbC and VC is similar, simi-
larly for the wear parameters, – the COFs and the wear rates. At a lower load of 5 N we found
more plastic deformation induced microfracture. As the contact stress increased, at the load
of 50 N, varieties of short cracks like partial cone cracks, lateral/shallow cracks, and radial
cracks etc. are generated intergranularly or transgranularly by friction around the Hertzian
contact zone. Such micro-cracks intersect each other and detach chunks of material. The
detached material is crushed into fine particles by further tribological contact and evolved
as wear debris. In NbC system the intergranular cracks dominate, while in VC there is a
mixture of intergranular and transgranular damage. The ZrC system shows different wear
behavior with no crack formation and with very limited grain boundary or transgranular
fracture caused material removal. It seems that during the wear the material removal without
crack formation dominates, with a sign of a significant plastic deformation of ZrC, which is
surprising taking into consideration the hardness of the system.

Acknowledgements
The authors gratefully acknowledge the financial support from projects: APVV-15-0469, APVV-0108-
12, VEGA 2/0163/16, VEGA 2/0189/15, MVTS 7RP ERA.NET-GRACE, NanoCEXmat II (ITMS
26220120035), FNP – No. POWROTY/2016-1/3.

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979
Organic – ceramic oxides hybrid material for blast effect mitigation
Eniko Volceanov1*, Simona Badea2, Adrian Volceanov3
1
University POLITEHNICA Bucharest, Center for Surface Science and NanoTechnology, Romania;
*
e-mail: [email protected]
2
Scientific Research Centre for CBRN Defence and Ecology, Bucharest, Romania
3
University POLITEHNICA Bucharest, Faculty of Applied Chemistry and Material Science, Romania

The improvements of physical, chemical and thermomechanical properties of polymer com-

posite materials has been a major research interest in the last few decades. Polymer nano-
composites represent a new class of materials alternative to conventional filled polymers. In
this new class of material, nanosized inorganic filler (at least one dimension) are dispersed in
polymer matrix offering tremendous improvement in performance properties of the polymer.
Nanoscale materials have been the subject of research interest in recent years because of
their unique properties as compared to the bulk counterparts and their potential applications
in a wide variety of areas such as information storage, electronics, sensors, structural compo-
nents, catalysis, and defence, etc.
The main challenge in fabrication of these polymer nanocomposites for structural ap-
plications is uniform dispersion of nanoparticles in the polymer matrix. However, good dis-
persion for nanoparticles in polymer composite materials is extremely difficult to achieve,
since nanoparticles tend to aggregate together during fabrication. The degree with which the
nanoparticles can be homogeneously dispersed in the polymer matrix would significantly
influence the thermal, mechanical and optoelectronic properties of the material. It has used
several techniques for dispersing nanoparticles. There is an ever-increasing demand for de-
velopment of processing of polymer nanocomposites for advanced structural applications.
This paper is focused on polymeric – organo-clay respectively on polymeric – fly ash nano-
composites for lightweight and high strength and temperatures application devoted mainly
for blast protection and mitigation of their effects.

399
Metallization of C12A7:e– ceramic for low ohmic resistance
Katja Waetzig1, Axel Rost1, Martin Tajmar2, Jochen Schilm1, Alexander Michaelis1
1
Fraunhofer IKTS, Institute for Ceramic Technology and Systems, Winterbergstrasse 28,
01277 Dresden, Germany
2
Institute of Aerospace Engineering, Technical University Dresden, 01307 Dresden, Germany
Keywords: metallization, contacting, electride, Calcium aluminate, resistance

The composition 12CaO.7Al2O3 (C12A7) crystallizes in a positive charged cage structure

([Ca24Al28O64]4+2O2–), wherein the cavities are occupied by O2– ions. Sintering this C12A7
oxide in a reducing atmosphere results in the substitution of the O2– ions by electrons, so that
the C12A7:e– ([Ca24Al28O64]4+4e–) ceramic becomes a material with high electrical conduc-

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tivity and low work function for emission of electrons. These properties make the material
suitable as an electron emitter for operating at temperatures above 250 °C what is interesting
for technological applications. Although the bulk material indicates these extraordinary prop-
erties, the surface of the ceramic has insulating properties. Therefore, a metallization film is
needed to realize an electrical contact, which minimizes ohmic losses. In this study, three dif-
ferent metal pastes (Pt, Au and Cusil-ABA®) for contacting the surface are investigated and
the reduction of the resistance during the firing process of the pastes was measured. The resis-
tivity of the contacted C12A7:e– was determined as a function of the temperature under inert
atmosphere. The lowest resistivity of about 1 Ω cm was measured with the Ag-based braze
(Cusil-ABA®), but resulted in cracking of the contacted ceramic after the firing process.
Alternatively the contacting with Au achieved a specific resistance of 5.4 Ω cm (T = 800 °C),
what allows the measurement of the work function of samples shaped as hollow cathodes.

357
The influence of microstructure on thermal residual stress and fracture
toughness of nickel aluminide-alumina composites – experiment and
numerical model
Witold Węglewski*, Michał Basista, Kamil Bochenek
Institute of Fundamental Technological Research, Polish Academy of Sciences, Warsaw, Poland;
*
e-mail: [email protected]
Keywords: thermal residual stress, neutron diffraction, metal matrix composite, numerical modelling

The NiAl–intermetallic based composites are potentially very attractive structural materi-
als for aerospace and automotive applications due to high corrosion resistance, low specific
weight and good strength properties at high temperatures However, the brittleness of NiAl
limits its today’s industrial use. In recent years a revival of research on improvement of NiAl
toughness is observed and many technological approaches were proposed.1
The purpose of this paper is to explore the effect of alumina ceramic addition to NiAl
using powder metallurgy route and to examine experimentally and numerically the effect of
microstructure on the fracture toughness of NiAl/Al2O3 composite with processing-induced
thermal residual stresses (TRS) being and additional factor taken into account. Powder mix-
tures with 30, 60 and 90 vol. % of Al2O3 and different NiAl particle size (5 vs. 45 microns)
were sintered by hot pressing. In the FEM model of TRS real microstructure images from
micro-CT were incorporated using the methodology developed in Basista et al.2, (Fig. 1). The
numerical results of TRS were compared with measurements by neutron diffraction method.
The fracture toughness was determined in SEVNB test in four point bending.

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a) b) c) d)
Fig. 1. MicroCT image of NiAl/Al2O3 composite (a), FE mesh (b) computed residual stresses for alu-
mina (c) and NiAl (d) phase

The scientific objective of this study, i.e. experimental exploration and predictive model-
ling of the influence of microstructure on the TRS and KIc was achieved and the obtained
results clearly confirm this effect.

Acknowledgements
This research was supported by Polish National Science Centre grant, Influence of Thermal Residual
Stresses on Fracture Behaviour and Selected Mechanical Properties of Metal-Ceramic Composites:
Experiments and Modeling (UMO-2014/15/B/ST8/ 04314).

References
1. K. Bochenek, M. Basista, “Advances in processing of NiAl intermetallic alloys and composites
for high temperature aerospace applications” Progress in Aerospace Sciences, pp. 136–146, 2015.
2. M. Basista, W. Węglewski, K. Bochenek, Z. Poniżnik, Z. Nowak, “Micro-CT Finite Element Ana­
lysis of Thermal Residual Stresses and Fracture in Metal-Ceramic Composites”, Advanced Engi-
neering Materials, 2017 (DOI: 10.1002/adem.201600725).

439
Verification of the lifetime of zirconia-alumina composites predicted by
using the constant stress rate test data
Agnieszka Wojteczko, Kamil wojteczko, Zbigniew Pedzich
AGH University of Science and Technology, Faculty of Materials Science and Ceramics, Krakow,
Poland

Proof Testing is a common method used in verification of ceramic components working un-
der loads. Assuming the existence of subcritical crack growth in a material, short-time load-
ing is not sufficient. There is a possibility to test samples for longer times, if the service time
is defined, but testing greater amounts of samples would be really inconvenient.

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Second approach, used in this case, involves testing with the Constant Stress Rate meth-
od. It allows authors to estimate subcritical crack growth parameters, and thereby, lifetime
predictions also for static loading. These type of tests were conducted for zirconia-alumina
composites with 5, 15 and 35 vol. % of inclusions. In order to complete these results, Proof
Testing was performed for chosen lifetimes and probabilities of survival.

Acknowledgements
This work was made with financial support of the Polish State Ministry of Science and Higher Educa-
tion under grant no. AGH 11.11.160.617. Support was also given from the Polish Ceramic Society.

327
Effect of fiber volume fraction on directional thermal conductivity in
liquid silicon infiltration composites
Sangkuk Woo*, Seyoung Kim, Insub Han, Young-Hoon Seong, Hyung-Joon Bang,
Seul Hee Lee
Energy Materials Laboratory, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu,
Daejeon, 34129 Republic of Korea; *e-mail: [email protected]
Keywords: ceramic matrix composites (CMC), thermal conductivity, LSI (liquid silicon infiltration),
fiber volume fraction, flexural strength

Ceramic matrix composites (CMC) were widely used for aerospace and high temperature
environment application because of its high thermal and structural stability. Especially, many
aerospace vehicles are protected from hot atmosphere during operation and this protective
structure needs high thermal conductivity for heat transfer. In case of in-plane thermal con-
ductivity could be increased by using high thermal conductive fiber, however transversal
thermal conductivity improvement is very difficult. In this study, LSI (liquid silicon infiltra-
tion) process was applied to fabricate CMC and its fiber volume fraction was controlled to
improve transversal thermal conductivity. The lower fiber volume fraction the higher thermal
conductivity obtained because of high thermal conductivity of matrix such as Si and SiC.
However low fiber volume fraction induced poor mechanical properties and high fiber vol-
ume fraction induced high residual stress that induced fiber/matrix debonding weakening
reinforced fiber during LSI process. The optimum fiber volume fraction with preserving its
mechanical and thermal property was deduced by investigating its thermal conductivity (LFA
method), mechanical properties (flexural strength), density and microstructure (SEM).

Reference
1. M. Bouchez and S. Beyer, “PTAH-SOCAR fuel-cooled composite materials structure”, Progress in
Propulsion Physics, 1, pp. 627–644, 2009.

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365
The effect of kaolin type on properties of metakolin-based geopolymer
Yıldız Yıldırım1, Ugur Cengiz2
1
Kale Ceramic ARGE Department, Canakkale, Turkey; e-mail: [email protected]
2
Department of Chemical Engineering, Canakkale Onsekiz Mart University, Canakkale, Turkey;
e-mail: [email protected]
Keywords: geopolymer, kaolin, XRD

Geopolymers are noncrystal alumina silicate polymers that formed with the combination of
reactive alumina silicate materials and silicate solutions.1 The mechanism is constituted on
the reaction of different SiO2-Al2O3-Na2O or K2O and H2O ratios. Metakaolin, fly ash, vol-
canic glass and perlite were used as reactive alumina silicate material. In this study metaka-
olin based geopolymer mechanism was investigated. Metakaolin was obtained with kaolins
which had different physical and mineralogical properties. The physical and mineralogical
properties of the kaolins was observed with XRF, XRD, STA, FTIR, SSA and particle size
distribution methods.2 Structural alteration of metakaolins which was obtained with sintering
of kaolins 700 °C, 8 h was tested with XRD-FTIR-STA-SEM methods. Particle size distri-
bution, pozzolanic activities, the change of Si/Al and aluminum coordination number was
analyzed.
In this work, SiO2/Al2O3: 4 mole, Na2O /SiO2: 0.35 mole, H2O/Na2O: 18 mole ratio was
fixed and according to this situation recipes were prepared to get geopolymer granules.
Geopolymer granules were pressed in order to give tile shape, physical and mineralogical
analysis were made with this geopolymer tiles. The bending strength of tiles varied with the
change of time 1 h, 1–3–7 days of waiting time. Also the tiles were kept in the water and
mechanic strength change was observed. Humidity adsorption-desorption performance of
the tiles were monitored. The variation between geopolymer structures were introduced with
XRD, SEM-EDS, FTIR, surface area and apparent density tests/analysis.
In conclusion metakaolin structures are changed with the kaolins which has different
chemical and physical properties. It was found that oxides such as Fe2O3 in the kaolin pre-
vents metakaolin formation. Geopolymer properties are affected due to the quartz and hy-
dromica in the structure come up %20 because metakaolin formation is influenced nega-
tively. It was seen that particle size also changes the reaction speed. The variation around the
Al affects the humidity control. As a result humidity control was succeeded with all recipes.

References
1. J. Davidovits. Geopolymer Chemistry and Applications, 4th ed. Institut Geopolymere, 2015.
2. H.K. Tchakoute, C.H. Rüscher, J.N.Y. Djobo, B.B.D. Kenne, D. Njopwouo. “Influence of gibbsite
and quartz in kaolin on the properties of metakaolin-based geopolymer cements”, Applied Clay
Science, 107, pp. 188–194, 2015.

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221
Mechanical properties of alumina carbon refractories with in-situ
synthesis of Si3N4-SiC composite whiskers
Chaofan Yin1, Xiangcheng Li1,2, Boquan Zhu1, Pingan Chen1
1
State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology,
Wuhan 430081, P.R. China; e-mails: [email protected], [email protected]
2
School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, UK

Whiskers or fibers in carbon-contained refractories take effect of the excellent reinforce-

ment and toughness. In this paper, the in-situ synthesized mechanics of Si3N4-SiC composite
whiskers in carbon refractories and their influence on the mechanical properties were inves-
tigated. The results showed that the large scale of Si3N4-SiC composite whiskers would be
generated at 1400 °C and the existence of rare earth La2O3 could improve the in-situ synthesis
of Si3N4 whiskers. Meanwhile, their strength could also be increased by above 30% due to the
deflection and bridging effect of Si3N4-SiC composite whiskers.

197
Ultra-fast fabrication of oriented 3C-SiC wafers by halide CVD
Song Zhang1*, Rong Tu1, Dingheng Zheng1, Hong Cheng1, Meijun Yang1, Mingxu Han2,
Yiguang Zhang3, Takashi Goto2, Lianmeng Zhang1
1
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,
Wuhan University of Technology, 122 Luoshi Road, Wuhan 430070, People’s Republic of China;
*
e-mail: [email protected]
2
Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577,
Japan
3
Hubei Academy of Spaceflight Technology overall Design
Keywords: 3C-SiC films, halide CVD, orientation, deposition rate (Rdep), growth mechanism

Φ80 mm-diameter, highly oriented 3C-SiC wafers were ultra-fast fabricated via halide chem-
ical vapor deposition (CVD) using tetrachlorosilane (SiCl4) and methane (CH4) as precur-
sors The effects of deposition temperature (Tdep) and total pressure (Ptot) on the orientations,
microstructures and deposition rate (Rdep) were investigated. Rdep dramatically increased with
increasing Tdep where maximum Rdep was 930 μm·h–1 at Tdep = 1823 K and Ptot = 4 kPa, leading
to a maximum of 1.9 mm in thickness in 2 hours deposition. The <110>-oriented 3C-SiC was
obtained at Tdep > 1773 K and Ptot = 1-4 kPa. Growth mechanism of <110>-oriented 3C-SiC
has also been discussed under consideration of crystallographic planes, surface energy and
surface morphology. The effects of molar ratio of C and Si precursors (RC/Si) on composition,
preferred orientation, microstructure and deposition rate (Rdep) were investigated. The de­

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posits transformed from silicon-rich to stoichiometric 3C-SiC to carbon-rich with increasing

­­RC/Si. <110>-oriented stoichiometric 3C-SiC with lower density of defects were obtained at
RC/Si in the range of 0.86 to 1.00, where the maximum Rdep was 883 μm/h at RC/Si = 1.00, lead-
ing to a thickness of 1.7 mm in 2 hour deposition. Formation of ridge-like morphology has
been discussed based on a twin plane propagation model.

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Invited lectures

658
All inorganic granular extrinsic multiferroics:
from nanomaterial engineering to magnetoelectric coupling
Ulises Acevedo1,2, Romain Breitwieser1, Rene Lopez Noda2,3, Raul Valenzuela2,
Souad Ammar1*
1
ITODYS, Université Paris Diderot, Sorbonne Paris Cité, CNRS UMR-7086, Paris, France;
*
e-mail: [email protected]
2
IIM, Universidad Nacional Autónoma de Mexico, 04510 Ciudad de Mexico, Mexico
3
Depto de Física Aplicada, Instituto de Cibernética, Matemáticas y Física, La Habana, Cuba
Keywords: multiferroics, polyol process, Spark Plasma Sintering, nanostructured ceramics

Since the observation in 1888 of a magnetization M in a dielectric material moving into an

electric field E and the reverse effect observed in 1905 of an electrical polarization P in a
dielectric system moving into a magnetic field H, the research on magnetoelectric materi-
als and devices grew up tremendously. At the 70s, both experiments and theory bring to
a saturation point, the scientific community focusing only on single-phase magnetoelectric
(ME) materials.1 In the early 90s, the renaissance of scientific interest into magnetoelectric-
ity took place thanks to the elaboration of multiferroic composites. Combining piezoelectric
and magnetostrictive and/or ferroelectric and ferromagnetic nanomaterials in new fancy ar-
chitectures, gave rise to the observation of higher ME effect at room temperature. Typically,
ME coefficient reached 130 mV.cm–1.Oe in granular CoFe2O4/BaTiO3 composite2 while it did
not exceed 0.8 mV.cm–1.Oe in Cr2O3 single-phase.3 In this context, we developed an original
material processing route to produce such composites, exacerbating the high value of the sur-
face/volume ratio of the involved phases. In practice nanoparticulated composites BaTiO3-
CoFe2O4 (BTO-CFO) in different atomic ratio were prepared by combining polyol method4
and spark plasma sintering5. High dense and ultrafine grained samples were obtained.6 Their
impedance response was measured in the 5 Hz–10 MHz frequency range, under 0–7.5 kOe
magnetic applied fields, between 40 and 170 °C.7 The best agreement to models for the result-
ing cole-cole plots was achieved by means of three parallel RC arrangements connected in
series; by their RC values, these circuits are representative of grain boundaries. An associa-
tion between each RC circuit and each interface, i.e., BTO-BTO, BTO-CFO, and CFO-CFO,
was successfully proposed on the basis of the temperature and magnetic behaviour of the
constituting phases.

References
1. K.H.J. Buschow, Handbook Magnetic Materials, 20, Elsevier Science, Amsterdam (2011).
2. J. van Suchtelen, Philips Res. Rep., 27(1972) 28.
3. D.N. Astrov, Sov. Phys. – JETP, 11 (1960) 708.
293 ECerS2017 / July 9–13, 2017 / Budapest, Hungary
T04: Electroceramics and optical materials – Invited lectures

4. M. Artus et al., J Phys.: Condens. Matter, 23 (2011) 506001.

5. T. Gaudisson et al., J. Magn. Magn. Mater., 370 (2014) 87.
6. J. Appl. Phys., 113 (2013) 17B519.
7. U. Acevedo et al., AIP Adv., 7 (2017) 055813.

159
SPS derived CaTiO3-based dielectric ceramics with high energy storage
density
X.M. Chen*, H.Y. Zhou, X.Q. Liu, X.L. Zhu
School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China;
*
e-mail: [email protected]
Keywords: dielectric ceramics, energy storage, SPS

CaTiO3 is a linear dielectric material with the high dielectric constant, low dielectric loss and
a wide band gap, which is a potential candidate for high density energy storage applications.
An energy density of 1.5 J/cm3 was obtained in CaTiO3 ceramics prepared by conventional
sintering process, and the dielectric strength was 435 kV/cm. On the other hand, the intrinsic
dielectric strength of CaTiO3 was predicted to be as high as 4.2 MV/cm, therefore, much
higher energy storage density could be expected. In the present work, the dielectric strength
of the CaTiO3 ceramics was remarkably enhanced to 910 kV/cm by spark plasma sintering
(SPS), and the corresponding energy density was 6.7 J/cm3, which was much higher than
that prepared by conventional sintering process. This could be interpreted as the result of
the lower electrical conductivity and higher thermal conductivity, associated with the finer
microstructures in the SPS derived samples. Moreover, the post-breakdown features were
motivated to investigate the breakdown process, it turned out that a micro breakdown channel
was formed due to the localized high temperature during breakdown process, accompanied
by the crack growth, re-crystallization and texture structure. It was suggested that thermal
breakdown was predominant in the present ceramics. In addition, the breakdown channel of
SPS sample was discontinuous while that was continuous for the sample by conventional
sintering process, implying a higher dielectric strength in CaTiO3 ceramics prepared by SPS
from the view point of microscopic.

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893
3D nanoarchitectures for energy energy conversion –
enhanced functionality through correlative microscopy
S.H. Christiansen1,2*
1
Freie University, Berlin, Germany; *e-mail: [email protected]
2
Helmholtz-Zentrum-Berlin, Germany

Complex nano-architectures of various material combinations (e.g. Si-nanostructures such

as wires (NW) and cones (NC), GaN nanostructures, transparent conductive oxides e.g. Al
doped ZnO, coinage metal nanoparticles e.g. wires, spheres, graphene and other 2D materi-
als) integrated on Si wafer platforms will be presented for light absorption, light emission
and sensing applications.
In this context we will show nano-material choices for surface enhanced Raman spec-
troscopy (SERS) and chemically functionalized SiNWs, SiNCs, GaN NWs with distinct
resonances for optical sensing or distinct electrical performance in electrical devices such
as resistors.
Materials and device optimization will rely on advanced correlated electron microsco-
py and optical spectroscopy (CORMIC) containing electron beam induced current (EBIC)
measurements, I-V characterization with and without illumination (with tunable power and
wavelength) inside a scanning electron microscope (SEM), cathodo-, photo- luminescence as
well as in-SEM micro-Raman spectroscopy.

205
Compositional tuning of Ba-based ferroelectrics and relaxors
Marco Deluca
Materials Center Leoben Forschung GmbH, Materials for Microelectronics, Kerpelystraße 2,
8700 Leoben, Austria

A- and B-site substitution of barium titanate with homovalent or heterovalent dopants is at

the basis of solid solutions that lately found increasing importance for dielectric, piezoelec-
tric, energy storage and microwave applications. High dielectric permittivity – stable over a
large temperature range – and large high-field piezoelectric coefficients are typically sought-
for figures of merit. Yet, compositional tuning to attain specific properties has been largely
based on macroscopic observations and very little is known about the fine material structure
on the short range that is necessary to induce those properties. In relaxors, for instance, it
is not yet clear whether their peculiar behaviour originates from random electric fields or
simple dipolar interactions.
Raman spectroscopy, being sensitive to the material’s short range structure, is a very at-
tractive technique to study structure-property relationships in Ba-based ferroelectrics and

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relaxors. In this presentation, an overview will be given on this technique and on the infor-
mation it can convey on these systems. It will be shown that the Raman method is comple-
mentary to diffraction and macroscopic property measurements, and can add decisive details
to understanding the whole picture, especially if coupled with atomistic simulations. We will
focus on both A- and B-site substituted BaTiO3 (with Bi and Zr, respectively) and also A- and
B-site co-doped systems (with Bi, Yb and Fe).

714
Local structure analysis of electroceramics via aberration-corrected
scanning transmission electron microscopy
Elizabeth C. Dickey1*, Matthew Cabral1, James M. LeBeau1, Shujun Zhang2
Department of Materials Science and Engineering, Center for Dielectrics and Piezoelectrics,
1

North Carolina State University, 911 Partners Way, Raleigh, NC 27695 USA;
*
e-mail: [email protected]
Institute for Superconducting and Electronic Materials, Australian Institute of Innovative Materials,
2

University of Wollongong, NSW, 2500, Australia

Keywords: relaxor ferroelectric, STEM

The quantification of local symmetry and structure, as opposed to global averaged structure,
is important to the fundamental understanding of structure and properties in many complex
oxides. This is particularly important in relaxor ferroelectrics, which contain “polar nanore-
gions” where local fluctuations in cation composition gives rise to inhomogeneities in lo-
cal strain and polarization on the nanometer scale. Prior experimental studies have focused
largely on x-ray and neutron diffuse-scattering and pair distribution function experiments
to understand local inhomogeneities and short-range ordering. While these techniques have
been invaluable in furthering our fundamental understanding of polar nanoregions and the
nature of relaxor behavior, they provide a statistical average over a large sampling volume
and, to date, do not provide correlations with local chemistry. With recent advances in quan-
titative aberration-corrected scanning transmission electron microscopy (STEM) that enable
picometer-scale precision in atomic column positions1 and the unprecedented spatial resolu-
tion and chemical sensitivity of energy-dispersive x-ray spectroscopy (EDS), we are poised
to provide direct correlations between compositional disorder and local polarization in these
complex ferroelectric materials as has been demonstrated recently in lanthanum strontium
aluminum tantalate (LSAT).2 The research discussed in this talk focuses on the application of
these techniques to relaxor ferroelectrics, such as lead magnesium niobiate (PMN), to pro-
vide spatially resolved quantification of local structure on a unit-cell by unit-cell basis. The
use of atom column indexing allows for direct measurement of local displacements within
the A and B sub-lattice positions and their local chemistry as evident in local column intensi-
ties. Through image simulations we evaluate optimal experimental conditions for, and limita-
tions of, STEM-based measurement for local structure analysis.

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Acknowledgements
This material is based upon work supported by the National Science Foundation, as part of the Center
for Dielectrics and Piezoelectrics under Grant Nos. IIP-1361571 and IIP-1361503. Support for M.
Cabral is provided by the National Science Foundation Research Traineeship on Data-Enabled Science
and Engineering of Atomic Structure under grant No. DGE-1633587.

References
1. X. Sang and J. M. Lebeau, Ultramicroscopy, 138, 28–35 (2014).
2. X. Sang, E.D. Grimley, C. Niu, D.L. Irving, J.M. LeBeau, Applied Physics Letters, 106, 061913
(2015).

878
Transparent ceramics and glasses containing TM+(RE+) cations:
spectroscopy, materials and applications
Adrian Goldstein
Israel Ceramic and Silicate Institute, Technion City, Haifa 3200003, Israel;
e-mail: [email protected]
Keywords: transparent, ceramics, spectroscopy, transition cations

Many applications (e.g. armor windows, missile noses, optical lenses, hot reactor inspection
windows) request robust solid parts exhibiting high transmission in various portions of the
NUV-FIR region (λ = 0.1–20 µm) of the electromagnetic radiation (EMR) spectrum.
A quite large number of inorganic glasses and ceramic (single or polycrystalline) materials
contain suitable mechanical, thermal and chemical (stability to environment attack) proper-
ties cobined with the required transparency. For other applications, besides transparency in
certain spectral domains, controlled absorption of other range(s), or EMR emission at certain
frequencies, is needed. For such applications the necessary components are obtained by dop-
ing the transparent materials mentioned above with suitable transition metal (TM+) or rare-
earth (RE+) cations.
Such cations, when present as unwanted impurities, are deleterious to the functioning of
many an optical component. In this lecture the way in which the presence of TM+(RE+) cat-
ions modifies the spectral properties of transparent inorganic solid hosts is reviewed, based
on data drawn both from the research of the author and the relevant literature.
First, a brief presentation of the theoretical instruments used for the interpretation of the
spectral (optical and magnetical) data is given. Then, examples of the effect of TM+(RE+)
cations, when present as impurities, are presented. The largest part of the lecture is devoted
to the description of selected applications made possible by the spectral features (absorption
and emission) of these cations.
The merits of glassy and ceramic hosts, related to these applications, are compared, with a
view of determining what can be done to increase the competitivity of the ceramics.

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532
Exploring relaxor-ferroelectric ceramics for electrocaloric cooling
applications
B. Malič1,2*, L. Fulanović1,2, M. Vrabelj1, H. Uršič1, S. Drnovšek1, M. Otoničar1,
A. Bradeško1,2, T. Rojac1,2, V. Bobnar1,2, Z. Kutnjak1,2
1
Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia; *e-mail: [email protected]
2
Jožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, Slovenia
Keywords: electrocaloric, relaxors, multilayers, microstructure

Increasing needs of society for electricity, heating, or cooling have become a global priority,
thus efficient ways of energy production, conversion, storage, and consumption are needed.
A contribution to solutions to such problems may be the innovative use of ferroelectric or
relaxor ferroelectric ceramic materials in dielectric cooling by exploiting the electrolaloric
effect (ECE). The latter is defined as a reversible temperature change in a material upon
application of an external electric field at adiabatic conditions. Materials exhibiting a large
ECE over a temperature range of a few 10 K close to room temperature include the (1-x)
Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-100xPT) solid solution, especially the PMN-rich composi-
tions with a pronounced relaxor character.
The largest EC temperature changes have been obtained in thin ceramic or polymer films,
exceeding for an order of magnitude the highest reported values obtained in bulk ceramics,
which is also a consequence of the high breakdown strength of the former. Nevertheless, bulk
ceramic cooling elements could be efficiently employed in cooling devices. By introducing
multilayer cooling elements, the applied voltages could be even further reduced as compared
to diced bulk ceramics.
In the contribution we discuss different effects introduced by processing and evidenced in
the microstructure which are reflected in the electrocaloric response of bulk relaxor ceramics.
The viability of relaxor ferroelectric ceramic materials in solid-state cooling is assessed both
from the points of view of processing and application in demonstrator devices.

492
Molecular design of organic ligands for functional inorganic
nanoparticles dispersion in organic solvents and polymer
Yohei Okada, Keisuke Asada, Kodai ishikawa, Naoya Maeta, Hidehiro Kamiya1*
1
Graduate school of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and
Technology, Koganei, Tokyo, Japan 184-8588; *e-mail: [email protected]
Keywords: nanoparticle/polymer composite, optical behaviour, interface structure design

In our previous study, TiO2 nanoparticles modified with a commercial phosphoric acid sur-
factant can be dispersed in both polar and less-polar organic solvents and polymers. How-
ever, the relationship between molecular structure and colloidal stability is not clear and the

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structure is not optimized for better dispersion. In this study, we designed and synthesized a
series of novel amphiphilic organic ligands with various molecular structure and used them to
modify TiO2, ZrO2 and Ag nanoparticles. We designed the amphiphilic organic ligands with
different lengths of alkyl and ethylene glycol chains and a phosphoric acid group for TiO2 and
ZrO2, and NH2 group for Ag. A series of the ligands were synthesized in 3 steps from com-
mercially available alkyl bromides. The modified nanoparticles were aggregated in the aque-
ous solution, which were then collected by centrifugation and washed with water to remove
free ligands and dried in vacuum. The resulting modified nanoparticles were then dispersed
in several organic solvents to study the relationship molecular structure and colloidal stabil-
ity. We discovered the optimum lengths of alkyl and ethylene glycol chains to disperse TiO2
nanoparticles into various polar and nonpolar organic solvents using sonication. Further-
more, this optimum ligand modified TiO2 nanoparticles were able to be uniformly dispersed
into polymer.in high concentration.

References
1. M. Iijima, M. Kobayakawa, M. Yamazaki, Y. Ohta and H. Kamiya, J. Am. Chem. Soc. 131(45)
16342–16343 (2009).
2. Y. Okada, K. Ishikawa, H. Kamiya, Langmuir, submitted.

842
Local field engineering for tailoring electrical properties in
ferroelectric-based composites
Leontin Padurariu*, Liliana Mitoseriu
Dielectrics, Ferroelectrics& Multiferroics Group, Departament of Physics, Al.I. Cuza University,
11 Bv. Carol I, 700506, Iasi, Romania; *e-mail: [email protected]

The interfaces between regions with contrasting permittivities in composites modify the lo-
cal field distribution. The effective macroscopic properties of composites are a result of this
local field inhomogeneity and therefore, the properties of ferroelectric-based composites can
be tailored by controlling the microstructure characteristics (local field engineering) or by
adequate choice of the phase constituents and phase interconnectivity. This approach can be
applied to design ferroelectric-magnetic composites with specific dielectric/ferromagnetic
properties. Since the local field inhomogeneity increases when the difference in permittivities
of the constituent phases is higher, porous ferroelectric structures ensuring a maximum per-
mittivity contrast have a great potential in order to reach desired ferro/dielectric properties,
although porosity is usually considered detrimental in electroceramics.
Based on this idea, 3D FEM models have been developed to compute local field distribu-
tions in realistic microstructures in order to explore the possibility to maximize their ferro-
electric (switching) or non-linear dielectric responses (tunability). The role of nanostructur-
ing and of porosity on the macroscopic properties (effective permittivity, tunability, P(E)
hysteresis loops) were studied theoretically and validated for BaTiO3 nanostructured ceram-

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ics, for a few types of PZT ceramics with various porosities, including anisotropic, and for
PbTiO3 films with vertical nanoporosity. As a first step, different realistic 3D microstructures
were generated. Local field distributions were computed by 3D FEM calculation and used
as inputs in switching (Preisach) or tunability (Johnson) models, in order to derive the ferro/
dielectric and tunability responses. If properly engineered in well-controlled microstructures,
porosity may be used as an elegant factor to enhance functionalities as result of the field
concentration in specific regions.

Acknowledgement
This work was supported by the Romanian CNCS PN II-RU-TE-2014-4-1494 project.

References
1. C. Padurariu et al., Ceram. Int. 43, 5767 (2017).
2. L. Padurariu et al., Acta Mater. 103, 724 (2016).
3. L. Padurariu et al., Phys. Rev. B 85, 224111 (2012).

946
Sucking the heat out of ceramic processing
Clive A. Randall
Director, Materials Research Institute, Professor, Materials Science and Engineering,
The Pennsylvania State University, University Park, PA 16802 USA

For over 30,000 years, the general practice of sintering ceramics has involved a high tem-
perature thermal treatment to drive the transport processes to densify the particles and mini-
mize the surface energy of the material. Typical sintering temperatures consider 0.6 to 0.8
of the melting temperature (Tm) for many oxides; this means we sinter around 800 °C to
1200 °C for 2 to 10 hours. Here we introduce a broad body of systems that utilize a transient
aqueous based liquid phase (1 to 10 wt%) that sinters under a uniaxial pressure, while being
heated from room temperature to 250 °C, over a time period of 10 to 60 minutes. During this
process, there are all the aspects of liquid phase sintering, namely particle rearrangement,
dissolution precipitation, and grain growth. We believe transport processes are enhanced
through mechanisms such as diffusiophoresis, which in turn is driven by concentration gra-
dients. This phenomenon has very fast transport velocities, and therefore does not require
high temperatures ~ 10 micrometers/sec. The driving for precipitation is also enabled by the
transient evaporation of the water and a sustained supersaturation under local hydrothermal
conditions. These mechanisms work together to create a pathway to sinter ceramics under ex-
tremely low temperatures and fast times; many of the systems that we will show are sintered
at 120 °C, 15 minutes, under 300 MPa uniaxial pressure. We have termed this fabrication
method the Cold Sintering Process (CSP). We fully realize that there are many subtle differ-
ences in the CSP of each system, but as this is the start of a new approach, we will share our
qualitative understanding, as determined from microstructural observations. We have also

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benchmarked and compared properties where possible, and it will be seen that the proper-
ties are in comparison to conventionally processed materials; we will in particular contrast
conduction and dielectric properties.
Given the massive drop in sintering temperature of the ceramic, this offers many new op-
portunities in material design, especially in composites. We will show three different types of
polymer ceramic composites with high percentages of ceramic, 100% to 60%, with the ther-
moplastic polymers for dielectric applications, ionic electrolytes, and semiconducting com-
posites. We will also show preliminary data with CSP with multilayer ceramics and printable
electronics.

833
Static and dynamic magnetoelectric coupling in multiferroic
hexaferrites
Jakub Vít1*, Filip Kadlec1, Christelle Kadlec1, Fedir Borodavka1, Yi Sheng Chai2,
Stanislav Kamba1
1
Department of Dielectrics, Institute of Physics, Czech Academy of Sciences, Na Slovance 2, 182 21,
Prague 8, Czech Republic; *e-mail: [email protected]
2
Institute of Physics, Chinese Academy of Sciences, Beijing, People’s Republic of China
Keywords: magnetoelectric effect, multiferroics, hexaferrites, electromagnon

The static magnetoelectric (ME) coupling, which is responsible for the magnetic-field-in-
duced electric polarization or the electric-field-induced magnetization, is well understood
in terms of symmetry.1,2 Several microscopic models were proposed to explain the observed
ME effects.1,2 In some hexaferrites, i.e. iron-containing oxides with hexagonal crystal struc-
tures, a ferroelectric polarization was observed due to conical spin arrangements in external
magnetic field at temperatures close to the room temperature,3 and even without external
magnetic field after a proper ME poling.4 The existence of the polarization can be explained
by the inverse Dzyaloshinskii-Moriya interaction.
Multiferroics combining magnetic and electric ferroic orderings also exhibit dynamic ME
effects, which are represented by electromagnons, i.e. electric-dipole active collective spin
excitations. Interestingly, the oscillating electric polarization emerging via the electromag­
nons usually appears in the direction perpendicular to that of the static polarization. We ob-
served such effect in the Y-type hexaferrite BaSrCoZnFe11AlO22 and in the Z-type hexafer-
rite (Ba0.2Sr0.8)3Co2Fe24O41.5 Although the static polarization lies in the hexagonal plane, we
detected electromagnons polarized along the hexagonal axis. The electromagnons are active
already in zero magnetic field and they disappear from the THz spectra at higher magnetic
fields (2–4 T), due to a change of the magnetic structure. The mechanisms of the electromag­
nons’ activation will be discussed.

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References
1. P.S. Wang, X.Z. Lu, X.G. Gong and H.J. Xiang., “Microscopic mechanism of spin-order induced
improper ferroelectric polarization”, Comp. Mat. Sci., 112, pp. 448–458, 2016.
2. Y. Tokura, S. Seki and N. Nagaosa, “Multiferroics of spin origin”, Rep. Prog. Phys., 77, 076501,
2014.
3. T. Kimura, “Magnetoelectric hexaferrites”, Annu. Rev. Condens. Matt. Phys. 3, 93, 2012.
4. Y.S. Chai, S. Kwon, S.H. Chun, I. Kim, B.G. Jeon, K.H. Kim and S. Lee, “Electrical control of large
magnetization reversal in a helimagnet”, Nat. Commun. 5, 4208, 2014.
5. F. Kadlec, C. Kadlec, J. Vít, F. Borodavka, M. Kempa, J. Prokleška, J. Buršík, R. Uhrecký, S. Rols,
Y.S. Chai, K. Zhai, Y. Sun, J. Drahokoupil, V. Goian and S. Kamba, “Electromagnon in the Z-type
hexaferrite (BaxSr1−x)3Co2Fe24O41”, Phys. Rev. B, 94, 024419, 2016.

822
Complex thin and ultrathin films through solution synthesis
Gunnar Westin
Chemistry-Ångström, Ångström Laboratory, 75121 Uppsala, Sweden

Solution based synthesis routes using metal alkoxides and organically coordinated metal
salts have been used to prepare complex oxides, nano-composites and nano-structured met-
als. Oxides of varying complexities including doped and non-doped Fe2O3, TiO2 and ZnO, as
well as spinels and perovskites have been prepared in the forms of thin- and ultra-thin films
on flat and nano-structured surfaces including wires and porous nano-structures. Further,
synthesis routes using organically coordinated metal salts developed to yield thin or ultra-
thin films and coatings of metals and metal-in-oxide nano-composites have been developed
and will be described. Synthesis of metals with crystallite sizes below 10 nm, as well as
ultra-thin coatings at temperatures in the range 150–500 oC have been achieved. Similar salt
based systems were also used for synthesis of thin- and ultra-thin metal-in-ceramic compos-
ite films with metal particle sizes down to a few nm and loadings of up to over 80%. The
influence of the precursor, reaction kinetics and thermal treatment will be discussed in rela-
tion to the structures and properties obtained, as well as the possible synthesis of oxides with
extended, metastable doping-levels. The syntheses and products were studied with a wide
array of analytical techniques including; SEM, TEM, XRD, TGA, DSC/DTA, IR and Raman
spectroscopy. Such simple low cost synthesis routes to highly complex nano-materials are
required for practical application in many areas of sustainable energy conversion and storage,
catalysis and magneto-electric applications.

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Oral presentations

122
Investigation of crystal structure and magnetic properties of Ba and Nd
co-doped BiFeO3 multiferroics at morphotropic phase boundaries
Ashish Agarwal*, Ompal Singh
Department of Physics, Guru Jambheshwar University of Science & Technology, Hisar,
Haryana – 125001, India; *e-mail: [email protected]

To investigate the crystal structure and magnetic properties Ba and Nd co-doped Bi0.8Ba0.2-
xNdxFeO3 (with x = 0.5, 0.1, & 0.15) multiferroics were synthesized by solid state reaction
method. The crystal structure (as evaluated by Rietveld refinement of XRD patterns through
FullProf Suite) of the samples is found to exhibit mixed symmetry in all three compositions.
With x = 0.05, the best fits were obtained with mixed symmetry of rhombohedral R3c (≈61%)
and triclinic P1 (≈39%), while at x = 0.10 the phase fraction changes to 51% R3c and 49%
P1. In the next composition with x = 0.15, the structure changes to mixed rhombohedral R3c
(≈88%) and orthorhombic Pnma (≈12%). The reason of such phase transition may again be
attributed to the mismatch in the ionic sizes of Ba2+ and Nd3+ in place of Bi3+ ion. This results
in disturbance of FeO6 octahedra and eventually in the phase transformation. Change in the
magnetisation is observed with increasing Nd content. It has been well established by the
previous reports that Ba doping destroys magnetisation in BiFeO3 by distorting the inherent
spirally modulated structure of spins which in turn locks the linear magnetisation. The dop-
ing of smaller sized Nd ion which causes the reorientation of magnetic dipoles may associate
different grounds for magnetisation via the in homogeneity in Ba doped BiFeO3.

629
Dielectric properties and interface effects in multilayer
BaTiO3/NiFe2O4 multiferroic thin films
Branimir Bajac
Department of Materials Engineering, University of Novi Sad, Faculty of Technology Novi Sad,
Novi Sad, Serbia; e-mail: [email protected]

Design and development of new materials have always been a base for new achievements in
modern technology. Composite multiferroic materials are a unique group of materials with
application in microchip components with a unique ability to exhibit more than one ferroic
property, and most importantly produce interaction between two phases giving rise to mag-
netoelectric coupling effect. In this research dielectric behavior of multilayer thin films com-
posed of ferroelectric BaTiO3 and ferromagnetic NiFe2O4 phases, obtained by obtained by
spin coating, have been analyzed at increased temperatures (30–200 °C) in frequency range

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from 100 Hz to 1 MHz. Characterization of different layer geometries have shown com-
plex influence on dielectric constant and loss tangent. Values of dielectric constant on room
temperature were almost constant and relatively low in whole frequency range, along with
very low loss tangent. Temperature induced charge transfer gradually increased loss tangent,
especially in frequency region below 10 kHz, as well as higher dielectric constant due to
charge accumulation on interfaces, closely resembling Debye behaviour. The conductivity of
multilayer films was limited by highly resistive titanate layers and fetire/titanate interfaces.

483
Dielectric and energy storage properties of Na(Nb1-xTax)O3 ceramics
prepared by spark plasma sintering
J.J. Bian1,2*, M. Otonicar2, M. Spreitzer2, D. Vengust2, D. Suvorov2
1
Department of Inorganic Materials, Shanghai University, China; *e-mail: [email protected]
2
Advanced Materials Department, Jožef Stefan Institute, Slovenia
Keywords: Na(Nb1-xTax)O3, spark plasma sintering, dielectric and ferroelectric properties, energy
storage

Na(Nb1-xTax)O3 (x = 0.2, 0.4, 0.6, 0.8) ceramics were prepared by spark plasma sintering
(SPS). The structure and microstructure were characterized by XRD, SEM, TEM and XPS
analysis. The dielectric and energy storage properties were investigated by impedance ana-
lyzer and ferroelectric analyzer. Single phase and dense Na(Nb,Ta)O3 ceramics could be
obtained by SPS. Reduction of Nb5+ was confirmed in Nb-rich compositions. The Tc tem-
perature decreased with the increased of x. Weak double P-E loops could be observed for x =
0.4 and x = 0.6 compositions. The x = 0.8 composition demonstrated incipient ferroelectric
characteristics. The temperature dependent dielectric permittivity exhibited hysteresis for x =
0.2 and x = 0.4 compositions. The dielectric loss decreased with the increase of x. The energy
storage properties were improved with the increase in Ta content. Maximum energy density
of ~0.90 J/cm3 could be obtained for x = 0.6 composition with the BDS of 159 kV/cm and
efficiency of 87.5%.

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544
Integration of screen-printed tunable BST thick films in LTCC modules
for microwave applications
J.R. Binder1, C. Kohler1, M. Nikfalazar2, H. Maune2, R. Jakoby2, A. Heunisch3, B. Schulz3,
T. Rabe3
Karlsruhe Institute of Technology, Institute for Applied Materials (IAM-KWT), Hermann-von-
1

Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

Technische Universität Darmstadt, Institute for Microwave Engineering and Photonik (IMP),
2

Merckstraße 25, 64283 Darmstadt, Germany

Federal Institute for Materials Research and Testing (BAM), Division Advanced Ceramics, Unter den
3

Eichen 44-46, 12203 Berlin, Germany

Reconfigurable microwave components play an important role in modern communication

systems to meet the increasing demands for functionality and flexibility of the systems.
Various technologies, such as semiconductor technology, microelectromechanical systems
(MEMS) or ferroelectric thin and thick films, are suitable for the realization of tunable mi-
crowave components. Ferroelectric materials are characterized by high tuning speeds, negli-
gible power consumption and low manufacturing costs. In particular, ferroelectric thick films
based on barium strontium titanate (BaxSr1-xTiO3, BST) are promising systems for use in
the frequency range up to approx. 12 GHz. However, due to the high sintering temperatures
above 1100 °C for pure BST thick films, the fabrication of tunable components based on
silver or gold electrodes is limited to planar structures, which are applied after the sintering
process.
In this presentation, it will be shown the development of BST-ZnO-B2O3 composite ma-
terials for reducing the sintering temperature to 850–900 °C. Furthermore, the material and
component properties of these composites or rather corresponding MIM (metal-insulator-
metal) varactors are presented and compared to planar-structured varactors. The LTCC in-
tegration potential of such fully screen-printed MIM varactors based on the developed low
sintering BST composites are investigated by the fabrication of phase shifters embedded in
LTCC modules.

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374
Transparent Cr:YAG ceramics: role of Cr2O3 and co-dopants on the
reactive sintering
Fabien Bouzat1,2, Rémy Boulesteix1,2, Alexandre Maître1,2, Lucie Chretien2,3,
Christian Salle2,3, Alain Brenier4
1
Université De Limoges, SPCTS, UMR CNRS 7315, 87000 Limoges, France
2
Laboratoire De Céramiques Transparentes Pour Lasers (LCTL), 87000 Limoges, France
3
CILAS, 8 Avenue Buffon, Z.I. La Source 45063 Orléans, France
4
Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière, F-69622,
Villeurbanne, France
Keywords: reactive sintering, transparent ceramics, Cr:YAG

Polycrystalline transparent ceramics have received considerable attention due to their appli-
cations as high-power laser gain media. Indeed, ceramics can be easily fabricated in relative-
ly large size and/or with complex architectures.1 In addition, these materials can incorporate
high amount of luminescent dopant. The flexibility of ceramic processes allows new designs
for laser amplifying media architecture to improve their thermo-optical efficiency.2 Accord-
ing to this approach, the present study concerns the manufacturing of Cr4+:YAG ceramic
which could be used as a saturable absorber (passive Q-switch) for high peak power pulsed
laser operation.
Since a Q-switch effect has been observed for a long time with a Cr4+:YAG single crystal,3
few recent works dealed with the elaboration of Cr4+:YAG ceramic, which can be considered
as a promising component for high peak power pulsed lasers. In YAG crystalline matrix, Cr4+
ions are preferentially substituted to the Al3+ ions and co-dopants have to be used for charge
balance. Ca2+ and Mg2+ are the most common co-dopants to ensure Cr4+ stability within the
YAG matrix.4,5
In this context, this study focused on the understanding of the role of Cr2O3 and co-dopants
(CaO and MgO) during sintering. The corresponding sintering maps (densification as func-
tion of the microstructure evolution) were built as a function of the composition of YAG
ceramics. Spectroscopic characterizations were also conducted to determine the respective
amount of Cr3+ and Cr4+ ions in transparent material so-obtained.

References
1. A. Ikesue, T. Kinoshita, K. Kamata, and K. Yoshida, J. Am. Ceram. Soc., 78 [4] (1995) 1033–1040.
2. A. Ikesue, Y.L. Aung, Ceramic Laser materials, Nature Photonics. 2 (2008) 721–727.
3. N.B. Angert, N.I. Borodin, V.M. Garmash, A.G. Zhitnyuk, A.G. Okhrimchuk, O.G. Siyuchenko, et
A.V. Shestakov, Soviet Journal of Quantum Electronics, 18 (1988) 7374.
4. A. Ikesue, K. Yoshida, et K. Kamata, Journal of the American Ceramic Society, 79 (1996), 507509.
5. H. Yagi, K. Takaichi, K. Ueda, T. Yanagitani, et A.A. Kaminskii, Optical Materials, 29 (2006),
392396.

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208
High-frequency dielectric spectra of BaTiO3-PbMg1/3Nb2/3O3 ceramics
Viktor Bovtun1*, Jan Suchanicz2, Martin Kempa1, Dmitry Nuzhnyy1, Krzysztof Konieczny2,
Tetyana Ostapchuk1, Jan Petzelt1, Stanislav Kamba1
1
Department of Dielectrics, Institute of Physics, Czech Academy of Sciences, Na Slovance 2,
182 21 Prague, Czech Republic; *e-mail: [email protected]
2
Institute of Technics, Pedagogical University, Cracow, Poland
Keywords: dielectric spectroscopy, ferroelectric ceramics, phase transitions

Dielectric spectra of the high-density perovskite ceramic solid solutions of (1-x)BaTiO3-

xPbMg1/3Nb2/3O3 (BT-xPMN, x = 0.075, 0.10, 0.15) prepared by a two-step conventional solid
phase sintering process1,2 were studied in the high-frequency, microwave and THz ranges
(106–1012 Hz). Dielectric dispersion was observed at all temperatures from 100 to 450 K in
the whole investigated frequency range. In contrast to relaxor ferroelectric PMN3, the ε’(T)
maximum does not shift remarkably with increasing frequency up to 1 GHz. The main dis-
persion takes place in the 109–1012 Hz range, similar to that in the ferroelectric BT ceramics.
THz spectra show presence of the relaxation (central) mode besides the soft phonon one,
similar to that observed in the tetragonal BT4 and PMN.3,5 Dielectric spectra of BT-xPMN are
analyzed and compared with those of BT ceramics and PMN single crystals.3 Origin of the
microwave dielectric dispersion is discussed in the framework of relaxor behavior, diffuse
phase transition and concept of polar nanoregions.

References
1. J. Suchanicz, K. Swierczek, E. Nogas-Cwikiel, K. Konieczny, D. Sitko, “PbMg1/3Nb2/3O3-doping
effects on structural, thermal, Raman, dielectric and ferroelectric properties of BaTiO3 ceramics”, J.
European Ceramic Society, 35, pp. 1777–1783, 2015.
2. J. Suchanicz, M. Karpierz, K. Konieczny, and K. Kluczewska, “Effect of PMN addition on the
structural, dielectric and ferroelectric properties of BT ceramics”, Ferroelectrics, 497:1, pp. 100–
106, 2016.
3. V. Bovtun, S. Veljko, S. Kamba, J. Petzelt, S. Vakhrushev, Y. Yakymenko, K. Brinkman, N. Setter,
“Broad-band dielectric response of PbMg1/3Nb2/3O3 relaxor ferroelectrics: Single crystals, ceramics
and thin films”, J. European Ceramic Society 26, pp. 2867–2875, 2006.
4. J. Hlinka, T. Ostapchuk, D. Nuzhnyy, J. Petzelt, P. Kužel, C. Kadlec, P. Vaněk, I. Ponomareva,
and L Bellaiche, “Coexistence of the phonon and relaxation soft modes in the terahertz dielectric
response of tetragonal BaTiO3”, Phys. Rev. Lett. 101, 167402, pp. 1–4, 2008.
5. V. Bovtun, S. Kamba, A. Pashkin, M. Savinov, P. Samoukhina, J. Petzelt, I.P. Bykov, M.D. Glin-
chuk, “Central-peak components and polar soft mode in relaxor PbMg1/3Nb2/3O3 crystals”, Ferro-
electrics, 298, pp. 23–30, 2004.

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264
The magnetic formation in oxide semiconductors under influence of
native defects and impurity atoms concentration
Musa Mutlu Can
Faculty of Science, Department of Physics, Istanbul University, Vezneciler, 34314, Istanbul, Turkey;
e-mail: [email protected]
Keywords: magnetotransport, oxide semcionductors

The control of native defects and impurity atoms concentration in the lattice manage the
electrical, optical and magnetic properties of semiconductors use in technology. The native
defects, forming the shallow energy levels that lead the physical properties, can be defined as
cation or anion vacancies, anti-site located host atoms and interstitial atoms.1–3
The wide band gap transparent conducting oxides, such as ITO, ZnO, SnO2, TiO2, etc., are
intensively investigated structures in technological usages. Additionally, the dependence of
magnetic structure on point defects is an important focus area in especially oxide semicon-
ductors. The magnetic semiconductors created by doping a few percent of transition metals
are known as diluted magnetic semiconductors (DMSs). Doping with transition metals, in
addition to defects in the lattice, is also known to be a necessary variable in oxide semicon-
ductors in order to generate magnetization and thus polarized spins currents. Many theories
on ferromagnetism defininion in oxide semiconductors are the strong exchange coupling
between 2p levels of oxygen and d levels of transition metals, transitions between different
valance states of transition atoms, shallow donors due to s-d interactions in n-type doping
and hybridization between the impurity bands of defects and 3d bands, known as d0 ferro-
magnetism.
In this study, solid state reaction technique and RF magnetron sputtering were used to syn-
thesize oxide semiconductors ((Zn1-x,Cox)O and (Zn1-x,Cox)Ga2O4 (x = 0.05, 0.10 and 0.20))
as powders and thin films, respectively. The characterization of the particles was also im-
proved using X-ray photoelectron spectroscopy (XPS), RAMAN and Fourier transforms in-
frared (FT-IR) spectroscopy measurements. The optical analyses were done with UV-visible
spectroscopy. Furthermore, the study is improved on understanding the magnetic formation
depending on Co atoms in both tetrahedral and octahedral sides in ZnO and (Zn1-x,Cox)Ga2O4
(x = 0.05, 0.10 and 0.20) structures. The effects of substituted Co atoms to magnetic charac-
ter were analyzed using Curie-Weiss law. The magnetic change was related to the high Co
amount in tetrahedral side which increasing the number of antiferromagnetic couplings.2–4

References
1. Tadatsugu Minami, Semicond. Sci. Technol., 20 (2005) S35–S44.
2. M.M. Can, S. Shawuti, T. Fırat, S. I. Shah, J Alloy Comp, 660 (2016) 423–432.
3. M.M. Can, S.I. Shah, T. Fırat, J Magn Magn Mater, 377, (2015) 229–238.
4. M.M. Can, Journal of Material Res, 29 (2014) 9.

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247
Phase transitions and polar order in BaCexTi1-xO3 (x = 0.02 – 0.30)
ceramics
Giovanna Canu1, Maria Teresa Buscaglia1, Giorgia Confalonieri2, Monica Dapiaggi2,
Lavinia Curecheriu3, Oana Condurache3, Marco Holzer4, Marco Deluca4,5,
Liliana Mitoseriu3, Vincenzo Buscaglia1
1
ICMATE-CNR, Via De Marini 6, 16149 Genoa, Italy
2
Department of Earth Sciences, University of Milan, via Botticelli 23, 20133 Milan, Italy
3
Alexandru Ioan Cuza University, Faculty of Physics, 11 Blvd. Carol I, 700506 Iasi, Romania
4
Materials Center Leoben Forschung GmbH, Roseggerstraße 12, 8700 Leoben, Austria
5
Institut für Struktur- und Funktionskeramik, Montanuniversität Leoben, Peter Tunner Straße 5,
8700 Leoben, Austria

The incorporation of homovalent M4+ ions at the Ti site of BaTiO3 with formation of the
BaMxTi1-xO3 solid solutions (M = Sn, Zr, Hf, Ce) determines interesting modifications of
the phase transitions, polar order and functional properties. In particular, an evolution of the
polar order from conventional ferroelectric to diffuse phase transition behavior and to re-
laxor state is observed with increasing x. Unlike the systems containing Sn and Zr, Ce-doped
barium titanate ceramics have not been fully investigated despite the potential applications
as lead-free dielectric and piezoelectric materials.
Dense (97–99% rel. density) ceramic samples with composition BaCexTi1-xO3 (x = 0.02,
0.05, 0.06, 0.10, 0.12, 0.15, 0.175, 0.20 and 0.30) were prepared by the conventional solid-
state route starting from fine precursor powders and sintered at 1450–1500 °C. The aver-
age crystal structure at different temperatures in the range 100–400 K has been determined
from the Rietveld refinement of high-energy X-ray diffraction data collected at ESRF. The
pair distribution function analysis has been used to investigate the local structure and the
level of disorder. The phase transitions and the evolution of polar order with composition
have been studied using dielectric permittivity measurements at 100 Hz-1 MHz between
–150 and 150 °C, variable temperature Raman spectroscopy (from –195 to 165 °C) and dif-
ferential scanning calorimetry (–100–150 °C). Overall, the data provide a detailed picture
of the BaCexTi1-xO3 system and a tentative composition-temperature phase diagram will be
proposed. The results indicate that the three transitions (rhombohedral/orthorhombic, or-
thorhombic/tetragonal and tetragonal/cubic) meet at a critical point located at x ≈ 0.10 and
T = 115 °C. Relaxor behavior is observed at x ≥ 0.20. In contrast to the homologous systems
BaSnxTi1-xO3 and BaZrxTi1-xO3, a diffuse ferro/para transition is already observed at x = 0.05
as a consequence of the high level of lattice disorder.

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312
Size effects of BiT template on piezoelectric properties of textured
BNKT ceramics by screen-printing method
Hyun Ae Cha, Jae-Ho Jeon
Funtional Nanopowder Materials Dept., Korea Institute of Materials Science, Changwon, Korea;
e-mails: [email protected], [email protected]
Keywords: Bi0.5(Na0.8K0.2)0.5TiO3, Bi4Ti3O12, topochemical microcrystal conversion, reactive-templat-
ed grain growth

The size effect of templates on the texturing and piezoelectric properties of textured
Bi0.5(Na0.8K0.2)0.5TiO3 (BNKT) ceramics prepared by reactive-templated grain growth (RTGG)
process using different sizes of Bi4Ti3O12 (BiT) template was investigated. The BiT template
was synthesized with 3 different sizes of 1.86, 4.37 and 10.31 um by molten-salt synthesis
at 3 different heating conditions. BiT templates were aligned in a matrix powder by screen-
printing process. Chemical reaction between the BiT template and the matrix powder during
calcination produced BNKT composite consisting of aligned plate-like BNKT templates and
randomly distributed BNKT matrix powders. Textured BNKT ceramics were prepared by
sintering the BNKT composite at 1150 °C for 4–50 h. The piezoelectric constant of textured
BNKT was dependent on the size of template due to the sintered density and grain orientation
factor. The grain orientation factor was increased while the sintered density was decreased as
increasing the size of BiT template. Regardless of sintering time, textured BNKT ceramics
prepared by 1.86 um BiT template exhibited higher piezoelectric constant than that of non-
textured BNKT ceramics. Piezoelectric constants of textured BNKT ceramics prepared by
4.37 and 10.31 um BiT templates were lower than that of non-textured BNKT ceramics when
the sintering time was 4 h while they were higher than that of non-textured BNKT ceramics
when the sintering time was longer than 20 h. In order to prepare textured BNKT with high
piezoelectric constant by improving grain orientation factor, larger BiT templates are favour-
able but, in this case, advanced sintering process to get high sintered density is needed.

References
1. E. Fukuchi, T. Kimura, “Effect of Potassium Concentration on the Grain Orientation in Bismuth
Sodium Potassium Titanate”, J. Am. Ceram. Soc., 85, pp. 1461–66, 2002.
2. K. Fuse, T. Kimura, “Effect of Particle Sizes of Starting Materials on Microstructure Development
in Textured Bi0.5(Na0.5K0.5)0.5TiO3”, J. Am. Ceram. Soc., 89, pp. 1957–1964, 2006.
3. W. Zhao, H. Zhou, Y. Yan, “Preparation and characterization of textured Bi0.5(Na0.8 K0.2)0.5TiO3
­ceramics by reactive templated grain growth”, Materials Letters, 62, pp. 1219–1222, 2008.

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341
Influence of yttria doped thoria microstructure on its compatibility with
liquid sodium
Yanis Cherkaski1,2, N. Clavier2, L. Brissonneau1, N. Dacheux2
1
CEA/DEN/DTN/SMTA/LIPC, Site de Cadarache, 13108 St-Paul lez Durance, France
2
ICSM – UMR 5257, CEA/CNRS/ ENSCM/Univ. Montpellier, Site de Marcoule, BP 17171,
30207 Bagnols/Cèze cedex, France
Keywords: ASTRID, electrochemical sensors, yttria-doped thoria, synthesis, oxides, sintering map,
sodium, impedance spectroscopy

In the framework of the development of the fourth generation of nuclear reactors, a Sodium
cooled Fast Reactor (SFR), named ASTRID (Advanced Sodium Fast Reactor for Industrial
Demonstration) is planned to be operated in France in the 2020s.
The sodium coolant in SFR must have specified oxygen content in order to control the
corrosion of the steels structures of the core (claddings…). Electrochemical sensors allow to
obtain a fast and specific measure in complement to other devices (plugging indicator). The
solid electrolyte has a fundamental role in the performance of the sensor. It should be com-
patible with sodium at high temperature (about 400 °C), mechanically resistant and a purely
ionic conductor. Yttria-doped thoria (i.e. Th1xYxO2-x/2) is well known as a potential electrolyte
material to be used in liquid sodium, provided its microstructure is controlled: low impurity
content, small grain size, high density...
The preparation of several Th1-xYxO2-x/2 ceramics was undertaken from oxalate precursors
to assess the influence of yttrium content on the material microstructure1. The sintering of the
oxide samples, obtained after a heat treatment at 600 °C of oxalate powder was investigated
to create sintering maps of Th1-xYxO2-x/2 by correlating the average grain size and the relative
density values. Theses maps show the different behaviour of the yttrium content on the final
microstructure of sintered thorium-yttrium oxides. Yttrium doping prevents the grain growth,
as the lowest yttrium content samples exhibit higher grain sizes. Impedance spectroscopy
measurements show that the electrical conductivity increases with the yttrium content up to
8% and then decreases for the highest doping value (22%).
In addition, the study of the compatibility of the ceramic with liquid sodium (100 hours
at 500 °C) shows a good chemical and mechanical resistance whatever the yttrium content
considered.
Finally, electric characterizations, provided by impedance spectroscopy, before and after
the different compatibility tests revealed a significant variation of the conductivity on the
grain boundaries while the conductivity response due to the grain were relatively the same.

Reference
1. M. Gabard, Y. Cherkaski et al., J. Alloys Compd., vol. 689, pp. 374–382, Dec. 2016.

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455
High transmittance infrared ray ZnS lens prepared by hot pressing
using homogeneous cubic ZnS nano-powders
Sung-Eun Choi, Ku-Tak Lee, Sahn Nahm*
Department of Materials Science and Engineering, Korea University, 1-5 Ga, Anam-Dong, Korea;
*
e-mail: [email protected]
Keywords: hydrothermal method, ZnS, cubic, hot pressing, IR lens

ZnS nanoparticles with various S/Zn ratios of 1.0~1.8 were synthesized using hydrothermal
treatment at 220 °C for 12 h and they were sintered using hot pressing under vacuum for the
application to the infrared ray lens. Crystal structure and grain morphology of ZnS nanopar-
ticles were investigated using XRD, SEM and TEM analysis. The homogeneous cubic ZnS
nanoparticles were formed in the specimens synthesized with S/Zn ratio of 1.3 under reaction
temperature of 220 °C and the average size of these ZnS particles was approximately 50 nm.
The optical properties of the ZnS nanoparticles with various S/Zn ratios were also measured.
A photoluminescence (PL) emission peak appeared at 495 nm for the specimen with low S/
Zn ratio of ≤ 1.0 due to sulfur vacancies. However, the specimens having high S/Zn ratio of
≥ 1.0 showed a PL emission peak at 520 nm due to the presence of elemental sulfur species.
In this work, these ZnS nanopowders were sintered via hot pressing under vacuum at vari-
ous sintering conditions and their microstructural and optical properties were investigated.
Moreover, the commercial ZnS powders were also sintered using hot press under vacuum
and their microstructures and optical properties were compared with those of the specimens
prepared by ZnS nanopowders.

Reference
1. Bo-Hee Hwang, “Structural and optical properties of solvothermally synthesized ZnS nano-materi-
als using Na2S·9H2O and ZnSO4·7H2O precursors”, Ceram. Int., 42, 11700–11708, 2016.

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412
Field-induced metastable ferroelectric phase in PLZT ceramics
I.V. Ciuchi1,2, C.C. Chung3, C.M. Fancher3, C. Capiani2, J.L. Jones3, L. Mitoseriu2,
C. Galassi2
CNR-ISTEC, Istituto di Scienza e Tecnologia dei Materiali Ceramici, Via Granarolo 64, I-48018,
1

Faenza, Italy
Dielectrics, Ferroelectrics & Multiferroics group, Faculty of Physics, “A. I. Cuza” Univ, .Bv.Carol I,
2

n. 11, 700506 Iasi, Romania

Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC,
3

27695, USA
Keywords: antiferroelectricity, ferroelectricity, field-induced antiferroelectric to ferroelectric transition

The polarization–electric field P(E) dependence of antiferroelectric (AFE) Pb0.97La0.03(Zr0.9

Ti0.1)0.9925O3 (PLZT 3/90/10) ceramic indicates that the AFE phase can be turned into a fer-
roelectric (FE) one. The FE phase can be maintained at room temperature after removal of
the electric field and it shows a remanent polarization Pr of 30 μC/cm2 and a piezoelectric
constant d33 = 100 pm/V.1 XRD analysis on virgin and poled ceramics evident a field-induced
phase transition during AFE-to-FE switching. It is of high scientific significance and poten-
tial technological impact to clarify the temperature stability of the induced FE phase. Dielec-
tric and temperature dependent in situ X-ray diffraction techniques were employed to study
the phase transition of virgin and poled PLZT 3/90/10 ceramic during heating from room
temperature up to 300 °C. When compared with the virgin sample, in addition to the AFE-PE
dielectric maximum, an anomaly was observed in the dielectric properties of poled ceramic.
This anomaly is observed at much lower temperatures with respect to the Curie range. In
situ temperature XRD data evident that the AFE phase recovered from FE phase in the same
temperature range. Thus, this dielectric anomaly corresponds to the AFE-to-FE temperature
induced phase transition. The temperature-induced FE-AFE transition is diffuse and it takes
place in the broad temperature range of (72–124 °C). Therefore, the field-induced FE phase
loses its stability and transforms back into AFE state when the temperature increases from
room temperature to 124 °C.

Acknowledgements
These results were obtained during the mobility of I.V. Ciuchi in NCSU (Raleigh, North Carolina,
USA) which was funded by JECS Trust (Contract No 201363-17). The COST Action MP1308 is ac-
knowledged as well. This work was performed in part at the Analytical Instrumentation Facility (AIF)
at North Carolina State University, which is supported by the State of North Carolina and the National
Science Foundation (award number ECCS-1542015). The AIF is a member of the North Carolina Re-
search Triangle Nanotechnology Network (RTNN), a site in the National Nanotechnology Coordinated
Infrastructure (NNCI).

Reference
1. I.V. Ciuchi, L. Mitoseriu, and C. Galassi, “Antiferroelectric to Ferroelectric Crossover and Energy
Storage Properties of (Pb1−xLax)(Zr0.90Ti0.10)1−x/4O3 (0.02 ≤ x ≤ 0.04) Ceramics”, J. Am. Ceram. Soc.
99, pp. 2382, 2016.

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339
Effect of porosity on the dielectric, switching and DC-tunability
properties of BaTiO3 ceramics
L.P. Curecheriu, C. Padurariu, L. Padurariu, R. Stanculescu, N. Horchidan, C. Ciomaga,
L. Mitoseriu
Dielectrics, Ferroelectrics& Multiferroics Group, Department of Physics, Al.I. Cuza University,
11 Bv. Carol I, 700506, Iasi, Romania

Materials with controlled porosity exhibit special properties that usually cannot be achieved
by their conventional dense counterparts. Porous materials find nowadays many applications
especially for environments where high temperatures, extensive wear and corrosive media
are involved as well as for advanced applications as magnetoelectric, piezoelectric energy
harvesting device. The advantages of using porous ceramics in these applications are usu-
ally the high melting point, tailored electronic properties and wear resistance in combination
with the features gained by the replacement of solid material by voids in the component. The
functional properties of the porous ceramics can be tailored for each specific application by
controlling the composition, type of porosity (open or closed), pore size distributions, pore
morphology and interconnectivity
Starting from this idea, our theoretical approach based on Finite Element Method (FEM)
calculations1 demonstrated that porous ferroelectrics might show promising tunability prop-
erties for applications in wireless technology. Using this approach, we proved that the case of
porous ferroelectrics with closed porosity is the best solution to fulfil the tunability require-
ments (low losses: tan δ < 3%, high tunability and moderate permittivity ε < 1000), because
the tunability is very sensitive to the dielectric permittivity of constituents.2 For this reason,
the highest contrast between dielectric phase permittivity (1 for pores) and permittivity of
regions (thousands in case of paraelectric/ferroelectric matrix) ensures highest local field
inhomogeneity and strongly enhance the nonlinear dielectric response.
The aim of the present work was to investigate in a systematic way the role of the pores
concentration and phase interconnectivity (0–3, 3–3 and 1–3) on the functional properties of
BaTiO3 porous ceramics. The obtained results show that by increasing porosity a systematic
reduction of permittivity was obtain, while the tunability is almost constant. The results were
explained using the concept of local field engineering, in order to propose new porous con-
figurations with improved tunable properties.

Acknowledgement
This paper was financial supported by Romanian CNCS-UEFISCDI PNII-RU-TE-2014-4-1494 project
EXPOFER.

References
1. L. Padurariu et al., Acta Mater. 103 (2016) 724.
2. A.K. Tagantsev et al., J. Electroceram. 11 (2003) 5.

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560
Textured PMN-PZT piezoelectric ceramics for high power applications
Sinan Dursun1,2, M. Unsal Unver1, Ebru Mensur-Alkoy3, Sedat Alkoy1,4*
1
Dept. of Materials Science and Engineering, Gebze Technical University, Gebze, Kocaeli, Turkey
2
International Center for Actuators and Transducers, The Pennsylvania State University, PA, USA
3
Faculty of Engineering and Natural Sciences, Maltepe University, Maltepe, Istanbul, Turkey
4
ENS Piezodevices Ltd., Gebze, Kocaeli, Turkey; *e-mail: [email protected]
Keywords: piezoceramics, texture, PMN-PZT, ultrasonic motors

High power piezoelectric materials combine “hard” and “soft” electrical characteristic for de-
vice applications such as ultrasonic motors, transformers and medical ultrasound. Therefore,
piezoelectric materials with a high mechanical quality factor (Qm) is desirable to meet the
high power requirement, and high piezoelectric constant and electromechanical coupling are
required for improved strain performance.
In this study, combination of two approaches has been used to obtain the high power
characteristics, namely; texturing to increase “soft” characteristics and Mn-doping to ob-
tain “hard” characteristics. Textured 0.4Pb(Mg1/3Nb2/3)O3-0.25PbZrO3-0.35PbTiO3 (PMN-
PZT) piezoceramics with properties that are comparable to single crystals in certain crys-
tallographic directions were synthesized by Templated Grain Growth (TGG) method using
BaTiO3(BT) template particles.
Textured PMN-PZT ceramics with Lotgering factors of up to 0.85 and with % 1.5 mol
MnO2 doping exhibited hard and soft combinatory properties with piezoelectric coefficients
of d33 = 600 pC/N, kp=0.78, tanδ=0.3 %, KT=1320 and Qm=550. The high power performance
of textured PMN-PZT was also successfully demonstrated in an ultrasonic motor with a cu-
bic and a hexagonal stator geometry.

Acknowledgement
The authors would like to thank the financial support of the Scientific and Technical Research Council
of Turkey (TUBITAK) through the Project #114M518.

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054
Structural and electrical characterisation of composite humidity fibre
sensors prepared by electrospinning
Pedro M. Faia1*, Juliano Libardi2, Evando S. Araújo3, Helinando P. de Oliveira3
CEMMPRE, Electrical and Computers Engineering Department, Faculty of Sciences and Technology
1

of the University of Coimbra, Polo 2, Pinhal de Marrocos, 3030-290 Coimbra, Portugal;

*
e-mail: [email protected]
Physics Department, Technological Institute of Aeronautics (ITA), Pç. Marechal Eduardo Gomes, 50,
2

12228-900 São José dos Campos, SP, Brazil

Institute of Materials Science, Federal University of Sao Francisco Valley, 48920-310, Juazeiro, BA,
3

Brazil
Keywords: humidity sensing, composites, impedance spectroscopy, electrospinning, fibres

The changes observed in a ceramic metal oxide impedance sensor exposed to a certain mois-
ture concentration, are a key role in the determination of its potential use for humidity mea-
surements: furthermore, the sensitivity of the ceramic sensor is influenced by the microstruc-
ture, viz. higher surface area, and surface reactivity with the relative humidity (RH). If the
sensitivity of these sensors depends on the microstructure, then their composition is a stra-
tegic tool to improve their response. The electric conduction mechanisms of the impedance
humidity sensors can be either ionic, either electronic, or mixed: the mixed ones may have
higher activity, and sensitivity. In a recent work by Farahani et al.1, a survey regarding mois-
ture sensing was presented: in addition to the electrical behaviour of several semiconducting
oxides, other aspects were reported: for instance, methods for optimization of the microstruc-
ture of sensors, usage of dopants or hybrid compositions on the sensing ceramic-based ma-
terials, fabrication techniques for producing sensors, and so on. With the study of composite/
doped materials, a better sensitivity of these sensors is aimed, comparing with the ones made
out of a unique metal oxide, due to the modifications established by the atomic disposition
of a more complex structure. In fact, the electrical response of a ceramic, is not only affected
by water adsorption on the oxide surface2, but also by factors such as stress-strain and atomic
defect distribution: so in the case of dominant single covalent/ionic adsorption, if some of
the positions initially occupied by atoms of one metal are now occupied by atoms of another
metal, the material electrical response to humidity is altered (the electronegativity of the oc-
cupying metal atoms may be used to regulate the sensitivity). In this work, the authors report
on the electrical response to moisture of sensors based on theTiO2:WO3 pair doped with
different proportions of V2O5: thick films with two different number of electrospun layers
and sintered at 500 ºC were prepared and characterised. The dependence of their complex
impedance spectra, measured in the range 400 Hz–40 MHz, on the relative humidity (RH) is
shown and discussed. Sensors structure was studied by means of several techniques (SEM,
X-ray diffraction, Raman spectroscopy) and is debated: explanations for the found sensors
microstructure and the observed electrical response relation, are advanced.

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References
1. H. Farahani, R. Wagiran, M.N. Hamidon, “Humidity Sensors Principle, Mechanism, and Fabrica-
tion Technologies: A Comprehensive Review”, Sensors 14(5), pp. 7881–7939, 2014.
2. M.T. Wu, H.T. Sun, L. Ping, “CuO-doped ZnCr2O-4-LiZnVO4 thick-film humidity sensor”, Sens.
Actuators B 17, pp. 109–112, 1994.

496
Antiferromagnetic crystal size dependence in exchange-biased
nanostructured ceramics
Giulia Franceschin1*, Thomas Gaudisson1, Nicolas Menguy2, Silvana Mercone3,
Raul Valenzuela4, Frederic Mazaleyrat5, Souad Ammar1
1
ITODYS, Paris Diderot University, 15 rue Jean Antoine de Baif, Paris, France;
*
e-mail: [email protected]
2
IMCPMC, Pierre and Marie Curie University, 4 place Jussieu, Paris, France
3
LSPM, Paris 13 University, 99 Avenue Jean-Baptiste Clément, Villetaneuse, France
4
IIM, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, Coyoacan,
04510, D.F., Mexico
5
SATIE, ENS Cachan, 61 Avenue du Président Wilson, Cachan, France
Keywords: permanent magnets, exchange-bias, Spark Plasma Sintering, nano-structured ceramics

The present research highlights the importance of antiferromagnetic phase crystals size in
establishing the exchange-bias inside nanostructured ceramics. Two different ferromagnetic
(FM) – antiferromagnetic (AF) systems were studied in order to compare their microstructur-
al and magnetic features. In both cases, Fe3O4 was used as FM phase, while the AF one was
varied between CoO and NiO. In both systems the mass ratio of FM and AF phases is about
75% and 25% respectively. Firstly, exchange-biased FM-AF core-shell nanoparticles (NPs)
were synthesized using the polyol method that is a soft chemistry route known to be efficient
for seed mediated growth of nanocrystals in solutions.1 Then, the NPs were consolidated by
Spark Plasma Sintering (SPS); this technique was performed within optimized conditions,
which allowed keeping nano-structuration inside the final ceramic.2 The microstructural anal-
ysis on powders and sintered ceramics shows that the epitaxy between the FM and AF phases
of core-shell NPs is kept after sintering, as well as the massive ratio composition adopted for
synthesis precursors. Nevertheless, the mean crystals size obtained for NiO is considerably
smaller than the CoO one also after sintering. The mean size of NiO crystals was observed
by High Resolution Transmission Electron Microscopy (HR-TEM) to be smaller than 10 nm
in the ceramic sample. Contrary in the case of CoO, grains of about 50 nm are observed in
the ceramic. The magnetic characterisations show evidences of exchange-bias only in the
Fe3O4-CoO system. This result is in agreement with the microstructural observations and al-
lows concluding that Fe3O4-NiO system is not favourable to create a spin coupling between
FM and AF phases. The small NiO domains size leads to stressed NPs surface that affect the
AF spin ordering of NiO in this region and thus the magnetic interactions between adjacent
phases.

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References
1. T. Gaudisson et al., J. Nanopart. Res. 16 (2014) 2359.
2. T. Gaudisson et al., IEEE. Trans. Magn. 49 (2013) 3356; T. Gaudisson et al. J. Appl. Phys. 115
(2014) 17E117.

411
Electrocaloric stability of relaxor multilayer elements
Lovro Fulanović1,2*, Jurij Koruz3, Nikola Novak3, Vid Bobnar1,2, Barbara Malič1,2
1
Jožef Stefan Institute, Jamova cesta 39, Ljubljana, Slovenia; *e-mail: [email protected]
2
Jožef Stefan International Postgraduate School, Jamova cesta 39, Ljubljana, Slovenia
Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Strasse 2,
3

Darmstadt, Germany
Keywords: electrocaloric, multilayer, relaxors, fatigue, PMN

Electrocaloric (EC) effect is an adiabatic temperature change induced in a polar material by

application or removal of an external electric field.1 Therefore it has a potential for exploita-
tion in cooling applications, especially where small and energy efficient devices are needed.
The highest temperature changes (~4 K) were measured in relaxor ferroelectric or ferroelec-
tric bulk ceramics at very high electric field amplitudes, i.e., in the range of 150 kV/cm, quite
close to the dielectric breakdown.1 Since in an EC cooling device the electric field will be
applied and removed numerous times, it is crucial to investigate the stability of EC effect dur-
ing high electric field cycling. The fatigue phenomena or deterioration of material properties
with electric field cycling is well-known in the field of ferroelectric actuators, but according
to our knowledge the studies on the EC fatigue have not been realized yet. Moreover the
fatigue investigation of the EC materials should be conducted at the conditions which are
representative for a real device, e.g., such as reported by Plaznik et al.2
In this contribution we report on the investigation of the stability of the EC effect with
electric field cycling performed on a relaxor Pb(Mg1/3Nb2/3)O3. The samples were prepared in
the form of multilayer (ML) elements, in which five ceramic layers with the thickness of 32
μm are separated by platinum electrodes of about 4 μm, following the procedure described
in Fulanović et al.3 By using ML elements the thickness of individual layers was reduced in
comparison to diced bulk ceramic samples, which resulted in lower applied voltages. The
electric field cycling at the amplitude of 110 kV/cm was carried out with a step signal and the
frequency of 2 Hz, while 5 mHz was used for control measurements.
The results are presented as the measured temperature change versus the number of elec-
tric field cycles. The initially measured EC temperature change of 1.45 K decreased only by
0.01 K after 106 cycles. In addition, the temperature dependant dielectric permittivity and
polarization versus electric field were measured prior and after cycling, exhibiting slight
changes. The microstructure of the cycled element was analysed with scanning electron mi-
croscope and no evidence of microcracking could be detected.

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References
1. M. Vrabelj et al., “Large electrocaloric effect in grain-size-engineered 0.9Pb(Mg1/3Nb2/3)O3–
0.1PbTiO3”, J. Eur. Ceram. Soc. 36, 75–80 (2016).
2. U. Plaznik et al., “Bulk relaxor ferroelectric ceramics as a working body for an electrocaloric cool-
ing device”, Appl. Phys. Lett. 106, 4–8 (2015).
3. L. Fulanović et al., “Multilayer 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 elements for electrocaloric cool-
ing”, J. Eur. Ceram. Soc. 37, (2017).

673
Milling and quite-fast sintering as key production steps to obtain fully
dense PZTN-CF particulate composites
Pietro Galizia, Claudio Capiani, Carmen Galassi*
CNR-ISTEC, Via Granarolo 64, I-48018 Faenza, Italy; *e-mail: [email protected]
Keywords: multiferroic particulate composites, PbO loss, quantitative XRD

In the near future (within ten years) magnetoelectric multiferroics could be implemented into
the emerging technologies such as wireless power, internet of things, machine-to-machine
communication services, mesh network, etc. Remarkable efforts have been done to develop
laminated bi-layer and multilayer multiferroic composites as bulk or thin films. These struc-
tures lead to remarkable magneto-electric coupling coefficients of a few Volts / cm∙Oe be-
cause the ferroic layer is a “full dielectric” which can be completely poled in the conventional
way. On the other hand in the particulate ceramic composites the requirement for “full dielec-
tric” is no longer applicable, since the ferroic phases are fully separated within the composite.
The strengths of particulate ceramic composites are low cost, simple production technology,
higher strain mediated magneto-electric coupling (since electric order phase/magnetic phase
interface density can be higher) and easy control of electrical and magnetic properties if the
ferroelectric phase (generally a perovskite) and the ferromagnetic one (a ferrite with spinel
structure) are mixed in a favourable proportion under the percolation threshold of the fer-
romagnetic phase.
A great research effort is in progress to improve the fabrication of PZT–CoFe2O4 (PZT–
CF) composites in order to avoid the unwanted reactions, which occur during densification of
PZT–CF materials at 1100–1200 °C, and to achieve the electric saturation during the poling.
Up to date, by setting a quite-fast sintering, full densification and prevention of unwanted
reactions were achieved for the PZT:CF 74:26 composites,1 but achieving electric saturation
is still a challenge. Further important results were: the understanding that the main cause of
reactions is the PbO loss;1 the proposal of an equation to calculate the PbO loss through XRD
analysis, considering the amount of ZrO2 and variation of perovskite’s tetragonality;1 and the
ability to design the ceramic process (milling of the CF powers in particularly) to control the
CF grain size distribution, which can be mono- or bi-modal, and overgrowth.1,2

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References
1. P. Galizia, C.E. Ciomaga, L. Mitoseriu and C. Galassi, “PZT-cobalt ferrite particulate composites:
Densification and lead loss controlled by quite-fast sintering”, J. Eur. Ceram. Soc., 37, pp. 161–168,
2016.
2. P. Galizia, C. Baldisserri, C. Capiani and C. Galassi, “Multiple parallel twinning overgrowth in
nanostructured dense cobalt ferrite”, Mater. Design, 109, pp. 19–26, 2016.

446
Photoluminescence of Eu3+/Eu2+ doped glass microspheres in the system
Y2O3-Al2O3 with eutectic composition
Katarína Haladejová, Robert Klement*, Anna Prnová, Dušan Galusek
Vitrum Laugaricio – Joint Glass Center of the IIC SAS, TnU AD, and FCHPT STU, Študentská 2,
SK-911 50 Trenčín, Slovak Republic; *e-mail: [email protected]
Keywords: aluminate glasses, YAG, Eu3+/Eu2+ doped glass, photoluminescence, lifetime, phosphors,
pc-WLED

The Eu3+ doped glasses in the Y2O3-Al2O3 system with eutectic composition (76.86 mol. %
(60 wt. %) Al2O3 and 23.13 mol. % (40 wt. %) Y2O3, corresponding to ~50 mol. % of YAG
and ~50 mol. % of Al2O3) were prepared by flame-spraying synthesis in the form of glass mi-
crospheres form precursor powder synthesized by sol-gel method.1 The doping level ranges
from 0.5 to 2.0 at. % of Eu3+. The prepared glass microspheres were found to be almost XRD
amorphous within detection limit. The DSC analysis revealed the two exothermic effects cor-
responding to crystallization of glasses at characteristic temperatures; peak 1: Tx1 ~ 920 °C
(onset), Tp1 ~ 935 °C (peak), peak 2: Tx2 ~ 990 °C and Tp2 ~ 1000 °C, respectively. The ori-
gin of the two crystallization peaks (exothermic effect) was examined by high temperature
XRD (HT XRD) that revealed the crystallization of YAG phase (Y3Al5O12) up to 1200 °C.
The crystallization of α-Al2O3 phase was observed at temperatures above 1300 °C. The both
exothermic effects in DSC traces thus unusually correspond to YAG phase crystallization; the
first peak mainly to nucleation and partial crystallization of YAG phase, the second peak to
crystal growth of YAG phase. The polycrystalline phosphors were prepared from the glasses
by controlled crystallization at selected temperatures. The photoluminescence (PL) proper-
ties (both steady-state and time-resolved PL) of glasses and polycrystalline phosphors were
studied in detail. In as prepared glasses the both oxidation states of europium, Eu3+ and Eu2+,
were found to coexist in glass matrix. The emission spectra of Eu3+ glasses under UV exci-
tation at 393 nm exhibit intensive red emission in the spectral range of 570–720 nm due to
intra-configurational 4f-4f transitions, while Eu2+ containing glasses (excited at 345 nm) emit
the light in broad spectral range from 400–700 nm with the emission maximum at ~520 nm.
The PL properties of Eu3+/Eu2+ glasses and corresponding polycrystalline phosphors were
compared. Moreover, the temperature dependent luminescence of the prepared phosphors
and the lifetime using the TCSPC technique were studied in detail. The prepared materials
are potential candidates for pc-WLED applications.

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Acknowledgement
The financial support of work by the project VEGA 1/0631/14 is gratefully acknowledged.

Reference
1. A. Prnová, K. Bodišová, R. Klement, M. Migát, P. Veteška, M. Škrátek, E. Bruneel, I. Van Driess-
che, and D. Galusek, “Preparation and characterization of Yb2O3-Al2O3 glasses by the Pechini sol
gel method combined with flame synthesis”, Ceram. Int., 40, pp. 6179–6184, 2013.

395
Magnetron sputtered ceramics for high temperature electrical
insulation
Benjamin V.T. Hanby1, David M. Grant1, Bryan W. Stuart1, Christopher Gerada2,
Miquel Gimeno-Fabra1
Advanced Materials Research Group, Faculty of Engineering University of Nottingham, Nottingham
1

NG7 2RD, UK
Power Electronics Machines and Control Group, Faculty of Engineering University of Nottingham,
2

Nottingham NG7 2RD, UK; e-mail: [email protected]

Keywords: magnetron sputtering, reactive sputtering, pulsed reactive sputtering, alumina, electrical
insulation

Thin films of Al2O3 up to 2.5 μm thick were deposited onto copper substrates for high thermal
stability electrical insulation, for application in aerospace and automotive industries. Inclu-
sion of SiO2 layers and blends have been investigated in an attempt to reduce leakage current.
Isolative measures with improved thermal stability are of great interest for high temperature
applications such as in motor windings. Current polymer insulation solutions can involve a
number of multi layers and normally have a maximum stability of about 300 °C, with poly-
imide insulation being a common solution. Ceramic insulation systems are often limited by
a thick coating which is normally deposited by solution based methods. These thicker coat-
ings can suffer from mechanical problems, poorer bending radius being a concern, especially
in winding applications. Thin films are of further interest within the electronics industry in
respect to capacitor and multi-layered electronics.1
Physical vapour deposition (PVD) using reactive magnetron sputtering was used as it is
highly tuneable and has the ability to deposit oxide and non-stoichiometric oxide coatings
with and without additions. Here direct current (DC) and pulsed DC power (PDC) have been
used to deposit Al2O3 films onto copper substrates in order to test mechanical and electrical
properties with respect to their substrate.2 Adhesion of DC films was improved by the incor-
poration of a mixed aluminium copper interlayer. Pull off adhesion tests showed good adhe-
sion ranging from 63.0 to 76.2 MPa strength for adhesive and cohesive failures. This criterion
was met for films below 2 μm thick, with thicker films failing below 25 MPa due to increased
stresses incorporated into the film during the longer depositions. Dielectric breakdown prop-
erties were unaffected by the use of this interlayer. However the use of pulsed power has
improved the film adhesion and electrical properties by removing damage caused by target

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arc events.3 Different pulsed power delivery profiles were investigated to optimise the re-
moval of target arcing seen in reactive DC sputtering and prevented deposition of elemental
aluminium as observed in DC films; while maintaining practical deposition rates. Pulsing
parameters including duty cycle and frequency and substrate bias were explored further to
maximise dielectric and adhesive strength and increase film density.

References
1. S.H. Song, M.Y. Lee, G.B. Lee and B.-H. Choi, J. Vac. Sci. Technol. A Vacuum, Surfaces, Film.,
2017, 35, 01B110.
2. H. Bartzsch, D. Glöß, B. Böcher, P. Frach and K. Goedicke, Surf. Coatings Technol., 2003, 174,
774–778.
3. M. Meissner, T. Tolg, P. Baroch and J. Musil, Plasma Process. Polym., 2011, 8, 500–504.

817
New ZnO-based glass ceramic sensor for H2 and NO2 detection
M. Hassan1, Ahmed S. Afify1, M. Ataalla2,3, D. Milanese1, J.M. Tulliani1
Politecnico di Torino, Department of Applied science and Technology, INSTM Research Unit
1

PoliTO, LINCE Laboratory, 10129 Torino, Italy

Department of Materials Science, University of Chemical Technology and Metallurgy, 1756 Sofia,
2

Bulgaria
Department of Chemical engineering, Faculty of Engineering, Badr University in Cairo (BUC),
3

Egypt

The demand for rugged and reliable chemical sensors able to operate in harsh industrial
environments, as well as for public health and security is still high. These sensors have to
cover a wide range of industries such as metallurgy, glass, ceramic, paper, automotive, aero-
space and energy.1 Yet, despite the high request, major advances in these sensors in terms of
simple structure, lower cost, better selectivity, durability and reliability are always needed.
Thus, in this research, ZnO crystals were grown from a glassy matrix having the composition
58ZnO:4WO3:4Bi2O3:33.3B2O3 by melt quenching technique. The powder was character-
ized by laser granulometry, thermal analysis and Field Emission-Electron Scanning Micros-
copy. XRD pattern evidenced the presence of two different crystalline phases: ZnO (JCPDS
card no°1389-0511) and Bi2WO6 (JCPDS card no°1373-2020). ZnO was the main crystalline
phase, whereas Bi2WO6 appeared as the secondary crystalline phase. A gas sensor was then
fabricated using a ZnO sol–gel phase as a permanent binder of the glass-ceramic to a com-
mercial alumina substrate with interdigitated platinum electrodes. The gas sensing properties
of this material were investigated at different operating temperatures with respect to water
vapor, NH3, H2 and NO2. The sensor response depends on the operating temperature and on
the concentration of the target gas. The highest response to NO2 was observed at an operating
temperature of 150 ºC. However, a certain interference with water vapor was evidenced at
this temperature, even if the higher the working temperature (250 °C in our case), the lower
the influence of water vapor is.

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Though the response of our sensor in the sub-ppm NO2 concentration range was not ex-
plored, the observed results are comparable with recent data from the literature.2–4
Glass ceramic materials are thus promising in sensors application not only as humidity
sensors but also for detecting other gases.

References
1. S.A. Akbar, C.-O. Park, J. Mat. Sci. 38 (2003) 4237.
2. K. Wetchakun, T. Samerjai, N. Tamaekong, C. Liewhiran, C. Siriwong, V. Kruefu, A. Wisitsoraat,
A. Tuantranont, S. Phanichphant, Sens. Actuator B Chem. 160 (2011) 580–591.
3. S. Liu, B. Yu, H. Zhang, T. Fei, T. Zhang, Sens. Actuators B Chem. 202 (2014) 272–278.
4. Z. Ul Abideen, A. Katoch, J.-H. Kim, Y.J. Kwon, H.W. Kim, S.S. Kim, Sens. Actuators B Chem.
221 (2015) 1499–1507.

090
Structural, optical, and optoelectronics properties of Cr incorporated
WSe2 layered compounds
Ching-Hwa Ho1*, Wei-Hao Chen2
1
Graduate Institute of Applied Science and Technology, National Taiwan University of Science and
Technology, Taipei 106, Taiwan; *e-mail: [email protected]
2
Department of Electrical Engineering, National Taiwan Ocean University, Keelung 202, Taiwan
Keywords: transition-metal dichalcogenides, 2D material, optical property, structural property, crys-
tal growth

We have grown chromium-incorporated W1-xCrxSe2 single crystals with different Cr compo-

sitions of x = 0, 0.01, 0.05, 0.1, and 0.2 using chemical vapor transport (CVT) method with
iodine as the transport agent. X-ray diffraction (XRD), Raman measurement, X-ray photo-
emission spectroscopy (XPS) are implemented to characterize structural phase and compo-
sition of the W1-xCrxSe2 (0 ≤ x ≤ 0.2) series crystals. Thermoreflectance (TR) measurement
investigates band-edge excitonic and interband transitions. The XRD results show that lattice
constants of the W1-xCrxSe2 (0 ≤ x ≤ 0.2) series crystals decreased with the Cr content was
increased in the layer compounds. For the higher Cr composition of x = 0.1 and 0.2 crys-
tals, some additional XRD peaks corresponding to the Cr-Se system (other than WSe2) are
detected. The Cr 2p1/2 and 2p3/2 electron peaks in the XPS spectra also reveal that Cr3+ and
Cr6+ features can be detected in the W1-xCrxSe2 series. Raman spectroscopy shows that the
general E12g and A1g related vibration modes shift to lower wavenumber with respect to the
increase of the Cr content in the W1-xCrxSe2 (0 ≤ x ≤ 0.2) series. For the higher Cr of x = 0.1
and x = 0.2 samples, two extra peaks related to the chromium dopant effect are also detected.
The XRD and Raman results show that the lower Cr content crystals (i.e. W0.99Cr0.01Se2 and
W0.95Cr0.05Se2) are maybe similar to that of WSe2, while the higher Cr compositions of x = 0.1
and x = 0.2 may coexist with major WSe2 and a little Cr-Se phase. The A and B excitons of
the Cr doped WSe2 demonstrate an energy blue shift behavior with respect to the increase of
the Cr content in the crystals detected by TR. The band gap enlargement can also be verified

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by surface Schottky diodes of undoped WSe2 and W0.8Cr0.2Se2 using Cu as the Schottky con-
tact. The forward cut-in voltage of the W0.8Cr0.2Se2 surface Schottky diode is increased with
respect to that of the undoped sample. Meanwhile the reversed breakdown characteristic has
also been improved in the Cr-incorporated WSe2 surface Schottky diode.

References
1. J.A. Wilson and A.D. Yoffe, “The transition metal dichalcogenides – discussion and interpretation
of the observed optical, electrical and structural Properties,” Adv. Phys., 18, pp. 193–335, 1969.
2. C.H. Ho, C.S. Wu, Y.S. Huang, P.C. Liao, K.K. Tiong, “Temperature dependence of energies and
broadening parameters of the band-edge excitons of Mo1-xWxS2 single crystals,” J. Phys. Condens.
Matter, 10, pp. 9317–9328, 1998.
3. C.H. Ho, “Thickness-dependent carrier transport and optically-enhanced transconductance gain in
III-VI multilayer InSe”, 2D Mater., 3, p. 025019, 2016.

277
Modification of a-site stoichiometry
in NayBixTiO3-BaTiO3 (NBT-BT)-based capacitor materials
Marion Höfling*, Sebastian Steiner, Till Frömling
Department of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Straße 2
64287 Darmstadt, Germany; *e-mail: [email protected]
Keywords: NBT-based, non-stoichiometry, impedance spectroscopy, capacitor

High-temperature capacitor materials are required to enable reliable electrical circuits in en-
gineering applications with elevated operation temperature. The demand for capacitor ma-
terials which can handle temperatures higher than 200 °C, with only a small deviation of
the key properties of a capacitor, has increased significantly in the last years.1 In future,
electronic components shall be placed close to areas with elevated temperatures for economic
reasons.1 Therefore, it is of major importance to identify promising candidates for capacitors
with advanced temperature stable properties such as capacitance, permittivity, loss factor,
energy density and volumetric efficiency.2 One of the most promising materials are the Nax-
BixTiO3 (NBT)-based materials. These show a broad permittivity plateau and good electrical
properties at elevated temperatures.1,3 However, to further decrease the dielectric loss of the
samples mobile ionic defects need to be reduced.4
In this work the impact of A-site non-stoichiometry on the loss will be evaluated. Three high-
temperature dielectric compositions, 0.82(0.94NaxBixTiO3-0.06BaTiO3)-0.18(K0.5Na0.5NbO3)
(NBT-BT-KNN), 0.85(0.94 NaxBixTiO3-0.06BaTiO3)-0.15(CaZrO3) (NBT-BT-15CZ) and
0.80(0.94 NaxBixTiO3-0.06BaTiO3)-0.20(CaZrO3) (NBT-BT-20CZ) with x = 0.49, 0.5 and
0.51 are synthesized with the solid state synthesis route to investigate their potential as high-
temperature capacitor materials. With the help of the Impedance Spectroscopy (IS), Permittiv-
ity measurements und E-P-Curves, the characteristic electrical properties of a capacitor mate-
rial are determined. Additionally, X-ray diffraction (XRD), Secondary Electron Microscopy
(SEM) are used to evaluate the influence of the Bi-non-stoichiometry on the microstructure.

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References
1. A. Zeb and S.J. Milne, “High temperature dielectric ceramics: A review of temperature-stable high
permittivity perovskites”, J. Mater. Sci.- Mater. Electron., 26, pp. 9243–9255, 2015.
2. A.J. Moulson and J.M. Herbert. Electroceramics: Materials, Properties, Application: Second Edi-
tion. Wiley, West Sussex, England, 2003.
3. R. Dittmer, W. Jo, D. Damjanovic, and J. Rödel, “Lead-free high-temperature dielectrics with wide
operational range”, J. Appl. Phys., 109, 034107, 2011.
4. I.-T. Seo, S. Steiner, T. Frömling, “The effect of A site non-stoichiometry on 0.94(NayBix)TiO3-
0.06BaTiO3”, J. Eur. Ceram. Soc., 37 pp. 1429–1436, 2017.

232
Investigation of silicon content and distribution in YAG ceramics
during the production process
Jan Hostaša1*, Andreana Piancastelli1, Sudeep Jung Pandey2, Mauro Martinez3,4,
Matthieu Baudelet2,3,5, Romain Gaume5,6, Thierry Epicier7
1
CNR-ISTEC, Institute of Science and Technology for Ceramics, National Research Council of Italy,
Via Granarolo 64, 48018 Faenza, Italy; *e-mail: [email protected]
2
Physics Department, University of Central Florida, Orlando, FL. 32816, USA
3
National Center for Forensic Science, University of Central Florida, Orlando, FL. 32816, USA
4
Chemistry Department, University of Central Florida, Orlando, FL. 32816, USA
5
CREOL – The College of Optics and Photonics, University of Central Florida, Orlando, FL. 32816,
USA
6
NanoScience Technology Center, University of Central Florida, Orlando, FL. 32816, USA
7
University of Lyon, INSA of Lyon, MATEIS UMR CNRS 5510, Bât. B. Pascal, 69621, Villeurbanne,
France
Keywords: transparent ceramics, YAG, silicon, sintering aid, SiO2, LIBS

Silica is typically used as a sintering aid in the production of transparent YAG (Y3Al5O12)
ceramics, allowing for the achievement of nearly pore-free microstructures and the lowering
of sintering temperatures. However, it was also found to introduce undesired color centers
in the sintered material1 as well as segregate at grain boundaries leading to the formation of
amorphous or crystalline secondary phases (Y2SiO5),2 which decrease the optical properties
and compromise the use of the material as a laser medium. Thus, while the addition of silicon
(in the form of SiO2 or as tetraethyl orthosilicate, TEOS) is often required, it is desirable
to obtain materials with low Si content and homogeneous distribution. This work studies
the amount of Si and its distribution in YAG and Yb:YAG ceramic materials produced by
reaction sintering of a mixture of oxide powders throughout the whole preparation process.
Monitoring the Si content step by step provides important information about the reproduc-
ibility and consistency of the fabrication process, crucial for any further optimization. We
have shown that Laser-Induced Breakdown Spectroscopy (LIBS) allows sensitive and ac-
curate quantification of silicon in ceramics down to 60 ppm and our experimental LIBS setup
was used to analyze the evolution of the silicon content in samples at various steps of the
fabrication process.3 The distribution of Si in sintered ceramics was studied with High Reso-

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lution TEM to detect any possible nano-precipitates, and EDX nano-probe chemical analysis
to check for segregation at grain boundaries and evaluate Si concentration within the YAG
grains. The amount of Si present in the sintered materials has been found to be as low as 30%
of that introduced into the initial mixture.

References
1. R. Gaume, Y. He, A. Markosyan and R.L. Byer, “Effect of Si-induced defects on 1 µm absorption
losses in laser-grade YAG ceramics”, J. Appl. Phys., 111, pp.093104, 2012.
2. L. Esposito, T. Epicier, M. Serantoni, A. Piancastelli, D. Alderighi, A. Pirri, G. Toci, M. Vannini, S.
Anghel and G. Boulon, “Integrated analysis of non-linear loss mechanisms in Yb:YAG ceramics for
laser applications”, J. Eur. Ceram. Soc., 32, pp. 2273–2281, 2012.
3. S.J. Pandey, M. Martinez, J. Hostaša, L. Esposito, M. Baudelet and R. Gaume, “Quantification of
SiO2 sintering additive in YAG transparent ceramics by Laser-Induced Breakdown Spectroscopy
(LIBS)”, Opt. Mater. Express (submitted)

382
Hexagonal tungsten trioxide produced by novel solution combustion
method
S. Samet Kaplan*, C. Bora Derin, Onuralp Yucel, M. Şeref Sonmez
Department of Metallurgical and Materials Engineering, Istanbul Technical University, Sarıyer,
34469, Istanbul, Turkey; *e-mail: [email protected]
Keywords: solution combustion synthesis, tungsten trioxide, fuel and oxidizer ratio

Solution Combustion Synthesis (SCS) is a novel method to produce powders having high
surface area and high purity within a short period of time. This uniqueness of the process
depends on three features. First, because of liquid reaction medium, reactants can be mixed
at molecular scale homogenously. Second, high reaction temperature allows to produce high
crystallinity and high purity products. Third, short process time and huge amount of gasses
released during reaction allows us to produce nano scale products with high surface area.
This method is based on self-propagating reaction after an ignition temperature is reached be-
tween oxidative precursor (metal nitrates) and fuels (urea, glycine, oxalic acid, etc.). There is
a critical ratio between fuel and oxidizer to control combustion efficiency and powder prop-
erties. Once that ratio is equal to 1, it means that reaction is occurring at highest efficiency.1
Tungsten trioxide is an attractive material because of its wide range of applications. Due to
its high coloration efficiency and high cyclic stability, it is a good candidate for thermochro-
mic applications such as smart windows, antiglare mirrors, high contrast displays, and active
camouflage. In these applications, WO3 is generally preferred to be amorphous because of
higher electrochromic performance than crystalline phase. However, amorphous phase is not
robust as crystalline phase, and causing to some problems in application. Nano structure can
resolve this problem by increasing the effective surface area.2,3
In this study, is aimed to develop a nano scale hexagonal WO3 having the same electro-
chromic efficiency as in amorphous state by using unique capability of SCS at producing

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nano sized powders. In that perspective, effect of SCS parameters such as fuel type, fuel
oxidizer ratio, homogenization on final product were studied. XRD, SEM, and BET analysis
were conducted to determine powder properties.

References
1. Mukaysan A.S., Epstein P., Dinka P., Solution Combustion Synthesis of Nanomaterials, Proceeding
of the Combustion Institute, 31, 2007, 1789–1795.
2. Ma D., Wang H., Zhangb Q., Li Y., Self-weaving WO3 nanoflake films with greatly enhanced elec-
trochromic performance, J. Mater. Chem., 2012, 22, 16633.
3. Rajagopal S., Nataraj D., Mangalaraj D., Djaoued Y., Robichaud J., Khyzhun O.Y., Controlled
Growth of WO3 Nanostructures with Three Different Morphologies and Their Structural, Optical,
and Photodecomposition Studies, Nanoscale Res Lett (2009) 4:1335–1342.

613
The effect of vibratory milling on the electrical properties of zinc oxide
varistors
Maura C. Kelleher1, M.S.J. Hashmi2
School of Mechanical & Design Engineering, Dublin Institute of Technology, Bolton Street,
1

Dublin 1, Ireland; e-mail: [email protected]

School of Mechanical Engineering, Dublin City University, Glasnevin, Dublin 9, Ireland;
2

e-mail: [email protected]
Keywords: ZnO varistors, vibratory milling, powder characteristics, zirconium concentration, electri-
cal properties

Zinc oxide varistors are surge protection devices which are typically made from zinc oxide as
the main constituent and smaller concentrations of bismuth, antimony, manganese, cobalt, tin
and nickel oxides. These smaller concentrations are collectively termed as multi-elemental
metal oxide additives (MMOA)1. Their quantity in total is 4 mol. %. The electrical proper-
ties are highly sensitive to the composition, phase, purity, size, morphology and fabrication
processes of all of the metal oxides present from the starting powder stage to the final surge
device. In this paper the authors describe and discuss the effect of multi-elemental oxide ad-
ditives, having been milled for different durations using a vibratory mill with cylindrical zir-
conia media, on the electrical properties. The electrical properties include each aspect of the
I-V curve and the energy absorption capability. A commercial ZnO varistor formulation was
used and the final sintered varistor devices formed were similar in size to commercial high
voltage devices. A strong relationship between the milling duration of the multi-elemental
oxide additives and most of the electrical properties are observed.

Reference
1. M.C. Kelleher and M.S.J. Hashmi, “The effect of vibratory milling on the powder properties of
zinc oxide varistors”, J. Mat. Proc. Tech., 201, pp. 645–650, 2008.

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680
Quality factor control of MgTiO3-based ceramics by cation substitution
Eung Soo Kim
Department of Materials Engineering, Kyonggi University, Suwon, Gyeonggi-do 16227, Korea;
e-mail: [email protected]
Keywords: magnesium titanate, microwave dielectric properties, ilmenite structure, octahedral distor-
tion

Microwave dielectric materials with high quality factor, required for rapid signal propagation
and prominent frequency selectivity at microwave and/or millimetre-wave frequencies, are in
great demand for 5G wireless communication systems, such as global communication satel-
lites, mobile communications, and radar detectors. MgTiO3-based ceramics, as high quality
factor dielectrics, have been widely investigated recently regarding the further improvement
of quality factor by the substitution of divalent and/or tetravalent cations for Mg2+ and/or Ti4+
of MgTiO3. Most of these studies discussed for the relationships between the dielectric prop-
erties of MgTiO3-based ceramics and extrinsic factors, such as a secondary phase, density,
and microstructure. However, fundamental studies should be carried out to understand the
dependence of the microwave dielectric properties on the structural characteristics, which
enables control and improvements in the microwave dielectric properties of MgTiO3-based
ceramics. MgTiO3-based ceramics with ilmenite structure are composed of two types of oc-
tahedra: divalent-cation octahedra (MgO6) and tetravalent-cation octahedra (TiO6). The two
types of octahedra share edges along the a-axis and faces along the c-axis. The bond lengths
between the cation and oxygen ions in oxygen octahedra are affected by the ionic charac-
teristics of the central ion. Therefore, the substitution of other cations at Mg or Ti sites may
change the bond length and bond strength, which affects the dielectric properties of MgTiO3-
based ceramics as well as the characteristics of the ilmenite crystal structure. By changing
the type of divalent and/or tetravalent cation, the characteristics of the bond between the cat-
ions and oxygen ions in oxygen octahedra can be modifies to affect the dielectric properties
of MgTiO3-based ceramics. Typically, three types of cation substitutions will be discussed;
single ion substitution for Mg- and/or Ti-site, aliovalent cations substitution for Ti-site, and
nonstoichiometric substitution for Ti-site, based on the relationships between the structural
characteristics and microwave dielectric properties of MgTiO3-based ceramics.

References
1. R.J. Cava, “Dielectric materials for applications in microwave communication”, J. Mat. Chem., 11,
pp. 54–62, 2001.
2. C.H. Shen, C.L. Huang, W.T. Chen, C.L. Pan, “Microwave dielectric properties of (1-x) (Mg0.95Ni0.05)
TiO3-x(Ca0.8Sr0.2)TiO3 ceramic system with near-zero temperature coefficient”, Int. J. Appl. Ceram.
Technol., 9, pp. 447–453, 2012.
3. H.J. Jo, E.S. Kim, “Effect of structural characteristics on microwave dielectric properties of
­MgTi1-x(Mg1/3B2/3)xO3 (B=Nb,Ta)”, J. Eur. Ceram. Soc., 36, pp. 1399–1405, 2016.

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038
Fabrication of transparent MgAl2O4 spinel via spray freeze drying of
microfluidized slurry
Ha-Neul Kim1, Jin-Myung Kim1, Mi-Ju Kim1, Jae-Woong Ko1, Young-Jo Park1, Kisu Lee2,
Doo Hyun Choi2
1
Engineering Ceramics Research Group, Korea Institute of Materials Science, 797 Changwondaero,
Changwon, Gyeongnam, 51508, South Korea
2
Agency for Defence Development, 488 Bugyuseongdaero, Yuseong, Daejeon, 34186, South Korea
Keywords: transparent, MgAl2O4, spray freeze drying, freeze granulation, microfluidization

Spherical granules were prepared from a monodispersed slurry by combining the microflu-
idization method1 and the spray freeze drying (SFD) process2,3. Starting with those prepared
granules, transparent MgAl2O4 ceramics were fabricated through the pressureless sintering
and following hot-isostatic-pressing. As a result of comparison with a poly-dispersed slurry
by ball-milling method, it was successful to have a mono-dispersed state by microfluidization
method, and 80% of visible in-line transmittance was obtained at 600 nm wavelength from
a process starting with the monodispersed slurry of low solid content. The microstructure
analysis of the green bodies, pre-sintered bodies and hot-isostatic bodies of MgAl2O4 ceram-
ics, revealed that the slurry dispersion process should be controlled to a high level in order to
suppress scattering sources such as pores and microcracks affecting the in-line transmittance
of visible light.

Fig. 1. (a) Spherical granules from SFD process (b) In-line transmittance of specimens

References
1. J.M. Kim, H.N. Kim, Y.J. Park, J.W. Ko, J.W. Lee, and H.D. Kim, “Fabrication of transparent
MgAl2O4 spinel through homogeneous green compaction by microfluidization and slip casting”,
Ceram. Int. 41, pp. 13354–13360, 2015.
2. M. Stuer, Z. Zhao and P. Bowen, “Freeze granulation: Powder processing for transparent alumina
applications”, J. Eur. Ceram. Soc., 32, pp. 2899–2908, 2012.
3. J. Binner and B. Vaidhyanathan, “Processing of bulk nanostructured ceramics”, J. Eur. Ceram. Soc.
28, pp. 1329–1339, 2008.

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452
Glass/Al2O3/GO,CNT composite with high bending strength and
thermal conductivity for package of super capacitor
Tae-Ho Lee, Sung-Hoon Cho, Sahn Nahm*
Department of Materials Science and Engineering, Korea University, 1-5 Ga, Anam-Dong, Korea;
*
e-mail:[email protected]
Keywords: LTCC, glass/Al2O3 ceramic, bending strength, thermal conductivity

A new LTCC ceramics consisting of CaO-B2O3-SiO2 (CBS glass)/Al2O3/GO,CNT are intro-

duced in this paper. Glass/Al2O3/GO,CNT composites were fabricated and their sintering
mechanism, mechanical and thermal properties were investigated. The composite containing
CBS, 40wt% Al2O3 and 1wt% GO0.25CNT0.75, which was sintered at 900 oC for 1 h and subse-
quently annealed at 850 oC for 1 h, showed a high relative density of 92.5% of the theoretical
density. Moreover, it also showed a high bending strength and good thermal conductivity of
420 MPa and 5.51 W/mk, respectively. Microstructure characterization and ceramic-metal
additive model analysis indicate that the increased thermal conductivity of this composites
was due to the formation of thermal connecting link networks in the composite by CNT. These
results showed that the CBS glass/Al2O3/GO,CNT composite can be used for the package of
super capacitors. In this work, the detailed investigation on variation of microstructure with
respect to sintering conditions was studied. Moreover, the relation between microstructure
and mechanical and thermal properties of the specimens were also discussed in this work.

687
New lead-free perovskite compounds
with (A1/2Bi1/2)(Mg1/3Nb2/3)O3 formula (A = Na,K)
Jerome Lelievre*, Pascal Marchet
Université de Limoges, SPCTS, UMR 7315, CEC, 12 rue Atlantis F-87000 Limoges, France;
*
e-mail: [email protected]
Keywords: lead-free materials, perovskite, electrical properties

Nowadays, PbZr(1-x)TixO3 (PZT) and Pb(Mg1/3Nb2/3)O3 – PbTiO3 (PMN – PT) compounds are
the most common piezoelectric ceramics owing to their high electromechanical performance
and low cost. However, because of the restrictions on the use of hazardous substances, such
as lead, the PZT and PMN materials must be substituted by lead-free compounds. These
new materials are thus highly investigated for their piezoelectric properties. Actually, the
most promising compounds are (i) alkaline-niobates, such as (Na,K)NbO3, (ii) alkaline and
bismuth titanates, such as (Na, K)1/2Bi1/2TiO3 (NBT and KBT), and (iii) solid solutions based
on these compounds such as Na1/2Bi1/2TiO3-BaTiO3.

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The present work is devoted to the search of new lead-free materials based on NBT and
KBT, initially reported by Smolenskii et al. in 1961. Indeed, these two compounds demon-
strate the possibility to replace the lead cations in A-site of perovskite compound PbTiO3 by
the alkali/bismuth pseudo-ion (Na+/Bi3+) or (K+/Bi3+). If this substitution has been success-
fully tested for NBT and KBT titanates, this is not the case for other perovskites compounds
containing lead in A-site of the perovskite lattice. For example, only one article reports brief-
ly this possibility in PMN. However, there is no more information about the structure of the
compounds or its properties, except that the synthesis induces a large number of secondary
phases.
Thus, the two compositions (Na1/2Bi1/2)(Mg1/3Nb2/3)O3 (NBMN) and (K1/2Bi1/2)(Mg1/3Nb2/3)
O3 (KBMN) have been synthesized by solid-state reaction, with a two steps B-site precur-
sor route, similar to the one used for PMN. In both case, the XRD patterns evidence for the
formation of a perovskite compound, though it is not a pure phase. Indeed, secondary phases
remained in each composition. But using a systematic study of the synthesis conditions, we
managed to have less than 5% of impurity at the end of the thermal cycles.
These two compounds have been studied by XRD and Neutron Diffraction, in order to
identify their crystalline structure and the nature of the secondary phases formed during syn-
thesis. The dielectric and ferroelectric / piezoelectric properties of these compounds are pres-
ently under investigation, in order to determine if they could be candidates to the replacement
of the PZT and PMN compounds.

755
Luminescent properties of lanthanide oxide and fluoride doped ternary
silicon nitride-based phosphors
Zoltán Lenčéš1, Ismail Ibrahim1, Adriana Czímerová1, Lubomír Benco2, Pavol Šajgalík1
1
Institute of Inorganic Chemistry, Slovak Academy of Sciences, 84536 Bratislava, Slovakia
2
Faculty of Physics and Centre for Computational Materials Science, University of Vienna,
A-1090 Wien, Austria
Keywords: luminescence, ternary nitrides, lanthanide

Lanthanide (Ln) doped LaSi3N5 based phosphors were prepared experimentally and their
electronic structure and band gaps were calculated using the screened Coulomb hybrid
HSE06 functional. The synthesized LaSi3N5:Ce phosphor emits violet-blue light, LaSi3N5:Eu
– green-yellow and LaSi3N5:Sm red light. There were a differences in the shape of emission
bands depending on the type of lanthanide dopant, i.e. oxide or fluoride.
The calculations showed that with increasing atomic number the band gap of Ln3+-doped
LaSi3N5 smoothly decreases from 4.6 eV (Ce) to 0.5 eV (Eu). The band gap of Ln2+-doped
LaSi3N5 increases from 0.80 eV (Ce, Pr) to 0.95 eV (Nd, Pm), 1.43 eV (Sm), and to 3.28 eV
(Eu). There was a reasonable agreement between the calculated band gaps and those data
published in the literature or measured on our samples using diffuse reflectance spectroscopy.

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The lanthanides were added experimentally in a form of fluorides (LnF3) and oxides
(Ln2O3). In the case of oxides also the influence of N/O substitution on the band gap of
LaSi3N5 was calculated. The results showed that with increasing oxygen content in the cell
of LaSi3N5 the band gaps decreased by 0.2–0.6 eV. Some of the lanthanides were added to
LaSi3N5 also in the form of fluorides and their photoluminescent properties were compared
with Ln2O3-doped phosphors.
The energy level locations were constructed from the ab initio calculated electronic struc-
tures and compared with the empirical energy level diagram. There is a good agreement
between calculated and experimental data and the method can be used for the design of
phosphors.
Similar to LaSi3N5, also LnF3 and Ln2O3 doped MgSiN2-based phosphors have been pre-
pared and their photoluminescent properties were characterized.

592
Electrical properties of barium titanate ceramics doped with 2.1% La
and 1.0% Mn as a function of temperature and oxygen partial pressure
M. Leprich, W. Preis
Chair of Physical Chemistry, Montanuniversitaet Leoben, Franz-Josef-Strasse 18, A-8700 Leoben,
Austria; e-mail: [email protected]
Keywords: donor-doped barium titanate, impedance spectroscopy, DSC measurements, defect chem-
istry

Donor doped BaTiO3 represents an important model system for interfacially controlled elec-
troceramics.1 It is the aim of this contribution to present the characterization of the electrical
properties of n-type barium titanate as a function of temperature and oxygen partial pressure.
The experimental results are interpreted in terms of a proper defect chemical model. Barium
titanate ceramics doped with 2.1% La and 1.0% Mn have been prepared by means of the Pechi-
ni process. Disk-shaped samples with the nominal compositions Ba0.979La0.021Ti0.99Mn0.01O3-δ
and Ba0.979La0.021Ti1.01Mn0.01O3- have been obtained by isostatic pressing and sintering in air
at 1350 °C. The relative densities are around 90–94% and the mean grain size is in the range
from 0.75 to 1.3 µm. The electrical properties have been measured in air by employing im-
pedance spectroscopy in the temperature range from 35 to 900 °C. Moreover, the oxygen par-
tial pressure has been varied between 1 and 10–20 bar at 900 °C by appropriate gas mixtures of
pure O2, Ar, 1%-O2/Ar, and 1%-H2/Ar. The temperature dependence of the dielectric constant
reveals a Curie-temperature for the ferroelectric - paraelectric phase transition of 70–72°C
which is in close agreement with DSC measurements where a peak of the heat capacity has
been found around 75 °C. In contrast to PTC resistors, the samples of the present study, con-
taining a fairly high amount of dopants, are insulating at room temperature most probably
because of ionic compensation by cation vacancies. The variation of the electronic conduc-
tivity of bulk regions with temperature shows an almost perfect Arrhenius-type behaviour
with activation energies around 1.3–1.4 eV which can be interpreted in terms of trapping

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equilibria of electronic charge carriers by the mixed-valent (redox-active) acceptor co-dopant

(Mn). The oxygen partial pressure dependence of the electronic conductivity under reducing
conditions follows the well-known power law σ ∞ p(O2)1/6 owing to the formation of oxygen
vacancies which are compensated by electrons. In the oxygen partial pressure region above
10–5 bar (oxidizing conditions) the bulk conductivity is almost independent of p(O2), indicat-
ing the predominant ionic compensation of the dopants by cation vacancies which are frozen-
in at 900 °C due to very low cation diffusivities in the perovskite lattice at this temperature.2

References
1. W. Preis, W. Sitte, “Electrical properties of grain boundaries in interfacially controlled functional
ceramics”, J. Electroceram., 34, pp. 185–206, 2015.
2. W. Preis, W. Sitte, “Electronic conductivity and chemical diffusion in n-conducting barium titanate
ceramics at high temperatures”, Solid State Ionics, 177, pp. 3093–3098, 2006.

165
The formation and high EM wave absorption properties of doped
barrium ferrite over millimeter frequency range
Chuyang Liu, Zongrong Wang, Ning Ma, Piyi Du*
School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China;
*
e-mail: [email protected]
Keywords: barium ferrite, Nb doped, absorber, high EM absorption properties

Nowadays, absorbing materials are important in one hand to attenuate electromagnetic pol-
lution arising from explosive development of information technology, and on the other hand
to defend against radar detection in use for the stealth. Recently, the barium hexaferrite Ba-
Fe12O19, a kind of versatile material, has been widely used as permanent magnet and high-
density recording media due to its large saturation magnetization, high coercive force and
corrosion resistivity. Herein, we investigate the ferrite as high quality EM absorption material
in this work, in which the Nb5+-doped barium ferrites of BaFe12-xNbxO19 is prepared by sol-
gel method. The perfect phase of BaFe12-xNbxO19 with x = 0~0.6 can be obtained as they are
prepared at 1100 °C~1300 °C for sintering time of 0~3 h. The plate-like grains form typically
in the ferrite with increasing Nb5+ from x = 0 at 1300 °C to x = 0.6 at 1100 °C, respectively.
Controlled by decreasing barrier of jumping atoms from one grain to the other, the large
grain size of the crystalline phase, reaching 4~6 μm, is obtained in the ferrite with doping
Nb5+ of x = 0.6 at 1300 °C for 3 h. The ε′ and ε″ of the ferrite are relatively high to be ~7.9
and ~0.95 respectively at microwave frequency, being about 2 and >10 times higher than the
ferrite without doping of Nb5+ ion. Controlled by intrinsic natural resonance of Fe3+ ions and
other associated Fe2+ and O– ions formed simultaneously, the multi resonant peaks at different
frequencies are formed in μ′ and μ″ of the ferrite with doping of Nb5+ ions. It will be modified
from the range at high frequency of >40+ GHz to low frequency range of 26~37 GHz based
on the decrease in Ha with substituting for Fe3+ ions by non-magnetic Nb5+ from x = 0 to x =
0.6. With respect to the modification of the multi natural resonance peaks, the related multi

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reflection loss peaks appear at frequency range around millimetre wave of ~35 GHz in the
ferrite with x = 0.6 sintered at 1300 °C for 3 h, with which the broad bandwidth of the wave
absorption of >12 GHz from 28 to 40+ GHz is obtained. Meanwhile, the small RLmin of <-40
dB is revealed with only thin dm of ~0.76 mm being requested in this case due to the high εr
which is much closer to the μr. It is obviously the excellent absorbing material at millimetre
wave absorption.

References
1. J.G. Jia, et al., “Exchange Coupling Controlled Ferrite with Dual Magnetic Resonance and Broad
Frequency Bandwidth in Microwave Absorption”, Sci. Technol. Adv. Mater., 14[4] 045002, 8pp,
2013.
2. C.Y. Liu, et al., “Zr4+ Doping-controlled Permittivity and Permeability of BaFe12-xZrxO19 and the
Extraordinary EM Absorption Power in the Millimeter Wavelength Frequency Range”, J. Mater.
Chem. C, 4[40] 9532–9543, 2016.

074
Broadband spectral upconversion in CaTiO3: Ni2+,Er3+ for solar energy
harvesting
Hom Nath Luitel, Shintaro Mizuno, Yasuhiko Takeda
Toyota Central R&D Labs., Inc., 41-1, Yokomichi, Nagakute, Japan;
e-mail: [email protected]
Keywords: broadband-sensitive upconverter, Ni2+ sensitizers, solar cell, energy

Solar energy harvesting is one of the most important and utmost research directions for the
sustainable society. Upconversion (UC) materials, that utilize two or more low energy pho-
tons to emit a high energy photon, can be applied to improve the conversion efficiency of
present solar cells. There are some reports to utilize Er3+-doped upconverters for solar energy
harvesting but marginal improvement has been realized due to the narrow absorption band
at 1450–1600 nm.1
Recently, we have reported broadband-sensitive UC in Er3+, Ni2+ codoped CaZrO32 and
La(Ga,Sc)O33 and demonstrated spectral conversion of 1100–1600 nm photons to 980 nm.
Ni2+ ions located at the centers of octahedrons absorb 1100–1450 nm photons and transfer
the energies to the Er3+ ions. Thus, 1100–1450 nm photons are also upconverted to 980 nm,
in addition to 1450–1630 nm photons that are directly absorbed by the Er3+ ions, as shown
by the excitation spectrum in Fig. 1. However, those upconverters suffer from low UC ef-
ficiency. Here, we report remarkable improvement of the UC efficiency in the newly devel-
oped CaTiO3:Er3+,Ni2+ broadband-sensitive upconverter. Effect of Ca/Ti composition played
a vital role to improve the UC emission due to more efficient Ni2+ sensitization and improved
UC of Er3+ itself.
The newly developed broadband-sensitive upconverter can be applied to boost the output
power of solar-pumped lasers. A 980 nm laser emission can be achieved using Er3+-doped
upconverters for the laser media, where photons with wavelengths longer than 980 nm would

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also contribute to laser emission. When these are coupled with crystalline silicon solar cells
(current density ~40 mA/cm2), 7.8 mA/cm2 gain can be achieved that accounts ~4.8% effi-
ciency improvement (absolute), supposing perfect UC.

Fig. 1. (a) Broadband-sensitivity of the CaTiO3:Er,Ni upconverter along

with Ni2+ and Er3+ absorption bands, and solar spectrum

Fig. 1. (b) Broadband-sensitivity of the CaTiO3:Er3+,Ni2+ upconverter compared

with AM1.5 solar spectrum

References
1. C.M. Johnson, S. Woo, and G.J. Conibeer, IEEE J. Photovolt., 4, 799–806, 2014.
2. H.N. Luitel, S. Mizuno, T. Tani, Y. Takeda, RSC Adv., 6, 55499–55506, 2016.
3. Y. Takeda, S. Mizuno, H.N. Luitel and T. Tani, Applied Physics Letters, 108, 043901, 2016.

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577
Synthesis and properties of lead-free BNBT-based PTCR thermistor
ceramics
Daniel Mächler, Jörg Töpfer
Department of SciTec, Univ. Applied Sciences Jena, Carl-Zeiss-Promenade 2 07745 Jena, Germany;
*
e-mail: [email protected]
Keywords: PTCR thermistors, perovskites, semiconducting oxides

PTCR (Positive Temperature Coefficient of Resistivity) ceramics show an anomalous in-

crease of their electrical resistance near the Curie temperature (Tc). These components are
typically used as over-current protection and as self-regulating heaters. Lead-substituted
barium titanate (BT) materials are typically used for heater applications. (1–x) (Bi1/2Na1/2)
TiO3 – (x)BaTiO3 (BNBT) perovskites were reported as alternative lead-free PTCR mate-
rial. We report on investigations of the PTCR behavior of several compositions of the BNBT
solid solution. Starting from BT, Tc is increased upon BNT addition. Since BNBT ceramics
are insulators, semiconducting behavior is achieved through n-type donor doping. Sinter-
ing in reducing atmosphere followed by a re-oxidation in air was investigated as alternative
route. Unfortunately, both methods result in limited PTCR performance. Recently, CaO-
substituted BNBT ceramics were proposed as alternative lead-free BNBT PTCR thermistor
compositions.1 We will present the results of CaO-substituted BNBT perovskites and will
discuss correlations between composition, microstructure and PTCR properties. Addition of
CaO significantly lowers the sintering temperature and allows sintering at 1235 °C. 0.05%
SiO2 effect the sintering behavior and increases the resistivity jump while keeping a low
room-temperature resistivity. 0.02% SiO2 addition increases the room temperature resistivity
significantly.2 Even larger amounts of SiO2 precipitate as second phase. Acceptor dopants Mn
or Fe are used to optimize the PTCR behavior. These dopants induce a sharper rise of resis-
tivity at the Curie temperature. We will discuss the synthesis, microstructure formation and
effect of dopants on the performance of CaO-substituted BNBT ceramics as PTC thermistors.

References
1. S.M. Sze. M.A. Zubair, H. Takeda, T. Hoshina, T. Tsurumi, “Synthesis of lead-free air-sintered Ba-
TiO3 – (Bi0.5Na0.5)TiO3 based positive-temperature-coefficient of resistance ceramics by Ca addition
and the defect chemistry of semiconductivity”, Jpn. J. Appl. Phys., 52, 09KG01-7, 2013.
2. D. Mächler and J. Töpfer, “Effect of SiO2 sintering additive on the positive temperature coefficient
of resistivity (PTCR) behavior of (Bi1/2Na1/2)0.10Ba0.90TiO3 + CaO ceramics”, Mat. Res. Bull.
89, pp. 217–223, 2017.

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453
Electrocaloric effects and temperature distribution analysis
of BaTiO3-based ceramics and multi-layer capacitor
Hiroshi Maiwa
Department of Materials and Human Environmental Sciences, Shonan Institute of Technology,
1-1-25 Tsujido-Nishikaigan, Fujisawa, Japan; e-mail: [email protected]
Keywords: electrocaloric effects, BaTiO3, lead-free, multi-layer capacitor

The electrocaloric effect (ECE) is a phenomenon in which a material shows a reversible

temperature change under an applied electric field. There has been some problem in the con-
ventional refrigerator. Since the conventional refrigerator operates by using a compressor,
vibration generation is inevitable. The other disadvantage includes the difficulty in down-
scaling. From the viewpoint of the refrigerator innovation, new refrigerators based on the
new mechanism are expected. ECE is considered to be one of the new cooling mechanisms.
By using ECE, the application to compact a high energy-effective, inexpensive, and safe re-
frigerator would be considered. In order to create ECE cooling devices, materials with large
ECEs are required. For direct measurement of the ∆T, there are some difficulties. Most prob-
ably due to these difficulties, the reports on the direct measurement of ∆T are limited thus far.
In this study, the electrocaloric temperature change, ∆T, due to applied ∆E, of the BaTiO3-
based ceramics is estimated and directly measured. Temperature-electric field (T-E) loops
of the Ba(Zr,Ti)O3 and (Ba,Sr) Ti)O3 ceramics and BaTiO3-based multi-layer capacitor are
measured. ∆T of 0.7K are observed in the BaTiO3-based multi-layer capacitor at room tem-
perature. The comparison with the estimations from indirect approach based on Maxwell’s
equation will be discussed. And temperature distribution analysis of the BaTiO3-based multi-
layer capacitor will be discussed for the realization of the cooling devices.

References
1. M. Valant, Progress in Materials Science, 157(6): pp.980–1009, 2012.
2. J. Wang, T. Yang, K. Wei, and X. Yao, Appl. Phys. Lett., 102: 152907, 2013.
3. H. Maiwa, Jpn. J. Appl. Phys., 54: 10NB08, 2015.
4. H. Maiwa, Jpn. J. Appl. Phys., 55: 10TB09, 2016.

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474
Effect of electrode configuration on dielectric strength testing
Bjoern Mieller, Wolfgang Guether, Torsten Rabe
Division Advanced Technical Ceramics, Bundesanstalt für Materialforschung und –prüfung (BAM),
Unter den Eichen 44-46, 12203 Berlin, Germany;
e-mails: [email protected], [email protected], [email protected]
Keywords: ceramic substrates, dielectric strength, thick-film hybrid technology, ASTM D149

Dielectric strength is a critical property for materials used as electrical insulators. The mea-
surement of dielectric strength is well established and straightforward, but the values deter-
mined in a measurement are strongly dependent on the measurement setup and the specimen
characteristics. For example, the size of the electrodes has a significant influence on the
results. ASTM D149 covers a range of electrode sizes and does not unambiguously prescribe
the quality of the electrodes. Thus, different test setups and procedures are used in the field.
Consequently, a comparison of dielectric strength values of different origins, for example
material supplier and customer, is often not meaningful.
To quantify the influence of the test procedure on the dielectric strength values, a batch of
industrial thick-film substrates has been tested with different electrode configurations under
AC conditions. Opposing cylinders with diameters of 6.4 mm and 25 mm, and a thick-film
metallization with a diameter of 25 mm were used in the study. At least 20 specimens were
tested with each type of electrodes. The results range from 21.7 ± 0.7 kV/mm measured with
printed electrodes to 26.7 ± 1.2 kV/mm measured with reused 6.4 mm cylinders. This means
a difference of 23%. Measurements performed with 6.4 mm cylinder electrodes produce
significantly lower values (ANOVA, α = 0.01) if a new set of electrodes is used for each
measurement instead of reusing the same pair of electrodes for the entire batch. The dielectric
strength measured with new 25 mm cylinders is 11.2% lower than the values determined with
new 6.4 mm cylinders. No significant difference (ANOVA, α = 0.01) was found for measure-
ments with printed electrodes and opposing 25 mm cylinders. Weibull evaluation of the data
showed that all tested electrode configurations result in a similar reliability of the specimen
(Weibull modulus) but in a significantly different characteristic dielectric strength (scale fac-
tor, Bonferroni, α = 0.05).
This study emphasizes the importance of a thorough and comprehensive documentation
and communication of the test procedure for dielectric strength measurements. It further
helps to evaluate the significance of differences in dielectric strength data provided by dif-
ferent sources.

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274
High permittivity BaT iO3 ceramics prepared by SPS
Rosa Moronta Pérez1*, Laurent Boilet1, Philippe Aubry1, Véronique Lardot1, Luc Henrard2,
Olivier Deparis2, Francis Cambier1
1
Belgian Ceramic Research Centre, 4, avenue Gouverneur Cornez, B-7000 Mons, Belgium;
*
e-mail: [email protected]
2
Physics Department, Namur University, 61, rue de Bruxelles, B-5000, Namur, Belgium
Keywords: BaTiO3, SPS, permittivity

Barium titanate (BaTiO3) is a perovskite structure material widely used for numerous electro-
ceramic applications. Its high relative permittivity makes it very common in electronic com-
ponents such as multilayer capacitors (MLCs), PTC thermistors, piezoelectric transducers
and a variety of electro-optic devices. Nevertheless, its applications as MLCs are reduced due
to its relative low Curie temperature (130 °C) and piezoelectric properties lower than those
of Pb(Zr,Ti)O3. However it remains attractive for environmental reasons and the progressive
replacement of lead-based components.1
BaTiO3 ceramics with relative densities above 95% and different grain sizes have been
prepared by Spark Plasma Sintering (SPS). This technique combines uniaxial pressure with
Joule heating and allows achieving fully dense ceramics at comparatively lower temperatures
and within several minutes.2 We have evaluated the sintering behaviour of a commercial
BaTiO3 powder and looked into how the microstructure and the density affect its electrical
permittivity. Some of the samples showed colossal permittivity up to 105 and we have tried
to explain the factors that induce this phenomenon.
This research reports some clues about the differences observed on the as-sintered samples
and after air-annealing and it also performs a comparison between the samples obtained by
conventional sintering in air and by SPS.

Acknowledgment
This study is supported by the FSE and the DGO6 of Wallonia region (Belgium) (Grant No.
ECV320600FD017F/1217883).

References
1. L. Simon-Seveyrat et al. “Re-investigation of synthesis of BaTiO3 by conventional solid-state reac-
tion and oxalate coprecipitation route for piezoelectric applications”, Ceramics International, 33,
pp. 35–40, 2007.
2. B. Li et al. “Densification of uniformly small-grained BaTiO3 using spark-plasma-sintering”, Ma-
terials Chemistry and Physics, 82, pp. 173–180, 2003.

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191
Flexible micro supercapacitor based on laser scribed graphene (LSG)
M. Namdar, Sh. Asl*
Dept. of Materials Eng., University of Tabriz, Tabriz 51666-16471, Iran;
*
e-mail: [email protected]
Keywords: graphene oxide, laser scribed graphene (LSG), scanning electron microscope (SEM),
cyclic voltammetry (CV), galvanostatic charge/discharge (CC)

In the present work, graphene powder has been synthesized by laser scribing method. The
resulted flexible light-scribed graphene is very appropriate to be utilized as micro-superca-
pacitors. Graphene conducts electricity and heat better than anything else and has combina-
tion of unique optical and mechanical properties. Electrons have nobilities in graphene over
a hundred times those in silicon.
In the present work we used a standard optical LightScribe DVD drive to directly do the
laser reduction of graphene oxide (GO) films to graphene. GO was prepared by the modified
Hummers’ method as reported elsewhere. Briefly, 2 g graphite powders was added to a mix-
ture of 1 g NaNO3 and 46 ml H2SO4 and the mixture was cooled to 10 °C using an ice bath.
In the next step, 6 g KMnO4 was gradually added to the solution and the reaction temperature
was maintained below 20 °C. The mixture was then stirred at 35 °C for 2 h. The resulting
solution was diluted by adding 92 ml of deionized water until a dark brown suspension was
obtained. Then, the solution was treated by adding 340 ml H2O2 solution. Finally, a uniform
suspension of GO nanosheets was obtained by adding water to the resulting precipitate and
12 h of sonicating. The resulting suspensions were uniformly drop casted on a LightScribe
DVD disk and then dried under the air at an ambient temperature. The GO coated DVD disk
was placed in a LightScribe DVD drive with a wavelength of 780 nm.
Raman result confirm that the laser irradiation properly reduce GO to graphene sheets.
The structure of graphene arrays were studied by SEM images the results indicated that the
laser based reduction was a useful method to production graphene layers. The CV curves of
pristine rGO at various scan rates showed that the ultimate product has the power of storing
energy in a supercapacitor level. Finally, the long-term charge-discharge stability of the LSG
has been plotted which indicates that specific capacitance has decreased very slightly from
its primary capacitance of ~ 10 F cm-3 and its cyclic stability is favorable over 1000 cycles.

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514
Chemothermal pulverization of perovskite-type titanates
Alfian Noviyanto1, Yoshio Matsui1, Toshiyuki Nishimura1, Masaaki Kitano2, Naoki Ohashi1,2*
National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan;
1

*
e-mail: [email protected]
Materials Research Center for Element Strategy (MCES), Tokyo Institute of Technology, 4529
2

Nagatsuta, Midori-ku, Yokohama 226-8503, Japan

Keywords: thermal treatment, nano-powder, titanate, pulverization

Recently, the authors have found that grain size of some titanate powders, e.g., BaTiO3,
can be reduced by thermal treatment in reactive atmosphere. Indeed, perovskite-type tita-
nates, including SrTiO3 bulk single crystals and dense BaTiO3 ceramic, were pulverized into
nano-sized powder by heating in gas stream containing air and ammonia (NH3) at high tem-
perature.1 In general, heating powder at high temperature results in grain growth of ceramic
powders and sintering of the powders. However, our observation have indicated that bulk
single crystals can be transformed into nano-sized powder by thermal treatment in air/NH3
mixture gas. We regard the observed phenomena as Chemo-Thermal-Pulverization (CTP).
In our previous report,1 some requirements to induce CTP phenomena were determined but
the mechanism behind this CTP process could not be clarified. As perovskite-type titanates
are absolutely important materials in the field of electroceramics, it is very important to de-
velop technologies relating to production of dielectric and conductive ceramics made from
perovskite-type titanates.
In this paper will focus on further detail of CTP process in order to reveal mechanism
behind the observed CTP phenomena. We have performed experimental studies to obtain
optimized CTP process conditions to achieve efficient production of nano-sized fine BaTiO3
powder from coarse BaTiO3 grains. In addition, detailed characterization, including high
resolution transmission electron microscope observation, for the powder obtained by CTP
process was performed in order to reveal the mechanism of CTP process. As a result, we
have obtained the optimized CTP process condition for BaTiO3 powder and observed very
characteristic grain structure of the powder obtained by CTP process.

Reference
1. A. Noviyanto, T. Nishimura, O. Masayuki, N. Ohashi, “Pulverization of oxide powders utilizing
thermal treatment in ammonia-based atmosphere”, J. European Ceram. Soc. 36[16] (2016) 4083–
4088 <DOI:10.1016/j.jeurceramsoc.2016.06.031>

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409
New dielectric material for co-sintering with LTCC microwave garnet
Lilia Qassym1*, Gérard Cibien1, Richard Lebourgeois1, Dorothée Colson2
1
Laboratoire de Chimie et des Matériaux Multifonctionnels, THALES Research and Technology,
1 avenue Augustin Fresnel, 91767 Palaiseau, France; *e-mail: [email protected]
2
Service de Physique de l’Etat Condensé, CEA Saclay, 91191 Gif sur Yvette, France
Keywords: ferrite, garnet, ferrimagnetism, circulators

Ferrite circulators and isolators, which are non-reciprocal microwaves components, are es-
sential in electronic modules for scanning antennas. The central part of these devices is the
low dielectric and magnetic losses ferrite1, which gives the non-reciprocal properties of the
circulator. Due to complex mechanical assembling of the different materials (ferrite, dielec-
tric and copper), the adaptation of these materials to a common LTCC2 (Low Temperature
Co-fired Ceramics) process could be valuable: the circulators would be produced with an
additive multilayer process. In our previous work, we showed that cationic substitutions
(bismuth, copper and vanadium) enable a dramatic decrease of the sintering temperature of
garnets, from about 1450 °C down to less than 900 °C, allowing co-sintering with gold or
silver for example.
First we tried to associate this new ferrite to a low sintering dielectric but we observed that
for some configurations, the co-sintering was problematic. It was essential to find a dielectric
material perfectly compatible with our garnet.
An idea was to find a garnet from the same family with dielectric properties.
Thanks to different cationic substitutions3, we have modified the properties of the micro-
wave garnet. The use of aluminium in iron crystallographic site leads to an important de-
crease of the saturation magnetization. Combined to gadolinium substitutions for yttrium, we
obtained a material with no magnetic losses, low dielectric losses and a really low saturation
magnetization (from 180 mT to about 0). When we add vanadium substitution, this material
reaches mechanical properties (shrinkage and coefficient of thermal expansion) close to the
properties of the central garnet allowing acceptable co-sintering.
Results of physical analyses will be exposed, such as thermomechanical analyses, coef-
ficient of thermal expansion … Magnetic and dielectric properties will be discussed (permit-
tivity, saturation magnetization, dielectric and magnetic losses). The compatibility between
our two low temperature materials will be described, combined with the use of gold and
silver.

References
1. V. Harris “Modern Microwave Ferrites”, IEEE Transaction on Magnetics, vol. 48, no. 3, Mars 2012.
2. T. Jensen, V. Krozer and C. Kjaegaard, “Realisation of microstrip junction circulator using LTCC
technology”, Electronic Letters, vol. 47, no. 2, Janv. 2011.
3. J. Nicolas, Ferromagnetic Materials, vol. 2, pp. 243–296, E.P. Wohlfarth, North-Holland Publishing
Company, 1980

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987
Electrical properties of ZnO varistors – inhomogeneities and
anisotropic effects on the macroscopic and microscopic scale
Nadine Raidl1*, Michael Hofstaetter1, Peter Supancic1,2, Robert Danzer1
1
Institut für Struktur- und Funktionskeramik, Montanuniversitaet Leoben, Peter Tunner Straße 5,
8700 Leoben, Austria; *e-mail: [email protected]
2
Materials Center Leoben, Roseggerstraße 12, 8700 Leoben, Austria
Keywords: varistor, asymmetric Double Schottky Barrier, piezotronic effect

Varistors are electroceramic components based on polycrystalline ZnO. They have a highly
nonlinear current-voltage relationship and are used for overvoltage protection of electric and
electronic systems. At small voltages varistors exhibit a high resistance which decreases dra-
matically if a certain threshold voltage is exceeded. This effect originates from so called
Double Schottky Barriers (DSBs) at the grain boundaries. These electrostatic barriers are the
origin of the high resistance at small voltages. Above the threshold voltage they break down
in a self-enhanced process, leading to a nonlinear increase of conductivity.
On the microscopic scale, a varistor can be represented by a 3-dimensional network of
highly nonlinear resistors. Due to the nonlinearity, energy dissipation cannot occur homo-
geneously throughout the whole material. This phenomenon will be demonstrated by means
of thermal microscopy. Experiments showed that current merely flows in narrow pathways
through the material.1 In low-voltage varistors (with only 1–2 grain boundaries in series), the
current flow can even be localized at one single grain boundary. Moreover, thermographic
studies revealed the occurrence of different current paths depending on the direction of the
applied electric field. This finding is the direct evidence of direction-dependent electrical
properties of single grain boundaries. Micro-4-point measurements not only confirmed the
anisotropic electrical behavior of single grain boundaries, but also exposed variations of the
breakdown voltage and the nonlinearity coefficients. These findings can be explained by a
natural piezotronic modification of DSBs. Due to the piezoelectricity of ZnO, mechanical
stresses lead to the generation of polarization charges, which modify the band structure at
the grain boundary and consequently the electrical characteristics (i.e., piezotronic effect).
Trough micro compressive tests, it was found that the piezotronic effect can not only lead
to an increase and decrease of DSBs, but also to an asymmetric potential offset. Since ZnO
grains contain residual stresses, it is assumed that DSBs are inherently modified by the piezo-
tronic effect, depending on grain orientation.2 It is concluded that there exists a broad distri-
bution of barrier properties in varistors, leading to the formation of preferential current paths
through the material. Possible approaches for the homogenization of the electrical properties
of ZnO varistors on the microscopic and macroscopic scale will be given.

References
1. N. Raidl, M. Hofstätter, P. Supancic and R. Danzer. “Piezotronic Effect on Electrical Characteristics
of Bulk ZnO Varistors”, Adv. Eng. Mater., 2016.
2. N. Raid, P. Supancic, R. Danzer and M. Hofstätter, “Piezotronically Modified Double Schottky
Barriers in ZnO Varistors”, Adv. Mater., 27 (12), S. 2031–2035, 2015.

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633
Thermal coarsening of metal-on-oxide nanowire thin films
Lidia Rossi*, Luka Ćirić, László Forró, Xavier Mettan, Endre Horváth
Laboratory of Physics of Complex Matter, Ecole Polytechnique Fédérale de Lausanne, Station 3,
CH-1015 Lausanne, Switzerland; *e-mail: [email protected]
Keywords: titanate nanowires, surface area, sintering, thin films, grain boundaries

From painting, biocompatible coatings to solar cells, titanium dioxide (TiO2) has a very wide
range of applications and is one of the most studied oxide material in the last 30 years.1,2,3 In
most of these applications, titanium dioxide is used in the form of nanoparticles as a start-
ing material. Much has learned on the coarsening behaviour of nano TiO2, mainly because
of recent studies almost exclusively addressed to the coarsening of these, nearly spherical,
isotropic nanoparticles. Indeed, the degree of the particle anisotropy might induce a strong
shape-dependent variation in properties of matter, which raises the question how the coarsen-
ing of anisotropic particles proceeds at various interfaces.
In this study coarsening behavior of 2D thin films of titanate nanowires coated with few
nanometer thick noble metal (Ag, Pt, Rh, Pd, Au) thin film were studied by using various
techniques: atomic force microscope (AFM), scanning electron microscopy (SEM), trans-
mission electron microscopy (TEM), X-ray diffraction (XRD) and resistivity measurements.
The aim of this study was to shed light on the temperature dependent structural and geometri-
cal evolution of ceramic/noble metal interfaces down to the single particle, the individual ti-
tanate nanowire and precious metal nanoparticle level. Thin films of titanate nanowires were
prepared by wet-chemical method. From room temperature up to 900 °C, different surface
diffusion regimes were identified which correspond to the different titanate phases, from tita-
nate H2Ti3O7 to anatase and to rutile phase. Understanding the sintering behavior of 1D oxide
nanowires and metal nanoparticles will open up new routes to design efficient heterogeneous
catalyst and photocatalyst systems.

References
1. P. Szirmai, B. Náfrádi, A. Arakcheeva, E. Szilágyi, R. Gaál, N.M. Nemes, X. Berdat, M. Spina, L.
Bernard, J. Jaćimović, A. Magrez. L. Forró, E. Horváth, Catalysis Today, 284, (2017), 52–58.
2. N. Tétreault, E. Horváth, T. Moehl, J. Brillet, R. Smajda, S. Bungener, N. Cai, P. Wang, S.M.
­Zakeeruddin, L. Forró, A. Magrez, and M. Grätzel, ACS Nano, 2010, 4 (12), 7644–7650.
3. P. Szirmai, J. Stevens, E. Horváth, L. Ćirić, M. Kollár, L. Forró, B. Náfrádi, Catalysis Today, 284,
2017, 146–152.

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393
Experimental and theoretical study of Yb:CAF2 transparent ceramics
thermal properties
Julia Sarthou1,3, Jean-Yves Duquesne2, Loïc Becerra2, Patrick Gredin1,3, Michel Mortier1*
1
Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris,
75005 Paris, France; *e-mail: [email protected]
2
Sorbonne Universités, UPMC Université Paris 06, CNRS-UMR 7588, Institut des Nanosciences de
Paris, 75005, Paris, France
3
Sorbonne Universités, UPMC Université Paris 06, 75005 Paris, France
Keywords: transparent ceramic, optical material, thermal conductivity, phonons scattering, fluoride
compounds

Since the first YAG transparent ceramic for laser applications was reported in 19951 which
demonstrated the advantages of ceramics with respect to single crystals, rare earth-doped
polycrystalline ceramics as solid-state laser host material have been widely used and studied.
In the past few years, our team has been focusing on a promising new class of transparent
ceramics for near-IR solid-state lasers, Yb:CaF2. We recently developed a new fabrication
process for such ceramics2 leading to better optical properties3.
However, despite their very good thermo-mechanical properties, transparent ceramics of-
ten demonstrate a lower thermal conductivity than single crystals due to their granular struc-
ture. This parameter is critical for laser material because of the heat that is generated during
laser emission.
We thus report here measurements of the thermal conductivity of Yb:CaF2 transparent ce-
ramics obtained with the new fabrication process. Samples with different doping levels were
studied in a temperature range from 15K to 310K. Comparisons were made with single crys-
tals thermal conductivity. The results for doped ceramics are very similar to those obtained
for Yb:CaF2 single crystals with the same doping levels, which demonstrates an important
improvement of the thermal properties over the previous fabrication process. However, re-
sults obtained for non-doped ceramic and single crystals differ for the maximum conductivity
due to the presence of grain boundaries inside the ceramic.
Theoretical calculations were also conducted using Callaway’s model4 and demonstrated a
very good agreement with experimental results. The fitting parameters found tend to indicate
that the introduction of a doping element in the lattice has more impact on thermal conductiv-
ity than the presence of grain boundaries in the material.

References
1. A. Ikesue et al., “Fabrication and Optical Properties of High-Performance Polycristalline Nd:YAG
Ceramics for Solid-State Lasers”, J. Am. Ceram. Soc., 78(4), pp.1033–1040, 1995.
2. J. Sarthou et al., “Wet-Route Synthesis and Characterization of Yb:CaF2 Optical Ceramics”, J. Am.
Ceram. Soc., 99, pp. 1992–2000, 2016.
3. P. Aballea et al., “Laser performance of diode-pumped Yb:CaF2 optical ceramics synthesized using
an energy-efficient process,” Optica, 2(4), pp. 288–291, 2015.
4. J. Callaway, “Model for lattice Thermal Conductivity at Low Temperatures”, Phys. Rev., 113(4),
pp. 1046–1051, 1959.

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306
Surface modification of staring powder for multifunctional transparent
titanate ceramics
Shao-Ju Shih1*, Zhi-Meng Wang2, Dušan Galusek2, Wei-Hsing Tuan3
1
Department of Materials Science and Engineering, National Taiwan University of Science and
Technology, Taiwan; *e-mail: [email protected]
2
Joint Glass Centre of the IIC SAS, TnU AD and FChFT STU, Trenčín, Slovakia
3
Department of Materials Science and Engineering, National Taiwan University, Taipei, Taiwan
Keywords: powder, SrTiO3, density, liquid phase sintering

Since multifunctional transparent titanate ceramics were reported, these materials have be-
come the potential materials for the electro-optical devices. So far, the applications are limit-
ed because the fabrication of transparent titanates involve the expensive sintering techniques
(e.g. hot iso-pressure sintering, vacuum sintering, and spark plasma sintering). Initially, this
study synthesized the surface modified SrTiO3 staring powders using spray dry. Then, the
dense SrTiO3 specimens were obtained using pressureless sintering. The experimental results
showed that the modified SrTiO3 powders exhibit a thin Ti-rich amorphous layer to increase
grain boundary mobility via liquid phase sintering for dense SrTiO3. Finally, the correspond-
ing mechanisms were discussed.

References
1. D. Völtzke, S. Gablenz, H.-P. Abicht R. Schneider, E. Pippel and J. Woltersdorf, “Surface modifica-
tion of barium titanate powder particles”, Mater. Chem. Phys., 61, pp. 110–116, 1999.
2. J. Liu, Z.J. Shen, W.L. Yao Y.H. Zhao and A.K. Mukherijee, “Visible and infrared transparency in
lead-free bulk BaTiO3 and SrTiO3 nanoceramics”, Nanotechnology, 21, pp. 075706 (5 pp.), 2010.

020
Synthesis and study of multiferroic – powders with structure
‘core-shell’ as a fillers for composite materials for electronics
and photonics
Olga Shilova
Laboratory of Inorganic Synthesis, Institute of Silicate Chemistry of the Russian Academy of
Sciences, Saint-Petersburg, Russia; e-mail: [email protected]

New composite powders, which have magnetic properties with the structure of the ‘core-
shell’, have been prepared. They are particles of barium titanate with a ‘skin- layer’ on their
surface. The ‘skin-layer’ is formed during treatment of a commercial powder BaTiO3 by
tetraethoxisilane-derived sols containing compounds of cobalt and iron. As a result, accord-
ing to SEM, XRD and X-ray spectral analysis, the silica ‘skin-layer’ containing uniformly

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distributed there nanoparticles of cobalt spinel ferrite (CoFe2O4) is formed on the surface
of the powder. The specific surface of BaTiO3 powder with a ‘skin-layer’, measured by the
method of low-temperature adsorption of nitrogen, was increases in ~17 times. This phenom-
enon can be bound up with the formation on the powder surface of a more or less uniform
layer, which changed the surface topography. To confirm this hypothesis, X-ray spectral map-
ping of barium titanate particles with a ‘skin-layer’ was carried out. It was shown that Si, Co
and Fe are uniformly distributed over the surface of the BaTiO3 particles. On the basis of the
zeta potential measurements the following assumption is made: the formation of ‘skin-layer’
takes place through the mechanism of electrostatic interactions of oppositely charged the
powder particles and the sol particles (ζBaTiO3 = −0,41, and ζsol = +2.57 at pH ~2).
Using the method of small-angle scattering of polarized neutrons it was found that the
powder with the structure of the ‘core (BaTiO3)-shell (CoFe2O4)’ is characterized by nuclear-
magnetic interference neutron scattering, the intensity of which is described satisfactorily by
the quad Lorenz. Thus, we can conclude that the barium titanate powder acquires magnetic
properties by modification of its surface using ‘skin-layer’, that contains the ferromagnetic
nanoparticles CoFe2O4 with a characteristic size ~13 nm, structured by type of short-range or-
der with the distance between their centers of ξ ≈ 150 nm. The larger particles CoFe2O4 ~20–
50 were observed using SEM. The magnetization curves for obtained materials were studied.
The synthesized powders, so called multiferroics, were used as functional fillers for dielectric
composites (polymer/filler) based on cyanoethyl ether of polyvinyl alcohol (CEEPVA).
It was found that the films based on the organic-inorganic composites (CEEPVA/BaTiO3−
CoFe2O4) were formed under the influence of the external magnetic field. The frequency
dependence of the dielectric permittivity, conductivity and dielectric loss of these composites
were studied. It was found the composites (CEEPVA/BaTiO3−CoFe2O4) based powders with
‘skin-layer’, especially, which were dried under the influence of a magnetic field, have higher
permittivity ε as compared to a reference sample (CEEPVA/BaTiO3) on the basis of the initial
powder.1 Thus, the dielectric loss tangent increases slightly. The synthesized composites can
find various useful applications including embedded capacitors and other electronics devices,
as well as sensors, electromagnetic radiation shields, etc.

Acknowledgements
The researches were funded by the Program № 7 of 2016 year of the Department of Chemistry and
Materials Science of the Russian Academy of Sciences.

Reference
1. Sychov M., Nakanishi Y., Vasina E., Eruzin A., Mjakin S., Khamova T., Shilova O., Mimura H.
Core-shell approach to control acid-base properties of surface of dielectric and permittivity of its
composite. (2015) Chem. Lett. 2015, 44, 2: 197–199, doi:10.1246/cl.140926.

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625
A 3-D phase diagram of lead-free z(Ba1-xCax)TiO3-(1-z)Ba(ZryTi1-y)O3
piezoceramics system determined by Raman spectroscopy
Chang Shu, Daniel Reed, Tim Button
School of Metallurgy and Materials, University of Birmingham, Birmingham, UK;
e-mail: [email protected]
Keywords: lead-free piezoceramics, phase transitions, Raman spectroscopy

Piezoelectric ceramics have been widely used in sensors, actuators and ultrasonic transducers
due to their ability to achieve efficient conversion between electric and mechanical vibrations.
There is an urgent desire to move to lead-free materials achieving comparable piezoelectric
performance to lead-based materials. The most promising alternative is the pseudobinary
system zBa0.70Ca0.30TiO3-(1-z)BaZr0.20Ti0.80O3 (BCZT) due to the presence of a morphotropic
phase boundary (MPB) in the phase diagram, and reports of large piezoelectric coefficients
comparable to lead-based systems1.
However, with the development of the structural study in this lead-free system, there was
a debate on the crystal structure of the MPB region: (1) MPB was a single phase boundary
separating the rhombohedral and tetragonal phases1; (2) the MPB region was actually with
orthorhombic (Amm2) symmetry, bridging the polymorphic phase transitions between the
rhombohedral and tetragonal phases2.
In this study, the Raman spectroscopy measurements of end member systems (i.e. Ba1-
x CaxTiO3 and BaZryTi1-yO3, abbreviated as BCTO and BZTO) were initially investigated to
observe the dependence of the structural phase transition behaviour on the substitution of Ca
on the Ba-site or Zr on the Ti-site in the parent BaTiO3 phase. The successful determination
of phase transitions by Raman spectroscopy in these end member systems inspired the further
investigation of structural phase transitions in the more complicated BCZT system to clarify
the crystal structure of the MPB region.
BCTO (x = 0–0.30), BZTO (y = 0–0.30) and BCZT (z = 0–1) samples were made by
solid state methods, where BCTO (x= 0–0.15) samples were ceramic powders. The amount
of Ca substitution in BCTO (x value), Zr substitution in BZTO (y value) and Ba0.70Ca0.30TiO3
content in BCZT (z value) were determined by XRD. In all three systems, the accurate deter-
mination of phase transition points through the rhombohedral, orthorhombic, tetragonal and
cubic phases were achieved by Raman spectroscopy measurement. The construction of a 3-D
phase diagram of the lead-free z(Ba1-xCax)TiO3-(1-z)Ba(ZryTi1-y)O3 piezoceramic system (x =
0–0.30, y = 0–0.20, z = 0–1) was therefore established.

References
1. W. Liu and X. Ren, “Large Piezoelectric Effect in Pb-Free Ceramics”, Phys. Rev. Lett., 103, pp.
257602, 2009.
2. D.S. Keeble, et al., “Revised structural phase diagram of (Ba0.7Ca0.3TiO3)-(BaZr0.2Ti0.8O3)”, Appl.
Phys. Lett., 102, pp. 092903, 2013.

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745
Preparation and characterization of Cerium-doped BaTiO3 nanotubes
structures
Catalina-Andreea Stanciu1,2, Adelina-Carmen Ianculescu1*, Bogdan Stefan Vasile1,
Lucian Trupina3, Roxana Trusca4, Marin Cernea3, Lucian Pintilie3
1
Faculty of Materials Science & Engineering, University POLITEHNICA of Bucharest, Bucharest,
Romania; *e-mail: [email protected]
2
National Institute of Materials Physics, Magurele, Romania
3
National Institute of Materials Physics, Magurele, Romania
4
S.C. METAV – Research & Development Bucharest, Bucharest, Romania
Keywords: barium titanate, sol-gel, nanotubes

In the last years, one-dimensional structures such as nanotubes, nanowires and nanorods of
ferroelectric complex oxides have attracted great interest, due to their potential applications
in miniaturized devices including various types of memory, capacitors and nanoelectrome-
chanical systems (NEMS).1–4
In the present study, we describe the preparation by the sol-gel method of Ce-doped Ba-
TiO3 tubes with the nominal formula Ba0.95Ce0.05Ti0.9875O3 and their microstructure and piezo-
electric properties. Porous polycarbonate membranes with channels diameter of 100 nm and
200 nm, respectively, were used as templates.
The uncalcined nanotubes obtained by using as template a polymeric membrane with
channels diameter of 200 nm show an average outer diameter and wall thickness of 190 nm
and 12 nm, respectively.
Crystalline Ce-doped BaTiO3 tubes obtained after thermal treatment in air, at 700 °C/ 1
hour, exhibit uniform morphology. Ba0.95Ce0.05Ti0.9875O3 tubes with diameter of 140–180 nm
show larger grains (average grain size of 30 nm) larger crystallites (10–15 nm) and higher
porosity.
PFM investigations indicated ferroelectric and piezoelectric characteristics for all the
Ba0.95Ce0.05Ti0.9875O3 tubes prepared in this study.

References
1. Y. Luo, I. Szafraniak, N.D. Zakharov, V. Nagarajan, M. Steinhart, R.B. Wehrspohn, J.H. Wendorff,
R. Ramesh, and M. Alexe, Appl. Phys. Lett., 83, pp. 440, 2003.
2. N. Bao, L. Shen, G. Srinivasan, K. Yanagisawa, A. Gupta, J. Phys. Chem. C, 112, pp. 8634, 2008.
3. Z. Wang., J. Hu, M-F. Yu, Appl. Phys. Lett., 89, pp. 263119, 2006.
4. J. Hong, D. Fang, Appl. Phys. Lett. 92, pp. 012906, 2008.

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537
Defect chemistry and conductivity mechanisms in B-site acceptor doped
and A-site non-stoichiometric Na0.5Bi0.5TiO3
Sebastian Steiner*, Leonie Koch, In-Tae Seo, Karsten Albe, Till Frömling
Institute of Geo- and Materials Science, Technische Universität Darmstadt, Germany;
*
e-mail: [email protected]
Keywords: impedance spectroscopy, ionic conductivity, NBT

As reported by Ming Li et al., the A-site non-stoichiometry as well as the B-site acceptor dop-
ing of Na0.5Bi0.5TiO3 (NBT) has a dramatic influence on the oxygen vacancy concentration
and ionic conductivity.1,2 Mg acceptor doped NBT, for instance, shows extremely high ionic
conductivity comparable with conventionally used solid ion conductor materials. Related to
the experience with other lead based or lead free ferroelectric ceramics, this behavior was
a rather unexpected result. The origin and defect chemical reason for these results are part
of important ongoing research approaches. In this work, we will discuss the formation and
effect of oxygen vacancies in A-site non stoichiometric B-site doped Na0.5Bi0.5TiO3. With
the help of temperature and DC-voltage dependent impedance spectroscopy (IS) the defect
chemistry and the charge carrier migration process was investigated. Furthermore, phase and
charge carrier dependent simulations are included according to get a deeper understanding of
the origin for this unexpected conductivity behavior. From these results we are able to pro-
pose how the investigated changes to NBT may affect other NBT related materials.

References
1. M. Li, M.J. Pietrowski, R.A. De Souza, H. Zhang, I.M. Reaney, S.N. Cook, J.A. Kilner, and D.C.
Sinclair, “A family of oxide ion conductors based on the ferroelectric perovskite Na0.5Bi0.5TiO3“,
Nat. Mater., 13, pp. 31–35, 2014.
2. M. Li, H. Zhang, N.S. Cook, L. Li, J.A. Kilner, I.M Reaney, and D.C. Sinclair, “Dramatic Influ-
ence of A-site Nonstoichiometry on the Electrical Conductivity and Conduction Mechanisms in the
Perovskite Oxide Na0.5Bi0.5TiO3“, Chem. Mater., 27, pp. 629–634, 2015.

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724
Structure and magnetoelectric properties
of 0.5BiFeO3 – 0.5Pb(Fe0.5Nb0.5)O3 solid solution
Pawel Stoch1*, Jacek Szczerba1, Agata Stoch2
1
Faculty of Materials Science and Ceramics, AGH – University of Science and Technology,
Mickiewicza 30, 30 – 059 Krakow, Poland; *e-mail: [email protected]
2
Institute of Electron Technology Krakow Division, Zablocie 39, 30 – 701 Krakow, Poland
Keywords: multiferroics, crystal structure, hyperfine interactions, ab initio calculations

Materials that exhibit magnetic and electric ordering in the same phase are named magneto-
electrics. They are part of a larger group of multiferroics which posses at least two ferroic-
orderings in the same phase. The most widely studied and used magnetoelectric oxides are
ABO3 perovskites which have the prototypical cubic structure. This structure is characterized
by a large A cation at the corners of the cubic unit cell and small B cation which is placed in
the middle of the cell in the centre of oxygen anion octahedra.
Bismuth ferrite BiFeO3 (BFO) is one of the most important multiferroic perovskite oxides.
It is ferroelectric with Curie temperature TC = 1100 K and antiferromagnetic with Neel tem-
perature TN = 643 K.
Lead iron niobate Pb(Fe0.5Nb0.5)O3 (PFN) is another type of magnetoelectric material
where ferroelectric active Nb5+ are partially substituted by magnetic Fe3+ of a different va-
lence state. PFN exhibits a broad ferroelectric transition around 370–380 K and two diffuse
magnetic transitions at 150 K and around 10 K.
Magnetoelectric 0.5BFO-0.5PFN solid solution adopt at room temperature rhombohedral-
ly distorted perovskite-like crystal structure (R3c space group). In which Fe3+/Nb5+ cations
are distributed randomly in the B sublattice. It was shown that increasing the number of
Fe-O-Nb linkages lead to reduction of iron magnetic moment. According to theoretical cal-
culations the solid solution has an insulating properties with energy band gap about 1.6 eV.1
Magnetoelectric properties of the above solid solution were characterized using Möss-
bauer spectroscopy, differential thermal analysis, impedance spectroscopy, magnetization
and magnetoelectric effect measurements. According to the obtained results the material is
antiferromagnetic with Neel temperature 460 K and ferroelectric with Curie temperature 630
K. Magnetic hysteresis loop is not fully saturated up to 56 kOe and is characterized by small
coercivity 1.5 kOe and saturation remanence 11 emu/mol.
The obtained experimental results will be compared and discussed with electronic band
structure calculations.

Acknowledgement
The work was partially supported by the statutory funds of the Faculty of Materials Science and Ceram-
ics No 11.11.160.617.

Reference
1. A. Stoch, J. Maurin, J. Kulawik and P. Stoch, “Structural properties of multiferroic 0.5BiFeO3–
0.5Pb(Fe0.5Nb0.5)O3 solid solution”, J. Eur. Cer. Soc., 37, pp. 1467–1476, 2017.

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116
Local distortion determination of the (1-x)(K0.5Na0.5)NbO3-x(Ba0.8Sr0.2)
TiO3 system and their influence on the electrical properties
S. Suasmoro1*, U. Nuraini1, N.A.T. Yuliana1, P. Kidkhunthod⁠2
Department of Physics, Institute of Technology ‘Sepuluh Nopember’ Surabaya, Kampus ITS
1

Sukolilo, Surabaya 60111, Indonesia; *e-mail: [email protected]

Synchroton Light Research Institute (Public Organisation), 111 University Avenue, Muang,
2

Nakhon Rattchasima 30000, Thailand

Keywords: KNN-BST, X-ray absorption spectroscopy, local structure distortion, conductivity, per-
mittivity

The composition of (1-x)(K0.5Na0.5)NbO3-x(Ba0.8Sr0.2)TiO3 and termed as (1-x)KNN-xBST

for x = 0, 0.1 and x = 0.2 were successfully synthesised using a combination of solid-state
reaction and co-precipitation oxalate methods. Structure and local distortion determination
were carried out using X-Ray diffraction (XRD), and X-ray absorption spectroscopy (XAS)
Ti K-edge data. The XRD was utilised to investigate the phase present in the sample and
crystal structure determination through Rietveld refinements, while local distortion due to
the defects were studied by XANES and EXAFS at the Ti K-edge. XRD analysis at room
temperature concluded that both KNN-BST samples behave tetragonal structure compared to
orthorhombic for KNN, while EXAFS analysis using Artemis software revealed the oxygen
octahedral distortion and distance of TiNb′ to its surroundings of A site ions (K, Na. BaK•, SrNa•)
and B site ions (Nb5+). Electrical characterisations of dielectric properties and conductivity
were investigated to elucidate the changes in local distortion. Conductivity measurements at
various temperatures showed an alteration of curves slope from positive at low temperature
region become negative at high temperature. The temperature inflection of ln σ vs 1/T curves,
was shift to higher temperature for doped samples, T ≈ 150 ºC for KNN and T ≈ 225 ºC for
KNN-BST. The characterisation of dielectric properties exhibited a broader peaks which is a
typical relaxor characteristic and was thought to be related to the distortion of oxygen octa-
hedral arrangement surrounding the B sites in the ABO3 structure.

References
1. U. Nuraini, et al., “The influence of local distortion on the electrical properties of the (1-x)(K0.5Na0.5)
NbO3-x(Ba0.8Ca0.2)TiO3 system”, Ceramics International 43 (2017) 3664–3669.
2. C.-W. Cho, et al., “Ferroelectric relaxor properties of (1−x)K0.5Na0.5NbO3–xBa0.5Ca0.5TiO3 ceram-
ics”, Curr. Appl. Phys. 12 (5) (2012) 1266–1271.
3. A. Bootchanont, et al., “Synchrotron X-ray absorption spectroscopy study of local structure trans-
formation behavior in perovskite Ba(Ti,Zr)O3 system”, J. Alloy. Compd. 616 (2014) 430–435.

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632
Overcoming barriers of lead-free piezoceramics – spray-pyrolysis as
a preferred synthesis route
Guttorm Syvertsen-Wiig, Andreas B. Richter, Sophie Labonnote-Weber
Ceramic Powder Technology AS (Cerpotech), Kvenildmyra 6, 7093 Tiller, Norway

Today, more than 98% of the world market for piezoceramic materials consists of lead-con-
taining materials (PZT). Even though RoHS and REACH regulations are pushing towards
a replacement of PZT, the absence of a reliable supply of lead-free materials is an impeding
factor during the transition phase. The state-of-the art process used to produce PZT materials,
solid-state synthesis, is not suitable for lead-free piezoceramics, mainly due to evaporation of
volatile species and poor sinterability of the powders. Therefore, substantial effort is needed
to develop and modify production and processing technologies to qualify lead-free piezo­
ceramic materials and prove their performance and durability on a component level.
Spray pyrolysis is a scalable synthesis route with the capability to produce lead-free pi-
ezoceramic materials in excellent quality and in industrial amounts, thereby, overcoming a
crucial barrier on the way to the large-scale commercialization of lead-free piezoceramics.
The process spray pyrolysis yields homogeneous materials, stoichiometric control and sub-
micron particles with excellent sinterability. Recent results from the production and subse-
quent characterization of lead-free piezoceramic powders will be presented.
Despite the properties and quality offered, component production protocols developed
for solid-state powders cannot be directly applied to spray pyrolysed materials. Additionally,
lead-free materials offer additional advantages such as the possibility to replace expensive
noble-metal electrodes with low-cost nickel. CerPoTech and partners are developing com-
ponents using spray-pyrolysis powders and employ industrial standard testing methods to
verify the performance and consistency of the materials and components. An outlook on the
demonstration of the components and the way to develop competitive products will be given.

663
Fabrication of translucent and fluorescent Eu doped CASN bulk
ceramics using a spark plasma sintering technique
Takuma Takahashi1*, Junichi Tatami2, Motoyuki Iiijima2
1
Kanagawa Academy of Science and Technology, KSP, 3-2-1 Sakado, Takatsu-ku, Kawasaki City,
Kanagawa, Japan; *e-mail: [email protected]
2
Yokohama National University, 79-1 Tokiwadai, Hodogaya-ku, Yokohama, Japan
Keywords: CaAlSiN3, spark plasma sintering, phosphor

Commercial white LEDs consist of excitation light source and SiAlON phosphor powders
dispersed in a resin. For high power application, the resin is not desired because of the low
thermal durability. In order to actualize the high power LEDs without a resin, transparent and

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fluorescent α- and β-SiAlON bulk ceramics were developed in our previous work. Although
they show the good fluorescence from blue to yellow, red colour has not been achieved, yet.
As a red phosphor, CaAlSiN3:Eu2+ has a high quantum efficiency due to 5d-4f transition even
at high temperatures. In this work, the transparent and fluorescent CaAlSiN3:Eu2+ ceramics
was fabricated by applying a spark plasma sintering. As raw powders, Si3N4 (SN-E10, Ube
Industries Co., Ltd., Japan), AlN (H-grade, Tokuyama Co., Ltd., Japan), Ca3N2 (Sigma-Al-
drich Co., USA) and Eu2O3 (Shin-Etsu Chemical Co., Ltd., Japan) were used. These powders
were mixed in toluene in N2 gas by ball-milling with SiAlON balls (φ5 mm). The mixed
powder was separated from toluene by centrifugalizing at 1000 rpm for 1 min and then dried
in N2 gas for 3 hours. The dried powder was milled by Al2O3 mortar and it was set into a car-
bon die (φ25 mm). Spark plasma sintering was carried out at the temperature from 1650 to
1750 °C for 10 min in N2 gas. The relative density was measured by Archimedes method. As
a result, the relative densities of CaAlSiN3:Eu2+ ceramics after spark plasma sintering were
over 99%. They have good translucency and red-color fluorescence excitated by blue-LED of
450nm. All specimens showed broad spectrum pattern due to 5d-4f transition. The emission
peak was shifted to longer wavelength depending on the concentration of added Eu2O3. It can
be considered that the peak shift resulted from an expansion of crystal lattice of CaAlSiN3 by
the substitutional solid solution of Eu2+.

432
Nanosized titania particles for application in photocatalysis
Nikola Tasić1, Zorica Branković1, Jovana Ćirković1, Tatjana Novaković2, Goran Branković1
Institute for Multidisciplinary Research, Department of Materials Science, University of Belgrade,
1

Kneza Višeslava 1, 11000 Belgrade, Serbia

IChTM-Department of Catalysis and Chemical Engineering, University of Belgrade, Njegoševa 12,
2

11000 Belgrade, Serbia

In this work we present simple synthetic route with low energy requirements, designed to pro-
duce high surface area titania (TiO2) photocatalyst. Method involves usage of titanium(IV)-
isopropoxide and chitosan, a polysaccharide rarely utilized in ceramics-related research.
Thorough characterization of the obtained powders was conducted using several instrumen-
tal techniques (FE-SEM, XRD, BET and UV-VIS-NIR spectroscopy) which revealed the
presence of sub-10 nm particles, and confirmed pure or predominant presence of anatase
crystallographic phase, higher surface area than in commercial referent samples, and slightly
enhanced absorption in the visible portion of the spectrum. The photocatalytic degradation
of textile azo dyes under UV-enriched light source was investigated (230 mW cm-2, 20 °C),
showing very high adsorption capability of the powders, and superior photocatalytic behav-
iour compared to referent samples.

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039
Giant dielectric permittivity and high tunability in Y-doped SrTiO3
ceramics tailored by sintering atmosphere
Alexander Tkach1*, Olena Okhay2, Abílio Almeida3, Paula M. Vilarinho1
CICECO – Aveiro Institute of Materials, Department of Materials and Ceramic Engineering,
1

University of Aveiro, 3810-193 Aveiro, Portugal; *e-mail: [email protected]

Nanotechnology Research Division, Centre for Mechanical Technology and Automation (TEMA),
2

Department of Mechanical Engineering, University of Aveiro, 3810-193 Aveiro, Portugal

IFIMUP and IN – Institute of Nanoscience and Nanotechnology, Department of Physics and
3

Astronomy, Faculty of Science of University of Porto, 4169-007 Porto, Portugal

Keywords: electroceramics, donor doping, polar clusters, Maxwell-Wagner interfacial polarization

Development of giant-permittivity and high-tunability dielectric materials has attracted great

interest because of growing demand for smaller and faster energy-storage and electronic
devices. Materials such as CaCu3Ti4O12, displaying the giant dielectric permittivity due to
extrinsic Maxwell-Wagner interfacial polarization effect, have previously been reported.1
Ferroelectric materials possessing intrinsic ionic polarization due to a phase transition to
the polar state have also been indicated to possess a high tunability of the dielectric permit-
tivity by dc electric field.2 Here, a class of the giant-permittivity materials based on SrTiO3
ceramics doped with up to 1% of yttrium and their processing concept, which yields the
dielectric permittivity up to ~209 000 at 10 kHz for nitrogen sintering atmosphere, and the
relative tunability up to ~74% under 20 kV cm–1 for oxygen sintering atmosphere, is reported.
The high tunability is proved to be due to polar clusters created at low temperatures by off-
central Y3+ ions on Sr2+ sites.3 The giant permittivity is explained by a coupling of the polar
clusters relaxation mode with the donor substitution induced electrons at low temperatures4
and by the Maxwell-Wagner relaxation around room temperature. Besides the fundamental
understanding, this discovery opens a new development window for high-frequency and low-
temperature electronic and energy-storage applications.

References
1. L. Singh, U.S. Rai, K.D. Mandal and N.B. Sing, “Progress in the Growth of CaCu3Ti4O12 and Re-
lated Functional Dielectric Perovskites”, Prog. Cryst. Growth Charact. Mater., 60, pp. 15–62, 2014.
2. A.K. Tagantsev, V.O. Sherman, K.F. Astafiev, J. Venkatesh and N. Setter, “Ferroelectric Materials
for Microwave Tunable Applications”, J. Electroceram., 11, pp. 5–66 (2003).
3. A. Tkach, P.M. Vilarinho and A. Almeida, “Low-temperature Dielectric Relaxations in Y-doped
Strontium Titanate Ceramics”, J. Phys. D: Appl. Phys., 48, p. 085302, 2015.
4. M. Maglione and M. Belkaoumi, “Electron–relaxation-mode Interaction in BaTiO3:Nb”, Phys. Rev.
B, 45, pp. 2029–2034, 1992.

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943
Ionic conductor device for selective detection of hydrocarbons on diesel
exhaust gases
Fidel Toldra-Reig, Jose M. Serra*
Instituto de Tecnología Química (Universidad Politécnica de Valencia - Consejo Superior de
Investigaciones Científicas), Valencia, Spain; *e-mail: [email protected]
Keywords: ethylene, sensor, ionic conductor, automotive

In the recent past years the detection of hydrocarbons in exhaust gas of diesel cars has in-
creasingly gained in importance due to air quality regulations. As hydrocarbons and other
pollutants are related to health issue problems in humans,1 both American and European
legislators are reducing the emissions of these pollutants allowed.2–4 Nowadays there are
restrictions because of the impossibility to detect HCs at lower concentrations. As a health
issue, more restrictive legislations will be legislated if sensors able to detect HCs at these
lower concentrations are provided.
Thus, in this work an ionic conductor device is made to detect selectively ethylene. 8YSZ
is pressed in order to obtain a disk, which is used as electrolyte as well as support. As work-
ing electrode FeCr2O4 is employed because of its catalytic activity toward ethylene. Platinum
is usually employed as reference electrode, but in this work we used a cheaper material with
ionic conductivity: LSM/8YSZ. This allows fulfilling two desired aims: the improvement
of the catalytic activity toward oxygen and reduce the cost. In addition, a functionalization
of the surface is performed on the WE to increase the catalytic activity toward ethylene and
reduce the cross sensitivity to CO. Thus, a selective device to C2H4 is obtained.
Materials are obtained by sol-gel Pechini method and screen-printed onto electrolyte sup-
port. A gold coating is made to ensure contact. Here is studied sensor response to C2H4 and
CO concentration. Voltage generated is recorded by KEITHLEY 2601 and 3706-NFP.
The structural, textural and morphological features of the resultant powders were investi-
gated by X-ray diffraction (XRD), while devices structural characterization is performed by
scanning electron microscopy (SEM).

References
1. M. Krzyzanowski, B. Kuna-Dibbert, J. Schneider, (2005) Health effects of transport-related air pol-
lution, World Health Organisation, Denmark.
2. https://www.dieselnet.com/standards/eu/ld.php
3. P.K. Sekhar, K. Subramaniyam, Electrical characterization of a mixed potential propylene sensor,
Sensors and Actuators B: Chemical Volume 188, (2013), 367–371.
4. I.A. Reşitoğlu, K. Altinişik, A. Keskin, The pollutant emissions from diesel-engine vehicles and
exhaust aftertreatment systems, Clean Technologies and Environmental Policy (2015) 17, 15–27.

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386
Internal field in asymmetric P–E curves of BaTiO3:Co piezo ceramics
by defect dipoles orientation
Rémy Ul1,2*, Mai Pham-Thi1, Louis-Pascal Tran-Huu-Hue2
1
Thales Research & Technology-France, 1 Avenue Augustin Fresnel, 91676 Palaiseau Cedex, France
2
GREMAN, INSA Centre Val de Loire, Rue de la Chocolaterie, Blois, France;
*
e-mail: [email protected]
Keywords: piezoelectric, ceramic, lead-free, doping, functional properties, charge compensation,
hysteresis loop

Barium titanate ceramic (BT) was one of the first materials used in the fabrication of piezo-
electric devices. However, BT was quickly supplanted by lead zirconate titanate ceramics
(PZT) which exhibit both lower sintering temperatures (1200 °C rather than 1350 °C) and
higher piezoelectric properties.The need for lead-free piezoceramics renewed the interest in
developing BaTiO3 ceramics. BT ceramics doped with Ca2+, Co2+/3+ and Nb5+ were synthe-
sized using a conventional ceramic process. The addition of Li2O as a sintering aid resulted
in very dense ceramics sintered at around 800 to 1100 °C. The substitution of Ti4+ by Co2+/3+
in the perovskite structure, increased the piezoelectric performance (d33 = 210pC/N and kp =
38%). The co-substitution with the pentavalent ion Nb5+ leads to a d33 of 250pC/N and kp =
42%. The same performance was measured for BT:Ca,Co ceramics.
The use of Co2+/3+acceptor doped BT ceramics leads to a significant increase in perfor-
mance and hard piezoelectric feature (Qm~1000). Indeed, if BT ceramics present a regular
P–E curve, Co2+/3+doped ceramic exhibits double-loop and asymmetric P–E curves in non-
poled and poled states, respectively (Fig. 1). This behavior is attributed to the creation of
electric dipoles between the acceptor dopants and the oxygen vacancies by charge com-
pensation during substitution of Ti4+ by Co3+. Acceptor doped BT ceramics exhibit a defect
chemistry dominated by oxygen vacancies and ionized acceptors rather than electronic car-
riers. The concentration of charged ionic point defects is orders of magnitude larger than the
concentration of electrons and holes at RT due to high concentration of the oxygen vacancies
fixed at high temperature. The defect dipoles in the material induce an internal field1 which
can be observed through the acquisition of the asymmetric ferroelectric hysteresis loop (Fig.
1b). This internal field which is tied to the concentration of defect dipoles is observed during
the insertion of Li+/Co2+ /3+. The decrease of the internal field by donor co doping (Nb5+) or
oxygen annealing could be consistent with the decrease in concentration of defect dipoles.
The trade-off between internal field and acceptor/donor concentration and the stability of the
material under electric stress will be presented.

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Fig. 1. Hysteresis curves of BaTi1-xCoxO3-2x/3, y Li2O ceramics; (a) non-poled samples, (b) poled
­samples

Reference
1. E. Sapper, R. Dittmer, D. Damjanovic, E. Erdem, D.J. Keeble, W. Jo, T. Granzow, J. Rödel, “Aging
in the relaxor and ferroelectric state of Fe-doped (1-x)(Bi1/2Na1/2)TiO3-xBaTiO3 piezoelectric
ceramics”, J. Appl. Phys., 116, 104102, 2014.

727
Tailoring strains and physical properties of epitaxial thin films on
vicinal substrates
Guang Yao1, Min Gao1, Chonglin Chen2, Yuan Lin1*
State Key Laboratory of Electronic Thin films and Integrated Devices,
1

University of Electronic Science and Technology of China, Chengdu, Sichuan 610054, P. R. China;
*
e-mail: [email protected]
Department of Physics and Astronomy, University of Texas at San Antonio, San Antonio, Texas
2

78249, USA

It is well known that controllable interfacial strain can manipulate the physical properties of
epitaxial thin films. Besides using normal lattice mismatch, by using a proper design of vici-
nal single-crystal substrate, the interface strain in epitaxial thin films can be well controlled
via a surface-step-terrace matching growth mode. Here, we demonstrate that LaAlO3 (LAO)
substrates with various miscut angles and miscut orietations were used to tune the dielectric
properties of epitaxial CaCu3Ti4O12 (CCTO) and Ba(Sr,Ti)O3 thin films. A model of coexis-
tent compressive and tensile strain domains is proposed to understand the stress relaxation
mechanism. The results may help open a new avenue to manipulate the strain and physical
properties of epitaxial thin films, which is critical for the design and integration of advanced
heterostructures for high performance device applications.

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055
TeO2/SnO2 hybrid nanowire structures for enhanced room-temperature
gas sensing
Bu-Yu Yeh, Ping-Fu Huang, Wenjea J. Tseng*
Department of Materials Science and Engineering, National Chung Hsing University,
250 Kuo Kuang Rd., Taiwan; *e-mail: [email protected]
Keywords: gas sensor, tellurium oxide, tin oxide, nanowires

We have synthesized two highly sensitive, room-temperature operating TeO2/SnO2 gas sen-
sors with hierarchical nanowire structures. One is a brush-like nanostructure by a two-step
thermal vapour-transport route, and the other one is a TeO2/SnO2 bead-like nanostructure
by annealing of the former one. The TeO2/SnO2 nanostructures exhibit a much enhanced
room-temperature gas-sensing response than the pristine TeO2 nanowires in a sequence that
the TeO2/SnO2 bead-like structure > the brush-like structure > the pristine TeO2 nanowires.
The response of the TeO2/SnO2 bead-like structure is in a range of 10 to 20 against NO2 gas
of ppm levels (3–100 ppm) at room temperature. This compares favourably to the response
smaller than 2 for the pristine TeO2 nanowires. Interestingly, the TeO2/SnO2 bead-like struc-
ture exhibits a typical n-type gas-sensing behaviour, in contrast to the p-type behaviour from
the brush-like and the pristine TeO2 structures. Possible hybrid growth and sensing mecha-
nisms are discussed. The nanohybrid structure has also been extended to other oxide combi-
nations for enhanced sensing response and gas selectivity.

Reference
1. B.-Y. Yeh, P.-F. Huang, and W.J. Tseng, “Enhanced room-temperature NO2 gas sensing with TeO2/
SnO2 brush- and bead-like nanowire hybrid structures”, Nanotechnology, 28, 045501, 2017.

375
Vanadium oxide production by solution combustion synthesis
Esma Yilmaz*, C. Bora Derin, Onuralp Yucel, M. Seref Sonmez
Department of Metallurgical and Materials Engineering, Istanbul Technical University, Sarıyer,
34469, Istanbul, Turkey; *e-mail: [email protected]
Keywords: solution combustion synthesis, vanadium oxide, optical properties, electrochemical
properties

Self-propagating high temperature synthesis called as a combustion synthesis is used for

the production of advanced materials, which consist of ceramic, intermetallic compound,
composite and functional materials close to the powder or final product. Solution combus-
tion synthesis is an easy, simple and rapid method that allows the production of many nano-
dimensional materials. This method involves the self-propagating reaction of homogeneous

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solutions which has different oxidative precursors (metal nitrates) and fuels (urea, glycine,
hydrazide, etc.).1,2
Vanadium is a metal that can take more than one valence and thus can form different oxide
compounds. These oxides have different properties due to their different compositions. For
example, VO2 and H2VO3O8 are used as an optical, electrical, electrochemical, thermochro-
mic and thermal switch material. VO2 has also different polymorphic forms which can reveal
stable and metastable phases. For instance, VO2, which is a monoclinic metastable phase, is
used as a cathode material especially in lithium ion batteries. Thin films of vanadium oxide
(V2O5) is used as electrochromic and thermochromic devices, uncooled bolometric detectors,
laser protection, solar cell windows, high-capacity lithium battery electrodes, electrical and
optical switching devices, light modulators.3,4
In this study, vanadium oxide nanoparticles were synthesised by solution combustion
method. Oxalic acid dihydrazide (ODH) (C2H6N4O2), citric acid (C6H8O7.H2O) and mix fuel
were used as a fuel material during solution combustion synthesis (SCS), while ammonium
meta-vanadate (NH4VO3) was used as an oxidant. The structure, morphology and chemical
composition of the samples were characterized by using XRD and SEM & EDS methods.
Surface area of synthesised particles were determined by BET analysis.

References
1. S.T. Aruna, A.S. Mukasyan, Current Opinion in Solid State and Materials Science, 12, 2008, 44–50.
2. K.C. Patil, M.S. Hedge, T. Rattan, S.T. Aruna, Chemistry of Nanocrystalline Oxide Materials, 2008,
Chapter 3.
3. Jagadeesh, A., Rattan, T.M., Muralikrishna, M., Venkataramaniah, K. 2014. “Instant one step syn-
thesis of crystalline nano V2O5 by solution combustion method showing enhanced negative tem-
perature coefficient of resistance”, 121, 133–136.
4. Kaid, M.A. 2006. “Characterization of electrochromic vanadium pentoxide thin films prepared by
spray pyrolysis”, J. Solids, 29, 273–291.

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Poster presentations

874
Strontium oxynitride phosphor doped with Eu2+ ions:
phase purity/optical properties relationship
Barbara Adamczyk1*, Dirk Poelman2, Małgorzata Sopicka-Lizer1, Katleen Korthout2,
Daniel Michalik1
Department of Materials Science and Metallurgy, Silesian University of Technology, Krasinskiego 8,
1

40-019, Katowice, Poland; *e-mail: [email protected]

Lumilab, Department of Solid State Sciences, Ghent University, Krijgslaan 281, S1, B-9000 Gent,
2

Belgium
Keywords: oxonitridosilicate, flux, phosphor, photoluminescence characterization, solid state synthe-
sis, gas pressure synthesis

Eu2+-doped SrSi2O2N2 was prepared via a gas pressure method or a solid state reaction meth-
od with various amount of Na2CO3 fluxing agent. The phase composition of obtained materi-
als was studied using X-ray diffraction. The local environment of the activator ions in the
structure was examined using X-ray absorption near-edge spectroscopy (XANES). The pho-
toluminescent properties were investigated by emission, excitation and quantum efficiency
measurements. Decay times and thermal stability of the powders were determined as well.
Obtained results show that nitrogen and CO partial pressure during the process of syn-
thesis influence the phosphor crystallization. It has been found that usage of Na2CO3 flux
improves crystallization of the desired phase, enhancement of optical properties was also
visible. An optimum concentration of the flux was 5 wt% since exceeding this value resulted
in formation of an excessive amount of glassy phase, as well as some evidence of the second-
ary phase formation.

094
Grain growth behaviors and piezoelectric properties of alkali ions
excess NKLNT ceramics
Jong-Gyeon Ahn, Bo Kun Koo, Soon-Jong Jeong, In-Sung Kim, Jaesung Song,
Min-Soo Kim*
Battery Research Center, Korea Electrotechnology Research Institute, Changwon, Gyeongnam,
Rep. of Korea; *e-mail: [email protected]
Keywords: piezoelectric, microstructure, NKLNT

Lead oxide-based ferroelectrics are the most widely used materials for piezoelectric actua-
tors, sensors and transducers due to their excellent piezoelectric properties. Considering lead
toxicity, there is great interest in developing lead-free piezoelectric materials, which are bio-

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compatible and environmentally friendlier. Recently (Na,K)NbO3 based ceramics have been
given attention in view of their ultrasonic application and also as promising candidates for
piezoelectric lead-free system. However, it is difficult to sinter the ceramics via conventional
sintering process. In this study, it was investigated that the effect of additions with A-site
ions in perovskite structure on electromechanical properties and grain growth behaviors in
(Na0.475K0.475Li0.05) (Nb0.95Ta0.05)O3 (NKLNT) ceramics. Sintering temperature was lowered
by adding A-site ions and abnormal grain growth in NKLNT ceramics was observed with
varying additions. These microstructural changes show the typical grain growth behavior
due to the change in critical driving force for rapid grain growth in structure of the faceted
interfaces or boundaries. The grain growth behavior can be explained in terms of interface
reaction-controlled nucleation and growth. The piezoelectric properties of NKLNT ceramics
were investigated as a function of concentration of additions. The electromechanical cou-
pling factor and piezoelectric constant were improved in the samples with A-site ions excess
NKLNT. These results show that the electromechanical properties of NKLNT ceramics can
be improved by controlling the microstructures.

References
1. Y. Saito, H. Takao, T. Tani, T. Nonoyama, K. Takaori, T. Homma, T. Nagaya, and M. Nakamura,
“Lead-Free Piezoceramics,” Nature, 432, pp. 84–87, 2004.
2. S.-J.L. Kang. Sintering: Densification, Grain Growth & Microstructure. Elesevier, 2005.
3. M.-S. Kim, D.-S. Lee, E.-C. Park, S.-J. Jeong and J. Song, “Effect of Na2O additions on the sinter-
ability and piezoelectric properties of lead-free 95(Na0.5K0.5)NbO3–5LiTaO3 ceramics”, J. Eur. Cer.
Soc., 27, pp. 4121–4124, 2007.
4. J.-F. Li, K. Wang, F.Y. Zhu, L.-Q. Cheng and F.-Z. Yao, “(K,Na)NbO3-Based Lead-Free Piezoce-
ramics: Fundamental Aspects, Processing Technologies, and Remaining Challenges”, J. Am. Cer.
Soc., 96, pp. 3677–3696, 2013.

024
Perovskite phase formation, microstructure and dielectric properties of
BaTiO3-based ceramic nanocomposites
Supon Ananta1*, Jeeranan Nonkumwong2, Laongnuan Srisombat2
1
Department of Physics and Materials Science, Faculty of science, Chiang Mai University, Chiang
Mai 50200, Thailand; *e-mail: [email protected]
2
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
Keywords: nanocomposites, barium titanate, gold nanoparticles, sintering

Owning to their non-toxic and variable electrical properties, perovskite ferroelectric barium
titanate (BaTiO3) BT-based ceramics are of interest as the promising smart materials in com-
mercial electrical components. However, they suffer from high sintering temperature require-
ment, low dielectric constant and high dielectric loss, causing a limitation for their practi-
cal utilizations, especially for the multilayer ceramic capacitors with ultrathin layers. Thus,
several solutions have been proposed to overcome these limitations including an approach of

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reinforcing the ferroelectric matrix phase with high electrical conducting phases. In the pres-
ent study, small amount of gold nanoparticles reinforced BT composites were developed by
employing a solid-state sintering techniques without any binders. Apart from their environ-
mental friendly, gold nanoparticles are thought to be reasonable candidate used for shorten-
ing the electrode distance in the nanometal/BT ceramics. These nanocomposites are expected
to synergistically combine the properties of both the ferroelectric BT and the conductive gold
nanoparticle, which could exhibit dielectric properties that are better than those of the mono-
lithic BT ceramics. By employing a combination of several characterization techniques,
the obtained results indicate that using different sintering temperature or gold nanoparticle
amounts to produce the composites greatly affect the perovskite phase formation, densifica-
tion, microstructure and dielectric properties of the materials. Microstructural investigation
revealed that some gold nanoparticles were heterogeneously dispersed in BT matrix and at
the matrix boundaries. The obtained results indicate that under suitable sintering condition
and nanogold content, both densification and dielectric properties of the composites with
fine-grained microstructure fabricated in this work were significantly improved, as compared
to the unmodified BT ceramics.

913
The decrease of depolarization temperature and
the improvement of pyroelectric properties by doping Ta in lead-free
0.94Na0.5Bi0.5TiO3-0.06BaTiO3 ceramics
Ahmed Balakt
Cranfield University, Bedford, UK; e-mail: [email protected]

Ta-doped lead-free 0.94NBT-0.06BT-xTa (x = 0.0 – 1.0%) ceramics were synthesized by a

conventional solid-state route. XRD shows that the compositions are at a morphotropic phase
boundary where rhombohedral and tetragonal phases coexist. The depolarization tempera-
ture (Td) shifted to lower temperature with the increase of Ta content. The pyroelectric coef-
ficient (p) of doped ceramics greatly enhanced compared with undoped material and reached
a maximum of 7.14 × 10–4 C.m–2.°C–1 at room temperature (RT) and 146.1 × 10–4 C.m–2 °C–1
at Td at x = 0.2%. The figure of merits, Fi and Fv, also showed a great improvement from 1.12
× 10–10 m.v–1 and 0.021 m2.C–1 at x = 0.0 to 2.55 × 10–10 m.v–1 and 0.033 m2.C–1 at x = 0.2% at
RT. Furthermore, Fi and Fv show the huge improvement to 52.2 × 10–10 m.v–1 and 0.48 × 10–10
m2.C–1 respectively at Td at x = 0.2%. FC shows a value between 2.26 to 2.42 × 10–9 C.cm–2.
°C–1 at RT at x = 0.2%. The improved pyroelectric properties make NBT-0.06BT-0.002Ta
ceramics a promising infrared detector material.

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103
Synthesis and properties of YBa2Cu3O7-δ – Y2Ba4CuWOx ceramics
composites
Vilém Bartůněk1, Tomáš Hlásek1,2, Vladimír Plecháček2, Filip Antončík1,
David Sedmidubský1, Ondřej Jankovský1,3*
1
Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5,
166 28 Prague 6, Czech Republic; *e-mail:[email protected]
2
CAN SUPERCONDUCTORS s.r.o., Ringhofferova 66, 251 68, Kamenice, Czech Republic
3
The Czech Ceramic Society, Novotného lávka 5, 110 01, Prague 1, Czech Republic
Keywords: YBCO, 2411 phase, bulk, nanosized, pinning, Y2Ba4CuWOx

YBCO is a well-known high-temperature superconductor (HTS); however, its critical cur-

rent density and thus the maximum trapped magnetic field can be improved significantly by
introducing the secondary phases (artificial pinning centers). In this contribution, we success-
fully prepared YBCO single-grain bulks with nanostructuralized Y2Ba4CuWOx (Y-2411W)
pinning phase. Y2411W phase was prepared by solid state reaction and further refined by
milling. In the next step single-grain YBCO bulks with homogenously distributed nanopar-
ticles of Y2Ba4CuWOx were prepared by top-seeded melt growth. Precursors as well as the
final product were characterized by XRD, SEM, EDS and PPMS. Oxygen stoichiometry was
studied by STA. Bulk superconducting properties such as levitation force and trapped field
ability were also measured. Obtained results are of significant importance for research and
applications in the field of superconducting ceramics.

465
Textured ternary PIN-PMN-PT systems and their characterization
Ayse Berksoy-Yavuz1, Ebru Mensur-Alkoy1,2*, Ebru Gozutok1, Sinan Dursun1, Sedat Alkoy1
1
Dept. of Materials Science and Eng., Gebze Technical University, Kocaeli, 41400, Turkey
2
Faculty of Engineering and Natural Sciences, Maltepe University, Istanbul, 34857, Turkey;
*
e-mail: [email protected]
Keywords: piezoceramics, textured, PIN-PMN-PT, electrical properties

Ferroelectric single crystal (1-x)Pb(Mg1/3Nb2/3)TiO3-xPbTiO3 (PMN-PT) and xPb(In1/2Nb1/2)

O3-(1-x-y) Pb(Mg1/3Nb2/3)O3-yPbTiO3 (PIN-PMN-PT) ternary systems have been drawn at-
tention in field of electronic device applications because of their giant piezoelectric coefficient
and outstanding coupling factors of <001> direction. The Curie temperature (Tc) of PMN-PT
is reported in literature between 130–170 oC, which is restricted to application areas. Beside
this, PIN-PMN-PT ceramics have thermal stability and Tc changes from 160 oC up to 320
o
C with regard to composition in morphotropic phase boundary (MFB).1,2 However, single
crystal growth techniques are required high cost equipment and single crystals show stoi-

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chiometric deviations for this kind of compositions. The crystallographic textured ceramics
exhibits higher electrical properties than conventional ceramics which is comparable with the
properties of single crystals.3 In this study, textured 0.26Pb(In1/2Nb1/2)O3-0.40Pb(Mg1/3Nb2/3)
O3-0.34PbTiO3 (PIN-5BT) and 1.5 mol. Mn % doped (PIN-5BT-1.5Mn) ceramics were syn-
thesized by templated grain growth method (TGG) by using 5 vol % plate-like BaTiO3 (BT)
templates. Random and textured PIN-PMN-PT ceramics were sintered at 1150oC for 6 h.
Lotgering factors of the both textured, PIN-5BT and PIN-5BT-1.5Mn ceramics were ob-
tained as 94%, respectively. The maximum field induced bipolar strain of PIN-R, PIN-T5,
PIN-1.5Mn and PIN-T5-1.5 Mn was measured as 0.16%, 0.25%, 0.12% and 0.24%at 40kV/
cm, respectively.

References
1. S.E. Park, T.R. Shrout,“Ultrahigh Strain and Piezoelectric Behavior in Relaxor Based Ferroelectric
Single Crystals”, J. Appl. Phys., 82, 1804–1811, 1997.
2. S. Zhang, J. Luo, W. Hackenberger, N.P. Sherlock, R.J. Meyer, Jr and T.R. Shrout, “Electromechan-
ical characterization of Pb(In0.5Nb0.5)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals as a function of crystal-
lographic orientation and temperature”, J. Appl. Phys., 105, 104506, 2009.
3. S. Kwon, E.M. Sabolsky, G.L. Messing, S. Trolier-McKinstry “High Strain, <001> Textured
0.675Pb(Mg1/3Nb2/3)O3-0.325PbTiO3 Ceramics: Templated Grain Growth and Piezoelectric Proper-
ties”, J. Am. Ceram. Soc., 88[2], 312–317, 2005.

334
Photoluminescence-structure correlations in ferroelectric Eu:Ba(Ti,Zr)
O3 ceramics: study of phase transitions and polar order
Gregorio Bottaro1, Giovanna Canu2, Maria Teresa Buscaglia2, Chiara Costa2,
Oana Condurache3, Vlad Preutu3, Lavinia Curecheriu3, Liliana Mitoseriu3,
Vincenzo Buscaglia2, Lidia Armelao1,4
1
ICMATE-CNR and INSTM, Department of Chemical Sciences, University of Padova, Via F.
Marzolo 1, 35131 Padova, Italy
2
ICMATE-CNR, Via De Marini 6, 16149 Genoa, Italy
3
Alexandru Ioan Cuza University, Faculty of Physics, 11 Blvd. Carol I, 700506 Iasi, Romania
4
Department of Chemical Sciences, University of Padova, Via F. Marzolo 1, 35131 Padova, Italy

BaTiO3-based ferroelectric ceramics show interesting properties such as high dielectric

constant, low losses, high hydrostatic piezoelectric coefficient and PTCR effect. For these
reasons, barium titanate is widely used in the electronic industry for manufacturing minia-
turized multilayer ceramic capacitors, underwater transducers and self-regulating thermis-
tors. BaZrxTi1-xO3 (BZT) solid solution shows a series of phase transitions and a progres-
sive evolution of ferroelectric order, from long-range order typical of classic ferroelectrics
(x = 0) to short-range order typical of relaxors (x ≥ 0.25), which consequently affects the
functional properties. This material can be considered as a model system for understanding
the composition-property correlations in ferroelectric ceramics. The trivalent europium ion
(Eu3+) is well known for its strong luminescence in the red spectral region. Even very small

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variations in the coordination sphere of europium ions induce major changes in the emission
spectrum. Thanks to these features, Eu3+ is a unique and powerful local structural probe. In
this framework, we used photoluminescence (PL) as a tool to investigate the phase transitions
and the ferroelectric order in BZT using Eu3+ as active centre. Dense ceramics (relative den-
sity: 96-99%) with composition EuyBa1-yZrxTi1-x-y/4O3 (y = 0.01, x = 0, 0.05, 0.15, 0.30, 0.50,
0.70, 1) were prepared by the classical solid-state route and sintered at 1450-1550 °C. The
dielectric permittivity of the samples was measured from –150 to 150 °C and at 102–106 Hz
to determine reference values of the phase transition temperatures. The study of PL spectra as
a function of temperature, in the interval –100 to 140 °C, revealed strong shape and intensity
variations of the emission bands in the proximity of phase transitions as well as a significant
dependence of their relative intensity for compositions having x ≥ 0.30, i.e. materials with
relaxor behaviour.

249
Preparation, characterisation and dielectric properties of
PVDF – BaTiO3 composites
Elisabetta Brunengo1, Chiara Costa2, Maria Teresa Buscaglia2, Giovanna Canu2,
Lucia Conzatti1, Ilaria Schizzi1, Lavinia Curecheriu3, Leontin Padurariu3,
Liliana Mitoseriu3, Paola Stagnaro1, Vincenzo Buscaglia2
1
ISMAC-CNR, Via De Marini 6, 16149 Genoa, Italy
2
ICMATE-CNR, Via De Marini 6, 16149 Genoa, Italy
3
Alexandru Ioan Cuza University, Faculty of Physics, 11 Blvd. Carol I, 700506 Iasi, Romania

The demand for high dielectric constant materials and high energy density capacitors has rap-
idly increased in recent years due to the continuous and rapid development of the electronic
industry and the need of storing electrostatic energy more efficiently. The combination of
dissimilar materials in a composite represents an effective approach for the optimization of
the dielectric properties. In particular, the addition of ferroelectric (barium titanate, BaTiO3)
nanoparticles with high dielectric constant (k ≈1000) enables the relative dielectric constant
of the polymer (usually in the range 3–10) to be significantly increased without compromis-
ing some of the most useful properties of the material, i.e. its flexibility and the high dielectric
breakdown field.
Polymer composites were prepared using poly(vinylidene fluoride) (PVDF, SOLEF 6008
Solvay) as a matrix and BaTiO3 nanoparticles (diameter: 100 nm) as inclusions. The BaTiO3
particles were prepared by a hydrothermal-like method starting from BaCl2 and TiCl4 pre-
cursors. The composites were fabricated by a two-step process. Firstly, PVDF and BaTiO3
particles were intimately melt-blended at 200 °C in an internal batch-mixer. Batches of about
100 g of composites containing 20–40 vol.% BaTiO3 were prepared each time. Films with a
thickness of 0.5–1 mm were then fabricated by compression moulding.
The composites were fabricated using bare and surface-modified BaTiO3 particles. Sur-
face modification included functionalisation with coupling molecules (silane derivatives) and

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coating with a thin TiO2 shell (thickness: 20–30 nm). These engineered polymer/ceramic
interfaces should facilitate the homogeneous dispersion of the inclusions and realise a more
homogeneous distribution of the electric field in the ensuing composite.
The composites were characterised with different techniques. The microstructure was ob-
served on fragile-fracture surfaces by scanning electron microscopy. The thermal behaviour
was investigated by TG and DSC analyses. The amount of the ferroelectric crystalline β phase
in the PVDF matrix was determined by FT-IR spectroscopy. The dielectric constant and loss
tangent were measured at different frequencies by impedance spectroscopy. Simulation of
the field distribution in model composites was performed by 3D finite element modelling.

Acknowledgement
Work carried out in the framework of project Polycom funded by Fondazione Bancaria Compagnia di
San Paolo.

258
Impedance spectroscopy study on the resistance degradation
of Zr-doped barium titanate dielectrics
Han-Ting Chang, Yu-Ju Kao, Che-Ching Liao, Chi-Yuen Huang*
Department of Resources Engineering, National Cheng Kung University, Tainan, Taiwan;
*
e-mail: [email protected]
Keywords: barium titanate, impedance spectroscopy, resistance degradation, zirconium

In this study, a series of Ba(ZrxTi1-x)O3 powders were prepared for x = 0, 0.02, 0.04, 0.06,
and 0.08 compositions using a solid-state reaction. It can be seen that the substitution of
Ti4+ (0.61 Å) by 4–8% Zr4+ (0.72 Å) changes the room temperature crystal structure from te-
tragonal to orthorhombic. The Ba(ZrxTi1-x)O3 powders were sintered under a reducing atmo-
sphere in a moisturized gas mixture of N2 with 1 vol% of H2, and the resulting average grain
size ranged from 0.58 to 0.66 μm. Electrical characteristics, such as electrical resistance
at high temperature (160 °C) and impedance spectroscopy were measured. The impedance
data were fitted with an equivalent circuit model of three RC elements, which correspond-
ing to the grain, grain boundary, and electrode. From the impedance spectroscopy analysis
and resistance degradation data, the behavior of resistance degradation is observed to be
improved with the decrease of both grain and grain boundary conductivities. However, the
incorporation of Zr has an insignificant effect on the space charge layer thickness and the
grain boundary potential barrier height. The insignificant or irregular variation in impedance
spectroscopy and resistance degradation might be attributed by the similarity between the
space charge layer thickness and the grain size because of the fine grain in this study, which
means the resistance value of grain and grain boundary is not very different and the two RC
responses of grain and grain boundary could not be separated easily.

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490
Multiferroic property of samarium doped bifeo3 ceramics at
morphotropic boundary by water-quenching method
Hai In Choi1, Myang Hwan Lee1, Jin Su Park1, Da Jeong Kim1, Myung-Ho Kim1,
Won Jeong Kim2, Tae Kwon Song1*
1
School of Materials Science and Engneering, Changwon National University, 51140, South Korea;
*
e-mail: [email protected]
2
Department of Physics, Changwon National University, 51140, South Korea
Keywords: multiferroic, samarium, bismuth-ferrite, ceramic

The bismuth ferrite (BiFeO3, BFO) is a room-temperature multiferroic material with high Curie
temperature (1100K) and high Neel temperature (653K). Base on the multiferroic order of BFO
system, it will be applied to sensor devices and multi-storage memory devices. However, the
BFO cannot be approached to single phase due to the bismuth volatility and valence electron
state transition of iron. It is a hinder to measure the multiferroic property. To approach the sin-
gle phase of BFO system, solid solution with rare-earth orthoferrite is the way to improve of the
multiferroic property. In a specific selected of solid solution, SmFeO3 (SFO) with BFO system
is improved the multiferroic property at morphotropic phase boundary (Bi0.86Sm0.14FeO3).1,2 In
this study, Bi0.86Sm0.14FeO3 ceramics are studied with different sintering method; water-quench-
ing (WQ), air-quenching (Q) and furnace-cooling (FC). The phase and structure are observed
rhombohedrally distorted perovskite structure with orthorhombic phase. The ferroelectric rem-
nant polarization observed with 20 μC/cm2, 17 μC/cm2 and 15 μC/cm2 from WQ, Q and FC.
Temperature-dependent dielectric constant is observed the ferroelectric to paraelectric transi-
tion temperature at 450 oC from WQ. The piezoelectric properties are measured with 32pC/N
and 30 pm/V from WQ. Other detail information will be present with poster.

References
1. C.-J. Cheng et al., Phys. Rev. B, 80, pp. 014109, 2009.
2. J. Walker et al., Scientific Reports 6, pp. 19630, 2015.

448
Athermal TA2O5 waveguide filter for Si photonics
A.K. Chu*, S.C. Pi, Y.J. Hung, Y.Y. Lu
Department of Photonics, National Sun Yat-sen University, Taiwan;
*
e-mail: [email protected]
Keywords: athermal, Ta2O5, waveguide filter, Si photonics

Athermal waveguide devices have been studied extensively recently due to their potential
of providing stable spectrum response with respect to ambient temperature. This is of great
importance for their applications to a wavelength division multiplexing (WDM) system.

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Conventional, an athermal waveguide device can be obtained by incorporating an optical

cladding on the device and using its negative thermo-optic (TO) coefficient to counterbalance
the positive TO coefficient of the waveguide core. However, this approach is not applicable
for Si waveguides because Si has a large TO coefficient (10–4/K).1
In this work, Ta2O5 waveguide device is proposed for athermal Si photonics. The TO
coefficient of Ta2O5 is two orders of magnitude lower than that of silicon.2 In addition, the
relatively large index contrast between Ta2O5 core and silica cladding limits only a small
portion of light to propagate within the cladding. For the 0.5 μm by 0.7 μm Ta2O5 waveguide
filter, the wavelength temperature shift is 0.22 pm/K, which is over 100 times lower than that
of normal silicon waveguides.
The grating structure of the Ta2O5 waveguide filter is shown in Fig. 1. The period and duty
cycle of the grating is 440 nm and 30%, respectively. The device was completed by spin coat-
ing a 2 μm thick SOG as the top cladding and cured at 250 °C for 1h. Fig. 2 shows the TE and
TM transmission spectra of the device at room
temperature. The FWHMs of the TE mode and
TM mode are 5.1 nm and 2.7 nm. Fig. 3 shows
the temperature dependent Bragg wavelength (λB)
shift of TE mode of the waveguide filter. A to-
tal wavelength shift of 22 pm was obtained with
a temperature change of 100 °C. This indicates
that the Ta2O5 waveguide devices can be used in a
practical WDM system without temperature con-
trol.
In conclusion, we successfully demonstrated
an athermal waveguide device based on Ta2O5
material system. We believe that the proposed
material system can be useful for applications in Fig. 1. The SEM photo of the Ta2O5 grating
many practical WDM systems.

Fig. 2. The transmission spectra of the Ta2O5 Fig. 3. The temperature dependent wavelength
waveguide filter drift of the Ta2O5 waveguide filter

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References
1. J.M. Lee, D.J. Kim, H. Ahn, S.H. Park, and G. Kim, J. Lightwave Tech., vol. 25, pp. 2236–2243,
2007.
2. A.K. Chu, C.H. Lin and W.H. Cheng, J. Electron. Material, vol. 26, no. 8, pp. 889–892, 1997.

618
Effect of chromium doping in polycrystalline CCTO
Eder Carlos Ferreira de Souza1*, João Frederico Haas Leandro Monteiro1,
Christiane Philippini Ferreira Borges1, André Vitor Chaves de Andrade2,
Sandra Regina Masetto Antunes1
Department of Chemistry, State University of Ponta Grossa, 4748 Carlos Cavalcanti Avenue,
1

Ponta Grossa, Paraná, Brazil; *e-mail: [email protected]

Department of Physics, State University of Ponta Grossa, 4748 Carlos Cavalcanti Avenue,
2

Ponta Grossa, Paraná, Brazil

Keywords: chromium, calcium titanate, electroceramics, non-ohmic

CaCu3Ti4O12 (CCTO) is a ceramic with perovskite-type structure and has attracted much
interest due to its high dielectric constant (up to 105) which is almost frequency-independent
until the order of MHz and weakly dependent on the temperature in the range between 100 K
and 400 K.1 However, the origin of this unusual dielectric behavior is still controversial. The
widely accepted mechanism is the Internal Barrier Layer Capacitor (IBLC), in which consid-
ers the material as being composed of semiconductor CCTO grains and a very thin copper-
rich secondary phase observed between the grains forming insulating barriers. The main
difference between the electrical properties in grains and at grain boundaries leads to electro-
static barriers, called Schottky potential barriers. The Schottky potential barriers inhibit the
electronic transport and establish a large boundary polarization, resulting in a giant dielec-
tric constant and a characteristic non-ohmic behavior on electric conduction. The dielectric
behavior can be manipulated by several modifications in the chemical composition as well
as preparation of the material. In this work, CaCu3Ti4-xCrxO12 samples were prepared (with
x = 0.00000, 0.00025, 0.00050, 0.00075 and 0.00100) by solid state reaction. The ­FE-SEM
analysis shows that the grains have different size, from few microns up to 40 microns. At the
grains boundaries it is possible to observe CuO and TiO2 as segregate secondary phases. The
X-ray powder diffraction pattern shows the CCTO and TiO2 as recognizable crystal phases.
The CuO phase was not identified by XRD technique due to its small amount in the sample.
The I-V curve in the electrical characterization shows the non-ohmic behavior over all sam-
ples and the chromium doping strongly affects dielectric properties. The activation energy
has a small increase with the concentration of chromium, with exception of doping 0.00075
which caused a sharp fall. However, the breakdown electric field and the leakage current had
a strong increase with the dopant concentration.

Acknowledgments
Authors are thankful to UEPG/CLABMU and the financial support of CAPES/PNPD, CNPq and
Fundação Araucária.

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Reference
1. M. Li, Z. Shen, M. Nygren, A. Feteira, D.C. Sinclair, A.R. West, “Origin(s) of the apparent high
permittivity in CaCu3Ti4O12 ceramics: clarification on the contributions from internal barrier layer
capacitor and sample-electrode contact effects”, J. Appl. Phys., 106, pp. 104106, 2009.

721
ZnO nanoparticles dielectric response determined
by Terahertz time domain spectroscopy
Daniel Furka1, Samuel Furka1, Mira Naftaly2, Marian Janek1,3*
1
Department of Physical and Theoretical Chemistry, Comenius University, Mlynská dolina Ch-1,
SK-842 15 Bratislava, Slovakia
2
National Physical Laboratory, Hampton Rd, Teddington, Middlesex TW11 0LW, UK
3
Department of Inorganic Materials, Slovak University of Technology, Radlinského 9, SK-81237
Bratislava, Slovakia; *e-mail: [email protected]
Keywords: ZnO nanoparticles, hydrothermal synthesis, THz-TDS, dielectric properties, far-infrared

Zinc oxide (ZnO) belongs to the II-VI group of semiconductors with a wide band gap of
~3.37eV, and crystallises commonly as hexagonal wurzite or cubic zincblende structure,
which is responsible for its piezoelectric and pyroelectric properties. Its native doping due
to oxygen vacancies or zinc interstitials results in n-type semiconductor properties with good
electron mobility. The large exciton binding energy (60 meV) can lead to lasing action based
on exciton recombination even above room temperature, promising potential ZnO applica-
tions in optoelectronic devices, such as light emitting diodes and lasers.1 It is of interest that an
increase in electrical conductivity and a decrease in thermal conductivity was observed in ZnO
co-doped with Ni and Al.2 The growing demand for materials with appropriate parameters that
can be produced by low cost synthesis – by e.g. hydrothermal synthesis – attracted our atten-
tion both to bulk ZnO crystals, and more particularly to crystalline ZnO nanoparticles.
The dielectric properties of ZnO can be affected by nanoparticle morphology3; however,
the effect of doping on these properties has not yet been clarified. For this purpose, THz time
domain spectroscopy can be employed for the investigation of solid material. The complex
dielectric permittivity ε̃S of sample (s) is frequency (ω) dependent, i.e.: ε̃S(ω) = εS’ (ω) – iε”S(ω),
where εS’ (ω) is the real part and εS’ (ω) is the imaginary part or loss factor. The aim of our
work was to characterize the dielectric properties of ZnO nanoparticles with different mor-
phologies, i.e. the frequency dependence of their dielectric permittivity. The doping during
hydrothermal synthesis of particles was used to obtain the changes in their intrinsic electric
conductivity and in their dielectric properties. Such well-defined ZnO nanoparticles can find
utilization in a variety of applications, such as gas sensors with high resolution and low noise,
and in photocatalytic and thermo-solar reactors or thermoelectric devices.

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References
1. M. Willander, O. Nur, Q.X. Zhao et al. “Zinc oxide nanorod based photonic devices: recent pro-
gress in growth, light emitting diodes and lasers”, Nanotechn., 20, 332001 (40 pp.), 2009.
2. H. Yamaguchi, Y. Chonan, M. Oda et al. “Thermoelectric Properties of ZnO Ceramics Co-Doped
with Al and Transition Metals”, J. Electr. Mater., 40(5), pp. 723–727, 2011.
3. J. Han, W. Chen, J. Zhang et al. “Terahertz Response of Bulk and Nanostructured ZnO”, Piers
Online, 4(3), pp. 391–395, 2008.

226
Stress release induced piezoelectricity in morphotropic phase boundary
Bi0.5Na0.5TiO3-BaTiO3 ceramics
José E. García1*, Fernando Rubio-Marcos2, Elena Cerdeiras3, Diego A. Ochoa1,
José F. Fernández2, Lourdes Mestres3
1
Department of Physics, Universitat Politècnica de Catalunya - BarcelonaTech, 08034 Barcelona,
Spain; *e-mail: [email protected]
2
Department of Inorganic and Organic Chemistry, Universitat de Barcelona, 08028 Barcelona, Spain
3
Department of Electroceramics, Instituto de Cerámica y Vidrio – CSIC, 28049 Madrid, Spain
Keywords: piezoceramics, lead-free, BNT-BT, MPB

The morphotropic phase boundary (MPB) is a compositionally-driven structural change re-

gion where the coexistence of two ferroelectric phases enhances the macroscopic properties,
as in the case of the well-known, lead-based PbZrxTi1-xO3 (PZT) system. Since the better
properties are achieved in MPB compositions, the search for lead-free ceramics with po-
tential high piezoelectric properties has therefore been focused on solid solutions present-
ing MPB. The (1-x)(Bi0.5Na0.5)TiO3-xBaTiO3 (BNT-BT) system has attracted a great deal of
interest because it presents a MPB between the rhombohedral and tetragonal phases (as in
the case of PZT) for 0.05 < x < 0.08. Finding the MPB in BNT-BT system often leads up to
obtain a material that shows a (pseudo)cubic X-ray diffraction (XRD) pattern. However, this
singular composition exhibits ferroelectricity, which has been explained as a consequence of
a field-induce phase transformation. In this work, we demonstrate that the stress release after
poling, from the virgin state of the sample, is a crucial phenomenon to obtain piezoelectric
response in MPB BNT-BT.

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311
Thermally conductive aluminum nitride thick films fabricated by
granule spray in vacuum
Byung-Dong Hahn, Yuna Kim, Cheol-Woo Ahn, Jong-Jin Choi, Jungho Ryu,
Woon-Ha Yoon, Dong-Soo Park
Functional Ceramics Department, Korea Institute of Materials Science, 797 Changwondaero,
Changwon, South Korea; e-mail: [email protected]
Keywords: insulation, low volumetric heat capacity, spray coating

A thick-and-dense film can be deposited by aerosol deposition (AD) method at room tem-
perature. However, in order to be commercialized, it must be modified, since a lump of pow-
der is formed at the bottleneck of a powder feeder with ease. The lump of powder hinders
the aerosol from flowing in the AD equipment. Hence, granule spray in vacuum (GSV) is
designed to improve the aerosol flow in this study. The lump of powder is not observed at the
bottleneck, when granules are used instead of fine particles. In addition, the film deposition
also becomes easy. AlN GSV films are deposited on Al substrates and their electric/thermal
properties are compared to those of AlN AD films. GSV films show the thermal properties
better than those of AD films. Moreover, the thermal resistance is significantly reduced by us-
ing AlN GSV films instead of AlN bulk-ceramics in thermal management systems. It is due to
the removal of a thermal interface material which has low thermal conductivity. In particular,
the dielectric strengths of AlN GSV films are much higher than those of AlN bulk-ceramics
which are commercialized, approximately 5 times.

Fig. 1. Microstructure of AlN AD film and AlN GSV film

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434
Formation reactions and intermediate compounds during solid state
synthesis of (Ba,Ca)(Zr, Ti)O3 relaxor ceramics
Isabel Hanghofer, Jörg Albering, Klaus Reichmann
Institute of Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9,
8010 Graz

Compounds of the system (Ba1-xCax)(ZryTi1-y)O3 [BCZT] are under investigation because of

their high potential to replace lead-based relaxor materials such as Lead-Lanthanum-Zir-
conate-Titanate (PLZT) and others. The highly flexible polarization of BCZT solid solutions
gives rise to outstanding relaxor properties exhibiting large relative permittivities and piezo-
electric constants.
The solid state synthesis of these compounds via mixed oxide route starting from oxides
and carbonates of Barium, Calcium, Zirconium and Titanium needs temperatures up to 1400
°C and long reaction times to get the desired perovskite phase. In this study we follow the
formation reaction of BZT (x = 0, y = 0.2), BCZ (x = 0.2, y = 1) and BCZT (x = 0.06, y = 0.2)
compounds with Simultaneous Thermal Analysis coupled with Mass Spectrometry (STA-
MS) and High Temperature X-Ray Diffraction (HT-XRD).
STA-MS clearly showed the decomposition of the carbonates by mass loss and the MS
signal (ion current at 44 amu) which was completed between 1000 °C (BZT) and 1200 °C
(BCZ). At higher temperatures only flat and diffuse endothermic DSC peaks could be ob-
served.
With HT-XRD we were able to identify intermediate compounds of this reaction mixture
and the onset temperature of the formation of the complex perovskite. In the BZT compound
first BaTiO3 is formed around 650 °C followed by BaZrO3 at 900 °C. Also an intermediate
compound with the structure of Ba2TiO4 appears between 900 °C and 1200 °C. The complex
BZT perovskite starts to appear at 1100 °C. In the BCZ compound the formation of several
modifications of BaCO3 can be observed due to the low reactivity of the Zirconium Oxide.
Traces of perovskite phase are observed from 800 °C onwards, but the increase of the por-
tion of perovskite phase starts not before 1050 °C. As intermediate compounds Ba2TiO4 and
(Ba,Ca)O can be identified.

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164
Dielectric tunable and ferromagnetic properties
of Ba0.5Sr0.5TiO3-MgFe2O4 composite ceramics
Yanyan He, Qing Ai, Yebin Xu*
School of Optics and Electronics Information, Huazhong University of Science and Technology,
Wuahn, Hubei, P. R. China; *e-mail: [email protected]
Keywords: ferroelectrics, ferromagnetic, tunability, composite

Ba0.5Sr0.5TiO3/MgFe2O4 ceramics were prepared and their dielectric and ferromagnetic

properties were investigated. XRD data show ceramics consist of only Ba0.5Sr0.5TiO3 and
­MgFe2O4. The permittivity of Ba0.5Sr0.5TiO3/MgFe2O4 decreases with the increase of ­MgFe2O4
content when the content of MgFe2O4 is small and the sintering temperature is low. For
Ba0.5Sr0.5TiO3/MgFe2O4 composite ceramics with high MgFe2O4 content (>40%), higher sin-
tering temperatures (≥1300 oC) result in dramatic increased dielectric constant and dielectric
loss due to percolation effects. The tunability of Ba0.5Sr0.5TiO3/MgFe2O4 sintered at 1300 oC
decreases with the increase of MgFe2O4 content. On the other hand, sintering temperature has
significant effect on the tunability. The tunability of 0.5BST/0.5MgFe2O4 decreases rapidly
with the increase of the sintering temperature. The tunability of 0.5BST/0.5MgFe2O4 sintered
at 1200 oC (21% under 3kV/mm) is even higher than that of 0.9BST/0.1MgFe2O4 sintered at
1300 oC (16% under 3kV/mm), although 0.5BST/0.5MgFe2O4 has higher MgFe2O4 content
than 0.9BST/0.1MgFe2O4. This interesting phenomenon may open a new route to control
the tunability of composites. For Ba0.5Sr0.5TiO3/MgFe2O4 composite ceramics with MgFe2O4
content > 10 wt%, the Lichtenecker model and the corrected Lichtenecker model predict the
relation between MgFe2O4 content and the permittivity very well. Saturation magnetization
of BST/MgFe2O4 composite ceramics increase with the increase of MgFe2O4 content.

References
1. H. He and Y.B. Xu, “A unified equation for predicting the dielectric constant of a two phase com-
posite”, Appl. Phys. Lett., 104, pp. 062906-1-062906-4, 2014.
2. S.S. Kalarickal, D. Ménard and J. Das et al., “Static and high frequency magnetic and dielectric
properties of ferrite-ferroelectric composite materials”, J. Appl. Phys., 100, pp. 084905-1-084905-
9, 2006.

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567
Graphitic C/cobalt core shell composites for magneto-optical
applications
Hua Shu Hsu1*, Yen Cheng Chang1, Ya Hui Huang1, Zdenek Remes2
1
Department of Applied Physics, National Pingtung University, No. 4-18, Taiwan, R. O. C.;
*
e-mail: [email protected]
2
Institute of Physics of the ASCR, v.v.i., Cukrovarnicka 10, Praha 6 16200, Czech Republic
3
Faculty of Biomedical Engineering of the Czech Technical University in Prague, nam. Sitna 3105,
272 01 Kladno, Czech Republic
Keywords: carbon, magneto-optical, graphitization

Carbon(C) based materials, due to its uniqueness of physical properties, have attracted in-
creasing interests for electronic applications. For example, amorphous carbon (a-C) thin film
which is a semiconductor with a mixture of sp2 and sp3 bond characteristics, can change its
optical, electrical, and mechanical properties by change its sp2/sp3 ratio.1 In addition, the inte-
gration of ferromagnetic materials (FMs) and a-C can reveal interesting magneto-electronic
and magneto-optical (MO) phenomena. The interfacial hybridization between FMs and a-C
has been considered as an important role for these observed results. In addition, there are also
reports that the presence of a metal can promote the formation of sp2-bonded C nanostruc-
tures by metal-contact-induced graphitization following suitable annealing.2 Therefore, in our
work, graphitic C/Co core shell composites could be fabricated by r. f. sputtering and rapid
thermal annealing (RTA). The metastable Co-C bonding in the as grown Co/a-C composites is
decomposed and graphitic C/Co interfaces after RTA are thus formed evidenced by our high
resolution transmission microscopy measurements. The x-ray absorption spectra also show a
strong hybridization between graphitic C and Co. In such samples, a following strong MO ef-
fect in graphitic C/Co core shell composites was observed. One broad MO signal (feature A)
below 4.1 eV was obtained, while the other (feature B) shows a peak at 5.5 eV while applied
a magnetic field. We propose that the broad MO signal arises from the optical transitions be-
tween Co d orbitals or bands of small clusters of metallic Co and the peak at 5.5 eV could be
related to C σ-σ* gap transition. The increase in MCD intensity of feature A and the decrease
in MO intensity of feature B from 15K to 300 K implies the existence of antiferromagnetic
coupling between Co d orbits and graphitic C πorbits, therefore, inducing the strong MO ef-
fect. We expect these results would open new a perspective for C based MO materials

Acknowledgements
This work is supported by the Ministry of Science and Technology of the Republic of China, Taiwan,
under Contract No. MOST 104-2112-M-153 -002 -MY3, MOST 105-2911-I-153 -501, and CSF project
16-10429J.

References
1. S.R.P. Silva. Properties of Amorphous Carbon, INSPEC IEE, London, 2003.
2. Hua-Shu Hsu, Yu-Ying Chang, Yi-Ying Chin, Hong-Ji Lin, Chien-Te Chen, Shih-Jye Sun, Sergey
M. Zharkov, Chun-Rong Lin and Sergey G. Ovchinnikov, “Exchange bias in graphitic C /Co com-
posites.” Carbon, 114, pp. 642–648, 2017.

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710
The integration of functional oxide thin film with GaAs by laser
molecular beam epitaxy
W. Huang
State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronics
Science and Technology of China, Chengdu, China; e-mail: [email protected]

Integration of crystalline oxide thin films with semiconductors has attracted considerable at-
tention in recent years. Compared to Si, GaAs have a higher saturated electron velocity and
electron mobility, transistors based on GaAs can function at a much higher frequencies. In
this talk, SrTiO3 films were grown on GaAs (100) substrates as an intermediate buffer layer
for the epitaxial growth of oxide thin films including ferroelectric BaTiO3 and semiconductor
ZnO by laser molecular beam epitaxy (L-MBE). The properties of the multilayers in terms
of growth modes, strain and interface structures were characterized by the in-situ reflective
high energy electron diffraction (RHEED) pattern. The crystalline quality and surface mor-
phology of the oxide/GaAs heterostructure were investigated respectively by a combination
of X-ray diffraction (XRD) and atomic force microscopy (AFM). These heterostructure ex-
hibit good functional properties such as ferrelectrisity and resistive switching. Furthermore,
the fundamental interface properties of these heterostructure with an emphasis on the strain
effect were discussed in relation with the electrical properties. The results provide an under-
standing of the integration of oxide/GaAs heterostructure with full control over the interface
structure at the atomic-scale.

781
Synthesis and electrical conductivity of Ba2MM’O6(M = La and In,
M’ = Bi and Sb) with double perovskite structure
Yoshihiko Inagaki, Susumu Takahashi, Akinori Kan*, Hirotaka Ogawa
Graduate School of Science and Technology, Meijo University, 1-501 Shiogamaguchi, Tempaku-ku,
Nagoya 468-8502, Japan; *e-mail: [email protected]
Keywords: electrical conductivity, double perovskite, Ba2LaBiO6

In recent years, the considerable attention has been paid to the characterization of perovskite-
structured electrolytes because of their proton conductivities for the application to the inter-
mediate temperature fuel cells which can operate at the lower temperatures below 600 °C.
In such the electrolytes, the acceptor doping has been performed to introduce the oxygen
vacancy which takes place the proton incorporation in the lattice.1,2 On the other hand, the
double perovskite-structured compounds with general formula A2MM’O6 have two octahe-
dral sites which correspond to the MO6 and M’O6 octahedra; the relationship between the
acceptor doping in M and M’ site and the electrical conductivity has not been clarified. Thus,

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two types of compounds such as Ba2LaBiO6 and Ba2InSbO6 were prepared and the influence
of Mg substitution for M (M = La and In) on the electrical conductivity was investigated in
this study. The Ba2(La1-xMgx)BiO6 and Ba2(In1-xMgx)SbO6 ceramics were synthesized using
the conventional solid-state reaction method, and sintered at 1200 °C for 2 h and 1550 °C
for 10 h in air, respectively. The XRPD profiles of the Ba2(La1-xMgx)BiO6 and Ba2(In1-xMgx)
SbO6 ceramics showed the single phase in the composition range of x = 0–0.15, suggesting
the introduction of oxygen vacancy in the lattice. In this case of Ba2(La1-xMgx)BiO6 ceram-
ics, the electrical conductivity of the ceramics was improved by the Mg substitution for La.
However, the electrical conductivities of Ba2(La1-xMgx)BiO6 ceramics were lower than those
of Ba2(In1-xMgx)SbO6 ceramics. As a result, the highest electrical conductivity of 5.4×10–2S/
cm was obtained for Ba2(In0.95Mg0.05)SbO6 (x = 0.05) ceramic at 500 oC.

References
1. H. Iwahara et al., Solid State Ionics 3/4 (1981) pp. 359–363.
2. H. Iwahara et al., Solid State Ionics 31 (1993) pp. 65–69.

776
Enhancement of piezoelectric properties of (K0.5Na0.5)NbO3-LiSbO3
ceramics by BaSnO3 addition
Akinori Kan*, Shinnosuke Ohhashi, Ryo Onishi, Hirotaka Ogawa
Graduate School of Science and Technology, Meijo University, 1-501 Shiogamaguchi, Tempaku-ku,
Nagoya, 4688502, Japan; *e-mail: [email protected]
Keywords: piezoelectric property, K0.5Na0.5NbO3

Recently, K0.5Na0.5NbO3(KNN)-based piezoelectric ceramics have been studied exten-

sively because they are considered to be one of the most promising lead-free piezoelectric
ceramics. These ceramics are known to possess a high Curie temperature (Tc = 420 °C),
a relatively high piezoelectric constant (d33 = 160 pC/N), and a large electromechanical
coupling coefficient.1 In addition, many attempts have been made to find alternative ways
to obtain KNN-based ceramics with appropriate piezoelectric properties, and the chemical
modification of KNN through forming solid solutions or the addition of sintering aids have
been performed to shift the orthorhombic-tetragonal transition temperature (TO-T) from ap-
proximately 200 °C to room temperature.2–4 Such the change in the transition temperature
generally leads to the enhancement of the piezoelectric properties, resulting the presence
of morphotropic phase boundary (MPB) between the orthorhombic and tetragonal phases.
For example, in the KNN-LiSbO3 system, it is reported that K0.474Na0.474Li0.052Nb0
.948Sb0.052O3 (KNLNS) ceramic at the MPB region exhibits a d33 value of 221 pC/N.4
Moreover, the chemical modification of KNLNS-based ceramics by ABO3 addition has also
been performed to clarify the possibility of the improvement in the piezoelectric properties.
As a result, the d33 value of 280 pC/N was obtained for (1-x)KNLNS-xBaTiO3 at x = 0.06.5
In this study, the cubic-structured BaSnO3(BS) addition into KNLNS was performed and the

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piezoelectric properties of (1-x)KNLNS-xBS was characterized. KNLNS and BS powders

were prepared separately via conventional solid –state reaction method and these powders
were weighed according to the stoichiometric composition of (1-x)KNLNS-xBS (x = 0–0.02)
and fired in the temperature range of 1080–1150 °C for 3 h. X-ray powder diffraction profiles
suggested the formation of MPB between the orthorhombic and tetragonal phases in the
composition range of 0–0.01; at x = 0.02, the secondary phase was detected. With increasing
the composition x from 0–0.01, the shifts of Tc and TO-T to lower temperatures were observed
from the evaluation of temperature dependence of the dielectric constant, and the dielectric
constant at room temperature increased in such composition range. The variation in the d33
value of the ceramics showed a similar tendency to that of the dielectric constant at room
temperature; the highest d33 value of 302 pC/N was obtained for x = 0.005.

References
1. R. Zou et al., Appl. Phys. Lett. 90 (9) (2007) 092904.
2. H. Du et al., J. Am. Ceram. Soc. 90(9) (2007) pp. 2824–2829.
3. B. Malic et al., J. Eur. Ceram. Soc. 28(6) (2008) pp. 1191–1196.
4. J. Wu et al., Jpn. J. Appl. Phys. 46 (11) (2007) pp. 7375–7377.
5. H. Ogawa et al., Ferroelectrics 497 (2016) pp. 52–61.

953
Electrical properties of 0.5PNN-0.5PZT ceramics and their 1-3
piezocompozites
Mustafa Yunus Kaya1, Mehmet Gurkan Ozyazici1, Ebru Mensur-Alkoy2, Sedat Alkoy1
1
Department of Materials Science and Engineering, Gebze Technical University, Gebze/Kocaeli,
Turkey; e-mails: [email protected], [email protected]
2
Faculty of Engineering and Natural Sciences, Maltepe University, Maltepe/Istanbul, Turkey
Keywords: lead nickel niobate, electrical properties, pieozocomposite, fibrous ceramic

In this study, lead nickel niobate (PNN)-lead zirconate titanate (PZT) system was investi-
gated. PNN was alloyed by a certain amount of PZT that formed a stoichiometric notation of
0.5[Pb(Ni1/3Nb2/3) O3]-.0.5Pb(Zr0.3-Ti0.7)O3. Powder synthesis was consisted of two step calci-
nation which is based on B-site precursor (NiNb2O6) preparation known as columbite method
and conventional solid state synthesis technique in order to attain not only perovskite phase
comparably but also conserving the stoichiometry. After calcination process, powders were
formed as disc shaped samples by uniaxial press. In addition to bulk ceramic processing,
PNN-PZT fibrous piezoceramics were also fabricated by alginate gelation technique, which
reported elsewhere.1,2 Sintering process was carried out for both bulk and fibrous ceramics at
1200 oC in a closed alumina crucible. Piezocomposites with 1–3 connectivity3 were prepared
by aligning the fibers in an ordered pattern then those were embedded into polyurethane
matrix. Upon completion of curing the polymer matrix, the piezocomposites were sliced
into appropriate thicknesses. Piezocomposite samples with 1–3 connectivity were polished
and surface of the samples were coated with silver electrode for electrical characterizations.

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Properties of ceramics were measured at room temperature as dielectric constant (K) 5530,
dielectric loss (tan δ) 0.02, piezoelectric charge constant (d33) 780 pC/N, saturation polariza-
tion (Ps) 36.4 μC/cm2, remnant polarization (Pr) 28.1 μC/cm2 electromechanical coupling (kp)
0.64 and mechanical quality factor (Qm) 97.

References
1. S. Alkoy, H. Yanik, and B. Yapar, “Fabrication of lead zirconate titanate ceramic fibers by gelation
of sodium alginate,” Ceram. Int., vol. 33,no. 3, pp. 389–394, 2007.
2. E. Mensur-Alkoy, M.Y. Kaya, D. Avdan and S. Alkoy, “Properties of [Pb(Zn1/3Nb2/3)O3]x –
[Pb(Zr0.48Ti0.52)O3](1–x) Ceramics With Low Sintering Temperature and Their 1–3 Piezocomposites,”
in IEEE Transactions on Ultrasonics, Ferroelectrics, and Frequency Control, vol. 63, no. 6, pp.
907–914, June 2016.
3. R.E. Newnham, D.P. Skinner, and L.E. Cross, “Connectivity andpiezoelectric-pyroelectric compos-
ites,” Mater. Res. Bull., vol. 13, no. 5, pp. 525–536, 1978.

575
Studies of photoluminescence and energy transfer in europium and
dysprosium co-doped oxyfluoride glasses and glass ceramics
Meldra Kemere*, Uldis Rogulis, Janis Sperga
Institute of Solid State Physics, University of Latvia, 8 Kengaraga Street, Latvia;
*
e-mail: [email protected]
Keywords: photoluminescence, RE ions, oxyfluoride glass ceramics, nanocrystallites, WLED

RE ions doped glass ceramics are considered as prospective materials for scintillators, lasers,
communications and lighting devices. RE doped oxyfluoride glass ceramics are promising
materials for lighting devices due to their advantages compared to other materials- the oth-
erwise hygroscopic fluoride nanocrystallites are isolated in a stable oxide matrix and are
characterized with low phonon energy.1 Much effort is aimed to develop highly efficient
white light emitting diodes (WLEDs) using RE ions co-doped glass ceramic materials as
phosphors. White light emission from Dy-Eu co-doped glasses and glass ceramics has been
reported.2
In the present work, series of SiO2-Al2O3-CaO-CaF2 glasses, doped with Dy2O3 (0–1mol%)
and Eu2O3 (0-1mol%) have been prepared, using the conventional melt quenching method.
Glass ceramics were obtained by heating the as-made glasses at temperature of 680 °C and
750 °C. Photoluminescence emission and excitation, as well as luminescence decay measure-
ments of the samples were performed. DTA and XRD measurements were performed as well.
The heat treatment temperatures were chosen on the basis of DTA data to obtain CaF2 crystal-
lites, XRD analysis approves the formation of nanosized CaF2 crystallites.
Single doped samples, activated with 0.5 mol% Dy3+ show the highest luminescence in-
tensity with respect to co-doped samples and samples with Dy3+ in higher concentrations.
Luminescence excitation measurements and luminescence decay kinetics approve the energy
transfer (ET) process from Dy3+ to Eu3+ ions in all samples, ET efficiency in the glasses

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and glass ceramics is similar. The luminescence lifetimes of Dy3+ ions decrease in the glass
ceramics. In the glass ceramics, a partly reduction from Eu3+ to Eu2+ ions is observed. The
luminescence of Eu2+ ions in the blue spectral range allows to obtain white light emission of
the glass ceramics under UV excitation.

References
1. C. Zhu, D. Wu, Y. Zhang, M. Zhang, Y. Yue, “Composition dependence of the optical and structural
properties of Eu-doped oxyfluoride glasses”, J. Alloys Compd., 632, pp. 291–295, 2015.
2. P.P. Fedorov, A.A. Luginina, A.I. Popov, “Transparent oxyfluoride glass ceramics”, J. Fluorine
Chem., 172, pp. 22–50, 2015.
3. J.L. Cai, R.Y. Li, C.J. Zhao, S.L. Tie, X. Wan, J.Y. Shen, “White light emission and energy transfer
in Dy3+/Eu3+ co-doped aluminoborate glass”, Opt. Mater., 34(7), pp. 1112–1115, 2012.

400
Two-step sintering of KNN-based ceramics for multi-layered
piezoelectric energy harvester
J.H. Kim1, D.S. Kim1,2, S.H. Ko1, J.S. Kim1, S.H. Han2, H.W. Kang2, H.G. Lee2, C.I. Cheon1*
Department of Materials Science and Engineering, Hoseo University, Asan,
1

Chungnam 336-795 Korea; *e-mail:[email protected]

Electronic Materials and Device Research Center, Korea Electronics Technology Institute,
2

Bundang-gu, Seongnam, Kyeonggi, 463-816, Korea

Keywords: piezoelectric, (K,Na)NbO3, energy harvester, multi-layered ceramic, two-step sintering

Piezoelectric materials have been applied in various electronic devices such as actuators, sen-
sors, and transducers. Recently, piezoelectric energy harvesters (PEH) that generate electrical
energy from environmental vibrations have been developed for applications such as wireless
self-powered sensor nodes.1 The standard electronic conversion circuitry and a normal bat-
tery voltage capacity of about 3V require multilayered PEH generating a large current and a
low voltage. As increasing concern of the global environment issue in Pb-based piezoelectric
ceramics, there have been considerable efforts to develop lead-free piezoelectric.2 (K,Na)
NbO3 (KNN) based ceramics have been considered as one of the most promising lead-free
ceramics due to large piezoelectric constants comparable to Pb-based ceramics. Low tem-
perature sintering is required for reducing the amount of noble metals in internal electrodes
of multilayered ceramics. CuO-doped KNN ceramics have been sintered successfully at low
temperature below 950 °C and demonstrated a high mechanical quality factor. However,
CuO-doped KNN ceramics displayed inhomogeneous microstructures resulting from an ab-
normal grain growth (AGG). KNN ceramics with large abnormally-grown grains are not
adequate for multilayered PEH. In this work, we tried to prepare CuO-doped KNN ceramics
with fine grains of a few micrometers at low sintering temperature for multi-layered PEH. A
two-step sintering process was tried to suppress AGG without scarifying good piezoelectric
properties. Two-step sintering process was verified to suppress AGG and demonstrate high
piezoelectric properties. Two-step sintering process was also applied for fabricating PEH.

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References
1. T. Rödig and A. Schönecker, “A Survey on Piezoelectric Ceramics for Generator Applications”, J.
Am. Ceram. Soc., 93, pp. 901–912, 2010.
2. J. Rödel, K.G. Webber, R. Dittmer, W. Jo, M. Kimura, D. Damjanovic, “Transferring lead-free
piezoelectric ceramics into application”, J. Eur. Ceram. Soc., 35, pp. 1659–1681, 2015.

786
Secondary phases in the system NBT-BT(-KNN)
Jakob König*, Danilo Suvorov
Advanced Materials Department, Jožef Stefan Institute, Jamova 39, Slovenia;
*
e-mail: [email protected]
Keywords: solid-state synthesis, secondary phases, electrical properties

After 15 years of investigations to replace lead-based materials in piezoelectric applications a

breakthrough in still lacking. One of the most promising materials are Na0.5Bi0.5TiO3 (NBT)-
based materials exhibiting incipient piezoelectric effect1.
We investigated solid-state synthesis of the composition NBT-6wt% BaTiO3 (NBT-6BT)
and the influence of the doping with 2wt% K0.5Na0.5NbO3 (KNN). The results show that
in NBT-6BT sample minor amount unidentified Na-, Ti- and Ba-rich secondary phases is
formed. When doping with KNN additional secondary phase is present, i.e. BaTi4O9 or
­Ba2Ti9O20 as suggested by electron dispersive spectroscopy (EDS). The amount of this phase
is much larger than the amount of secondary phase in NBT-6BT. In the latter, secondary
phase forms a transient liquid, which results in a growth of matrix grains in the areas with the
secondary phase. On the contrary, in KNN-doped sample the secondary phases are present
in needle- or plate-like shape. However, none of these secondary phases can be detected by
X-ray powder diffraction (XRD).
The processing of the samples (calcinations, milling, raw materials, sintering, etc.) has a
great influence on electrical properties. Dielectric properties of KNN-doped sample indicate
presence of an additional phase which reacts with humidity. Such behaviour deteriorates
electrical properties, similar as in K0.5Bi0.5TiO3 (KBT)2. Control of the stoichiometry is the
key factor securing good electrical properties. Excess of alkali elements has to be avoided.

References
1. W. Jo et al, “Giant electric-field-induced strains in lead-free ceramics for actuator applications –
status and perspective”, J. Electroceram., 29, pp. 71–93, 2012.
2. J. König and D. Suvorov, “Evolution of the electrical properties of K0.5Bi0.5TiO3as a result of
prolonged sintering”, J. Eur. Ceram. Soc., 35, pp. 2791–2799, 2015.

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573
Lead free piezoelectric system by solid state microwave synthesis
Anggel Lagunas-Chavarría1,2, Maria Guadalupe Navarro-Rojero1,
María Dolores Salvador2, Amparo Borrell2*
1
CIATEQ A.C. Av. del Retablo 150 Col. Constituyentes Fovissste, 76150, Querétaro, México
2
Instituto de Tecnología de Materiales (ITM), Universitat Politècnica de València, Camino de Vera,
s/n, 46022 Valencia, Spain; *e-mail: [email protected]
Keywords: microwave processing, calcination, sintering, piezoelectric properties

The remarkable piezoelectric properties of (Zr,Ti)PbO3 ferroelectrics systems make them

suitable for applications in sensors, transducers and actuators, however, it is necessary to find
alternative systems capable of achieving their properties without the lead presence. A promis-
sory alternative are the based (K,Na)NbO3 (KNN) ceramics systems due to their relatively
strong piezoelectricity at high temperatures1. The synthesis of this lead-free piezoelectric
materials is very complex due to the volatility of alkali elements and the moisture sensitivity.
The microwave processing is a method which involve a volumetric heating by the absorption
of electromagnetic energy and has been reported as an excellent via to improve the proper-
ties of several ceramic systems. The microwave heating mechanism of synthesis involve the
energetic efficiency and enhanced reaction rates, furthermore, microwave technique is a very
clean process and non-polluting method which results in improved properties2.
In this work, the KNN based system (K0.44Na0.52Li0.04) (Nb0.84Ta0.10Sb0.06)O3 piezoelectric
ceramic have been synthetizing by the microwave solid state synthesis and their comparison
with conventional mixed oxide route. The microwave calcination is being carrying out at
different temperatures in air. The results obtained by X-Ray diffraction shows the formation
of the perovskite structure. The structural and microstructural evolution is studied by the
shift on microwave calcination temperatures and compared with the conventional synthesis
process.

Acknowledgements
This work has been supported by the Spanish Ministry of Economy and Competitiveness MINECO by
Juan de la Cierva-Incorporación contract (IJCI-2014-19839) and Polytechnic University of Valencia
and CIATEQ (ref. 13865).

References
1. F. Rubio-Marcos, R. López-Juárez, R.E Rojas-Hernandez, A. del Campo, N. Razo-Pérez and J.F.
Fernandez, “Lead-Free piezoceramics: Revealing the role of the rhombohedral–tetragonal phase
coexistence in enhancement of the piezoelectric properties”, ACS applied materials & interfaces,
7, pp. 23080–23088, 2015.
2. M. Feizpour, H. Barzegar Bafrooei, R. Hayati and T. Ebadzadeh, “Microwave-assisted synthesis
and sintering of potassium sodium niobate lead-free piezoelectric ceramics”, Ceram. Int., 40, pp.
871–877, 2014.

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749
Growth and characterization of GAN and InGaN nanostructures on
carbon nanotubes
Sung-Nam Lee
Department of Nano-Optical Engineering, Korea Polytechnic University, Siheung, 15073,
South Korea; e-mail: [email protected]
Keywords: GaN, InGaN, CNT, nano-structure, MOCVD

Nanostructures have attracted significant attention for high performance electronic and op-
toelectronic devices because of their superior physical and chemical properties.1 Among
nanostructures, the carbon nanotube (CNT) is a particularly important material because it
will be applied to many technologies, such as transparent electrode, gas reservoirs, and field
emission displays. In addition, GaN-based nanostructures have studied to improve the emis-
sion efficiency of light-emitting devices such as quantum well, quantum dots, nanorods and
nanowires. Although both material systems are in the commercialized-step, there are only a
few reports to combine nitride-binary system and CNT. Until now, most research groups have
studied on the binary InN or GaN to form nanostructure such as nanotube, nanorods, nano­
wires and nanocomposites on CNTs.2,3 Due to the growth difficulties of ternary nitrides such
as InGaN or AlGaN, there is no report to study on the visible green emission of InGaN on
CNT template. In this study, we systematically studied the growth and optical characteriza-
tion of GaN and InGaN nanostructure on CNT template.
We have successfully grown GaN and InGaN nanostructures on CNT/Si template by using
MOCVD. From SEM results, we found that the bundled CNTs are embedded with discon-
tinuous GaN hexagonal island structure. InGaN nanostructures were directly grown on the
edges of CNTs and they are estimated to be polygonal crystal structure with the dimension
of 100 ~ 270 nm. From high-resolution X-ray diffraction measurements, we found that (002)
GaN was the main crystallographic plane of GaN hexagon columns, rather than (101)GaN. In
addition, two low-angle side peaks and the asymmetric (002)GaN peak were observed to be re-
lated a low In content InGaN nanostructure. Moreover, the selected area electron diffraction
(SAED) patterns shows that the crystallites of InGaN nanostructures formed in random direc-
tions, but that single InGaN nanostructures were single crystal. We observed the strong green
(~500 nm) photoluminescence (PL) and cathodoluminescence spectra from InGaN nano-
structures, indicating excellent optical properties of InGaN nanostructure grown on CNT
template. In addition, we found that the internal quantum efficiency of InGaN nanostructure
is 11.4% by using the temperature dependent PL measurements. Based on these results, we
suggest that GaN and InGaN nanostructures be successfully grown on CNT template and can
improve the emission efficiency for green gap region.

References
1. F.A. Ponce and D.P. Dour, Nature, 386, 351, 1997.
2. J. Zhu and S. Fan, J. Mat. Res., 14, 1175, 1999.
3. P.V. Chandrasekar, H. Jung, C.G. Kim and D. Kim, CrystEngComm., 14, 2166, 2012.

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852
Amorphous In-Zn-Sn oxide-based thin film transistors:
channel thickness dependence
Annisa Dwi Lestari, Imas Noviyana, Maryane Putri, Hee Young Lee*
Department of Materials Science and Engineering, Yeungnam University, Gyeongsan,
Republic of Korea; *e-mail: [email protected]
Keywords: InZnSnO, amorphous oxide semiconductor (AOS), thin film transistor (TFT)

Amorphous oxide semiconductor (AOS) thin films within the ternary oxide system com-
prised of In2O3-ZnO-SnO2 components were investigated for possible application toward
transparent thin film transistor devices. Radio frequency (RF) magnetron sputtering tech-
nique was used in the deposition of amorphous In-Zn-Sn-O (a-IZTO) films which served as
an active channel layer between Cu/Ti bilayer source and gate contacts of oxide thin-film
transistors (TFTs). Test device was prepared using a SiO2/n++ Si substrate and adopted the
so-called “bottom gate” structure. Thickness of the channel varied from 15 to 150 nm. It was
found that the excellent performance was realized from thus prepared a-IZTO TFTs with
field effect mobility of 25 cm2V–1s–1, high on/off current ratio of >108, low threshold voltage
of –0.1 V and a subthreshold swing of 0.14 Vdec–1 when the device was fabricated from 30
nm a-IZTO films. TFT devices with higher channel thickness showed the degradation of
TFT performance.1 To investigate device stability, positive and negative bias stress (PBS and
NBS) measurements were also conducted up to 3600 sec in the dark chamber. A small deg-
radation was observed where threshold voltage value shifted to the positive direction while
field effect mobility decreased as a function of time under positive and negative bias stress
for all a-IZTO film thicknesses. This certainly indicates the viability of a-IZTO TFTs as one
of alternatives replacing current LTPS TFT device. Moreover, due to its high optical trans-
parency, a-IZTO TFT could also be used in transparent devices such as transparent displays.

Reference
1. S.M. Sze. Physics of Semiconductor Devices. John Willey and Sons, New York, 1981.

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332
Preparation of indium oxide-coated tin oxide nanoparticle and its
application to low temperature carbon monoxide sensor
I-Chen Lin, Chin-Yi Chen*
Department of Materials Science and Engineering, Feng Chia University, Taichung 407, Taiwan;
*
e-mail: [email protected]
Keywords: SnO2, In2O3, CO sensor, low temperature, thermal decomposition, sensitivity

Gas sensor which is composed of nanostructured oxide semiconductor with extremely high
specific surface area possesses competitive advantages for achieving a high sensitivity and
rapid response,1 due to the high sensing reaction involving redox interaction between the
target gas and the charged oxygen adsorbed on the surface. Generally, the metal oxides need
to be heated to high temperature (~300–500 °C) to obtain appropriate sensitivity levels, re-
sulting in high power consumption.2 In the present study, a low operating temperature carbon
monoxide (CO) sensor was fabricated from a nanometer-scale tin oxide (SnO2) powder. The
SnO2 nanoparticles in a size range 10–20 nm were synthesized as a function of surfactant
(tri-n-octylamine) addition (0–1.5 mol%) via a simple thermal decomposition method. The
resulting SnO2 nanoparticles were first screen-printed onto an electrode patterned substrate
to be a thick film, and then indium oxide (In2O3) was coated on the surface of the SnO2 thick
film by photochemical reduction. Subsequently, the composite film was heat-treated to be a
device for sensing CO gas. The thermal decomposed powders were characterized by field-
emission scanning electron microscopy (FESEM), X-ray diffractometry (XRD), and surface
area measurements (BET). The CO-sensing performance of all the sensors was investigated.
The experimental results showed that the tri-n-octylamine addition significantly decreased
the particle size of the resulting SnO2 nanoparticle. However, the smaller particle tended to
cause the formation of agglomeration, resulting in the decline of surface area and reducing
the reaction site during sensing. As a CO sensing material, the SnO2 nanoparticle (~12 nm in
diameter) prepared with 1.25 mole% tri-n-octylamine addition exhibited most stable electri-
cal performance. When In2O3 was photo-chemically coated onto the SnO2 sensing material,
the sensor was able to perform a superior sensing property at a relatively low working tem-
perature < 50 °C.

References
1. C.S. Moon, H.-R. Kim, G. Auchterlonie, J. Drennan, J.-H. Lee, “Highly sensitive and fast respond-
ing CO sensor using SnO2 nanosheets”, Sens. Actuators B, 131, pp. 556–564, 2008.
2. H. Long, A. Harley-Trochimczyk, T. He, T. Pham, Z. Tang, T. Shi, A. Zettl, W. Mickelson, C. Car-
raro, R. Maboudian, “In situ localized growth of porous tin oxide films on low power microheater
platform for low temperature CO detection”, ACS Sens., 1, pp. 339–343, 2016.

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319
Precursor influence on morphology and photoluminescence properties
for Eu-doped gehlenite glassy particles
Shih-Heng Lin1, Shao-Ju Shih1, Abadi Hadush1, Dušan Galusek2, Wei-Hsing Tuan3
1
Department of Materials Science and Engineering, National Taiwan University of Science and
Technology, Taiwan; e-mail: [email protected],edu.tw
2
Joint Glass Centre of the IIC SAS, TnU AD and FChFT STU, Študentská 2, 911 50 Trenčín, Slovakia
3
Department of Materials Science and Engineering, National Taiwan University, Taipei, Taiwan
Keywords: gehlenite, glass, spray pyrolysis, morphology, photoluminescence

The Eu-doped gehlenite glassy particles were synthesized using spray pyrolysis. For mor-
phology control, the porous and hollow glassy particles were synthesized using the common
pore-forming agents of polyethylene glycol and hydrogen peroxide, respectively. The ex-
perimental results revealed that the hollow particles exhibited the higher photoluminescence
properties than porous and solid particles. So, the hollow Eu-doped gehlenite glassy particles
could be one of the potential candidates for future phosphor applications.

References
1. V. Natarajan, K.V.R. Murthy and M.L. Jayanth Kumar, “Photoluminescence investigations of
­Zn2-SiO4 co-doped with Eu3+ and Tb3+ ions”, Solid State Commun., 134, pp. 261–264, 2005.
2. S.J. Shih, Y.C. Lin, S.H. Lin and C.Y. Yu, “Correlation of morphology and photoluminescence
properties of gehlenite: Eu glassy phosphors”, Int. J. Appl. Ceram. Technol., 14, pp. 56–62, 2017.

192
Synthesis of graphene by laser scribed graphene (LSG) method
M. Namdar, Sh. Asl*
Dept. of Materials Eng., University of Tabriz, Tabriz 51666-16471, Iran;
*
e-mail: [email protected]
Keywords: graphene oxide, laser scribed graphene (LSG), scanning electron microscope (SEM)

Graphene conducts electricity and heat better than anything else and has combination of
unique optical and mechanical properties. Electrons have nobilities in graphene over a hun-
dred times those in silicon.
In the present work we used a standard optical LightScribe DVD drive to directly do the
laser reduction of graphene oxide (GO) films to graphene. GO was prepared by the modified
Hummers’ method as reported elsewhere. Briefly, 2 g graphite powders was added to a mix-
ture of 1 g NaNO3 and 46 ml H2SO4 and the mixture was cooled to 10 °C using an ice bath.
In the next step, 6 g KMnO4 was gradually added to the solution and the reaction temperature
was maintained below 20 °C. The mixture was then stirred at 35 °C for 2 h. The resulting
solution was diluted by adding 92 ml of deionized water until a dark brown suspension was

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T04: Electroceramics and optical materials – Poster presentations

obtained. Then, the solution was treated by adding 340 ml H2O2 solution. Finally, a uniform
suspension of GO nanosheets was obtained by adding water to the resulting precipitate and
12 h of sonicating. The resulting suspensions were uniformly drop casted on a LightScribe
DVD disk and then dried under the air at an ambient temperature. The GO coated DVD disk
was placed in a LightScribe DVD drive with a wavelength of 780 nm.
Raman result confirm that the laser irradiation properly reduce GO to graphene sheets. The
structure of graphene arrays were studied by SEM images the results indicated that the laser
based reduction was a useful method to production graphene layers.

185
New insights about dielectric relaxation in relaxor ferroelectrics
Diego A. Ochoa*, Rafael Levit, José E. García
Department of Physics, Universitat Politècnica de Catalunya - BarcelonaTech, C/ Jordi Girona 1-3,
08034 Spain; *e-mail: [email protected]
Keywords: ferroelectric ceramics, relaxors ferroelectrics, dielectric relaxation

Relaxor ferroelectrics are characterized for a broadened and dispersive permittivity peak in
their temperature-dependent dielectric spectra. Although several models have been proposed
to explain the dielectric behaviour of relaxor ferroelectrics,1–5 the identification of the na-
ture of the dielectric response in relaxors systems still remains open and requires additional
theoretical and experimental explanation. The nature of the relaxor behaviour is determined
by the existence of polar nanoregions (PNRs), which possess different relaxation times (τ).
The distance above which such PNRs become non-interactive regions is formed by changes
in cluster size which are strongly affected by the temperature, giving rise to a distribution
function of activation energy. This striking situation dominates the dynamic of the relaxors in
terms of a functional behaviour of the dielectric relaxation time as function of temperature,
τ(T). To elucidate the most consistent functional τ(T) constitutes a fundamental issue to un-
derstand the very attractive physical properties of ferroelectric relaxors. By using alternative
model-equations of τ(T), we are able to reveal strong evidences that the ‘classical’ parameter-
ization of the dielectric relaxation in relaxor ferroelectrics is not the only route to disentangle
the dynamic of these materials. A model-free route solution for describing super-Arrhenius
dynamics in complex systems is proposed as an effective method to elucidate the relaxation
dynamics of relaxor ferroelectrics.

References
1. L.E. Cross, “Relaxor ferroelectrics”, Ferroelectrics, 76, pp. 241–267, 1987.
2. D. Viehland, S. Jang, L.E. Cross and M. Wuttig, “Freezing of the polarization fluctuations in lead
magnesium niobate relaxors”, J. Appl. Phys., 68, pp. 2916–2921, 1990.
3. A.A. Bokov and Z.-G. Ye, “Recent progress in relaxor ferroelectrics with perovskite structure”, J.
Mat. Sci., 41, pp. 31–52, 2006.
4. W. Kleemann, “Random fields in relaxor ferroelectrics: a jubilee review”, J. Adv. Dielect., 2, art.
1241001, 2012.
5. A.A. Bokov and Z.-G. Ye, “Dielectric relaxation in relaxor ferroelectrics”, J. Adv. Dielect., 2, art.
1241010, 2012.

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773
Influence Sr2TiMnO6 addition on piezoelectric properties of
Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 system near MPB region
Hirotaka Ogawa, Daiki Iida, Akinori Kan*
Graduate School of Science and Technology, Meijo University, 1-501 Shiogamaguchi, Tempaku-ku,
Nagoya, 4688502, Japan; *e-mail: [email protected]
Keywords: piezoelectric property, K0.5Na0.5NbO3,

In the various perovskite materials, bismuth sodium titanate, i.e., Bi0.5Na0.5TiO3 (BNT), is
known to be one of the lead–free piezoelectric ceramics with rhombohedral perovskite struc-
ture at room temperature. Although the BNT ceramic has a relatively large remanent polar-
ization (Pr), its high coercive field (Ec) has a detrimental effect on the poling treatment of
the ceramics. Sasaki et al.1 reported the piezoelectric properties of (1-x)BNT–xBi0.5K0.5TiO3
(BKT) system which exhibited a MPB between rhombohedral (R3c) and tetragonal (P4mm)
in the compositions 0.16 ≤ x ≤ 0.20; the highest piezoelectric constant (d33) of 151 pC/N
was obtained for 0.8BNT–0.2BKT (BNKT) ceramic. Recently, most of the recent works of
BNKT-based ceramics have been focused on the evaluation of piezoelectric properties in
BNKT–ABO3 system to clarify the relationships between the formation of MPB and piezo-
electric properties.2–4 However, the detail on the piezoelectric properties of BNKT-ABB’O6
system, where ABB’O6 has a double perovskite structure, has not been clarified to date. Thus,
double perovskite-structured SrTiMnO6 (STM) addition was performed for BNKT ceramics
and their piezoelectric properties were investigated in this study. No secondary phase was
detected for (1–x)BNKT–xSTM in the composition range of 0–0.05; the diffraction peak
shifts to low angle was also observed with increasing x. From the Raman spectroscopy, a
shoulder peak around 320 cm–1, which corresponds to Ti-O vibration mode, was observed
in the compositions below 0.02, implying the coexistence of rhombohedral and tetragonal
phases. As for the composition dependence of Pr and Ec values, the Pr values increased from
38 to 45 μC/cm2 with increasing the composition up to x = 0.005, though the Ec values of the
ceramic were almost constant (27 kV/cm). The piezoelectric constant (d33) of the ceramics
significantly varied for the composition x; the highest value was obtained at x = 0.005 (d33 =
204 pC/N). Therefore, it is considered that the addition of SMT is effective in enhancing the
piezoelectric constant of BNKT-based ceramics in MPB region.

References
1. A. Sasaki et al., Jpn. J. Appl. Phys. 38 (1999) 5564–5567.
2. H. Nagata et al., Jpn. J. Appl. Phys. 42 (2003) 7401–7403.
3. G. Dong et al., J. Am. Ceram. Soc. 98 (2015) 1150–1155.
4. D. Iida et al., Jpn. J. Appl. Phys. 54 (2015) 10ND12.

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778
Dielectric and piezoelectric properties of (1–x)(K0.474Na0.474Li0.052)
(Nb0.948Sb0.052)O3–xBaMnO3 ceramics
Shinnosuke Ohashi, Kan Akinori*, Ryo Onish, Hirotaka Ogawa
Graduate School of Science and Technology, Meijo University, 1-501 Shiogamaguchi, Tenpaku-ku,
Nagoya 468-8502, Japan; *e-mail: [email protected]
Keywords: KNN, lead-free ceramic, piezoelectric properties, MPB, BaMnO3

Piezoelectric ceramics of Pb-based material have been widely used as actuators, transduc-
ers, sensors, etc. However, the various commercial products which consist of lead-based
piezoelectric ceramics may induce the continuous damage to environment.1 Therefore, there
has been significant effort in the research of new lead-free perovskite piezoelectric ceram-
ics. The (K,Na)NbO3(KNN)-based materials have been received the considerable attention
due to their excellent piezoelectric properties and high-Curie temperature;2 the existence of
a morphotropic phase boundary (MPB) between the orthorhombic and tetragonal phases in
KNN-based systems has been reported.3 For example, Wu et al.,4 reported the piezoelectric
properties of KNN-LiSbO3 system and K0.474Na0.474Li0.052Nb0.948Sb0.052O3 (KNLNS) ceramic in
the MPB region exhibited a high d33 value of 221 pC/N.5 However, the details on the (1–x)
KNLNS–xBaMnO3 ((1–x)KNLNS–xBM) have not been reported to date. Therefore, in order
to clarify the compositional dependence of piezoelectric properties for (1–x)KNLNS–xBM
ceramics, these materials were synthesized in the present work and the relationships between
crystal structure and d33 value were investigated. (1–x)KNLNS–xBM ceramics were syn-
thesized by the conventional solid-state reaction method. K2CO3, Na2CO3, Li2CO3, Nb2O5,
Sb2O5, BaCo3 and MnO2 powders were used as the starting materials. KNLNS and BM ce-
ramics were separately synthesized and single phase of KNLNS and BM was obtained after
calcining at the optimum temperature. Subsequently, (1–x)KNLNS–xBM ceramics were sin-
tered 1095 °C to 1170 °C for 3 h in air. X-ray powder diffraction (XRPD) profiles of ceramics
showed a single phase in the composition range of x = 0 to x = 0.02. Since the diffraction
peak profile of KNLNS-BM ceramics are similar to those of KNN-LiSbO3 ceramics with
MPB region,5 it is considered that MPB region may also be formed in the (1–x)KNLNS–xBM
ceramics. The Pr values of (1–x)KNLNS–xBM ceramics increased from 18 to 31 μC/cm2,
whereas Ec values of (1–x)KNLNS–xBM ceramics decreased from 17 to 11 kV/cm. The d33
value of (1–x)KNLNS–xBM ceramics increased from 217 to 288 pC/N in the composition
range of 0–0.005.

References
1. C. Zhou and X. Liu, J. Mater Sci.43(1), 1016–1019 (2008).
2. R.Z. Zou, X.S. Fang and C. Ye, Appl. Phys. Lett, 90, 092904 (2007).
3. K. Wang and J.F. Li, J. Adv. Ceram, 1, 24–37 (2012).
4. W. Wu, D. Xin, J. Wu, J. Lee and J. Zuo, J. Ceram. Soc. Jpn. 119, 654–657 (2011).
5. J. Wu, Y. Wang, D. Xiao, J. Zhu, P. Yu, L. Wu and W. Wu, Jpn. J. Appl. Phys. 46(11), 7375–7377
(2007).

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780
Effect of LiMO3 (M = Nb, Ta and Sb) additions on dielectric and
piezoelectric properties of (1-x)K0.5Na0.5NbO3 – xBa(Li1/4Nb3/4)O3
ceramics
Ryo Onishi, Akinori Kan, Shinnosuke Ohashi, Hirotaka Ogawa
Graduate School of Science and Technology, Meijo University, Tempaku-ku, Nagoya, Japan
Keywords: KNN, lead-free piezoelectric properties, Ba(Li1/4Nb3/4)O3, MPB

Pb(Zr, Ti)O3 (PZT) ceramics are widely used in sensors and actuators as well as microelec-
tronic devices due to their superior piezoelectric properties. However, the use of lead-based
ceramics has caused the serious environmental problems.1 Therefore, much attention has been
paid for the characterization of the lead-free piezoelectric ceramics such as K0.5Na0.5NbO3
(KNN)- and Bi0.5Na0.5TiO3-based ceramics. KNN is considered to be one of the most promis-
ing candidates for alternative lead-free piezoelectric ceramics because of its very high Curie
temperature (Tc = 420 °C), a relatively high piezoelectric constant, and a large electrome-
chanical coupling coefficient.2 In addition, further improvement in the piezoelectric proper-
ties has been carried out by the chemical modification in KNN – ABO3 system which leads
to the formation of morphotropic phase boundary (MPB). For example, KNN – LiSbO3 (LS)
ceramics3 exhibit the coexistence of orthorhombic and tetragonal phases, implying the for-
mation of MPB where the piezoelectric constant (d33) of 286pC/N is obtained. The Li substi-
tution for A site in KNN is considered to play an important role in improving the piezoelectric
properties with formation of MPB. On the other hand, Ba(Li1/4Nb3/4)O3 (BLN) ceramics is
known as a perovskite structure in which Li+ cation occupied the B site in the structure,
though the effect of BLN addition on the piezoelectric properties of KNN has not been clari-
fied to date. Thus, (1–x)KNN – xBLN ceramics were synthesized by the conventional solid
state reaction method, using K2CO3, Na2CO3, Nb2O5, BaCO3 and Li2CO3; the ferroelectric
and piezoelectric properties were investigated in this study. The X-ray powder diffraction
profiles of ceramics showed a single phase in the composition range of 0–0.02. From the
variation in the diffraction peak intensity of (002) and (200) refrections, the coexistence of
tetragonal and orthorhombic phases was suggested in the composition range of 0.005–0.02.
As x increased, the piezoelectric constant (d33) improved significantly in the composition
range up to x = 0.02 and d33 of 193.5 pC/N was obtained at x = 0.01. From the results of Ra-
man spectroscopy, the formation of MPB was also suggested in such the composition range.
In addition, LiMO3 (M = Nb, Ta and Sb) additions into KNN – BLN ceramics were performed
to enhance the piezoelectric properties of the ceramics in this study.

References
1. Dunmin Lin et al., J. Appl. Phys. 101, 074111 (2007).
2. R. Zou et al., Phase structures and electrical properties of new lead-free (Na0.5K0.5)NbO3 – (Bi0.5Na0.5)
TiO3 ceramics, Appl. Phys. Lett. 90(9), pp. 092904/1-092904/3 (2007).
3. Zang Guo-Zhong et al., Applied Physics Letters (2006), 88(21), 212908/1-212908/3.

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777
Electrical conductivity of Fe-doped SmTiNbO6 ceramics
with Aeschynite structure
Kohei Ono, Kan Akinori*, Hirotaka Ogawa
Graduate school of Science and Technology, Meijo University, 1-501 Shiogamaguchi, Tenpaku-ku,
Nagoya 468-8502, Japan; *e-mail: [email protected]
Keywords: SmTiNbO6, electrical conductivity, Aeschynite structure

Solid oxide fuel cells (SOFCs) are considered to be one of the energy conversion systems
with high energy efficiency. However, since the high operating temperature of SOFCs gener-
ally limits their technological applications, many attempts have been performed for the char-
acterization of SOFCs which can operate at the intermediate temperature range. Accepter-
doped perovskite compounds, such as BaZr1-xYxO3-δ1,2 and BaZr1-xScxO3-δ,3 are known as the
appropriate candidates for the application to the intermediate temperature SOFCs. The for-
mation of oxygen vacancy by accepter doping allows the proton incorporation in perovskite
structure which leads to the enhancement of proton conductivity. However, BaZrO3 must be
sintered at high temperature and it is necessary to improve conductivity at lower temperature.
Therefore, we focused on the characterization of Fe-doped SmTi1-xFexNbO6-δ (0 < x < 0.05)
with Aeschynite structure which consists of SmO8 polyhedra and (Ti,Nb)O6 octahedra as a
proton conductive electrolyte for intermediate temperature SOFCs. SmTi1-xFexNbO6-δ ceram-
ics were synthesized by the conventional solid state reaction method, using Sm2O3, TiO2,
Fe2O3 and Nb2O5. The crystal structure and electrical characterization of prepared samples
were performed by using the X-ray powder diffraction (XRPD) and AC impedance spec-
troscopy methods. From the XRPD profiles, a single phase was obtained in the composition
range of x = 0–0.05. The electrical conductivity was measured in the temperature range of
100–800 °C under the different atmospheres. The conductivity of SmTi1-xFexNbO6-δ increased
with increasing temperatures; the electrical conductivity of 4.60 × 10–3 S/cm was obtained
for x = 0.05 at 600 °C.

References
1. K. D. Kreuer et al., Solid State Ionics 145 (2001) pp. 295.
2. Daniele Pergolesi et al., Nature Materials 9 (2010) pp. 846.
3. Itaru Oikawa et al., Chem. Mater. 27 (2015) pp. 6660.

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304
Fabrication of nanoparticles incorporated waveguide based transparent
flexible display
Bong Je Park1*, Suntak Park1, Ki-Uk Kyung1, Ho Seong Jang2
Electronics and Telecommunications Research Institute (ETRI), 218 Gajeong-ro, Yuseong-gu,
1

Daejeon 34129, Republic of Korea; *e-mail: [email protected]

Materials Architecturing Research Center, Korea Institute of Science and Technology, 5 Hwarang-ro
2

14-gil, Seongbuk-gu, Seoul 02792, Republic of Korea

Keywords: upconversion, nanoparticle, waveguide, display

Even though upconversion nanoparticles(UCNPs) have been attractive due to their unique
optical properties, great attentions have not been given to them because of their limited appli-
cations such as biomolecules and three dimensional (3D) volumetric displays.1,2 We suggest a
highly transparent and flexible display device based on core/shell(C/S) UCNPs incorporated
polymer waveguide as a new application. C/S-structured Li(Gd,Y)F4:Yb,Er/LiYF4 UCNPs
for green, Li(Gd,Y)F4:Yb,Tm/LiYF4 UCNPs for blue, and NaGdF4:Yb,Tm/NaGdF4:Eu UC-
NPs for red were successfully synthesized and characterized. For the fabrication of wave-
guide, the mixture of these blue-, green-, and red-emitting C/S UCNPs and bisphenol A
ethoxylate diacrylate (na = 1.5647 at 632 nm) is used as core material and tetra(ethylene
glycol) diacrylate (na = 1.5031 @ 632 nm) is used as clad materials, respectively. The display
was fabricated by spin-coating and RIE process. Waveguide pattern was confirmed by SEM
images. The thickness of fabricated display is so thin (~ 40 um) that it can be easily bendable.
It also shows transmittance > 90% in the spectral range of 443–900 nm. The non-patterned
and patterned polymer waveguide-based devices exhibited bright blue-, green-, and red-color
under coupling with a 980 nm NIR laser even in a severe bending condition. Those emission
colors of displays are well matched with those of UCNPs themselves.

References
1. D.K. Chatterjee, A.J. Rufaihah, Y. Zhang, Biomaterials 2008, 29, 937.
2. E. Downing, L. Hesselink, J. Ralston, R. Macfarlane, Science 1996, 273, 1185.

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619
Transparent glass-ceramics: fabrication during heat treatment or
femtosecond laser irradiation
Joanna Pisarska1*, Marta Sołtys1, Joanna Janek1, Lidia Żur1, Tomasz Goryczka2,
Wojciech A. Pisarski1
1
Institute of Chemistry, University of Silesia, Katowice, Poland; *e-mail: [email protected]
2
Institute of Materials Science, University of Silesia, Chorzów, Poland
Keywords: glass-ceramics, heat treatment, fs laser irradiation, rare earths, luminescence

Micro/nanocrystals are formed during heat treatment1 or laser irradiation2 of precursor glass-
es. These new materials are well-known in the literature as transparent glass-ceramics. Dif-
ferences in the luminescence characteristics of rare earth-doped glass samples before and
after heat treatment or laser irradiation can be explained by structural changes in the environ-
ment around the optically active ions. In this work, two completely different lead-based and
lead-free germanate glass-ceramic systems were examined. In PbO-PbF2-GeO2 glass-host
compositions cubic β-PbF2 nanocrystals are well formed, whereas quite different situation
is observed for lead-free germanate samples containing BaO/BaF2.3,4 Single fluoride nano-
crystals BaF2 are not formed during heat treatment of precursor glasses. The presence of four
crystalline phases BaF2, BaO, Ba3Ga2Ge4O14 and GeO2 was confirmed by X-ray diffraction.
Structural aspects for germanate glass-ceramic samples fabricated under fs laser irradiation
are also presented and discussed in details. Finally, the up-conversion luminescence spectra
of erbium ions in two different lead-based and lead-free germanate glass-ceramic systems
were studied in relation to potential temperature sensor applications.

Acknowledgment
The National Science Centre (Poland) supported this work under research project 2014/13/B/ST7/01729.

References
1. J. Pisarska, I. Czopek, R. Lisiecki, W. Ryba-Romanowski, T. Goryczka, W.A. Pisarski, “PbWO4
formation during controlled crystallization of lead borate glasses”, Ceram. Int., 39, pp. 9151–9156,
2013.
2. M. Rada, S. Rada, E. Culea, “Structural properties of the tungsten–lead–borate glasses before and
after laser irradiation”, J. Non-Cryst. Solids 357, pp. 2024–2028, 2011.
3. L. Żur, J. Janek, M. Sołtys, T.Goryczka, J. Pisarska, W.A. Pisarski, “Structural and optical inves-
tigations of rare earth doped lead-free germanate glasses modified by MO and MF2 (M = Ca, Sr,
Ba)”, J. Non-Cryst. Solids 431, pp. 145–149, 2016.
4. L. Żur, J. Janek, M. Sołtys, J. Pisarska, W.A. Pisarski, “Effect of BaF2 content on luminescence of
rare-earth ions in borate and germanate glasses”, J. Amer. Ceram. Soc., 99, pp. 2009–2016, 2016.

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220
Multicaloric effect in Pb(Fe1/2Nb1/2)O3 ceramics
Uros Prah1,2, Magdalena Wencka3, Zdravko Kutnjak1,2, Marko Vrabelj1, Silvo Drnovsek1,
Barbara Malic1,2, Hana Ursic1,2
1
Jožef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia
2
Jožef Stefan International Postgraduate School, Jamova cesta 39, 1000 Ljubljana, Slovenia
Institute of Molecular Physics, Polish Academy of Sciences, ul. Smoluchowskiego 17, 61-179
3

Poznań, Poland
Keywords: caloric, multicaloric effect, PFN, multiferroic, mechanochemical activation

The search for caloric materials has recently become one of the most active fields in con-
densed-matter science with applications in solid-state refrigeration technology. The caloric
effect is related to a change of the material’s entropy under the application of an external
stimuli: magnetic, electric, or mechanical. Depending on the origin of the entropy change, the
caloric effects can be classified as magnetocaloric (MC), electrocaloric (EC) and mechanoca-
loric effects.1 Bulk caloric materials are currently not showing sufficiently large caloric tem-
perature change (only a few degrees) for their commercial use. One idea how to overcome
this problem is to prepare a material exhibiting more than one caloric effect - multicaloric
material, in which the application of both stimuli can enhance the total caloric effect. Even
more, different caloric modes can be applied in different temperature regions extending the
operating temperature range of the cooling device. The coexistence of the MC and EC effects
had been theoretically proposed five years ago2 followed by experimental conformations.3,4 It
is very challenging to prepare efficient multicaloric materials and the search for them is not
finished yet. In this work we experimentally prove that the Pb(Fe1/2Nb1/2)O3 (PFN) exhibits
both MC and EC effects and is therefore the multicaloric material.
For the preparation of the PFN the homogenized, stoichiometric powder mixture was
mechanochemically activated in a high-energy planetary mill for 30 h at 300 rpm and milled
in an attrition mill for 4 h at 800 rpm. The powder compacts were isostatically pressed and
sintered in an oxygen atmosphere at 1273 K for 2 h. This method yielded PFN ceramics
with a theoretical density of 96% and uniform microstructure with average grain size of 2.3
μm. The dielectric permittivity and dielectric losses at room temperature and 10 kHz were
measured with a HP 4284A precision LCR Meter and were 3580 and 0.038, respectively. For
the indirect EC measurements, the polarization versus electric field hysteresis loops were
measured by an Aixacct TF analyser 2000. At room temperature the EC temperature change
was 0.81 K at 80 kV/cm. The maximum EC temperature change of 1.29 K was obtained at
80 kV/cm and 373 K. The magnetization vs. temperature at different magnetic fields was
measured using a Superconducting Quantum Interference Device. The maximum MC tem-
perature change of 0.16 K was obtained at 50 kOe and 2 K.

References
1. X. Moya, S. Kar-Narayan and N. D. Mathur, Nat. Mater., 13, pp. 439–450, 2014.
2. M. M. Vopson, Solid State Commun., 152, pp. 2067–2070, 2012.
3. H. Ursic et al., Sci. Rep., 6, 26629, pp. 1–5, 2016.
4. J. K. Murthy and A. Venimadhav, J. Phys. D: Appl. Phys., 47, 445002, pp. 1–6, 2014.

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897
Piezoelectric, ferroelectric and conduction mechanisms analyses of
BCTZ ceramics for different temperatures ranges
A. Reyes-Montero1, L. Pardo2, A. M. González3, R. López-Juárez4, P. Ramos-Alvarez1,
A. García2, M. E. Villafuerte-Castrejón1
Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México,
1

Circuito Exterior S/N, A.P. 70-360, México, D.F., México; e-mail: [email protected]
Instituto de Ciencia de Materiales de Madrid, ICMM-CSIC, Sor Juana Inés de la Cruz, 3.
2

Cantoblanco, 28049 Madrid, España

Grupo POEMMA, ETSIT Telecomunicación, Campus Sur, Universidad Politécnica de Madrid, Ctra.
3

Valencia Km 7, 28031 Madrid, España

Unidad Morelia del Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de
4

México, Antigua Carretera a Pátzcuaro No. 8701, Col. Ex Hacienda de San José de la Huerta, C.P.
58190, Morelia, Michoacán, México
Keywords: BCTZ, ferroelectrics, piezoelectric, conduction mechanisms

BaTiO3-based compositions have gain considerable attention due to their optimum properties
produced by the substitution of the A and/or B site of the perovskite structure. In this way
Ba1-xCaxTi0.9Zr0.1O3 (BCTZ) properties are enhanced near the morphotropic phase boundary
(MPB).
Electrical characterization of BCTZ ceramics is accomplished with a set of independent
piezoelectric, elastic and dielectric coefficients by means of different symmetry modes: ra-
dial, thickness and shear. An automatic iterative method developed at Spanish CSIC was
implemented for all the resonances and resonator shapes needed for the determination of all
piezoelectric ceramic materials including losses. Moreover, associated physical properties
related to the nature of conductivity are calculated using complex impedance spectroscopy
(CIS). The Impedance data obtained is associated to grain (bulk), grain boundary and inter-
face/polarization effects.
In this work BCTZ ceramics (x = 0.10–0.18) were prepared by conventional ceramic
method. Homogeneous and dense materials (up to 95% of theoretical density) were sintered
at 1400 ºC (2 h). XRD analysis, ferroelectric hysteresis loops, piezoelectric and dielectric
characteristics, as a function of frequency and temperature is presented. Measurements of
material parameters at resonance were performed on ceramic shear plates, thickness-poled,
and results were discussed in terms of the loss mechanisms of the ceramic. Besides, CIS was
employed to explore dielectric relaxation as well as conductive behavior at a high tempera-
ture range.

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451
Gold nanoparticles decorated oxide catalyst for oxygen reduction
reaction
Jiseung Ryu1*, Hyoung Seuk Choi2, Yong-Nam Kim3, Heesoo Lee1
1
Department of Materials Science and Engineering, Pusan National University,
Busandaehak-ro 63beon-gil, Geumjeong-gu, Busan, Rep. of Korea;
*
e-mail: [email protected]
2
Korea Institute of Ceramic Engineering and Technology, Jinju, Rep. of Korea
3
Korea Testing Laboratory, Jinju, Rep. of Korea
Keywords: SOFC, cathode, perovskite, gold nanoparticle, oxygen reduction reaction

Many researches have been investigated to improve catalytic activities of the surface for vari-
ous oxide electrodes.1 The self-regeneration and exsolution are the state-of-the-art method
to form nanoparticles on the surface of perovskite type oxide. They can form well-dispersed
catalytic nanoparticles on the surface, but they must be needed a reduction step at a high tem-
perature. In the case of an electrode material for oxygen reduction reaction, a method of car-
rying catalyst particles on the surface by a physical mixing method and infiltration is mainly
used,2 and a surface particle forming method using physical vapor deposition (PVD) is also
attracting attention. Anastasopoulos et al. reported a 30% improvement in the efficiency of
oxygen reduction over conventional catalysts by using PVD method coated with 10 nm dis-
persed Pt and Pd catalyst particles.
The gold nanoparticles (NPs) were decorated on the surface of the PrBaCo1.9Cu0.1O5+δ
(PBCCO) electrode by sputtering, and their electrochemical properties were investigated.
Gold NPs were well dispersed, and the size of 10 nm was maintained even under the heat
treatment condition of 950 °C. We hypothesized that the aggregation of gold NPs is inhibited
by the combination of gold and copper, and the binding relationship between gold and cop-
per on the surface was investigated by in-situ high temperature XPS and DFT analysis. The
decoration of gold NPs on the PBCCO also decreased the polarization resistance 1.4 times
less than the non-coated PBCCO electrode in air atmosphere.

References
1. D. Ding, M. Liu, Z. Liu, X. Li, K. Blinn, X, Zhu, and M. Liu, Adv. Energy Mater., 3, pp. 1149–1154,
2013.
2. D. Ding, X. Li, S. Y. Lai, K. Gerdes, and M. Liu, Energy Environ. Sci., 7, pp. 552–575, 2014.

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212
Effect of CuO to microstructure and properties of Bi0.5Na0.5TiO3-SrTiO3
Mohsin Saleem1,2, In-sung Kim2, Min-Soo Kim1, Soon-Jong Jeong1*
1
Battery Research Center, Korea Electro-technology Research Institute, Changwon,
Republic of Korea; *e-mail: [email protected]
2
University of Science and Technology, Daejeon, Republic of Korea, 305-333
Keywords: electromechanical, doping, polarization, copper, ceramic

This report describes the sintering and ferroelectric characteristic of 0.76 Bi0.5Na0.5TiO3
(BNT)-0.26SrTiO3 (ST) (BNT-26ST) with CuO addition synthesized by using a solid-state
reaction. The XRD, microstructure and density results reveal that Cu element reduces sin-
tering temperature from 1150 oC to 1000 oC. In dielectric study, CuO addition induces the
increase of relaxation behavior for 26ST ceramic in high temperature regime. In low tem-
perature regime (< Tm ~ 150 oC), the Cu doping to 26ST accelerates the degree in freezing of
dipole presumably due to the interaction between A site vacancy and nano domain boundar-
ies. The electromechanical properties of BNT-26ST ceramics with CuO doping exhibited a
significant decay in frequency dependence of polarization and strain, which might be related
to formation of A-site cation vacancy.

References
1. T. Takenaka, and H. Nagata, “Current status and prospects of lead-free piezoelectric ceramics”, J.
Eur. Ceram. Soc., 25, pp. 2693–2700, 2005.
2. M. Acosta, W. Jo and J. Rodel, “Temperature- and Frequency-Dependent Properties of the
0.75Bi1/2Na1/2TiO3–0.25SrTiO3 Lead-Free Incipient Piezoceramic”, J. Am. Ceram. Soc., 97, pp.
1937–1943, 2014.

121
Structural transformation and enhancement in magnetization via
sintering time variation in Bi0.8Pr0.2FeO3 multiferroics
Sujata Sanghi, Ompal Singh
Department of Physics, Guru Jambheshwar University of Science & Technology, Hisar-125001,
Haryana, India; e-mail: [email protected]

Pr doped Bismuth Ferrite multiferroics; Bi0.8Pr0.2 FeO3 samples were synthesized via two step
solid state reaction method with calcination at 400 ºC and sintered at 800 ºC. To study the sin-
tering time effect on structural stability, sintering time was varied to 1 hour, 2 hour, and 3 hour.
The different samples prepared showed a continual change in structure with sintering time as
revealed through observed XRD patterns. Rhombohedral R3c (91.12%) + triclinic P1 (8.88%)
phases were observed in sample sintered for 1 hour while with increasing time the percentage
of rhombohedral phase decreases with evolution of orthorhombic Pbam phase. For the 2 hour

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sintered sample, combined symmetry of rhombohedral and orthorhombic with R3c (61.06%)
and Pbam (34.94%) was deduced by the best fits. With increasing sintering time to 3 hour,
orthorhombic phase (59.91%) leads over rhombohedral R3c phase (40.06%). Enormous en-
hancement was observed in the magnetization with increasing the sintering time. Such robust
change in the magnetic properties may be attributed to the increase in canting angle of spins.

542
The influence of the dispersants on printing ink properties of metal
oxides nanoparticles
Slavica M. Savić1*, Jaroslav Katona2, Marko Radović1, Jovana Stanojev1,
Georgios Niarchos1, Georges Dubourg1, Vesna Crnojević-Bengin1
1
Biosense Institute, University of Novi Sad, Zorana Đinđića 1, 21000 Novi Sad, Serbia;
*
e-mail: [email protected]
2
Faculty of Technology, University of Novi Sad, Bulevar Cara Lazara 1, 21000 Novi Sad, Serbia
Keywords: metal oxides, dispersants, milling, inkjet printing

Colloidal stability of inkjet printing inks is one of the key parameters for their good printing
performance. The stability of particles dispersed in water–based inks is usually achieved by
electrostatic, steric, or electrosteric stabilization. Adsorption of polyelectrolytes of increased
molecular weight at the solid interface of dispersed particles is responsible for electrosteric
stabilization. In this work, stable homogeneous suspensions of MOx (TiO2 and ZnO) were
prepared using gum arabic (GA) and solsperse 40000 as dispersants. GA is a natural polyan-
ionic polysaccharide with carboxylic groups as anchors, while Solsperse 40000 is an anionic
phosphated alkoxylated polymer of Lubrizol. Both dispersants provide electrosteric stabili-
zation of pigments in water based inks. GA was employed as dispersant to study the effect
on the surface properties of MOx nanoparticles. GA has been used as the stabilizing agent
for ink pigments for a long time. It is well known that GA can make the MOx nanoparticles
have a good dispersibility and stability in GA colloidal solution for its low viscosity. The in-
vestigations on the optimum concentration of dispersants and the mechanism determining the
dispersion behavior of MOx in aqueous dispersants solution were performed. Suspensions
of MOx and GA/Solsperse were prepared first by dissolving dispersants in water. MOx were
added in appropriate amounts. The weight ratio between MOx and GA (solsperse) was varied
from 1/1 to 3.5/1. The ball milling was performed in a Retch PM 100 planetary ball mill at
constant milling speed of 250 rpm using YSZ jar and balls. The effects of different milling
time (15, 30, 60, 90 and 180 min) on average particle sizes were investigated. Results show
improved dispersion with reduction of average particle sizes with increasing of milling time.
Different ink formulations composed of MOx/dispersants (with addition of 1, 2 propylene
glycol and n-propanol) were prepared and their printability properties were tested using Ink-
jet printer Fuji Dimatix DMP-3000. The main goal of this work is to analyse the influences
of different quantity of dispersants and milling conditions on the printing quality parameters
of the ink using different substrates.

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955
Structural and optical properties of agricultural-food waste derived
glasses/glass ceramics
Gaurav Sharma*, K. Singh
School of Physics and Materials Science, Thapar University, Patiala, India;
*
e-mail: [email protected]
Keywords: agricultural waste, food waste, glasses/glass ceramics wide semiconductor

Agricultural waste ashes and food waste are used to synthesise glass and glass ceramics. The
as prepared materials are characterized using X-ray diffraction and UV-Visible spectroscopy
for their structural and optical properties to check their suitability in various applications. The
addition of Eggshell powder promotes the glass formation due to higher alkali content (CaO).
The optical band gap of as prepared samples are in the wide semiconductor range. Probably,
these as prepared glasses/glass ceramics can be used in high temperature and power genera-
tion.

171
Processing of cermet nanomembranes
Jovana Stanojev*, Jovan Matovic
BioSense Institute, Novi Sad, Serbia; *e-mail: [email protected]
Keywords: cermet, nanomembranes, sputtering, etching

Nanomembranes can be defined as quasi 2D structures, with thicknesses far below 100 nm,
and large aspect ratio up to 1,000,000, considering their lateral dimensions and their thick-
ness. Unlike thin films, nanomembranes are freestanding structures not supported by con-
ventional substrate. They can be processed from a wide range of materials, depending of
their purpose and field of application which ranges from infrared detectors, optical filters,
plasmonic arrays and photonic bandgap structures, to catalytic reactors and biosensors.
Cermet is a generic name for a certain type of composites which consist of ceramic materi-
als and metals, and in this work we present cermet nanomembranes (Cr-Si-O), processed via
reactive sputtering and wet etching.
Namely, nanomembrane was deposited on the top of silicon substrate via reactive sputer-
ring and the metal which was deposited was chromium. As chromium atoms penetrated into
silicon substrate, they dislodged Si atoms from the lattice. Due to the fact that sputtering
was performed in oxygen atmosphere, partial oxidation of the film occurred. The thickness
of the formed composite Cr-Si-O nanomembrane was 8 nm, which approximately equals 20
atomic layers. The composition of the obtained composite layer was 52% chromium, 28%
oxygen and 20% silicon, which was confirmed by EDAX analysis. The following step in the
processing of cermet nanomembrane was to release it from the silicon substrate, which was

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done by wet anisotropic etching of silicon. Solution of KOH and 2-propanol was used as
etchant, whilst etching was performed at temperature of 80 °C for around one hour in order
to completely remove Si. Removal of silicon was observed via optical microscope and SEM.
Transmittance and absorbance of the nanomembrane were measured and it was proved that
the nanomembrane behaves as an ideal absorber. Also, the processed cermet nanomembranes
have a long lifetime.

References
1. J. Matovic, Z. Jaksic, Simple and reliable technology for manufacturing metal-composite na-
nomembranes with giant aspect ratio, Microelectronic engineering 86 (2009) 906–909.
2. J. Matovic, Z. Jaksic, Three-dimensional surface sculpting of freestanding metal-composite na-
nomembranes, Microelectronic engineering 87 (2010) 1487–1490.
3. I. Barycka, I. Zubel, Silicon anisotropic etching in KOH-isopropanol etchant, Sensors and Actua-
tors A 48 (1995) 229–238.
4. K.E. Peterson, Silicon as mechanical material, Proceedings of the IEEE, Vol. 70, No. 5, May 1982.

942
Sputtered thin film protective layers for the operation of OTMs in
oxyfuel-like environments
Fidel Toldrá, Julio Garcia-Fayos, David Catalán, Jose Manuel Serra*
Instituto de Tecnología Química (UPV-CSIC), Avenida de Los Naranjos s/n 46022 Valencia, Spain;
*
e-mail: [email protected]
Keywords: oxygen, membranes, perovskites, dual-phase, sputtering, thin films, oxyfuel, CO2

Oxygen transport membranes (OTM) based on mixed ionic and electronic conducting
(MIEC) ceramics have attracted much interest as they can be directly integrated in a furnace
for oxyfuel technology, constituting an inexpensive alternative for cryogenic air separation1.
The absence of N2 in this oxyfuel technology, that consists of fuel combustion by using
O2 (instead of air) in a CO2 sweeping stream, allows more efficient combustion processes,
minimizing NOx formation, and the direct CO2 sequestration process2. OTMs based on MIEC
ceramic oxides present 100% selectivity, but the performance is limited by the ambipolar
conductivity of the constituent material and –especially– by the stability in CO2 containing
atmospheres.
Amongst all the studied materials, BSCF is the one presenting the highest O2 fluxes3. Nev-
ertheless and despite its outstanding performance under clean environments, BSCF presents
very poor permeating rates when exposed to CO2 environments, yielding to an immediate
cessation in the permeation and to the formation of carbonates eventually producing a mate-
rial breakage.
A way to increase the stability of these perovskites is by CO2 protection layers deposition4.
Therefore, in the present work BSCF membranes performance is studied when applying
protective thin-film layers by means of RF-sputtering. This technique is chosen in order to
ensure the crystallinity properties together with a small thickness, necessary for maintaining

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the high BSCF permeation properties. First the growth of films consisting of pure ionic and
nanograined dual-phase structures was studied as a function of different deposition tempera-
tures, and then the best films were grown on BSCF bulk membranes for permeation measure-
ments under CO2 containing atmospheres.

References
1. Badwal, S.P.S.; Ciacchi, F.T., Ceramic membrane technologies for oxygen separation. Advanced
Materials 2001, 13 (12–13), 993-+.
2. MacDowell, N.; Florin, N.; Buchard, A.; Hallett, J.; Galindo, A.; Jackson, G.; Adjiman, C.S.; Wil-
liams, C.K.; Shah, N.; Fennell, P., An overview of CO2 capture technologies. Energy & Environ-
mental Science 2010, 3 (11), 1645–1669.
3. Baumann, S.; Serra, J.M.; Lobera, M.P.; Escolastico, S.; Schulze-Kueppers, F.; Meulenberg, W.A.,
Ultrahigh oxygen permeation flux through supported Ba0.5Sr0.5Co0.8Fe0.2O3-delta membranes.
Journal of Membrane Science 2011, 377 (1–2), 198–205.
4. Garcia-Torregrosa, I.; Lobera, M.P.; Solis, C.; Atienzar, P.; Serra, J.M., Development of CO2 Pro-
tective Layers by Spray Pyrolysis for Ceramic Oxygen Transport Membranes. Advanced Energy
Materials 2011, 1 (4), 618–625.

510
Investigation of structural and functional properties of doped BaTiO3
thin films for potential application in tunable microwave devices
Jelena Vukmirovic1, Branimir Bajac1, Jovana Stanojev2, Jelena Bobic3,
Mirjana Vijatovic Petrovic3, Elvira Djurdjic4, Zeljka Cvejic4, Vladimir V. Srdic1
1
Faculty of Technology Novi Sad, University of Novi Sad, Serbia
2
BioSense Institute, Novi Sad, Serbia
3
Institute of Multidisciplinary Research, University of Belgrade, Serbia
4
Faculty of Sciences, University of Novi Sad, Serbia
Keywords: barium titanate, dielectric properties

Ferroelectric behavior of perovskites makes these materials very popular for various ap-
plications in microelectronics. Barium titanate is one of the most popular representatives
of perovskites and probably the most investigated material from these group. Addition of
dopants such as strontium and zirconium can change ferroelectric nature of barium titanate.
Different concentration of mentioned dopants has huge influence on barium titanate struc-
tural and functional properties. Aim of this work was to approach the paraelectric state of
barium titanate for potential application in tunable microwave devices such as varactors,
phase shifters, etc. Barium strontium titanate (BST) is mainly used for production of tunable
devices, but some other materials as barium zirconium titanate (BZT) can be also interest-
ing for investigation. Precursor solutions were made from barium carbonate and tetrabu-
tylorthotitanate, and as sources of Sr2+ and Zr4+ were used strontium acetate and zirconium
(IV) oxychloride octahydrate, respectively. Acetic acid and 2-methoxy ethanol were used as
solvents. Prepared sols were used for production of multilayered thin films with spin coating
method on silicon and platinized (bottom electrode) substrates. After thermal treatment on

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different temperatures (750, 900, 1000 °C), prepared samples were structurally characterized
by X-ray diffraction, Raman spectroscopy and scanning electron microscopy. After structural
characterization samples were prepared for functional measurements and gold electrodes
were deposited on top. Dielectric properties were measured with LCR meter, up to 1 MHz.
We also measured ferroelectric properties.

360
Aqueous TAPE casting of transparent yttrium aluminum garnet doped
with neodymium (Nd:YAG) or chromium (Cr:YAG) ceramics
Anna Wajler*, Helena Węglarz, Agata Sidorowicz
Department of Ceramics, Institute of Electronic Materials Technology, Wolczynska 133
01-919 Warsaw, Poland; *e-mail: [email protected]
Keywords: yttrium aluminun garnet, tape casting, transparent ceramics

One of the advantages of ceramic manufacturing process over single crystals is a feasibility
of obtaining composite multilayered structures aimed at optimizing of the thermal properties
and lowering optical losses of laser materials. According to the current knowledge the typical
examples of the composite ceramic laser materials are cylindrical clad-core structures or a
layered structures. This latter can be conveniently produced by tape casting and laminating.
This method also, as a one of the colloidal forming techniques, is more attractive processes
for manufacturing transparent YAG ceramics than dry pressing.
The main objective of this work was fabrication and characterization of YAG/Nd:YAG,
Cr:YAG/Nd:YAG layered-composite ceramics with the use of aqueous-suspensions tape
casting. The effect of ceramics foils preparation parameters, laminating and sintering con-
ditions on the and microstructure and optical properties of Nd:YAG and Cr:YAG ceramics
was studied. Also composite YAG/Nd:YAG, Cr:YAG/Nd:YAG ceramics were fabricated and
their properties have been studied and described.

Acknowledgements
The work was supported by the National Science Centre (NCN, Poland), project number 2015/17/D/
ST8/02607.

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T04: Electroceramics and optical materials – Poster presentations

458
Nonstoichiometry effects on ferroelectric and charge transport
properties of Bi1±xFeO3±δ ceramics
Jeong Wook Woo1, Seung Bong Baek1, Soonil Lee2, Tae Kwan Song1, Won Jeong Kim1,
Rizwan Ahmed Malik1, Myong Ho Kim1*
School of Advanced Materials Engineering, Changwon National University, Changwon,
1

Gyeongnam 51140, Republic of Korea; *e-mail: [email protected]

Energy & Environmental Materials Division, Korea Institute of Ceramic Engineering and
2

Technology, Jinju, Gyeongnam 52851, Republic of Korea

Keywords: bismuth ferrite, ferroelectric, electrical conductivity, defect, nonstoichiometry

We synthesized nonstoichiometric Bi1±xFeO3±δ ceramics by a conventional solid-state reac-

tion method and studied their structural, dielectric and high-temperature charge transport
properties to understand defect chemistry of the multiferroic BiFeO3-based systems. Incor-
poration of the excess amount of Bi2O3 lowered the Bi deficiency in BiFeO3, in which the
nonstoichiometry was able to be engineered through controlling the excess amount. Polariza-
tion versus electric field (P-E) hysteresis loops and dielectric properties showed enhancement
with the Bi2O3 addition. To better understand the defect effects on the multiferroic properties,
the high temperature equilibrium electrical conductivity was measured under various oxygen
partial pressures. The charge transport behavior was also examined through thermopower
measurement. With those analyses, the point defect types and defect energetics in terms of
thermodynamics will be discussed in details.

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406
The jump-like PTCR effect in metal-BaTiO3 composite PTC
thermistors
Igor Zajc
Department for Materials Synthesis, Jožef Stefan Institute, Ljubljana, Slovenia;
e-mail: [email protected]

A composite composed of a highly conducting phase and a high-resistivity BaTiO3 phase was
prepared. The high-resistivity BaTiO3 was realized using a high-temperature treatment, while
alloy powder was used as the conducting phase. The composite was prepared from a mixture
of the constitutive phases: a highly conducting alloy powder and high-resistivity BaTiO3
grains. The composition, the compacting pressure and the sintering temperature (under 1000
o
C) were optimized in order to obtain a low-resistivity (less than 1 Ωcm) metal-BaTiO3 com-
posite with a remarkable, jump-like, anomaly (more than 104) in the electrical resistivity at
the Curie temperature of BaTiO3. It was postulated that the PTCR anomaly was obtained ex-
clusively as a result of the disconnection of the conducting alloy network due to the volume
changes associated with the phase transformation between the tetragonal and cubic BaTiO3
at the Curie temperature.
Microstructural analyses, scanning electron microscopy, dilatometry and electrical mea-
surements were used to characterize the materials that showed the PTCR (positive tempera-
ture coefficient of the electrical resistivity) effect.

405 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T05: Ceramics for novel energy conversion,
storage and use
Invited lectures

844
Mixed ionic-electronic conducting membranes:
fundamentals and challenges
Henny J.M. Bouwmeester
Electrochemistry Research group, Membrane Science Technology, MESA+ Institute for
Nanotechnology, University of Twente, P.O. Box 217, 7500 AE, Enschede, The Netherlands;
e-mail: [email protected]

Mixed oxygen ionic-electronic conducting (MIEC) oxides hold promise for use as oxygen
transport membranes to produce high-purity oxygen. Such membranes may further be in-
tegrated in ceramic membrane reactors for oxy-fuel combustion and syngas applications.
In addition to reliability of operation under actual operating conditions, the challenge to
researchers is to develop membrane materials showing fast oxygen diffusion and surface
exchange kinetics. The present paper surveys theory and research on oxygen transport in the
MIEC materials, with emphasis on defect chemistry and surface exchange kinetics; progress,
problems and perspectives in the development of membrane materials; and identifies direc-
tions for future research.

899
Design principles for perovskite photoferroics
Nicholas C. Bristowe
School of Physical Sciences, University of Kent, Canterbury CT2 7NH, UK;
e-mail: [email protected]

Photovoltaics rely on the separation of photoinduced charge carriers, which normally re-
quires careful engineering of electron and hole attracting electrodes or p-n junctions, as in
conventional solar cells. However, ferroelectrics display a spontaneous polarisation that can
induce spontaneous photocurrents, allowing for greater flexibility in photovoltaic device
architectures and the potential to circumvent the Shockley-Queisser.1–3 Unfortunately most
known ferroelectrics are poor absorbers of sunlight and poor conductors due to their rela-
tively large optical band gaps.
In this talk I will discuss one strategy to induce ferroelectricity in the halide hybrid
perovskites, which have recently received heightened attention due to their promising pho-

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tovoltaic properties. Most perovskites are not ferroelectric, but instead show a non-polar
lattice distortion called octahedral tilting. This tilting competes with the polar ferroelectric
mode rendering systems paraelectric.4,5 I will discuss i) why this tilting is amplified in hybrid
perovskites and how this effects the electronic structure,6,7 and ii) how the competitive cou-
pling between these lattice modes can be designed to become cooperative such that the tilting
can instead induce what is called improper ferroelectricity.8–12 This will be shown using a
group theoretical analysis, and demonstrated using first principles calculations.

References
1. W. Shockley & H. J. Queisser, J. Appl. Phys. 32, 510 (1961).
2. V. Fridkin & R. Magomadov, ZhETF Pisma Redaktsiiu 30, 723 (1979).
3. C. Paillard et al., Advanced Materials 28, 5153(2016).
4. N. Miao, N. Bristowe, B. Xu, M. Verstraete & P. Ghosez, J. Phys. Condens. Matter. 26, 035401
(2014).
5. N. Benedek & C. Fennie, J. Phys. Chem. C 117, 13339 (2013).
6. J.H. Lee, N. Bristowe, P. Bristowe & A. Cheetham, Chem. Commum. 51, 6434 (2015).
7. J.H. Lee, N. Bristowe et al., Chem. Mater. 28, 4259 (2016).
8. E. Bousquet et al., Nature Letters 452, 732 (2008).
9. T. Fukushima, A. Stroppa, S. Picozzi & J.M. Perez-Mato, Phys. Chem. Chem. Phys. 13, 12186
(2011).
10. N. A. Benedek & C. J. Fennie, Phys. Rev. Lett. 106, 107204 (2011).
11. J. Rondinelli & C. J. Fennie, Adv. Mater. 24, 1961 (2012).
12. McMahon, N. Bristowe et al., in preparation.

862
High-throughput screening of ceramic materials for light absorption
Ivano E. Castelli
Department of Chemistry, University of Copanhagen, Universitetsparken 5, Copenhagen Ø,
DK-2100, Denmark
Keywords: light absorption, band gap, density functional theory, high-throughput

Design novel materials for energy production in a photoelectrochemical cell, where water
is split into hydrogen and oxygen by solar light, is one possible solution to the problem of
increasing energy demand and storage as well as increase in pollution. A screening procedure
based on ab-initio density functional theory calculations has been applied to guide the search
for novel materials.
I will start describing various screening criteria and descriptors that connect the micro-
scopic quantities calculated with computer simulations with the macroscopic properties of
the device. The main descriptors used in the screening are: stability against phase separation
and in water,1 size and position of the band gap, using the GLLB-SC exchange-correlation
functional.2 These descriptors have been applied to a set of 19000 cubic perovskite structures
resulting in a handful of materials for experimental investigation.3,4 This set has also been
used to identify trends that can help in speeding up the calculations for novel perovskite ma-

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T05: Ceramics for novel energy conversion, storage and use – Invited lectures

terials.5,6 I will then present our results for the screening of hybrid halide perovskites, which
are very promising for photovoltaics due to their high absorption properties and photogen-
erated charges mobility.7
At last, I will show the importance of the cooperative interaction in the calculation of ad-
sorption energies on semiconducting materials.

References
1. I.E. Castelli, K.S. Thygesen, and K.W. Jacobsen, Topics in Catalysis 57, 265 (2014).
2. M. Kuisma, J. Ojanen, J. Enkovaara and T.T. Rantala, Phys. Rev. B 82, 115106 (2010).
3. I.E. Castelli, T. Olsen, S. Datta, D.D. Landis, S. Dahl, K.S. Thygesen and K.W. Jacobsen, Energy
Environ. Sci. 5, 5814 (2012).
4. I.E. Castelli, D.D. Landis, K.S. Thygesen, S. Dahl, I. Chorkendorff, T.F. Jaramillo and K.W. Jacob-
sen, Energy Environ. Sci. 5, 9034 (2012).
5. I.E. Castelli, and K.W. Jacobsen, Modelling Simul. Mater. Sci. Eng. 22, 055007 (2014).
6. I.E. Castelli, J.M. Garcia-Lastra, F. Huser, K.S. Thygesen, and K.W. Jacobsen, New Journal of
Physics 15, 105026 (2013).
7. I.E. Castelli, J.M. Garcia-Lastra, K.S. Thygesen, and K.W. Jacobsen, APL Materials 2, 081514
(2014).

861
Prospects and challenges of solid oxide electrolysis
P.V. Hendriksen*, M. Chen, S. Molin, A. Hauch, S. Ovtar, L. Han, H.L. Frandsen
Department of Energy Conversion and Storage, Technical University of Denmark,
DTU Risø Campus, Frederiksborgvej 399, Roskilde, DK-4000, Denmark; *e-mail: [email protected]
Keywords: high temperature electrolysis, degradation, SOEC, multi-layer tape casting

Concerns to reduce adverse effects on the climate have led to increased focus on reducing
anthropogenic CO2 emission and consequently the amount of electricity generated globally
from renewable and intermittent sources (e.g. wind and sun) is increasing. High temperature
electrolysis of CO2 and/or H2O using solid oxide electrolysis cells (SOECs) can become a
key enabling technology to reduce emissions by providing an energy efficient way to “store”
electricity from periods of surplus production. The energy can, in the form of gaseous or
even liquid hydrocarbons be transferred to the transport sector, where emission reduction is
especially difficult. In this presentation the prospects of the SOEC technology for enabling
larger shares of intermittent electricity production in the energy system will be exemplified
by scenario analyses of a 100% fossil free systems.
Whereas state of the art SOFCs cells are reversible, there are important differences be-
tween SOFC and SOEC operation in terms of degradation phenomena. Highlights from the
past decade of SOEC R&D at DTU Energy will be presented. Introduction of new ceramic
manufacturing routes and better oxygen electrode materials has brought down the degrada-
tion rate at –1 A/cm2 from 40%/kh to 0.4%/kh. Recent attempts to push up the maximum cur-

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rent density limit further by infiltration of nano-sized CGO in the Ni/YSZ structure will also
be presented (so far a factor 4 reduction in degradation rate at 1.25 A/cm2 has been observed).
Finally, a more general discussion about life time limiting degradation phenomena in
SOEC operation will be given, based on own findings and literature including phenomena
both at cell and stack level. Special focus will be given to mechanical issues.

827
Investigation of the BZCY72-BaPrO3 system for high-temperature
electrochemical applications: thermal evolution of structures and
electrical properties
G. Heras-Juaristi1, U. Amador2, D. Pérez-Coll1, R.O. Fuentes3, A.L. Chinelatto4,
J. Romero de Paz5, D.P. Fagg6, G.C. Mather1*
1
Instituto de Cerámica y Vidrio, CSIC, 28049 Madrid, Spain; *e-mail: [email protected]
2
Departamento de Química, Universidad CEU-San Pablo, Boadilla del Monte 28668 Madrid, Spain
3
Departamento de Física de la Materia Condensada, CNEA, Av. Gral. Paz 1499, Buenos Aires
Argentina
4
Departamento de Engenharia de Materiais, Universidade Estadual de Ponta Grossa, Av. Gal. Carlos
Cavalcanti, 4748, 84300-900 Ponta Grossa-PR, Brazil
5
C.A.I. Técnicas Físicas, Facultad de Ciencias Físicas, Universidad Complutense, 28040 Madrid,
Spain
6
Department of Mechanical Engineering, University of Aveiro, 3810-193 Aveiro, Portugal
Keywords: BaZr0.7Ce0.2Y0.1O3-δ, PCFC, membrane reactor, cathode, mixed conductor

The perovskite system BaCeO3-BaZrO3 substituted with trivalent dopants is a strong candi-
date for protonic ceramic fuel cell (PCFC) electrolytes and membrane reactors1. The compo-
sition BaZr0.7Ce0.2Y0. 1O3-δ (BZCY72) offers a useful compromise of moderately high proton
conductivity and good stability. PCFCs may operate at lower temperature, ~600 °C, than
oxide-ion based SOFCs; however, decreasing the operation temperature leads to greater
overpotentials at the electrode/electrolyte interface. Recently, much effort is devoted to find-
ing materials with high mixed protonic-electronic conductivity and the requisite stability for
electrodes and membrane components at the lower temperature range. Praseodymium is an
interesting dopant for perovskite proton conductors since considerable electronic conductiv-
ity is generated at sufficient dopant levels2. Mapping the structural phase transitions and elec-
trical behaviour with temperature and composition is critical for the development of these
materials. In this work, Ba-stoichiometric and substoichiometric solid solutions between
BZCY72 and BaPrO3 are studied by neutron diffraction, revealing higher symmetry for low
Pr contents and high temperatures, and lattice parameter contraction on heating attributable
to dehydration for low Pr contents. Conductivity is p-type in dry air and N2, increasing with
greater Pr content. Magnetic and structural studies suggest that Pr much prefers the IV oxida-
tion state on the perovskite B site; the positive transport species are thus suggested to exist as

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T05: Ceramics for novel energy conversion, storage and use – Invited lectures

polarons in the oxygen band3. The preference for hole rather than proton or oxide-ion forma-
tion with increasing Pr content is discussed. Intermediate solid-solution members warrant
further study for PCFC and membrane applications.

References
1. S.H. Morejudo, R. Zanon, S. Escolastico, I. Yuste-Tirados, H. Malerod-Fjeld, P.K. Vestre, W.G.
Coors, A. Martinez, T. Norby, J.M. Serra and C. Kjolseth, Science, 353, pp. 563–566, 2016.
2. E. Fabbri, I. Markus, L. Bi, D. Pergolesi and E. Traversa, Solid State Ionics, 202, pp. 30–35, 2011.
3. S.J. Stokes and M.S. Islam, J. Mater. Chem., 20, pp. 6258–6264, 2010.

200
Stereolithographic additive manufacturing of ceramic structures
Soshu Kirihara
Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka Ibaraki,
567-0047 Osaka, Japan; e-mail: [email protected]
Keywords: additive manufacturing, stereolithography, nanoparticles paste, laser scanning, pattern
exposing

Through computer aided design, manufacturing, and evaluation (CD/CAM/CAE) ceramic

structures with spatially ordered micro cavities were successfully fabricated using stereo-
lithography, an additive manufacturing technology. Titania micro photonic crystals with
dendritic patterns were fabricated to control electromagnetic waves in terahertz frequency
ranges. Subsequently, solid electrolyte dendrites of yttria-stabilized zirconia (YSZ) with spa-
tially ordered pores were processed for fuel cell miniaturization. Moreover, ceramic sheets of
lithium-lanthanum-titanate (LLT) with micro emboss patterns were developed for all-solid
batteries. Designed models with intended 3D structures were converted into the stereolithog-
raphy (STL) file format through polyhedral approximations and sliced into a series of 2D
layers. The slicing pitches were defined as 10 and 50 μm for fine pattern exposing and speedy
laser scanning stereolithography, respectively. The numerical data were transferred into each
stereolithographic system to create bit map images for micro pattering and raster patterns for
laser scanning. A photosensitive acrylic resin, including 40 vol. % of ceramic particles with
200 nm diameter, was spread on a flat metal stage using a mechanical knife edge. The thick-
ness was automatically controlled to maintain the value given by the model slicing pitch. In
the case of speedy laser scanning stereolithography, a ceramic slurry was scanned using an
ultraviolet laser with a wavelength of 355 nm in order to create cross sectional planes with
an edge part accuracy of 5 μm. The laser beam was adjusted to 100 μm in spot size and 100
mW in power. After the solid pattern was formed, the stage was lowered by 50 μm in layer
thickness and the next cross section layer was stacked. Three dimensional structures were
fabricated by stacking the two dimensional layers. In the case of fine pattern exposing ste-
reolithography, two dimensional solid patterns were obtained on the slurry surface by light
induced photo polymerization. High resolution images had been achieved by using a digital
micro mirror device. In this optical device, micro aluminum mirrors with 14 μm edge length

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were assembled in an array of 1024 × 768 mirrors. Each mirror could be tilted independently
by piezoelectric actuators. Ultraviolet light with a wavelength of 405 nm was introduced
into the digital micro mirror device and the cross sectional image was reduced by 1/10 using
an objective lens set; the light was focused onto a 1.3 × 1.7 mm exposing area. Using the
described computer controlled layer stacking process, an acrylic resin component contain-
ing a dispersion of ceramics particles was obtained. Part accuracies of green bodies could be
measured and observed by using a digital optical microscope (DOM). The formed models
were dewaxed at 600 ºC for 2 hs in air with a heating rate of 1.0 ºC/min; full ceramic com-
ponents were obtained after sintering. The microstructures of the sintered components were
observed using a scanning electron microscope (SEM). Relative densities of these ceramic
components were measured by the Archimedean method.

859
Nanostructure engineering in oxide ceramics for high-temperature
thermoelectric energy conversion
Michitaka Ohtaki1,2
Interdisciplinary Graduate School of Engineering Sciences, Kyushu University,
1

6-1 Kasugakouen, Kasuga, Fukuoka 816-8580, Japan; e-mail: [email protected]

Research and Education Center for Advanced Energy Materials, Devices, and Systems,
2

Kyushu University, 6-1 Kasugakouen, Kasuga, Fukuoka 816-8580, Japan

Keywords: oxide thermoelectrics, phonon scattering, grain boundary, nano-inclusion

Thermoelectric energy conversion has been widely recognized to be particularly suitable for
waste heat energy recuperation and energy harvesting, since it generates electricity directly
from a heat flux penetrating a solid device consisting of n- and p-type semiconductors. Al-
though thermoelectric (TE) power generation has been very successful due to its extremely
high reliability in space and remote applications such as power sources for deep space probe
missions, limitations in elemental abundance and thermal durability of the conventional TE
materials have prevented a wide commercialization of the TE power generation.
Metal oxides are ionic compounds consisting of metal cations and oxygen anions alter-
nately placing with the Coulombic attracting interaction between them. Since the metal-
oxygen bonds are largely polarized, conducting electrons tend to localize on the positively
charged metal cations, resulting in the carrier mobility generally 2–3 orders lower than those
of Si and other covalent compounds. Furthermore, strong interatomic bonding predominantly
by the Coulombic force in oxides coupled with the small atomic mass of oxygen leads to a
high velocity of the elastic waves propagating the crystal lattice of oxides, yielding a high
lattice thermal conductivity. These inherent tendencies of metal oxides had kept them away
from consideration as a TE candidate until mid 90s. Nevertheless, boosted by the global
environment issues and carbon dioxide mitigation problems, oxide TE materials, which are
highly durable at high temperature in air, non-toxic, low cost with minimal environment
impact, are becoming more and more of vital importance for recuperation of decentralized
waste heat energy for higher energy efficiency.
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In this paper, nanostructure engineering in TE oxides will be depicted with focuses on

thermal conductivity reduction by introducing complex microstructure, and by carefully
choosing the crystal structure. The former approach is exemplified by multinary-doped ZnO
with a spontaneously formed microstructure in sintered bodies,1 while the latter strategy is
demonstrated by an ultra-low lattice thermal conductivity found in β-pyrochlore (defect py-
rochlore) oxides having an oversized cage-like structure surrounding a small atom inside.2,3
Current issues of TE oxides will be discussed with a future prospect of the materials and
applications.

References
1. M. Ohtaki, K. Araki, K. Yamamoto, J. Electron. Mater., 38, 1234 (2009).
2. M. Ohtaki, S. Miyaishi, J. Electron. Mater., 42, 1299 (2013).
3. K. Mizuta, M. Ohtaki, J. Electron. Mater., 45, 1695 (2016).

830
Processes and materials for solar thermochemical production of fuels
and chemical commodities
Martin Roeb
German Aerospace Center, Institute of Solar Research, Linder Hoehe 51147 Koeln, Germany

To use heat from carbon-free sources like concentrated solar radiation to drive chemical
reactions for the production of transportation fuels or of chemical commodities represents a
promising way to replace established industrial processes and to avoid substantial amounts of
climate relevant emissions. Recent developments offer attractive medium- to long-term pros-
pects for the provision of chemicals like ammonia, sulfur, phosphates or cement and fuels
like hydrogen and synthesis gas. The direct use of solar heat to drive endothermal chemical
reactions in a temperature range between 500 and 1800 °C is possible. In the field of solar
fuels production so-called thermo-chemical cycles are a viable option to produce hydrogen
from water or syngas from water and CO2 at an acceptable temperature level. The most
prominent examples are cycles from the so-called sulphur family, the hybrid sulphur and the
sulphur-iodine process, and redox cycles applying metal/metal oxide pairs or multi-valent
metal oxides which are capable to reversible incorporate oxygen in this lattice. The present
analysis gives an overview on recent developments and the state-of-the art of high tempera-
ture fuels or chemical commodities producing solar processes. It will have a look on the most
important performance parameters involved and will give an outlook on further potential
and necessary developments. In addition we look at variants of such processes offering the
chance to use them for thermo-chemically storage of solar heat or for air separation.

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860
Quantification of degradation in infiltrated SOFC anodes
Enrique Ruiz-Trejo*, Antonio Bertei, Kristina Kareh, Farid Tariq, Vladimir Yufit,
Samuel J. Cooper, Nigel P. Brandon
Department of Earth Science and Engineering, Imperial College London, SW7 2AZ, London, UK;
*
e-mail: [email protected]

Solid Oxide Fuel Cells (SOFC) are a mature technology and large SOFC stacks have been
tested under operation for periods of more than 5 years showing a remarkable resilience
but showing signs of degradation.1 Nickel coarsening is one the main degradation mecha-
nisms that affect the lifetime of the anodes and it is still yet to be fully understood. The next
generation of electrodes, Ni-infiltrated anodes, have shown remarkable improvement of the
electrochemical performance2 but show a fast degradation compared with the conventional
anodes.3 In this work we present an integrated experimental/modelling approach to quantify
the effect of the Ni microstructural evolution on the electrochemical performance of the next
generation of anodes.
Scaffolds of scandia-stabilised zirconia (ScSZ) impregnated with different volume frac-
tions of Ni were fabricated and characterised. Symmetrical cells were then annealed at con-
stant temperature while recording the impedance as a function of time for several days; the
polarisation of the bulk and electrode response was de-convoluted from the spectra and fol-
lowed as a function of time and nickel content. The microstructure of the initial and degraded
samples was precisely reconstructed with focused ion beam SEM tomography and analysed
to quantify the change in three-phase boundary (TPB) density, Ni percolation and Ni particle
size upon annealing. A physically-based electrochemical model, based on conservation equa-
tions, was used to establish a link between microstructural degradation and the evolution of
the impedance spectra.4

References
1. Tanasini, Pietro, et al. “Experimental and theoretical investigation of degradation mechanisms by
particle coarsening in SOFC electrodes.” Fuel Cells 9.5 (2009): 740–752.
2. Ruiz-Trejo, E., and J. T. S. Irvine. “Electrolysis of CO2 in a proton conducting membrane.” Solid
State Ionics 252 (2013): 157–164.
3. Klemensø, Trine, et al. “Stability of Ni–yttria stabilized zirconia anodes based on Ni-impregna-
tion.” Journal of Power Sources 195.21 (2010): 7295–7301.
4. Bertei, A., et al. “Validation of a physically-based solid oxide fuel cell anode model combining
3D tomography and impedance spectroscopy.” International Journal of Hydrogen Energy 41.47
(2016): 22381–22393.

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829
Manufacturing of proton conductive ceramics for hydrogen separation
membranes and fuel cells
Alessandra Sanson
Institute of Science and Technology for Ceramics, National Council of Research (ISTEC-CNR),
Via Granarolo 64, 48018, Faenza, Italy; e-mail: [email protected]
Keywords: barium-cerate based materials, ceramic processing, tape casting

High temperature proton conducting ceramics based on perovskites of a general formula

ABO3 (BaCeO3, SrCeO3, BaZrO3 and SrZrO3), have received increasing interest as hydrogen
separation membranes and as electrolytes in proton-conducting intermediate-temperature
solid-oxide fuel cells and/or electrolysers (SOFCs/SOECs). These materials however still
require ad-hoc investigations from the ceramic-technology point-of-view to boost their wide-
spread deployment in the abovementioned applications.
This work aims to highlight and solve all the most critical issues linked to the ceramic
process needed to obtain planar, defect free, proton conductive membranes based on barium
cerate perovskites for hydrogen separation and SOFC/SOEC applications. Tape casting was
exploited as industrial easy-scalable ceramic technology for both membranes and Solid oxide
cells.
In particular for H2 separation, asymmetric BaCe0.65Zr0.2Y0.15O3-δ-Gd0.2Ce0.8O2-δ mem-
branes, constituted by a porous support and a dense active layer, were produced for the first
time. The strict control of the sintering atmosphere was found to be one of the most critical
parameter to obtain dense active layers. On the other hand, the possibility to produce a dense/
porous/dense BaCe0.85Y0.15O3-δ (BCY) sandwich-structure electrolyte for SOFC/SOEC ap-
plication was evaluated. The obtained samples were carefully characterized either in SOFC
and SOEC mode.

Fig. 1. Asymmetrical ceramic membrane for H2 separation (a) and sandwich-structure electrolyte for
SOFC/SOEC application (b)

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954
Low cost Sodium batteries based on ceramic materials –
an old idea revisited
Michael Stelter1,2*, Roland Weidl1, Matthias Schulz1
1
Department of Energy Systems, Fraunhofer IKTS, Hermsdorf, Germany;
*
e-mail: [email protected]
2
Center of Energy and Environmental Chemistry CEEC, Jena, Germany
Keywords: beta Alumina, battery, Sodium battery, NaNiCl, extrusion

During their first commercial development in the 1980s and 1990s, batteries based on ­Sodium
and Sodium conducting ceramics had been seen as a high energy storage device for electric
vehicles. As Lithum batteries proved to be a more convenient alternative for electrical mobil-
ity in the last couple of years, Na batteries effectively went to a state of scientific and com-
mercial hibernation.
Only recently, with the advent of extremely low cost solar and wind electricity and the
decentralizaion of the energy system, the demand for large scale electrical storage systems
arose. Stationary power systems require very low cost. Na batteries do consist only of cheap,
abundant materials, such as Alumina, Nickel, rock salt, and sheet metal, so in theory they
could deliver on that promise. However, real-world Na batteries today still are manufac-
tured with complex shapes and expensive production methods. In order to overcome these
limitations, IKTS has fundamentally revisited Na battery design and manufacturing for mass
production and cost reduction.
Low cost batteries for Gigawatt scale stationary energy storage can be manufactured from
Na-beta-Alumina ceramics. Candidate battery cells for this applications are Sodium-Nickel-
Chloride (NaNiCl) and Sodium-Sulphur (NaS) batteries. To achieve a total cost of the battery
cell of under 100 $/kWh, both the ion conducting ceramic material as well as the design of
the ceramic component need to be optimized for mass production. IKTS has achieved several
breakthroughs in the shaping of beta-Alumina components, such as cold plastic extrusion
and tape casting. These components are designed according to a set of rules derived from
cost and manufacturing requirements. It is discussed, how electrochemical component design
and mechanical requirements interact with shaping methods and the route to beta-Alumina
phase formation. Several problems needed to be solved for high-throughput manufacturing
of Na-beta-Alumina, such as the very high pH value in the feedstock, the automated shaping
of tubes with one end closed and the phase stability during sintering. Material qualities with
a phase content of > 96% ß“ and conductivities of > 240 mS/cm have been achieved from
extrusion at IKTS.
Extruded ceramic tubes and sheets have been investigated electrochemically with very
promising results. Several components have undergone electrochemical and thermomechani-
cal testing in IKTS designed real-world battery cells based on Nickel cathodes (NaNiCl de-
sign) with capacities of well over 100 Ah.

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Fig. 1. Large-scale beta-Alumina tubes (left) and 100 Ah stationary NaNiCl battery cell from Fraunhofer
IKTS

Acknowledgment
Financial support for parts of the work by the Federal State of Thuringia, the German Ministry of Eco-
nomics and Trade and the Fraunhofer Future Foundation is greatfully acknowledged.

044
Full picture discovery for flux-grown crystals and interface designs on
next-generation all-solid-state LIB
Katsuya Teshima1,2*, Nobuyuki Zettsu1,2
1
Center for Energy and Environmental Science, Shinshu University, 4-17-1 Wakasato,
Nagano 380-8553, Japan; *e-mail: [email protected]
2
Department of Materials Chemistry, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan
Keywords: all-solid-state LIB, flux growth, single crystals, crystal morphology, surface/interface
design

Lithium ion secondary batteries (LIBs) have been intensively developed due to strong indus-
trial demands of high-performance electric storage devices especially for mobile electron-
ics and green mobilities. In particular, LIBs with both higher energy and power densities
compared to those of conventional ones have attracted research interests for future energy
storage applications. All-solid-state LIBs are candidates for next-generation LIBs because
of their safety, stability and non-flammability. In addition, high volumetric energy densities
can be achieved when cathode-solid electrolyte-anode units are stacked in a multilayered
manner in a single package. However, it is still difficult to achieve all-solid-state LIBs with
desired properties mainly because of difficulty in smooth lithium ion diffusion, i.e., diffu-
sion of lithium ions and electrons are interfered at interface of different materials and also

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inside of them. In this regards, we have tried to control and design the interface and prepare
materials for all-solid-state LIBs on the basis of the crystal science and engineering1–4. Our
research group has developed flux and its expanded methods for preparing highly crystalline
materials used to all-solid-state LIBs. Flux method is a liquid phase crystal growth method in
which idiomorphic highly crystalline particles can be obtained under the melting point of the
target ones. Therefore outmost crystal planes are tuned by our techniques where they have
desired lithium ion paths. In addition, the grown crystals are expected to have high crystallin-
ity because diffusion and rearrangement of atoms easily occurred compared to conventional
particle fabrication methods. Recently, we have developed flux method to fabricate crystal
layers (films) on various substrates, which is named “flux coating method”. It has enabled
us to grow crystals directly on current collector (and solid electrolytes) with good interfaces.
Furthermore, we are focusing on a glass-flux method to make fine active materials/solid
electrolyte interfaces. The details of crystal growth and interface design by use of our flux
concept will be presented in the ECerS2017 conference.

Acknowledgements
This work was partly supported by JST Core Research for Evolutional Science and Technology
(CREST) and Grant-in-Aid for Scientific Research (A) (KAKENHI), Grant Number: 25249089.

References
1. N. Zettsu, K. Teshima et al., Scientific Reports, 6 (2016) 31999.
2. S. Uchida, N. Zettsu, K. Teshima et al., RSC Advances, 6 (2016) 67514.
3. T. Kimijima, N. Zettsu, K. Teshima et al., Journal of Materials Chemistry A, 4 (2016) 7289.
4. T. Kimijima, N. Zettsu, K. Teshima, Crystal Growth & Design, 16 (2016) 2618.

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Oral presentations

046
Three-dimensional polymer-derived ceramic composite paper electrode
for electrochemical energy storage applications
M. Abass, L. David, G. Singh1*
1
Kansas State University, Manhattan, KS, USA; *e-mail: [email protected]

We present a rational method of synthesizing silicon oxycarbide (SiOC) supported on re-

duced graphene oxide (rGO) paper. We show that by controlling the amount of pre-ceramic
polymer i.e., polysiloxane, it is possible to tune interlayer spacing and obtain an optimized
composite electrode that may find use in electrochemical energy storage devices. In this
composite configuration, the SiOC provides ample sites for reversible storage of lithium-ions
while rGO acts as an electrical conductor and robust support against mechanical degradation
at high currents. In this study, a reversible electrochemical capacity of ca. 600 mAh g-1 was
recorded for the composite as a Li-ion battery electrode. While a specific capacitance of >75
F g-1, at a current density of >6 A g-1, was observed as working electrode in supercapacitor
configuration.

574
Development of porous electrodes with tailored microstructure for high
temperature and pressure alkaline electrolysis cells (HTP-AEC)
Jens Q. Adolphsen1*, Vanesa Gil1, Bhaskar Reddy Sudireddy1,
Christodoulos Chatzichristodoulou1, Lennart Bergström2
Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej
1

399, 4000 Roskilde, Denmark; *e-mail: [email protected]

Department of Materials and Environmental Chemistry, Stockholm University, Stockholm 10691,
2

Sweden
Keywords: processing, porous electrodes, electrolysis

The development of porous electrode structures with tailored microstructures is necessary

to reach high current densities, of several A/cm2 in High Temperature and Pressure Alkaline
Electrolysis Cells (HTP-AEC) while maintaining high electrical efficiency (>80%). In this
work we demonstrate how a porous ceramic structure can be processed using commercial
LaNi0.6Fe0.4O3 powder and sacrificial pore formers. The microstructure is optimized to ac-
commodate a high interfacial surface area between the solid electrode and the liquid electro-
lyte, and at the same time allow the produced O2 to escape through gas diffusion pores. The
aim is therefore to achieve a mixed pore size distribution that can accommodate these two
constraints.

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511
The template-assisted wet-combustion synthesis of fibrous nickel-based
catalyst for carbon dioxide methanation and methane steam reforming
M. Aghayan1, D.I. Potemkin2,3, F. Rubio-Marcos4, S.I. Uskov2,3, P.V. Snytnikov2,3,
I. Hussainova1,5,6
1
Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia
2
Boreskov Institute of Catalysis, Pr. Lavrentieva, 5, Novosibirsk, 630090, Russia
3
Novosibirsk State University, Pirogova St., 2, Novosibirsk, 630090, Russia
4
Instituto de Cerámica y Vidrio (ICV-CSIC), C/Kelsen, 5, 28049 Madrid, Spain
5
ITMO University, Kronverkskiy 49, St. Petersburg, 197101, Russia
6
University of Illinois at Urbana-Champaign, 1206 West Green Street, Urbana, IL 61801, USA
Keywords: Ni-based catalyst, combustion synthesis, carbon dioxide metanation, methane steam
reforming

Template-assisted wet-combustion synthesis was used to prepare one-dimensional nickel-

based catalyst for carbon dioxide methanation and methane steam reforming using highly
aligned alumina nanofibers with an average single fiber diameter of 10 nm as a support. X-ray
diffraction, field-emission scanning electron microscopy, transmission electron microscopy,
and high-resolution transmission electron microscopy demonstrated that the as-synthesized
catalyst composed of double core-shell structured fibers (NiO/NiAl2O4/Al2O3). Due to a high
temperature achieved in a short time during reaction and a large amount of gases evolved, the
wet-combustion synthesis yielded homogeneously precipitated nanoparticles of NiO with av-
erage particle size of 4 nm on alumina nanofibers covered with NiAl2O4 nanolayer. To prove
the role of the properly chosen fuel on the product morphology and chemical composition,
Ni-based catalyst was prepared using fuel-less reactive solution. The results demonstrated
that the average particle size of deposited NiO is ~40nm was obtained.
Nickel-based catalyst synthesized by wet-combustion method exhibited excellent activity
in steam reforming of methane and sufficient activity in carbon dioxide methanation. The
fiber-type structure of the catalyst was unchanged after the processed.

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541
Deciphering the influence of microstructure and crystal structure on
the temperature dependent ion conductivity of Sodium-β’’-alumina
Marie-Claude Bay1,2*, Meike V.F. Heinz1, Lorenzo Pusterla1, Marta Dai Prè3,
Nicola Zanon3, Ulrich F. Vogt1,2, Corsin Battaglia1
1
Empa, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129,
8600 Dübendorf, Switzerland; *e-mail: [email protected]
2
Institute for Environment and Natural Resources, Albert-Ludwigs-University Freiburg,
Crystallography, 79098 Freiburg, Breisgau, Germany
3
FZSONICK SA, 6855 Stabio, Switzerland
Keywords: Na-β’’-alumina, microstructure, crystal structure, ion conductivity, non-Arrhenius behav-
iour

Na-β’’-alumina is a fast sodium ion conductor at elevated temperature and thus favoured as
electrolyte in Na/NiCl2 batteries. Although the material is known since the 1970s, sodium
ion conductivities reported in literature show a large variation1. While it is generally agreed
that this is related to compositional as well as grain size effects, the detailed relationships are
still unclear2,3. In addition, Na-β’’-alumina is a non-stoichiometric material which makes it
difficult to prepare with defined composition as sodium evaporates at the high temperatures
required for sintering4.
Based on a detailed experimental study we show that the sintering conditions affect not
only grain growth, but also sodium content and crystal structure of Na-β’’-alumina ceramics
and explain how this affects the ion conductivity. Furthermore, the temperature-dependent
conductivity data between room temperature and 400 °C feature a deviation from exponential
behaviour. We discuss different interpretations of this “non-Arrhenius behaviour” as well as
possibilities and limitations of extracting the contributions of grain and grain boundary con-
ductivity from impedance spectroscopy data.

References
1. X. Lu, G. Xia, J.P. Lemmon, Z. Yang. “Advanced materials for sodium-beta alumina batteries:
Status, challenges and perspectives.” J. Power Sources, 195, pp. 2431–2442, 2010.
2. Zhu C., Xue J., Ji G. “Effect of Na2O content on properties of beta alumina solid electrolytes.”
Materials Science in Semiconductor Processing, 31, pp. 487–492, 2015.
3. Chen G., Lu J., Chen L., Jiang X. “Microstructure control and properties of β’’-Al2O3 solid electro-
lyte.” J. of Alloys and Compounds, 673, pp. 295–301, 2016.
4. Stevens R., Binner J.G.P., “Review Structure, properties and production of β-alumina.” J. of Mate-
rials Science, 19, pp. 695–715, 1984.

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198
ZnFe2O4/C nanoparticles by laser pyrolysis: new anode material for
lithium-ion batteries
Samantha Bourrioux1*, Yann Leconte1, Moulay Tahar Sougrati2, Lorenzo Stievano2,
Laure Monconduit2, Zhichuan J. Xu3, Madhavi Srinivasan3, Alain Pasturel4
1
CEA, IRAMIS, NIMBE, CNRS UMR 3685, F- 91191, GIF-SUR-YVETTE, France;
*
e-mail: [email protected]
2
Institut Charles Gerhardt-CNRS Université Montpellier II Place Eugène Bataillon, 34095
Montpellier, France
3
School of Materials Science and Engineering, Nanyang Technological University, Singapore
4
SIMAP, UMR CNRS 5266, Grenoble INP, BP 75, 38402 Saint-Martin D’Heres, France
Keywords: laser pyrolysis, zinc iron oxide, carbon coating, ZnFe2O4/C, composite, lithium-ion bat-
teries

With the depletion of fossil fuels and the growing environmental concerns, lithium-ion bat-
teries received considerable attention to contribute to the development of electric vehicles
and storage for renewable energies. However, existing lithium-ion batteries cannot reach suf-
ficient energy density to address the needs for such applications. One of the issues limiting
the energy density is the low specific capacity of the graphite anode (372 mAh/g). Mixed-
transition metal oxides with a spinel structure (AB2O4 – A, B transition metals) appear as a
promising solution to replace graphite with a higher theoretical capacity (between 750 and
1000 mAh/g). Among various oxides, ZnFe2O4 is an interesting substitute for graphite, as
an abundant, cheap, non-toxic and environmental-friendly material with a high theoretical
capacity (1000 mAh/g). The nanostructuration of this material as well as a carbon coating
around the particles can also help to maintain a mechanical stability during cycling and en-
hance the lithium kinetics.
ZnFe2O4/C nanoparticles presented in this work were synthesized by laser pyrolysis. In
this vapor-phase process, a CO2 laser is used to thermally decompose the precursors and
synthesize nanoparticles. A solution containing ZnCl2 and FeCl3.6H2O dissolved in ethanol
in a stoichiometric ratio was used for the synthesis of ZnFe2O4/C nanoparticles. Ethylene was
chosen as absorbent of the CO2 laser to allow the precursors decomposition and air as the
carrier gas. To vary the carbon content of the as-synthesized nanopowders, annealings under
air atmosphere were realized (Fig. 1).

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Fig. 1. Particles morphology before annealing (left) and after annealing (right)

Electrodes were then prepared using ZnFe2O4/C (70% wt.), CMC (12% wt.) and carbon
additives (VGCF 9% wt., carbon black 9% wt.) to be cycled vs. lithium metal and post-
mortem SEM was done to observe the electrodes morphology after cycling.

473
Pressure assisted sintering of tape casted calcium cobaltite
Sophie Bresch1, Bjoern Mieller1, Ralf Moos2, Torsten Rabe2
Division Advanced Technical Ceramics, Bundesanstalt für Materialforschung und -prüfung (BAM),
1

Unter den Eichen 44-46, 12203 Berlin, Germany;

e-mails: [email protected], [email protected], [email protected]
Lehrstuhl für Funktionsmaterialien, Fakultät für Ingenieurwissenschaften, Universität Bayreuth,
2

Universitätsstr. 30, 95447 Bayreuth, Germany; e-mail: [email protected]

Keywords: thermoelectrics, calcium cobalite, tape casting

Thermoelectric materials can convert waste heat directly into electrical power by utilizing
the Seebeck effect. Calcium cobaltite Ca3Co4O9 is a promising p-type oxide thermoelectric
material for applications between 600 °C and 900 °C in air. The properties and morphology
of Ca3Co4O9 are strongly anisotropic because of its crystal structure of alternating layers
of CoO2 and Ca2CoO3. The electrical conductivity is for example 13.5 times higher in a/b-
direction than in c-direction.1 By aligning the plate-like grains, the anisotropic properties can
be assigned to the component. Hot-pressing of tablets is a well-known technology for grain
alignment of Ca3Co4O9 and increases the thermoelectric properties in a/b-direction remark-
ably.1–3 It also increases the relative density.1–3 However, hot-pressing of tablets is limited

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by the tablet size. An interesting alternative for larger components is the pressure assisted
sintering of panels from tape casted layers. Tape casting already leads to a grain alignment
during green body forming. By combining tape casting and pressure assisted sintering (50
kN maximum force) of Ca3Co4O9, high densities and high thermoelectric properties can be
reached for large components up to 200 mm edge length.
Ca3Co4O9 was successfully tape casted with the doctor blade technique (binder: polyvinyl
butyral, organic solvent). Several layers of tape were stacked and laminated to 5 cm × 5 cm
panels. These panels were sintered with different applied pressures in a LTCC sintering press
with combined in-situ shrinkage measurement. Pressure-less sintered panels have a 2.5 times
higher electrical conductivity at room temperature than test bars with randomly orientated
particles. By applying a uniaxial pressure of 10 MPa during sintering, the electrical conduc-
tivity increases by the factor of 6 compared to the pressure-less sintered panels. About 40%
linear shrinkage are reached in pressing direction. The Seebeck coefficient (S25 °C=146 µV/K)
and the electrical conductivity (σ25 °C=15100 S/m) are in good agreement with the values
published in literature for hot-pressed tablets.1,3

References
1. D. Kenfaui et al., “Development of multilayer textured Ca3Co4O9 materials for thermoelectric
generators: Influence of the anisotropy on the transport properties”, J. Eur. Ceram. Soc., 32, pp.
2405–2414, 2012.
2. G. Xu et al., “Thermoelectric properties of the Bi- and Na-substituted Ca3Co4O9 system”, Appl.
Phys. Lett., 80, pp. 3760–3762, 2002.
3. D. Kenfaui et al., “Anisotropy of the Mechanical and Thermoelectric Properties of Hot-Pressed
Single-Layer and Multilayer Thick Ca3Co4O9 Ceramics”, Int. J. Appl. Ceram. Tec., 8, pp. 214–
226, 2011.

329
High-temperature mechanical behavior of fully dense
La9.33+XSi6O26+3X/2 oxyapatite electrolyte materials for SOFCs
Desirée Ciria1,2, Manuel Jimenez-Melendo2, Fabienne Karolak1, Véronique Aubin3,
Guilhem Dezanneau1
Laboratoire SPMS, CentraleSupélec, CNRS, Université Paris-Saclay, 92290 Chatenay-Malabry,
1

France
Departamento de Física de la Materia Condensada and Instituto de Ciencia de Materiales,
2

CSIC-Universidad de Sevilla, Ap, Aptdo, 1065, 41080 Sevilla, Spain

Laboratoire MSSMAT, CentraleSupélec, CNRS, Université Paris-Saclay, 92290 Châtenay-Malabry,
3

France
Keywords: creep, mechanical properties, oxyapatite, electrolyte, SOFCs

Lanthanum silicates is considered as a potential alternative to yttria-stabilised zirconia to be

used as electrolyte material in Solid Oxide Fuel Cells. While numerous studies have dealt
with the influence of composition on conduction properties, very little is known about the

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mechanical properties of lanthanum silicate compounds. We have thus started an exhaustive

study of mechanical properties of La9.33+xSi6O26+3x/2 sintered compounds, taking benefit from
our previous experience in oxyapatites preparation1,2 and from our knowledge of oxide me-
chanical properties characterization3–5.
High density (<96%) oxyapatite material, made through conventional sintering (CS) and
Spark Plasma Sintering (SPS), were prepared from nanopowders synthesized through freeze-
drying. Samples were then characterized mechanically at both intermediate and high tem-
perature.
Firstly, compressive mechanical tests have been performed at solid oxide fuel cell op-
erating temperatures (700 ºC) under different atmospheres, including air, argon and pure
hydrogen. And secondly, we performed Compressive creep tests at constant speed and load
at temperatures ranging from 1000 to 1300 °C. The objective was determine the effective dif-
fusion coefficient and identify the atomic mechanisms of plastic deformation and the origin
of failure of these materials at high temperature.
The experimental results have been correlated with microstructural observations by scan-
ning and transmission electron microscopy.

References
1. A. Chesnaud, G. Dezanneau, C. Estournes et al., Solid State Ionics, 179, 33–34, 2008.
2. A. Chesnaud, C. Bogicevic, F. Karolak et al., Chem. Comm. 15, 1550–1552, 2007.
3. Y. Li, V. Aubin, C. Rey et al. , Inter. J. Fatigue, 42, 71–81, 2012
4. M. Oliva-Ramirez, F. Huaman-Mamani, M. Jimenez-Melendo, Fuel Processing Technology, 103,
45–50, 2012.
5. M. Jimenez-Melendo, C. Vaquero-Aguilar, F. Huaman-Mamani, Fuel Processing Technology, 103,
146–150, 2012.

029
The proton in nominally anhydrous oxides: content, nature and
dynamics
Philippe Colomban1,2
1
Sorbonne Universités, UPMC Univ Paris 06, UMR 8233, MONARIS, 75005, Paris, France
2
CNRS, UMR 8233, MONARIS, F-75005, Paris, France; e-mail: [email protected]

The attempts to develop stable ceramic electrolyte membranes for H2 production (electrolys-
ers), conversion (fuel cells, CO2 converters) or purification (membranes) led to select various
anhydrous oxide frameworks (perovskites, apatites) with high ionic conduction at medium
temperature (400–700 °C). The use of medium pressures (20–30 bars) allows to optimize
the economic efficiency of H2-based systems but implies high chemical resistance vs. water
pressure, CO2, etc. Different materials have been tested and some of them have recently
reached the demonstrator scale. Techniques able to study H-containing frameworks are mul-
tiple ­(X-ray and neutron diffraction, TGA, IR & Raman spectroscopies, Elastic, Quasi-elastic
and inelastic neutron scattering, PIGE/ERCS, Nuclear Reactions, etc.) but their comprehen-

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sive use limited. However, the fundamental knowledge on the proton chemical nature at the
operating temperature (hydroxyl group, interstitial proton or proton gas), the exact content
(differentiation between defect, surface or bulk protons), the location and the dynamics of
protons remains poor and highly debated. Ion/proton dynamic and conduction take place
when the species escape from the potential well, i.e. in a very anharmonic regime, very far
away from the conditions of many studies. Furthermore, the unique properties of hydrogen
and its low amount (i.e. a doping) in these membranes make the study difficult because of
the confusion with surface species. Reasonable answers to all the above mentioned questions
will be discussed at the light of recent works.

References
1. Ph. Colomban, Proton and Protonic Species: the Hidden Face of Solid State Chemistry. How to
Measure H-Content in Materials? Fuel Cells 13[1] (2013) 6–18.
2. A. Slodczyk, Ph. Colomban, S. Upasen, F. Grasset, G. André, Structural stability of anhydrous pro-
ton conducting SrZr0.9Er0.1O3-δ perovskite ceramic vs. protonation/deprotonation cycling: neutron
diffraction and Raman studies, J. Physics & Chemistry of Solids 83 (2015) 85–95.
3. A. Pons, J. Jouin, M. Colas, E. Béchade, P.-M. Geffroy, M. Smirnov, O. Masson, P. Thomas, I.
Kagomiya, T. Asaka, K. Fukuda, A. Slodczyk, Ph. Colomban, Structural modifications lanthanum
silicate oxyapatite exposed to high water pressure, J. of the European Ceramic Society (2017).

166
MgAl2O4-based catalyst deposition over nickel-chromium alloy for
steam methane reforming in millimetric-channel reactor
Baptiste Croissant1,2*, Fabrice Rossignol1, Thierry Chartier1, Raphael Faure2
1
SPCTS – UMR CNRS 7315, Université de Limoges, CEC, 12 rue Atlantis 87068 Limoges, France;
*
e-mail: [email protected]
2
Air Liquide, CRPS, 1 chemin de la Porte des Loges, BP126, 78354 Jouy en Josas, France
Keywords: millistructure, catalyst slurry, dip-coating, adherence, substrate pre-oxidation

Functionalized metallic millistructured reactors-exchangers are promising solutions for in-

tensification of steam methane reforming.1 High temperature metals, resistant to corrosion,
usually Iron/Chromium or Nickel/Chromium alloys, are used to fulfill the severe conditions
occurring in this catalyst reaction (20 bars, steam/carbon molar ratio over 3, temperature
between 800 and 900 °C). To perform the catalytic conversion of methane inside millistruc-
tured reactors-exchangers, thin catalyst film deposition is required. Among all the existing
coating techniques (plasma spraying, CVD, sol-gel…), washcoating is probably the most
described in the literature for coating structured catalysts and monolithic reactors.2 It is a reli-
able technique that is easily scalable (e.g. for automotive application) and that can be adapted
to several kind of substrates (ceramic, metallic). For washcoating complex geometries with
limited accessibility (e.g. monolithic reactor having tortuous channels), slurry infiltration
methods may be preferred. Solvent choice, solid concentration, particle size distribution, pH
and additives (binders, plasticizers, wetting agents, …) are the main determining parameters.

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Though MgAl2O4-based catalysts have proven to be reliable for methane conversion into
hydrogen, very few studies in the literature have described its deposition on chromium oxide
forming alloys.3
The goal of this work is to coat a homogeneous and adherent MgAl2O4-based catalyst
layer by dip-coating technique onto nickel-chromium alloy foils (Inconel 625). Thermal
pre-treatment in controlled atmosphere is used in order to enhance the catalyst adhesion by
producing an oxide layer onto the surface. Morphology of the powder, particle size, catalyst
slurry formulation, rheological properties and dip-coating parameters have been studied and
optimized in order to improve the coating quality. Coating thickness, coating load and adhe-
sion measured by weight loss under ultrasonic tests are also reported after calcinations.4 Re-
sults obtained by application of the solution developed to washcoating of millimetric chan-
nels reactors are presented as well.

References
1. M. Mbodji, J. M. Commenge, L. Falk, D. Di Marco, F. Rossignol, L. Prost, S. Valentin, R. Joly, and
P. Del-Gallo, “Steam methane reforming reaction process intensification by using a millistructured
reactor” Chem. Eng. J., vol. 207–208, pp. 871–884, Oct. 2012.
2. V. Meille, “Review on methods to deposit catalysts on structured surfaces,” Appl. Catal. Gen., vol.
315, pp. 1–17, Nov. 2006.
3. J. Guo, H. Lou, H. Zhao, and X. Zheng, “Improvement Of Stability Of Out-layer MgAl2O4 spinel
for a Ni/MgAl2O4/Al2O3 Catalyst” React. Kinet. Catal. Lett., vol. 84, no. 1, pp. 93–100, Jan. 2005.
4. Michela Valentini, Pio Forzatti, Enrico Tronconi, Marinella Levi, Cinzia Cristiani, and Gianpiero
Groppi, “The deposition of Gamma-Al2O3 layers on ceramic and metallic supports for the prepara-
tion of structured catalysts,” Appl. Catal. Gen., 2001.

383
Stability and sintering of magnesium oxide as a substrate material for
lanthanum tungstate membranes
Wendelin Deibert, Mariya E. Ivanova, Wilhelm A. Meulenberg
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, Materials Synthesis and
Processing (IEK-1), 52425 Jülich, Germany
Keywords: hydrogen, ceramic membranes, lanthanum tungstate, magnesium oxide, sintering

Hydrogen is an important resource for different applications in chemical industry, power

plant technology, and mobile systems. One possibility of producing hydrogen is the water-
gas-shift-reaction where hydrogen is synthesized from fossil fuels like natural gas. In order
to separate H2 from gas mixtures and achieve high purity, the use of dense mixed protonic-
electronic conducting ceramic membranes shows a large potential.
Lanthanum tungstate (LaWO) with a composition of La6−xWO12−δ (with d = 1.5x + δ and
x = 0.5−0.6) is a promising material for these applications due to its high chemical stabil-
ity and proton conductivity. LaWO has already been investigated for structural properties,
conductivity and H2 permeation. To achieve the maximum performance of the membrane
material one effective way is to reduce the membrane thickness to around 20 µm to lower

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the transport resistance. To maintain the mechanical stability of such a thin ceramic layer a
support structure is needed. A cheap, mechanically and chemically stable material is needed
for this task. Furthermore, the substrate structure has to be porous to ensure the gas transport
and has to be inert towards the LaWO membrane material.
In this study we present magnesium oxide (MgO) as a substrate material for LaWO mem-
branes.1 For this purpose, MgO supports were prepared for sintering studies and stability tests
under application conditions (H2, CO, CO2, H2O). MgO powder was commercially available.
The powder properties were monitored by particle size analysis and BET measurements.
Stability tests were performed in two different atmospheres which represent the situations at
the entrance and at the exit of a water-gas shift reactor. Sintered MgO pellets were exposed
to the atmospheres for 72 h at temperatures of 600–900 °C. No reactions of the MgO with
the gases could be found by XRD analysis. For the fabrication of MgO support layers the
tape-casting technique was chosen. The powder properties were tailored by annealing and
subsequent ball milling in ethanol. Tape-cast samples were studied for their sintering behav-
ior using an optical dilatometer. The shrinkage rate of the MgO layer was compared to that
of a LaWO membrane layer and they appeared to be quite different but still in a tolerable
range. Due to this, asymmetric structures with a LaWO membrane and an MgO substrate
layer were successfully fabricated by sequential tape-casting and co-firing. The two materials
showed some interdiffusion during the co-firing process and consequentially the formation
of a second phase inside of the MgO substrate. No crack-formation or other harmful effects
of this second phase were found. Finally, the stability of the asymmetric membranes was
investigated by exposing the samples to application atmospheres at 900 °C for 96 h. No reac-
tion was visible in SEM and XRD, proving the excellent perspective of MgO in the field of
hydrogen separation membranes.

Reference
1. W. Deibert, F. Schulze-Küppers, E. Forster, M.E. Ivanova, M. Müller, and W.A. Meulenberg, “Sta-
bility and sintering of MgO as a substrate material for Lanthanum Tungstate membranes,” Journal
of the European Ceramic Society, vol. 37, pp. 671–677, 2017.

556
Cr/Si-poisoning of La2NiO4+δ used as air electrode in solid oxide cells
Andreas Egger*, Nina Schrödl, Werner Sitte
Chair of Physical Chemistry, Montanuniversitaet Leoben, Franz-Josef-Strasse 18, 8700 Leoben,
Austria; *e-mail: [email protected]
Keywords: rare earth nickelates, SOFC, SOEC, poisoning

High-temperature steam electrolysis (HTSE) offers a way for highly efficient water split-
ting if thermal coupling to existing heat sources is available. HTSE technology is based on
solid oxide electrolyzer cells (SOECs) which are operated at temperatures between 600 and
1000 °C. Compared to their galvanic counterpart – solid oxide fuel cells (SOFCs) – degrada-
tion rates of SOECs are currently roughly one order of magnitude higher than for SOFCs. In

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this work the promising electrode material La2NiO4+δ is characterized as air electrode mate-
rial for high temperature fuel cells and electrolyzer cells. La2NiO4+δ is a member of the rare
earth nickelate series An+1BnO3n+1 (A = La, Pr, Nd; B = Ni; n = 1, 2, 3 ...) which are among
the most promising materials when high oxygen diffusivities, good electronic and high ionic
conductivities are required.1 In addition to their use as air electrodes for intermediate tem-
perature SOFCs and SOECs, these compounds offer applications as ceramic membranes for
selective oxygen separation, electrochemical oxygen sensors and heterogeneous catalysts.
In this work special emphasis is put on the Cr/Si-tolerance of La2NiO4+δ, which is an
important property for SOEC and SOFC air electrodes when applied in stacks containing
metallic interconnects or glass sealings. Electrochemical properties of bulk samples are de-
termined between 700 °C and 800 °C in synthetic air over a period of several thousand hours
in the presence of a Cr-source in dry and humid atmospheres.2 Moreover, symmetrical cells
with porous La2NiO4+δ electrodes are prepared and the effect of Cr-poisoning on electrode
performance is investigated both under anodic and cathodic polarization.3 Degradation pro-
cesses are continuously monitored by different experimental techniques such as conductivity
relaxation measurements, current voltage analysis and impedance spectroscopy. Extensive
analytical investigations are performed at several stages of the degradation process by SEM,
TEM and XPS in order to determine the deposition and distribution of contaminants as well
as to identify the composition of secondary phases.4 The analytical findings are correlated
with results from electrochemical measurements allowing the identification of potential deg-
radation mechanisms.

References
1. E. Boehm, J.M. Bassat, P. Dordor, F. Mauvy, J.C. Grenier, P. Stevens, Solid State Ionics, 176, pp.
2717–2725, 2005.
2. N. Schrödl, E. Bucher, A. Egger, P. Kreiml, C. Teichert, T. Höschen, W. Sitte, Solid State Ionics,
276, pp. 62–71, 2015.
3. A. Egger, N. Schrödl, C. Gspan, W. Sitte, Solid State Ionics, 299, pp. 18–25, 2017.
4. N. Schrödl, E. Bucher, C. Gspan, A. Egger, C. Ganser, C. Teichert, F. Hofer, W. Sitte, Solid State
Ionics, 288, pp. 14–21, 2016.

944
OTM performance optimization for oxyfuel applications by catalytic
layer functionalization
Julio Garcia-Fayos, Laura Navarrete, Jose Manuel Serra*
Instituto de Tecnología Química (UPV-CSIC), Avenida de Los Naranjos s/n 46022 Valencia, Spain;
*
e-mail: [email protected]
Keywords: dual-phase, composite, oxyfuel, optimization, surface modification, infiltration, oxygen
permeation, ceramic membrane

Material stability along with performance is the most critical issues when Oxygen Transport
Membranes (OTMs) are exposed to CO2&SO2-containing oxyfuel atmospheres. Under such
conditions the typical mixed ionic-electronic materials used as OTMs are neither chemically

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nor mechanically stable. Nevertheless, recent investigations conducted on composite materi-

als have demonstrated a good behaviour and performance of these when exposed to oxyfuel
environments1. Amongst these materials, one of the most interesting is the dual-phase mate-
rial with composition 60% Fe2NiO4 – 40% Ce0.8Tb0.2O2-δ (NFO-CTO), showing an outstand-
ing stability and a promising performance2. However, the obtained oxygen fluxes should be
improved in order to meet the techno-economic targets.
Since oxygen permeation becomes limited by surface exchange reactions, especially at
low temperatures and when reducing membrane thickness, it is possible to achieve an im-
provement in oxygen fluxes by surface modification. One of the most considered options
is the addition of porous layers on membrane surfaces, thus allowing the enhancement in
surface exchange reactions rates mainly due to the increase of surface specific area. A mem-
brane presenting a larger active area also presents a higher number of active sites for oxygen
reactions and a higher TPB length, and therefore, more sites available for O2 molecules to be
incorporated/released to/from membrane. However, the performance of these systems will
remain limited by the oxygen reaction kinetics involved in the oxygen dissociation/recom-
bination and adsorption processes. Therefore, by using suitable elements presenting redox
character and adsorption properties these reactions can be boosted and thus, the oxygen per-
meation can be improved. Several oxides containing some lanthanides and metals meet these
requirements.
Therefore, it has been considered the catalytic activation of NFO-CTO porous backbones
with different elements by capillary infiltration. A first screening of the activated cases has
been done by Electrochemical Impedance Spectroscopy, studying their performance under
representative oxyfuel environments. The most interesting cases were later studied in oxygen
permeation tests, obtaining up to 6-fold J(O2) improvements at 850 ºC with respect to the not
activated case.

References
1. Luo, H.; Klande, T.; Cao, Z.; Liang, F.; Wang, H.; Caro, J., A CO2-stable reduction-tolerant Nd-
containing dual phase membrane for oxyfuel CO2 capture. Journal of Materials Chemistry A 2014,
2 (21), 7780–7787.
2. Garcia-Fayos, J.; Balaguer, M.; Serra, J.M., Dual-Phase Oxygen Transport Membranes for Stable
Operation in Environments Containing Carbon Dioxide and Sulfur Dioxide. ChemSusChem 2015,
8 (24), 4242–4249.

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069
Microstructural and phase evolution of atmospheric plasma sprayed
manganese cobalt iron oxide protection layers in solid oxide fuel cells
N. Grünwald1, N.H. Menzler1, O. Guillon1,2, R. Vaßen1
1
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research – Materials Synthesis
and Processing (IEK-1), 52425 Jülich, Germany
2
JARA-Energy, Jülich/Aachen, Germany
Keywords: SOFC, MCF, APS, protective coating, self-healing, Mn1,0Co1,9Fe0,1O4

Chromium containing steels are widely used as interconnects in solid oxide fuel cell stacks
(SOFCs) because of their advantageous mechanical and electrical properties. The major
drawback of this material is the evaporation of chromium containing species at the high
SOFC operation temperatures, which lead to a strong degradation of commonly used cathode
materials. Covering the interconnect’s surface with a protection layer enables a strong reduc-
tion of the chromium related degradation. The use of dense layers of atmospherically plasma
sprayed (APS) Mn1,0Co1,9Fe0,1O4 (MCF) showed remarkably low degradation rates within
operated stacks in Jülich. Although the stacks show good performance, the APS-MCF layers
undergo strong changes that are just partially described in literature,1,2 but not fully under-
stood yet. This study analyses the microstructural evolution and phase changes of APS-MCF
layers within samples tested for annealing times of up to 10.000 hours and also within com-
ponents of test stacks operated at JÜLICH. A crack healing effect is observed by annealing in
air at low temperature of 500 °C. Measurements with X-ray diffraction, wet chemical analy-
ses and thermo gravimetry support a theory describing this effect by a volume expansion that
is induced by an oxidation process of the plasma sprayed MCF. Air leakage measurements
reveal a strong increase of gas-tightness providing increased chromium retention. Annealing
at higher temperatures of 700 °C to 850 °C leads to a segregation and a phase separation
observed in electron microscopic images. Oxidation driven diffusion of Cobalt ions to the
layer’s surface build up a dense Co3O4 layer in a spinel crystal structure. This layer deceler-
ates further oxidation of the coatings bulk. Combining these results with the performed long-
term annealing tests can provide lifetime predictions of APS-MCF protective layers. Thereby
a reduction of the cathode related degradation can be achieved.

References
1. R. Vaßen, N. Grünwald, D. Marcano, N.H. Menzler, R. Mücke, D. Sebold, Y.J. Sohn, O. Guillon,
Aging of atmospherically plasma sprayed chromium evaporation barriers, Surface and Coatings
Technology 291 (2016) 115–122.
2. J. Puranen, M. Pihlatie, J. Lagerbom, G. Bolelli, J. Laakso, L. Hyvärinen, M. Kylmälahti, O.
Himanen, J. Kiviaho, L. Lusvarghi, P. Vuoristo, Post-mortem evaluation of oxidized atmospheric
plasma sprayed Mn–Co–Fe oxide spinel coatings on SOFC interconnectors, International Journal
of Hydrogen Energy 39 (2014) 17284–17294.

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231
La0.5Sr0.5Fe0.7Ga0.3O3-δ perovskite membrane produced by electrophoretic
deposition process
Laure Guironnet1,3*, Pierre-Marie Geffroy2, Cécile Pagnoux1, Nicolas Richet2, Thierry
Chartier1
1
SPCTS, CNRS, ENSCI, Université de Limoges, CEC, 12 rue Atlantis 87068 Limoges, France;
*
e-mail: [email protected]
2
Air Liquide CRCD, 1 chemin de la Porte des Loges, BP126, 78354 Jouy en Josas, France
3
ADEME, 20 rue du Grésillé, BP 90406, 49004 Angers Cedex 1, France
Keywords: perovskite membrane, electrophoretic deposition, oxygen semi-permeation flux, surface
exchanges

Mixed ionic and electronic conducting materials with perovskite structure are of great inter-
est for their potential application as membrane materials for oxygen separation applications.1
However, considering industrial applications, membranes must meet several criteria: good
chemical stability, suitable mechanical properties under a wide range of oxygen partial pres-
sure at high temperature and good compromise between cost and oxygen semi-permeation
fluxes (≈ 10–1 mol.m².s–1 at 900 °C).
The first step to improve the oxygen semi-permeation is the identification of the oxygen
transport rate determining step. It depends mostly of the membrane chemical composition.
Then, it is possible to increase the oxygen flux through the membrane, with the elaboration
of appropriate membrane architecture. If oxygen flux is limited by surface exchange kinetics,
surface properties (microstructure, chemistry, …) must be modified.2 Numerous solutions
are reported in the literature, as the coating of porous layer obtained by screen printing, or
dip-coating, but also electrodeposition in the SOFC field3… If oxygen flux is limited by bulk
diffusion, the thickness of the membrane is the most important parameter.
Oxygen permeation through La0.5Sr0.5Fe0.7Ga0.3 membrane is limited surface exchange
kinetics. The goal of this work is to increase surface kinetics by a deposit a thin layer of
La0.6Sr0.4Fe0.8Co0.2. In addition to the chemical effect of cobalt containing perovskite, small
grains size will be used to increase even further the surface kinetics (d50 = 0.4 µm). The de-
posit will be realized by an electrophoretic deposition process.4
Electrochemical performances of membranes have been measured using a specific device
developed jointly between SPCTS and LEPMI (Grenoble). This device gives access in a
single measurement to oxygen semi-permeation flux, oxygen diffusion coefficient and sur-
face exchanges kinetics at both surfaces of the membrane.

References
1. P.-M. Geffroy, J. Fouletier, N. Richet, T. Chartier, Rational selection of membrane materials of
MIEC materials in energy production processes, Chemical Engineering Science, 87 (2013), 408–
433.
2. K. Watanabe, M. Yuasa, T. Kida, Y. Teraoka, N. Yamazoe, K. Shimanoe, High-performance
­oxygen-permeable membrane with an asymmetric structure using Ba0.95La0.05FeO3-δ perovskite-type
oxide, Advanced Materials, 22 (2010), 2367–2370.

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3. H.J.M. Bouwmeester, H. Kruidhof, A. Burggraaf, Importance of the surface exchange kinetics as

rate limiting step in oxygen permeation through mixed-conducting oxides, Solid State Ionics, 72
(1994), 185–194.
4. K. Moritz, U. Ballaschk, G. Schmidt, J. Hubálková, C. Aneziris, Oxide ceramics with unidirec-
tional pore channels by electrophoretic deposition, Journal of the European Ceramic Society, 36
(2016), 333–341.

831
Overview of the electrical properties of yttrium-doped strontium
zirconate as a proton-conducting component in high-temperature
electrochemical devices
Gemma Heras-Juaristi1, Domingo Pérez-Coll1*, Duncan P. Fagg2, Glenn C. Mather1
1
Instituto de Cerámica y Vidrio, CSIC, Cantoblanco, 28049 Madrid, Spain;
*
e-mail: [email protected]
2
Department of Mechanical Engineering, University of Aveiro, 3810-193 Aveiro, Portugal
Keywords: protonic ceramic cells, yttrium-doped strontium zirconate, mixed ionic-electronic conduc-
tion properties

Proton-conducting ceramic materials may be used for efficient production of pure, dry hy-
drogen by steam electrolysis in a high temperature range, 600–900 °C.1 However, much
investigation of the transport properties under a relevant range of conditions is still needed
for development of promising devices such as protonic ceramic fuel cells (PCFCs) and pro-
tonic ceramic electrolyser cells (PCECs). SrZrO3-based perovskites have emerged as strong
PCEC electrolyte candidates due to their good chemical and mechanical stability. In this
work yttrium-doped strontium zirconate (SrZr0.9Y0.1O3-δ) was synthesised by solid-state reac-
tion following the ceramic method and sintered in the range 1300-1600 ºC with and without
the addition of minor contents of Zn as sintering additive. The microstructural components
of electrical transport such as grain and grain boundary were carefully studied in dry and wet
O2, revealing a clear effect from the sintering conditions.2 The addition of Zn and lowering
the sintering temperature improved the grain and grain boundary transport processes consid-
erably. The ionic and electronic contributions to the electrical transport were also analysed
under wet and dry oxidising and reducing conditions by impedance spectroscopy and by a
modification of the electromotive force methodology.3 All the samples exhibited a p-type
electronic contribution under oxidising conditions with a dominant protonic contribution for
higher values of pH2O; oxide-ionic conductivity was negligible in wet atmospheres. Pro-
tonic transport numbers close to unity were obtained under highly reducing conditions in the
temperature range 600–700 ºC for pH2O≈ 0.023 atm, with an increasing n-type contribution
exhibited for higher temperatures and lower humidifications.

References
1. T. Sakai, S. Matsushita, H. Matsumoto, S. Okada, S. Hashimoto, T. Ishihara, “Intermediate tem-
perature steam electrolysis using strontium zirconate-based protonic conductors”, International
Journal of Hydrogen Energy, 34, pp. 56–63, 2009.

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2. G. Heras-Juaristi, D. Pérez-Coll, G.C. Mather, “Effect of sintering conditions on the electrical-

transport properties of the SrZrO3-based protonic ceramic electrolyser membrane”, J. Power Sourc-
es, 331, pp. 435–444, 2016.3.
3. D. Pérez-Coll, G. Heras-Juaristi, D.P. Fagg, G.C. Mather, “Transport-number determination of
a protonic ceramic electrolyte membrane via electrode-polarisation correction with the Gorelov
method”, J. Power Sources, 245, pp. 445–455, 2014.

180
Chemical stability of ceramic dual-phase membrane materials for
H2-separation in water-gas shift reactors
Alexandra M. Heymann*, Patricia Batista Grau, Emanuel Forster, Mariya E. Ivanova,
Wilhelm A. Meulenberg, Michael Müller
Institute of Energy and Climate Research, Forschungszentrum Jülich GmbH, D-52428 Jülich,
Germany; *e-mail: [email protected]
Keywords: dual-phase materials, mixed electronic protonic conductors, H2 membrane, high-temper-
ature WGS

Hydrogen can be produced by gasification of solid fuels with subsequent water gas shift
(WGS) reaction to oxidize the produced carbon monoxide with steam to carbon dioxide
while the steam is reduced to hydrogen. The separation of carbon dioxide using conventional
techniques like physical or chemical absorption leads to high efficiency losses. In contrast, a
membrane reactor containing a catalyst provides the opportunity for significantly reduced ef-
ficiency losses. The high efficiency is realized because the catalytic membrane reactor com-
bines the two process steps of water gas shift reaction and gas separation into a more efficient
single step process. The gas separation is realized by hydrogen selective membranes. The
continuous removal of hydrogen provides an additional advantage because it shifts the reac-
tion equilibrium to the product side. The WGS reaction is exothermic and the equilibrium
conversion is very limited at temperatures above 450 °C but the reaction kinetics is strongly
promoted in the high temperature range. As a consequence, integration of high temperature
highly-permeable hydrogen membranes into the WGS reactor will enable the operation at
high space velocities.
Ceramic materials gained more and more importance for the application in WGS reac-
tors as mixed protonic-electronic conducting membrane materials. These materials offer high
selectivity and are stable at temperatures of 600 °C and above. However, the aggressive gas
compositions in a gasification plant, containing not only CO, CO2, H2, and H2O but also inor-
ganic contaminants from the gasified fuel, leads to very challenging conditions for the dense
H2-selective membranes. Therefore, suitable membrane materials are required not only to
provide high H2-flux but also to be stable under operating conditions.
This work deals with the development of respective membrane materials. Therefor dual-
phase membranes of the type BaCe0,8M0,2O3-δ:Ce0,8M0,2O2-δ (M=Y, Yb, Eu, Sm, Tb, Gd) were
synthesised. The sintered samples were first characterized via Inductively Coupled Plasma
– Atomic Emission Spectroscopy, X-Ray Diffraction and Scanning Electron Microscopy.

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Besides the particle size, the thermal expansion coefficient and the conductivity in different
atmospheres were measured. Subsequently, the materials were exposed to two different coal-
gasification-related atmospheres (CO- and CO2-rich streams) at 600–900 °C and afterwards
investigated regarding chemical reactions of the two contained phases via XRD.
Although the materials show a very promising hydrogen flux, the chemical stability under
membrane reactor conditions up to 900 °C is rather limited and leads to challenges with re-
gard to finding more stable materials.

053
Phase equilibria modelling in Bi-Sr-Co-O system involving phases with
variable oxygen stoichiometry
Ondřej Jankovský*, David Sedmidubský
Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5,
166 28 Prague 6, Czech Republic; *e-mail: [email protected]
Keywords: phase diagram, mixed oxides, thermoelectric materials, oxygen stoichiometry

High-temperature thermoelectrics are mainly represented by transition metals mixed oxides

including cobaltites. In this contribution, high-temperature phase equilibria of the partly
open Bi–Sr–Co–(O) system with fixed oxygen activity, pO2/p0 = 0.21 (p0 = 101.3 kPa), were
modelled based on the experimentally determined phase diagram. Samples with different
Bi : Sr : Co ratios were prepared by solid state reaction and analysed by X-ray diffraction
to map the thermodynamically stable quasiternary phases and their fields of stability. For
the assessment, we also used the previously reported thermodynamic data and phase equi-
libria for the quasibinary Bi–Co–(O), Sr–Co–(O) and Bi–Sr–(O) subsystems as well as the
thermodynamic data of quaternary phases assessed from calorimetry, thermogravimetry and
high temperature phase equilibria. Namely, the oxide melt is modelled based on the Redlich-
Kister parameters of the corresponding quasibinary systems and the solid oxides such as the
misfit phase Bi2Sr2Co1.85Ox, tubular phase Bi3.7Sr11.4Co8Ox, superconducting cuprate analogue
Bi2Sr2CoO6+δ and tetragonal 121 type phase Bi0.4Sr2.6CoO5-δ are considered as stoichiometric
concerning the cation composition, their heat capacity and entropy is determined from calo-
rimetry (PPMS, DSC, drop calorimetry) and the enthalpy of formation is refined to reproduce
their melting behaviour. The variable oxygen stoichiometry is described by fitting the partial
molar enthalpy and entropy of oxygen on the thermogravimetry data. The constructed phase
diagram is particularly important for designing the experiments of single crystal growth of
these highly significant cobaltites.

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303
Effects of substrate contamination of photocatalytic TiO2 thin films
Imrana I. Kabir, Wen-Fan Chen, Pramod Koshy, Charles C. Sorrell
School of Materials Science and Engineering, UNSW Sydney, Sydney, NSW 2052 Australia

Although there are many reports of the fabrication and performance of photocatalytic TiO2
thin films, there are relatively few reports of the effects of contamination from the substrates.
The present work reports data for TiO2 thin films spin coated on four different substrates
that were annealed at 200°, 350°, 450°, or 550 °C for 8 h in air. The substrates used were
soda-lime-silica (SLS), sodium borosilicate (SBS), fused silica (FS), or single crystal TiO2
(T). Characterisation and testing consisted of glancing-angle X-ray diffraction (GAXRD),
laser Raman microspectroscopy, atomic force microscopy (AFM), UV-VIS spectrophotom-
etry (UV-VIS), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry
(SIMS), and methylene blue (MB) degradation.
The recrystallisation temperature of anatase depended on the type of substrate, where the
films deposited on SLS were essentially amorphous at 200° and 350 °C, those deposited on
SBS and FS remained amorphous only at 200 °C, and those deposited on T were crystalline
at all temperatures. The XPS and SIMS data indicated that these results were due principally
to the effects of the extent of sodium contamination. At the highest annealing temperature
of 550 °C, the contaminants detected by XPS and SIMS were as expected: Na, Mg, Ca, and
Si from SLS; Na from SBS (boron was not detectable by these techniques); Si from FS; and
none from T. All of the films had consistent thicknesses of ~370 nm and transparencies in the
range 70-80%. For the crystalline films, the grain sizes and surface roughnesses increased
slightly (~5%) and the optical indirect band gaps decreased consistently from 3.59 eV to 3.47
eV with increasing annealing temperature. The photocatalytic performances were linked di-
rectly to the Na contamination level rather than the Si level, giving performances of the crys-
talline films annealed at all temperatures in the order T > FS > BS > SLS. XPS data before
and after MB testing revealed that the contaminants were located on the grain boundaries and
were washed out during the testing. Consequently, the effect on the band gap was an artifact
of the alteration of the nanostructure and hence the performance was dependent on blockage
of the active sites by the diffused contaminants.

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669
Development of all-oxide thermoelectric stacking device
Nikola Kanas1,2*, Michael Bittner2, Kjell Wiik1, Tor Grande1, Armin Feldhoff2, Truls Norby3,
Mari-Ann Einarsrud1
1
Department of Material Science and Engineering, NTNU, Trondheim, Norway;
*
e-mail: [email protected]
2
Institute of Physical Chemistry and Electrochemistry, Leibniz University, Hannover, Germany
3
Department of Chemistry, University of Oslo, Norway
Keywords: processing, oxides, thermoelectric device

Due to high stability, environmental friendly

impact and reasonable cost, oxides are inter-
esting for thermoelectric devices for energy
conversion at high temperature. Besides the
advantages, oxides have challenges due to ef-
ficiency and processing. The efficiency of a
single TE material is described by the ZT or
figure of merit, which includes Seebeck co-
efficient, electrical and thermal conductivity.
An all-oxide thermoelectric device (Fig. 1)
contains an n- and a p-type conductor sepa-
rated by an insulator. The direct p-n junction
is the crucial part of the device having the
same function as the metal current-collector
being the limitation for high temperature ap-
plications for conventional devices.
Development of this new device design re-
quires improved efficiency of the oxide mate-
rials through designed microstructure followed
by an advanced ceramics processing approach.
For our all-oxide device, we have selected
Ca0.932MnO3 (CMO), Ca3Co4O9 (CCO) and
LaAlO3 (LAO) as n-type, p-type and insulator
materials respectively, based on coefficients of
thermal expansions. Each of these three oxides
were synthetized and sintered using spray py- Fig. 1. A single pair of thermoelectric device
rolysis and spark plasma sintering (SPS). The
all-oxide thermoelectric device was developed
using aqueous tape casting followed by co-sintering using SPS. Power output and efficiency
of the device were recorded from 700 to 800 °C in air. We observed reaction layer at the p-n
junction. Chemical stability and compatibility of the three materials are discussed. The work
will report on the fabrication of the TE materials and device with their TE properties.

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Acknowledgement
Financial support from The Research Council of Norway (RNC) - Nano2021, THELMA-project (Proj.
no. 228854) is gratefully acknowledged.

References
1. S. Walia et al. “Transition metal oxides Thermoelectric properties”, progress in Materials Science,
58 (2013) 1443–1489.
2. M. Bittner et al. “Oxide-Based Thermoelectric Generator For High-Temperature Application Using
p-Type Ca3Co4O9 and n-type In1.95Sn0.05O3 Legs”, Energy Harvesting and Systems. DOI: 10.1515/
ehs-2016-0002.

770
The photoluminescent properties of rare-earth
Sm1.90Eu0.10Zr2O7 zirconate pyrochlore
Erkul Karacaoglu*, Esra Öztürk
Department of Metallurgy and Materials, Karamanoglu Mehmetbey University,
Faculty of Engineering, Turkey; *e-mail: [email protected]
Keywords: rare-earth zirconate pyrochlore, solid-state reaction, Eu3+

Rare-earth zirconate pyrochlore materials have a chemical form of A2B2O7, where a triva-
lent rare-earth occupy the A site and Zr occupies the B site (RE2Zr2O7). They have complex
crystal structures having a variety of physical and chemical properties as well as stability in
extreme environments. These materials have been used as high-temperature thermographic
phosphors because of their intense light emission and high-temperature stability1. They also
exhibit excellent ionic conductivity and high tolerance to defects2. In this research, the zir-
conate type pyrochlore was chosen and synthesized by high temperature solid state reaction
method under open atmosphere. The phase formation process was investigated by thermal
analysis (DTA/TG) until 1600 °C. The X-ray diffraction (XRD) analysis resulted as the cubic
phase structure with lattice parameters a = b = c = 10.59 Å and α = β = γ = 90°. The rare-earth
based zirconates, Ln2Zr2O7 (Ln = Tb→Lu), with the ionic radius ratio, ranging from 1.44 to
1.35, crystallize in a defect-fluorite structure. Compounds Ln2Zr2O7 (Ln = La→Gd), with
the ionic radius ratio, ranging from 1.61 to 1.46, adopt the cubic pyrochlore structure2. At
high temperature (T>1500 °C), Ln2Zr2O7 (Ln = Nd→Gd) undergo an order–disorder transi-
tion from a pyrochlore to a defect-fluorite structure. The transition temperature depends on
the nature of the rare-earth ion. Therefore, rare-earth zirconate exists only in the pyrochlore
form, whereas for neodymium, samarium, and the gadolinium zirconates, a transition from
a pyrochlore to a defect-fluorite structure occurs at 2300, 2000, and 1530 °C respectively3.
The photoluminescence (PL) analysis including excitation, emission and decay time were
determined by a PL spectrometer under room temperature. The sample was excited at 286
nm that is based on ligand-to-Eu3+ charge-transfer transitions (LMCT). The pyrochlore have
emissions at 486 nm, 614 nm, 663 nm and 718 nm concerning the typical 5D2→7F2, 5D0→7F2,
5
D0→7F3 and 5D0→7F4 transitions of the Eu3+-ions, respectively4.

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Acknowledgement
The authors would like to thank TUBITAK (The Scientific and Technological Research Council of
Turkey) for the support to the project numbered 114Z438.

References
1. Q.Y. Zhang, K. Pita, S. Buddhudu, C.H. Kam, “Luminescent properties of rare-earth ion doped
yttrium silicate thin film phosphors for a full-colour display,” J. Phys. D, Appl. Phys., vol. 35, pp.
3085–3090, 2002.
2. M.A. Subramanian, G. Aravamudan, G.V. Subba Rao, “Oxide pyrochlores-a review”, Prog. Solid
State Chem., 15, 55, 1983.
3. D. Michel, M.P.Y. Jorba, R. Collongues, “Etude de la transformation ordre-desordre de la structure
fluorite a la structure pyrochlore pour des phases (1−x)ZrO2−xLn203”, Mater. Res. Bull., 9, 1457,
1974.
4. C.H. Liang, Y.C. Chang, Y.S. Chang, “Synthesis and photoluminescence characteristics of color-
tunable BaY2ZnO5:Eu3+ phosphors”, App. Phy. Lett., 93, 211902, 2008.

743
Functional layers for solid oxide electrolyzers
Jakub Karczewski1*, Aleksander Chrzan2, Justyna Bartoszek2, Sea-Fue Wang3,
Piotr Jasinski2
Faculty of Applied Physics and Mathematics, Gdansk University of Technology, Gdansk, Poland;
1

*
e-mail: [email protected]
Faculty of Electronics, Telecommunications and Informatics Gdansk University of Technology,
2

Gdansk, Poland
Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei,
3

Taiwan
Keywords: solid oxide electrolyzer, functional layer, distribution of relaxation times, impedance
spectroscopy

In order to increase efficiency of solid oxide electrolyzers, it is necessary to reduce electrode

area specific resistances. To minimize, electrode losses, a layered cell structure is proposed,
which implements thin interface layers on oxygen electrode side. This work is aimed to study
how the functional layers influence the ASR of an oxygen electrode /electrolyte interface.
To understand the polarization processes and their dependences on operational and material
parameters, the electrochemical impedance spectroscopy (EIS) is widely used. However, a
typical analysis of the spectra requires a priori assumptions of equivalent circuit. An alterna-
tive method for analyzing impedance spectra using distribution of relaxation times (DRT) is
applied. In this approach each process is represented by a peak in the distribution function.
The peak is characterized by relaxation frequency, area (polarization resistance) and the char-
acteristic shape, bearing information about the electrochemical process. This allows better
understanding the impact of applied functional layers.

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Fig. 1. Example of impedance spectrum and its corresponding DRT plot

Acknowledgement
This work is supported by National Center for Research and Development under Polish-Taiwanese/
Taiwanese-Polish Joint Research project “Innovative Solid Oxide Electrolyzers for Storage of Renew-
able Energy” based on decision DZP/PL-TW2/6/2015.

392
Mechanical properties of porous Ni(O)-YSZ solid oxide cell supports
with varying Y-content
Peyman Khajavi*, Peter Vang Hendriksen, Karen Brodersen, Henrik Lund Frandsen
Department of Energy Conversion and Storage, Technical University of Denmark,
Frederiksborgvej 399, 4000 Roskilde, Denmark; *e-mail: [email protected]
Keywords: solid oxide cell support, Ni(O)-YSZ, strength, yttria content

Enhancing the cell strength is essential for the robustness of solid oxide cell (SOC) technolo-
gies, especially when enlarged footprints and taller stacks are needed for large-scale instal-
lations. Yttria stabilized zirconia with different stabilizer contents (3YSZ, 8YSZ) forms the
structural component in most SOC cell designs. The tetragonal to monoclinic phase transfor-
mation that may occur during crack growth in 3YSZ at room temperature strongly improves
its fracture toughness compared to fully stabilized cubic 8YSZ. For the SOC technology,
however, it is necessary to consider effects of high temperature processing and operating
conditions, as this will affect the tetragonal phase stability and transformability.
In this work, the possible improvement of the mechanical properties of SOC supports by
lowering the stabilizer amount in Y-doped zirconia was studied. Four different Y contents
were considered (2, 2.3, 3 and 8) and the phase stability of nanocrystalline powders with
temperature and after heat treatment at 1350 °C was investigated. The results showed that a
significant amount (95%) of tetragonal phase can be maintained in the 2.3Y powder even af-

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ter 2h calcination at 1350 °C, whereas only 28% remains in the 2Y sample. Besides the phase
stability results, fracture strength of porous Ni(O)-YSZ supports prepared using the powders
both at room and high temperatures are reported.

075
Long-term degradation study of anode supported flat-tubular solid
oxide fuel cells
Muhammad Zubair Khan1,2, Muhammad Taqi Mehran1,2, Rak-Hyun Song1,2*,
Jong-Won Lee1,2, Seung-Bok Lee1,2, Tak-Hyoung Lim1,2, Seok-Joo Park1,2
Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon 34129,
1

Republic of Korea; *e-mail: [email protected]

Department of Advanced Energy and Technology, Korea University of Science and Technology
2

(UST), 217 Gajeong-ro, Yuseong-gu, Daejeon 34113, Republic of Korea

Keywords: SOFC, current density, degradation, ASR, particle coarsening

Degradation investigation and life time prediction are crucial factors in improving durability
of solid oxide fuel cells (SOFCs). We have investigated the effect of applied current density
on the long-term degradation of anode supported flat-tubular SOFC. The flat-tubular SOFC
was comprised of nickel oxide (NiO)-8mol%.Y2O3-stabilized ZrO2 (8YSZ) anode support,
NiO-Sc2O3 stabilized ZrO2 (SSZ) anode functional layer (AFL), SSZ electrolyte, Gd2O3
doped CeO2 (GDC) interlayer and (La0.60Sr0.40)0.95Co0.20Fe0.80O3-x (LSCF)-GDC composite
cathode. Performance degradation in terms of voltage loss was evaluated during long-term
operation up to 1000 h at constant current densities of 200 and 1000 mAcm–2 at 800 oC. Elec-
trochemical impedance spectroscopy (EIS) was performed to examine the cell polarization
during long-term operation. The flat-tubular SOFC tested at high current density showed
high performance degradation due to large increase in cell polarization during operation. In
combination to EIS, the backscattered scanning electron microscopy results revealed that
higher Ni particle coarsening and reduction of triple phase boundary length in the AFL of cell
tested at high current density led to the fast performance degradation.

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782
Improvement of solid oxide fuel cell performance by tailoring
the electrolyte-electrode interface using laser micro patterning
Miguel A. Laguna-Bercero*, José A. Cebollero, Ruth Lahoz, Ángel Larrea
Instituto de Ciencia de Materiales de Aragón, U. Zaragoza-CSIC, C/ María de Luna 3,
E-50.018 Zaragoza, Spain; *e-mail: [email protected]
Keywords: laser ablation, laser patterning, SOFC, interface, YSZ, LSM

The aim of this work is to increase the power density but also reducing size, weight and cost
of Solid State Fuel Cell (SOFC) systems by the use of laser surface processing techniques.
By modifying the electrolyte surface at the mesoscale, the cell power density will be im-
proved.1 Increasing surface corrugation directly produces an enlargement in the effective
interface area between the electrode and the electrolyte. Laser processing also produces a
nanoparticle coating which is deposited on the surface, generally of the same composition
but different microstructure. The initial objective is to study these effects as a function of the
processing parameters and surface composition, and also to demonstrate the power enhance-
ment associated to the interface modification.
The experimental studies were performed using commercial YSZ (yttria stabilized zir-
conia) plates of about 150 µm in thickness, using a Q-switched diode-pumped laser (Rofin
PowerLine S3 SHG) emitting at 532 nm wavelength. The currently processed area is about
60 × 60 mm2. The experiments were performed using the minimum pulse width of the laser
source (5 ns) in order to enhance material evaporation processes minimizing thermal effects.2
Processing parameters such as laser power, laser focalization, machining mode (percussion,
scanning,…), processing temperature and atmosphere will be experimentally determined as a
function of surface parameters such as wide, depth, shape, distance between grooves, damage
produced in the processed material, changes in microstructure, laser plasma plume effects,
nanoparticle surface dressing, etc. Preliminary studies show groove sizes and depths in the
range of 5 to 30 microns, which are in the desired patterning range.
Symmetrical cells, using LSM (lanthanum strontium manganite)/YSZ cathodes were fab-
ricated. Electrochemical Impedance Spectroscopy (EIS) measurements were then performed
on both non-machined and corrugated samples. The polarization resistance of the corrugated
samples is decreased by at least 30% in comparison with the non-machined samples, mea-
sured at temperatures between 600 and 900 ºC.

References
1. A. Konno et al., “Mesoscale-structure control at anode/electrolyte interface in solid oxide fuel cell”
J. Power Sourc. 196 (2011) 98–109.
2. J. A. Cebollero et al. “Characterization of laser-processed thin ceramic membranes for electrolyte-
supported solid oxide fuel cells,” Int. J. Hydrogen Energy (2017) in press.

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484
Mechanical characterisation of multi-layered ceramic systems for SOC
Alessia Masini1*, Filip Šiška1, Oldřich Ševeček2, Zdeněk Chlup1, Ivo Dlouhý1,2
1
Institute of Physics of Materials, AS CR, Zizkova 22, Brno, Czech Republic; *e-mail: [email protected]
2
Faculty of Mechanical Engineering, Brno University of Technology, Czech Republic
Keywords: Solid Oxide Cells, mechanical properties, layered structure, cell, mechanical testing

Solid Oxide Cells technology promises to revolutionise the energy market; however, its reli-
ability and efficiency have to be further improved. SOCs operate in harsh conditions and
have to withstand considerable static and cyclic stresses, both mechanical and thermal. Thus,
their mechanical stability is threatened. One fundamental aspect is the structural integrity of
the cell. In fact, mechanical failure of a single cell can damage the whole stack, reducing the
lifetime and the efficiency of the entire system.
This study is targeted to the ceramic layered structure of an Yttria-stabilised electrolyte
supported cell. Its mechanical characterisation has been performed through destructive and
non-destructive techniques (three-point bending test, impulse excitation technique, tensile
test).1 Many literature sources deal with properties of the most common electrolytes and
electrodes,2–4 yet co-sintering effects and interaction between layers are up to now not well
understood. In this contribution the overall behaviour of the cell has been investigated, focus-
ing on the role that the interface between layers plays in the changing of resulting mechanical
properties. To investigate the mentioned aspects, layers were added to the electrolyte one
by one. This way, individual interactions could be distinguished with the help of numeri-
cal simulations. Results obtained for consecutive samples through different techniques have
been compared and discussed.

Acknowledgements
Project leading to this presentation has received funding from the European Union’s Horizon 2020
research and innovation programme under the Marie Skłodowska-Curie grant agreement no 642557.

References
1. M. Wesolowski, E. Barkanov, S. Rucevskis, A. Chate and G. La Delfa, Characterisation of Elastic
Properties of laminated composites by non-destructive techniques, ICCM International Confer-
ences on Composite Materials, Edinburgh, 2009.
2. T. Kushi. K. Sato, A. Unemoto, S. Hashimoto, K. Amezawa, T. Kawada, Elastic modulus and in-
ternal friction of SOFC electrolytes at high temperatures under controlled atmospheres. Journal of
Power Sources, 196, pp. 7989–7993, 2011.
3. S. Giraud, J. Canel, Young’s modulus of some SOFCs materials as a function of temperature. Jour-
nal of the European Ceramic Society, 28, pp. 77–83, 2008.
4. T. Kushi. K. Sato, A. Unemoto, K. Amezawa, T. Kawada, Investigation of High Temperature Elas-
tic Modulus and Internal Friction of SOFC Electrolytes Using Resonance Method. 216th ECS
Meeting, Abstract #1237, Vienna, Austria, 2009.

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631
Screen printed cathode layers with enhanced adhesion through plasma-
modification of substrates surface
Elisa Mercadelli1*, Angela Gondolini1, Alex Sangiorgi1, Daniel Montaleone1, Rémi Costa2,
Giovanna Gautier3, Alessandra Sanson1
Institute of Science and Technology for Ceramics, National Council of Research (ISTEC-CNR), Via
1

Granarolo 64, 48018, Faenza, Italy; *e-mail: [email protected]

German Aerospace Centre (DLR), Institute of Technical Thermodynamics, Pfaffenwaldring 38-40,
2

70569 Stuttgart, Germany

Institute for Agricultural and Earthmoving Machines, National Council of Research (IMAMOTER-
3

CNR), Strada delle Cacce, 73, 10135 Torino, Italy

Keywords: screen printing, wettability, SOFC, cathodes

Manufacturing of cathode layers in Solid Oxide Cells, requires high temperature sintering
step in air (>1050 °C). For advanced SOC architectures like Metal Supported Cells, func-
tional ceramic layers are processed directly onto a porous metal substrate, and those harsh
conditions for the cathode sintering cause destruction of the metallic component. In this
study, we report a vacuum plasma surface method to assist the screen printing of cathodic
layers with improved adhesion at lower sintering temperatures for metal-supported fuel cells.
A vacuum plasma treatment was used to chemically activate/etch the gadolinium-doped ceria
(CGO) substrate to improve its wettability towards the screen printing cathodic inks. The
plasma parameters such as vacuum level, Ar/O2 flow, system power, number of plasma treat-
ments, were optimized in order to modify the CGO surface in terms of surface energy and
roughness. Scratch tests results highlight that the critical load of the sintered cathodic films is
enhanced by the 50% exploiting a plasma surface treatment.

Fig. 1. Effect of the plasma treatment of CGO substrates on

the surface roughness and wettability

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645
Recent findings on the selective thermal emission
of Al2O3-YAG:eR solidified eutectics
R.I. Merino1*, A. Orera1, M.L. Sanjuán1, P.B. Oliete2
Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza - CSIC, Pedro Cerbuna 12,
1

50009 Zaragoza, Spain; *e-mail: [email protected]

Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza - CSIC, María de Luna 3,
2

50018 Zaragoza, Spain

Keywords: directionally solidified oxide eutectics, selective thermal emitters, Al2O3, Er:YAG

Al2O3-Rare Earth Garnet directionally solidified eutectics (DSE) are candidate selective
emitters for thermophotovoltaic (TPV) devices, by virtue of their good mechanical proper-
ties, microstructural stability at high temperatures, good thermal shock resistance and their
selective thermal emission provided by the rare earth ions.1 With the appropriate rare-earth
garnet, emission bands matched to the optimum absorption of the photovoltaic cells can
be chosen, and in particular Er3Al5O12 has one band centred at 1.5 μm, suitably matched to
­InGaAs or GaSb cells.
DSE oxides can be solidified by different procedures as Bridgman, micro-pulling down or
laser floating zone (LFZ) method. They can also be prepared in the form of dense solidified
coatings on different substrates, thereby allowing manufacture adapted to the TPV device. As
the solidified composite ceramic is translucent, its emissivity will be a volume property and
light scattering can affect the thickness contributing to emission as well as its selectivity. Pre-
vious studies show that thermal emission of Al2O3-Yb3Al5O12 eutectics2 appears to saturate at
high temperatures (1500 ºC). Here we aim at shedding light on the mechanisms responsible
of this behaviour, as well as quantifying the scattering.
For that purpose we have prepared Al2O3-Y3-xErxAl5O12 (x = 0.03, 0.3, 3) eutectics with
different microstructural sizes in the form of 1mm diameter rods (by LFZ) and of flat, surface
resolidified plates (using surface laser melting). We have measured the emissivity at RT on
the flat plates. Specific emissivity obtained from RT measurements is mainly proportional to
the Er concentration of the material. The experiments show that the emissivity at 1540 nm is
already saturated for 600 μm thick samples irrespective of the Er concentration or solidifica-
tion rate (coarse or fine microstructures).
The thermal emission has been measured in rods and plates, that is, heating the samples
with a CO2 laser or with electrical resistance heating respectively. Each method allows dif-
ferent temperature ranges. The selective emission in the NIR (bands at 970 nm and 1540 nm)
in the diluted samples (x = 0.03 or 0.3) increases with temperature only slightly slower than
the black body (BB) radiation in all the temperature range (700 ºC to 1600 ºC), while for the
fully concentrated one, the selective emission above 1300 ºC is only slightly temperature de-
pendent, thus deviating much faster form BB behaviour. Aided by available data and ad-hoc
luminescence lifetime measurements in diluted and concentrated garnets, plausible explana-
tions for this effect will be given and discussed.

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References
1. N. Nakagawa et al. J. Eur. Ceram. Soc., 25, pp. 1285–1291, 2005.
2. P.B. Oliete et al. Solar Energy Mat. And Solar Cells 144, pp. 405–410, 2016.

730
Synthesis, structure and electrical properties of Pr, Co-doped SrTiO3
novel SOEC cathode material
T. Miruszewski*, B. Kamecki, J. Karczewski
Department of Solid State Physics, Faculty of Applied Physics and Mathematics,
Gdansk University of Technology, Gdansk Poland; *e-mail: [email protected]
Keywords: syngas, perovskite, SOEC

Solid Oxide Electrolyzer Cells (SOECs) are very promising electrochemical devices for the
production of syngas (H2/CO) by H2O and/or CO2 electrolysis. The understanding of degra-
dation processes of fuel electrode in the solid oxide electrolysis cell (SOEC) occurring during
syngas production is crucial. Particular attention should be paid to the processes taking place
in extreme conditions - high current density and high concentration of steam and carbon di-
oxide. Thus a new alternative, to the widely used Ni/YSZ, cathode materials should be found
and widely investigated. The impact of the microstructure of the new cathode material on its
electrical properties has a great influence on performance and stability of the cell producing
synthesis gas, operating under heavy load.1,2
Donor and acceptor co-doped SrTiO3 ceramics are known to exhibit phase stability under
both oxidizing and reducing conditions. High electrical conductivity can be obtained by re-
duction at high temperatures and low oxygen partial pressures.3,4
Perovskite-like Pr1-xSrxTiO3-δ material attracted attention as a potential anode material for
SOFC or cathode materials for SOECs. A high electronic conductivity under reducing atmo-
sphere (~100 S/cm at 800 °C and 10–20 atm. pO2) is reported for 20 mol% of Pr in SrTiO3.5
Co-doped SrTiO3, was reported to have a very good performance as anode materials for
SOFC and cathode material for SOEC. The Co acceptor doping on the B site of SrTiO3 can
significantly change the defect formation and charge compensation mechanisms, thus alter-
ing the electrical conduction behavior, especially the ionic conductivity and the catalytic
activity.6
In the present study, Pr and Co-doped PrxSr1-xTiyCo1-yO3-δ material is proposed as an SOEC
cathode material. In the investigated powders, the constant 7 mol% (y = 0.07) of Co acceptor
dopant amount and the various Pr donor dopant amount x = 0.1–0.3 was used in investi-
gated samples. The powders of these were prepared by a solid-state reaction (SSR) process.
The structure and morphology of obtained samples was analyzed by the X-ray diffraction
technique (XRD) and scanning electron microscopy (SEM). The relative length change was
examined by Netsch DIL 402 PC/4 dilatometer in temperature range from 25 oC to 800 oC
while the thermal stability of samples was examined via Termogravimetry with Differential
Scanning Calorimetry (TG-DSC) using Netsch STA449F1. In order to analyze the electrical

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properties and the possibilities to use of these materials in SOEC cathodes, the total electri-
cal conductivity of samples was measured by DC 4-wire method in range of 500–850 oC in
different gas conditions (H2 and O2 atmospheres). The obtained results were discussed and
analyzed in comparison to the previous literature reports.

Acknowledgement
This work is supported by project founded by National Science Centre Poland based on decision DEC-
2015/19/D/ST8/02783.

References
1. P. Kazempoor, R.J. Braun, Int J Hydrogen Energy 40 (2015) 3599–3612.
2. X. Sun, M. Chen, Y.L. Liu, P.V. Hendriksen, ECS Trans 68 (2015) 3359–3368.
3. J.W. Fergus, Solid State Ionics 177 (2006) 1529–1541.
4. A. Orera, P.R. Slater, Chem. Mater. 22 (2010) 675–690.
5. A.A. Yaremchenko, S.G. Patrício, J.R. Frade, Journal of Power Sources 245 (2014) 557–569.
6. X. Li , H. Zhao, F. Gao, Z. Zhu, N. Chen, W. Shen, Solid State Ionics 179 (2008) 1588–1592.

262
Non hydrophobic CNT/mesoporous carbon monolith as high energy
performance flow through electrodes in CDI process
Hesam Alddin Mohammadi, Ali Beitollahi*, Hossein Sarpoolaky
Center of Excellence for Ceramic Materials in Energy and Environment Applications, School of
Metallurgy and Materials Engineering, Iran University of Science and Technology (IUST), Narmak,
Tehran 16846, Iran; *e-mail: [email protected]
Keywords: capacitive deionisation, mesoporous carbon, carbon nanotube, energy storage and recov-
ery

Capacitive deionization (CDI) is an energy-efficient procedure for water desalination, us-

ing ion absorption by forming electrical double layers on the surface of nano porous car-
bon based electrodes1,2. In the cell structure known as flow-through CDI, the electrodes are
clamped together and the feed water flows through electrodes and the separator. These all
result in CDI performance enhancement2.
Mesoporous carbon (MC) monoliths, used as CDI electrodes were synthesized with hier-
archical porosity by a hydrothermal based process. The samples were carbonized under N2
at 600 to 900 °C. In the case of synthesizing MC/CNT monoliths, 0.5 to 2 W% multiwall
carbon nanotubes were added to the solution exactly before transferring to the autoclave. The
sample’s microstructure, investigated by FESEM, showed interconnected uniform macro
pores which acted as suitable paths for the flowing electrolyte. Furthermore FESM studies
demonstrated well distribution of CNTs in the monolith matrix. Mercury porosimetry also
confirmed hierarchical macro pore structure with size range of 5 to 15 µm. N2 absorption
analyses by BET and BJH methods indicated total specific surface area of about 600–700
m2/g ,total pore value of 0.45 m3/g and pore size distribution of 1–5 nm. The electrochemical

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tests of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were
carried out by a three electrode setup. Electrodes conductivity and specific capacitance in-
creased by increasing CNT content. This trend was more obvious for the samples calcined
at low temperature so that for the samples calcined at 600 °C, electrical conductivity raised
about 20 times. By increasing carbonization temperature the electrical resistance reduced
sharply, though specific capacitance did not increase proportionally, as these electrodes be-
came highly hydrophobic. In this regard the electrolyte could not pass through the 900 °C
samples; so despite of high electrical conductivity and high porosity these electrodes did not
perform efficiently in the flow through CDI process.
The most proper electrodes with suitable electrical conductivity and water permeability,
were set in a designed flow through CDI cell and different voltages were applied in order to
measure cell parameters. Highest charge and discharge current of 250 mA, cell capacitance
of 4 F, specific capacitance of about 80 F/gr, 1.2 mg NaCl per g electrode per min, charge ef-
ficiency of 0.85 and ion absorption of 10 mg/g, were achieved. To increase energy efficiency,
the discharge current was stored in a battery which had the duty of supplying the charge step
energy. The primary energy of the battery was provided by a solar panel.

References
1. Y. Liu, C. Nie, X. Liu, X. Xu, Z. Suna and L. Pan, RSC Adv., 2015, 4, 1166–1169.
2. S. Porada, R. Zhao, A. van der Wal, V. Presser and P. M. Biesheuvel, Prog. Mater. Sci., 2013, 58,
1388–1442.

068
Preparation and mechanical properties of SrTi1-xFexO3-δ
(x = 0.25, 0.35, 0.5) for oxygen transport membranes
Rafael Oliveira Silva1, Falk Schulze-Küppers1,2, Jürgen Malzbender1, Stefan Baumann1,2,
Olivier Guillon1,2
1
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, 52425 Jülich, Germany
2
Jülich Aachen Research Alliance: JARA-Energy, 52425 Jülich, Germany
Keywords: oxygen transport membrane, tape casting, freeze casting, fracture strength

Oxygen transport membranes (OTM) based on mixed ionic-electronic conducting ceramics

allow oxygen ion diffusion through the lattice and, therefore, can be used to separate gases
at elevated temperatures.1 These membranes can achieve a remarkable competitor of existing
state-of-the-art processes for oxygen production in small and medium scale.2 Typically, such
membranes have to be operated at 800–900 °C and under large pressure gradients, which
challenges significantly chemical and mechanical stability of the respective brittle ceramic
components.3,4 In order to increase transport, advanced membrane modules that enable high-
performance rely upon an asymmetric design consisting of a thin dense membrane layer
supported by a porous substrate, where the substrate warrants the long term reliability of the
mechanical integrity at process conditions.

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Thus, the current work concentrates on the preparation and mechanical characterization
of promising mixed conducting oxygen transport perovskite based membranes,5,6 based on
SrTi1-xFexO3-δ, (STF-X) with x = 0.25, 0.35 and 0.5. The materials were synthesized through
solid state reaction process and most mechanical testing relevant dense and porous specimens
were obtained by tape casting, where the mechanical stability of porous tape cast specimens
was assessed via ring-on-ring bending tests serving the estimate of materials’ reliabilities.
Furthermore, aiming towards an optimization of the oxygen permeation flux and mechani-
cal stability of the supported membranes, hierarchically porous specimens were successfully
obtained by freeze drying, where complementary systematic investigations of the mechani-
cal stability aim towards a determination of the influence of the complex pore structure on
the mechanical properties. Overall, the current study aids to adjust the membrane support
structure regarding the process requirements. At the same time, data for mechanically derived
lifetime and reliability predictions is acquired for STF based membranes.

References
1. J. Sunarso, S. Baumann, J.M. Serra, W.A. Meulenberg, S. Liu, Y.S. Lin, J.C. Diniz da Costa, Mixed
ionic–electronic conducting (MIEC) ceramic-based membranes for oxygen separation, Journal of
Membrane Science 320 (2008) 13–41.
2. A.C. Bose, Inorganic Membranes for Energy and Environmental Applications, Springer New York,
2010.
3. G. Pećanac, S. Foghmoes, M. Lipińska-Chwałek, S. Baumann, T. Beck, J. Malzbender, Strength
degradation and failure limits of dense and porous ceramic membrane materials, Journal of the
European Ceramic Society 33 (2013) 2689–2698.
4. M. Lipińska-Chwałek, G. Pećanac, J. Malzbender, Creep behaviour of membrane and substrate ma-
terials for oxygen separation units, Journal of the European Ceramic Society 33 (2013) 1841–1848.
5. F. Schulze-Küppers, S.F.P. ten Donkelaar, S. Baumann, P. Prigorodov, Y.J. Sohn, H.J.M.
­Bouwmeester, W.A. Meulenberg, O. Guillon, Structural and functional properties of SrTi1-xFexO3-d
(0 ≤ x ≤ 1) for the use as oxygen transport membrane, Separation and Purification Technology 147
(2015) 414–421.
6. S.F.P. ten Donkelaar, V. Stournari, J. Malzbender, A. Nijmeijer, H.J.M. Bouwmeester, High-temper-
ature compressive creep behaviour of perovskite-type oxides SrTi1-xFexO3-δ, Journal of the European
Ceramic Society 35 (2015) 4203–4209.

797
Development of advanced electrodes by metal oxide impregnation for
microtubular solid oxide fuel cells
Alodia Orera*, Jorge Silva, Miguel A. Laguna-Bercero
Instituto de Ciencia de Materiales de Aragón, U. Zaragoza-CSIC, Pedro Cerbuna 12,
50009 Zaragoza, Spain; *e-mail: [email protected]
Keywords: SOFC, microtubular, anode-supported, infiltration, praseodymium oxide

Microtubular Solid Oxide Fuel Cells (mT-SOFC) have attracted special interest as they are
more resistant to thermal cycling and they present shorter start-up/shut-down times and high-
er volumetric power densities in comparison to those with the traditional planar geometry.

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Standard NiO-YSZ (yttria stabilized zirconia) anode tubes used in our laboratory are fabri-
cated by extrusion of NiO, YSZ and pore former powders, followed by dip-coating of the
YSZ electrolyte. Both components are then co-sintered at 1500 ºC. Typical oxygen electrodes
such as LSM (lanthanum strontium manganite)/YSZ are deposited by dip-coating and sin-
tered at 1150 ºC.1
In order to increase fuel cell performance, infiltration/impregnation (generally by means
of nitrates) of nanocatalyzers has been established as an important method in the devel-
opment of high performing electrodes, improving their oxygen reduction or fuel oxidation
properties. Infiltration can enhance the catalytic activity (via fine dispersed particles), and
ionic and/or electronic conductivity (via connected particles) of fuel cell electrodes leading
to a cell power enhancement.2
In the present work, different amounts of praseodymium oxide were impregnated into
the cathode of Ni-YSZ/YSZ/LSM-YSZ anode supported microtubular cells. The fuel cell
performance enhancement compared to the non-infiltrated standard was very significant, as
about the same current density was obtained (above 1 A cm–2 at 0.5V) but lowering the op-
eration temperature 100 ºC (800 ºC for a standard cell and 700 ºC for the Pr6O11 infiltrated
cell). Experiments under electrolysis mode as well as durability studies are currently being
performed.

References
1. H. Monzon et al. “Design of industrially scalable microtubular solid oxide fuel cells based on an
extruded support,” Int. J. Hydrogen Energy 39 (2014) 5470–5476.
2. D. Ding et al. “Enhancing SOFC cathode performance by surface modification through infiltra-
tion,” Energy Environ. Sci. 7 (2014) 552–575.

808
Mixed glass former effect on ionic conductivity of lithium
borophosphate glasses with So3 addition
Cem Eren Özbilgin*, Emrah Dölekçekiç, Kamil Burak Dermenci, Servet Turan
Department of Materials Science and Engineering, Anadolu University, Eskişehir, Turkey;
*
e-mail: [email protected]
Keywords: lithium-ion batteries, solid electrolyte, borophosphate glasses, ionic conductivity, mixed
glass former effect

High-performance and smaller electronic devices have become a part of everyday life. In
this regard, the studies about batteries focus not only on performance enhancement, but also
on the utilization safety. In portable consumer electronics, generally Lithium-Ion Batteries
(LIB) are used due to their promising properties such as high energy density and high cycle
capacity. Glass and glass-ceramic solid electrolytes have significant advantages over liquid
ones since they do not have inflame and/or explosion risk and not require separator integra-
tion.

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Mixing glass formers has been reported as an effective way to increase the ionic conduc-
tivity of certain glass electrolyte systems.1 Besides, there are several studies that suggest
using SO3 may increase the ionic conductivity of alkali phosphate ternary glass system up
to two orders of magnitude.2 However, the combination of these approaches has not been
examined yet. This study aims to enhance the ionic conductivity of 40Li2O.10SO3.xB2O3.
(50-x)P2O5 quaternary glass electrolyte composition via mixed glass former effect and SO3
addition. Glass compositions that contain different B2O3 ratios changing from 5 to 25 mol
% were produced by conventional melt quenching technique at 850–1000 °C temperature
range. Produced glasses were annealed at about 400 °C for 2 hours. XRD analysis results
indicate that there is no crystallization observed in the samples. Ionic conductivity of the
samples was measured by Electrochemical Impedance Spectroscopy (EIS) technique and
qualitative chemical analyses were conducted by FTIR and Raman spectrometer methods.

References
1. T. Tsuchiya, T. Moriya, J. Non-Cryst. Solids, “Anomalous behavior of physical and electrical prop-
erties in borophosphate glasses containing R2O and V2O5” 38–39, pp. 323, 1980.
2. N. Hémono and F. Muñoz, Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B, “Dissolution of SO3
within a lithium phosphate glass network and structure-property relationships” 51, pp. 121, 2010.

086
Defect engineering in development of low thermal conductivity
materials
Wei Pan
State Key Lab of New Ceramics and Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing, China; e-mail: [email protected]

Increasing thermal efficiency and lower emissions require gas turbine designers to further
increase the combustion temperature that leads to the high temperature components such as
combustion chambers, blade and vanes surfaces face more rigorous conditions. Therefore,
there is urgent demand to develop new ceramic coatings with even lower thermal conductiv-
ity, higher stability and durability than currently used thermal barrier coatings coating on the
surface of high temperature alloy components.
Defect engineering has attracted much attention in seeking better low thermal conductivity
materials since lattice defects play a crucial role in phonon scattering and thermal conductiv-
ity reduction. Oxygen vacancies and substitutions are proven to be the most effective, while
the accompanying lattice distortion is also of great importance. In this talk, recent advances
of reducing the thermal conductivity of potential thermal barrier coating materials by defect
engineering are comprehensively reviewed. Effects of the mass and size mismatch between
the defects and the host lattice are quantitatively estimated and unconventional thermal con-
ductivity reduction caused by the lattice distortions is also introduced. Finally, challenges and

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potential opportunities are briefly assessed to further minimize the thermal conductivity of
thermal barrier coatings materials in the future.
In this presentation, effects of macro defects on the heat transfer in porous ceramics are
also talked including the characterization method as well as modeling.

References
1. Wan CL, Pan W, Xu Q, Qin YX, Wang JD, Qu ZX, Fang MH, Effect of point defects on the ther-
mal transport properties of (LaxGd1-x )2Zr2O7: Experiment and theoretical model. Phys. Rev. B 74,
144109-1~9 (2006).
2. Wan CL, Qu ZX, He H, Luan D, Pan W, Ultralow thermal conductivity in highly anion-defective
aluminates, Phys. Rev. Lett. 101, 085901 (2008).
3. J. Feng, C. Wan, B. Xiao, R. Zhou, W. Pan, D.R. Clarke, Calculation of the thermal conductivity of
R2SrAl2O7 (R = La, Nd, Sm, Eu, Gd, Dy), Phy. Rew. B, 84, 024302 (2011).
4. ZX Qu, T Sparks, W Pan, and DR Clarke, Thermal conductivity of the gadolinium calcium silicate
apatites: Effect of different point defect types, Acta Mater. 59 (2011) 3841–3850.
5. CL Wan, W Zhang, YF Wang, ZX Qu, AB Du, RF Wu, W Pan, Glasslike thermal conductivity in
ytterbium doped lanthanum zirconate pyrochlore, Acta Mater. 58 (2010) 6166–6172.
6. XR Ren, W Pan, Mechanical properties of high temperature degraded yttria stabilized zirconia,
Acta Mater. 69 (2014) 397–406.
7. J. Feng, B. Xiao, R. Zhou, W. Pan, Anisotropy in elasticity and thermal conductivity of monazite-
type REPO4 (RE = La, Ce, Nd, Sm, Eu and Gd) from first-principles calculations, Acta Mater. 61
(2013) 7364–7383.
8. M Zhao, W Pan, Effect of lattice defects on thermal conductivity of Ti-doped, Y2O3-stabilized ZrO2,
Acta Mater. 61 (2013) 5496–5503.
9. CL Wan, ZX Qu, AB Du, W Pan, Influence of B site substituent Ti on structure and thermophysical
properties of A2B2O7-type pyrochlore Gd2Zr2O7, Acta Mater., 57 (2009) 4782–4789.
10. ZX Qu, CL Wan, W Pan, Thermophysical properties of rare-earth stannates: Effect of Pyrochlore
Structure, Acta Mater. 60 (2012) 2939–2949.

734
Nickel oxide doped barium yttrium zirconate nanostructures
Ivar Reimanis1, Amy Morrissey2, Jim R. O’Brien3
1
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden,
CO 80401, USA; e-mail: [email protected]
2
CoorsTek Incorporated, Golden, CO 80401, USA; e-mail: [email protected]
3
Off Grid Research 6501 South Goodwin Street, San Diego, CA 92111, USA;
e-mail: [email protected]
Keywords: barium yttrium zirconate, nickel oxide, magnetometry, selective reduction, nanostructures

The design of high surface area, nanostructured metal-ceramic systems is important for a
wide range of energy related applications, including catalysts, fuel cells, and ionic transport
membranes. Yttrium doped barium zirconate (BZY) is an important material in this realm,
and when doped with nickel oxide, and subsequently exposed to reducing conditions, some
very interesting nanostructures form. In the present work SQUID magnetometry and trans-
mission electron microscopy is used to describe these structures. It is shown that the nickel-

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oxide doped BZY may be designed so that a shell structure dominates the surface character-
istics and that it ultimately leads to a barium nickel oxide phase that is selectively reduced to
nickel metal. The resulting material should exhibit superb catalytic reactivity.

738
Testing oxygen separation membranes based upon novel materials
Vladislav Sadykov1,2*, Alexey Krasnov1, Yulia Fedorova1, Anton Lukashevich1,
Pavel Skriabin1, Nikita Eremeev1, Konstantin Valeev1, Oleg Smorygo3
1
Boreskov Institute of Catalysis SB RAS, pr. Akad. Lavrentieva 5, Novosibirsk 630090, Russia;
*
e-mail: [email protected]
2
Novosivirsk State University, Pirogova str. 2, Novosibirsk 630090, Russia
3
Powder Metallurgy Institute, Platonova str. 41, Minsk 220005, Republic of Belarus
Keywords: oxygen separation membranes, testing, methane conversion, nanocomposites

Design of materials for producing syngas from biofuels by selective oxidation with oxygen
separated from air using catalytic membranes reactors is important problem of hydrogen
energy field. Nanocomposites based on Pr nickelate-cobaltite are promising materials due to
a high oxygen mobility and relatively good chemical stability in working conditions.1,2 This
work aims at studying performance of membranes based on such nanocomposites.
PrNi0.5Co0.5O3δ (PNC), Ce0.9Y0.1O2δ (YDC), Ce0.9Gd0.1O2δ (GDC) and MnFe2O4 (MF)
were synthesized by modified Pechini route. PNC – YDC and MF – GDC nanocompos-
ites were prepared using ultrasonic dispersion in isopropanol. A few PNC – YDC func­
tional layers with various porosity, dense MnFe2O4 – Ce0.9Gd0.1O2δ buffer layer and porous
Pt/Sm0.15Pr0.15Ce0.35Zr0.3O2δ or LaNi0.9Pt0.1O3/Pr0.3Ce0.35Zr0.35O2δ/Al2O3 catalytic layers were
consecutively deposed on Ni/Al foam substrate. The membranes obtained were tested in CH4
selective oxidation into syngas/oxidry reforming using specially built setup.
To measure the sample temperature, new visible spectra pyrometry technique by analysis
of the working membrane images was developed. Pyrometry measurements revealed a non-
uniform or Gaussian temperature profile on the surface of membranes. The oxygen perme-
ability of membranes (the oxygen flux is up to 10 ml O2/cm2min at 950 °C under air/methane
gradient) meets criteria of the practical application.3 Syngas yield and methane conversion
increase with temperature and contact time. CH4 conversion is up to 50–60% with H2 content
in the outlet feed being up to 25% at 900 °C. H2/CO concentration ratio is >1, which is good
for the practical application. Stable performance of the membrane was demonstrated for at
least 200 h time-on-stream.

Acknowledgement
Support by Russian Scientific Foundation (16-13-00112 Project) is gratefully acknowledged.

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References
1. V.A. Sadykov et al. “Oxygen mobility and surface reactivity of PrNi1xCoxO3δ perovskites and their
nanocomposites with Ce0.9Y0.1O2δ by temperature-programmed isotope exchange experiments”,
Solid State Ion., 273, pp. 35–40, 2015.
2. V.A. Sadykov et al. “Structure studies of Pr nickelate-cobaltite – Y doped ceria nanocomposite”, J.
Ceram. Sci. Tech., in press, DOI: 10.4416/JCST2016-00099.
3. V.A. Sadykov et al. Perovskites: Structure, Properties and Uses. Nova Science Publishers, New
York, 2010.

340
Permeability and ionic conductivity of CaTi0.9Fe0.1O3-δ
Corinne Salles1*, Marlu César Stail2,3, Jacques Fouletier2,3, Jean Marc Bassat4,
Daniel Marinha1
1
LSFC- SAINT-GOBAIN CREE, 550 Rue Alphonse Jauffret, 84300 Cavaillon France;
*
e-mail: [email protected]
2
Univ. Grenoble Alpes, LEPMI, F-38000 Grenoble France
3
CNRS, LEPMI, F-38000 Grenoble France
4
Univ. Bordeaux, CNRS, ICMCB, F-33608 Pessac France
Keywords: oxygen semi-permeation, iron-doped calcium titanate, oxygen diffusion, ionic conduc­
tivity

Oxygen transport membranes (OTM) are dense membranes that allow oxygen diffusion
along a chemical potential gradient. OTMs can increase the efficiency and lower emissions
of oxycombustion processes or partial oxidation of methane. The oxygen semi-permeability
is proportional to the ambipolar conductivity of the OTM material. However, OTM materials
with the highest conductivity also suffer from fast degradation under operation conditions.
In this regard, CaTi0.9Fe0.1O3−δ (CTF) exhibits a promising trade-off, with an intermediate
oxygen flux that is compensated by its superior thermal, mechanical and chemical long-term
stability1.
In this study, we interpret the oxygen transport properties of CTF in light of the struc-
tural and electrical characterization as functions of temperature (150–900 °C) and oxygen
partial pressure (1 and 10–27 bar). CTF is a p-type conductor, where transport is mainly due
to electronic conductivity at low temperature (T <700 °C)2. The ionic conductivity becomes
predominant for temperature above 700 °C and PO2 higher than 10–5 bar, whereas n-type con-
ductivity dominates at low PO2 (≈ 10–25 bar). The semi-permeation measurements confirmed
these results, showing that the flux was limited by the electronic conductivity for tempera-
tures higher than 800 °C whereas at lower temperature the ionic conductivity was limiting3.
We also find that the ionic transport number is higher than typical OTM materials. Nev-
ertheless, under usual operating conditions, conductivity is never solely provided by either
type of charge carriers, and must be considered as mixed conductor. Ionic conductivity values
determined by isotopic exchange, semi-permeation measurements, and impedance spectros-
copy were compared.

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We tested the stability of CTF under reactive atmospheres (CO/CO2 and H2O/H2). CTF
shows a remarkable stability under H2 and CO/CO2, with a constant flux during 1300 h.
The oxygen flux decreases quickly in presence of humidity (by 66%), but recovers (by 33%
in 60 h) when water vapour is removed. It is thus promising for oxycombustion process of
partial oxidation of methane.

References
1. F.M. Figueiredo, J. Waerenborgh, V.V. Kharton, H. Näfe, and J.R. Frade, “On the relationships be-
tween structure, oxygen stoichiometry and ionic conductivity of CaTi1-xFexO3-δ (x=0.05, 0.20, 0.40,
0.60)” Solid State Ionics, 156, pp 371–381, 2003.
2. S. Marion, A.I. Becerro, T. Norby, “Ionic and electronic conductivity in CaTi1−xFexO3−δ (x=0.1–
0.3)”, Ionics, 5, pp 385–392, 1999.
3. C. Salles, J. Fouletier, D. Marinha, M.-C. Steil, “Determining the rate-limiting step during oxygen
semi-permeation of CaTi0.9Fe0.1O3-δ oxygen transport membranes” J. Memb. Sci. 527, pp 191–197,
2017.

706
Development of asymmetric dual phase composite oxygen transport
membranes
Falk Schulze-Küppers*, Stefan Baumann, Madhumidha Ramasamy, Wilhelm A. Meulenberg
Forschungszentrum Jülich, Institute of Energy and Climate Research, D-52425 Juelich, Germany;
*
e-mail: [email protected]
Keywords: oxygen transport membrane, cer-cer dual phase, asymmetric membrane, tape casting

Mixed Ionic electronic conductors (MIEC) are potential candidates for various applications
including oxygen transport membranes (OTM) due to their high efficiency and infinite selec-
tivity towards oxygen at elevated temperatures.1 Possible applications for OTM are supply of
highly pure oxygen or membrane reactors, in which the separated oxygen is directly utilized
to form valuable products such as synthetic fuels or bulk chemicals. OTM transport oxygen
ions by solid state diffusion through oxygen vacancies, which cannot be occupied by other
ions. However, the transport is based on lattice defects and, thus, high-performance OTM
materials mainly perovskites (with high defect density and mobility) suffer from limited
stability in application conditions with potentially reducing and/or acidic gas atmospheres
(requiring low defect density and mobility).
One approach to face the trade-off between chemical stability and oxygen flux perfor-
mance are dual phase composites. In such cer-cer composites two phases are coupled to
provide pure electronic and ionic conducting pathway, respectively. In this work, composites
of 20 mol% Gadolinia doped ceria (GDC) as ionic conductor and FeCo2O4 spinel (FCO) as
electronic conductor are investigated.2 GDC-FCO ratio is varied proving that spinel content
as low as 10 wt-% is sufficient to ensure oxygen permeability, although well below the per-
colation threshold. In addition, the influence of the powder synthesis route on microstructure

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and corresponding oxygen permeation properties is investigated and compared to state-of-

the-art single phase material, i.e. La0.58Sr0.4Co0.2Fe0.8O3-δ (LSCF).
In order to increase oxygen flux further, by microstructural optimization of the mem-
brane layout, asymmetric membranes were manufactured by sequential tape casting. Such
membranes consist of a thin (~15 µm), dense membrane layer and a porous support porosity
(>40%) for mechanical stability. An important issue in tape casting is the used raw materials.
In order to realize cost efficient manufacturing, a reactive sintering of the membranes was
developed, using commercially available CGO, Fe- and Co-oxides as raw material. Oxygen
flux in such membranes is clearly limited by surface exchange, due to the low electrochemi-
cally active triple phase boundary length, at which oxygen exchange takes place. The per-
formances of bulk and asymmetric membranes are analysed and the potential of this type of
materials is discussed with regard to microstructural optimization.

References
1. J. Sunarso, et. al. “Mixed ionic–electronic conducting (MIEC) ceramic-based membranes for oxy-
gen separation”, J. Mem. Sci., 320, pp. 13–41, 2008.
2. M. Ramasamy, et al. “Influence of Microstructure and Surface Activation of Dual-Phase Membrane
Ce0.8Gd0.2O2 - FeCo2O4 on Oxygen Permeation” J. Am. Ceram. Soc., 99, pp. 349–355, 2016.

651
Thermoelectric properties of (La0.12Sr0.88)0.95TiO3-δ between 100
and 900 oC at reducing conditions
Sathya Prakash Singh1*, Nikola Kanas1, Mari-Ann Einarsrud1, Mats Johnsson2, Kjell Wiik1
Department of Material Science and Engineering, NTNU, Trondheim, Norway;
1

*
e-mail: [email protected]
Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University,
2

Sweden
Keywords: A-site deficient, La-substituted strontium titanate, nanostructuring, thermoelectrics

La-doped strontium titanate (STO) is a promising n-type thermoelectric material at moder-

ate temperatures (500–600 oC). Due to the perovskite type of structure, the material has
an exceptional ability to accommodate donor-dopants and still maintain chemical stability,
hence offering the opportunity to control critical properties such as electrical conductivity
and Seebeck coefficient. (La0.12Sr0.88)0.95TiO3-δ samples were prepared by spray pyrolysis fol-
lowed by spark plasma sintering (SPS) at 925, 1100 and 1200 oC or solid-state reaction (SSR)
followed by conventional sintering at 1500 oC. Thermoelectric performance was evaluated
by measuring the Seebeck coefficient, electrical and thermal conductivity. The samples sin-
tered by SPS between 1100 and 925 oC showed a low thermal conductivity ranging from 3
to 1.3 Wm–1K–1.1 The low thermal conductivity is correlated with a low grain size combined
with a highporosity. The electrical conductivity (4-point, DC) and Seebeck coefficient were
measured in reducing atmosphere (humidified 5% H2 in Ar) at temp-eratures between 100

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and 900 oC. The electrical conductivity increased significantly with grain size (40 nm–4 µm)
as shown in Fig. 1. At T<450 oC the Seebeck coefficient decreased with increasing grain size.
The highest figure of merit, ZT=~0.2, was observed at 500 oC for the material prepared by
conventional sintering.

Fig. 1. Temperature dependence of electrical conductivity measured at reducing conditions for (La0.12Sr0.88)0.95TiO3-δ
sintered at 925 oC(SPS), 1100 oC(SPS), 1200 oC(SPS) and 1500 oC(SSR)

Acknowledgement
Financial support from The Research Council of Norway (RNC)- Nano2021, THELMA-project (Proj.
no. 228854) is gratefully acknowledged.

Reference
1. T.E. Loland, J. Sele, M.-A. Einarsrud, P.E. Vullum, M. Johnsson and K. Wiik, “Thermal Conductiv-
ity of A-Site Cation-Deficient La-Substituted SrTiO3 Produced by Spark Plasma Sintering”, Energy
Harvesting and Systems, 2(1–2), 63–71, 2015.

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606
Development of porous SiC using the sacrificial template technique for
nuclear fusion applications
Carlota Soto1, Carmen García-Rosales1, Jon Echeberria1, Jose M. Martínez-Esnaola1,
Teresa Hernández2, Marta Malo2
1
Ceit-IK4 Technology Center and TECNUN (Universidad de Navarra), P. Manuel Lardizábal 15,
20018 San Sebastián, Spain
2
CIEMAT, Laboratorio Nacional de Fusión, Avenida Complutense 40, 28040 Madrid, Spain
Keywords: porous SiC, FCI, DCLL blanket, sacrificial template, thermal conductivity

One of the main technological challenges towards the attainment of nuclear fusion as energy
source is the development of materials able to withstand the extreme conditions present in
a future fusion reactor. In the so-called blanket, the energy of the neutrons produced in the
fusion reaction is transformed into thermal energy, and tritium –one of the fuel elements- is
generated out of lithium. In the blanket design named Dual Coolant Lead Lithium (DCLL)
a PbLi alloy flows inside hollow channels called Flow Channel Inserts (FCIs), capturing the
neutron flux energy and thus increasing its temperature up to about 700 °C. FCIs are key
elements in the DCLL blanket design because they provide the necessary thermal insulation,
allowing the fluid to retain the highest possible heat energy and preventing the steel structure
to reach its maximum allowable temperature. The high PbLi temperatures allow high reactor
efficiency, but impose a considerable thermal gradient across the FCI’s walls. This gradient
generates mechanical stresses that must be supported by the FCIs during operation without
damage. Besides, FCIs must withstand the contact with the hot PbLi without corrosion dam-
age, and must provide enough electrical insulation to minimize interactions of the flowing
liquid metal with the high magnetic field present in a magnetically confined fusion environ-
ment. SiC is the main candidate material for FCIs. However, the relatively high thermal con-
ductivity of SiC for FCIs application requires the development of SiC-based materials with
sufficiently low thermal conductivity.
In the present research, a SiC sandwich material, formed by a core of porous SiC covered
by a dense SiC layer, is proposed for FCIs. The dense coating is produced by chemical vapor
deposition (CVD). According to thermomechanical calculations and FEM models, and as-
suming a CVD SiC dense coating of 200 µm and a porous SiC core of ≈5 mm thickness, the
core material should present a thermal conductivity near 7 W/m·K at 700 °C with a mechani-
cal strength above 50 MPa, to ensure the insulation and mechanical integrity that the applica-
tion requires. The electrical conductivity should be maintained below 1-10 S/m. To develop
a porous SiC with such properties, a method based on the sacrificial template technique is
proposed; in order to achieve a high porous/high strength material a spherical powder with
particle size about 30 times larger than the SiC powder is proposed as sacrificial phase, to
achieve a sponge like microstructure. In the proposed process, a spherical mesocarbon mi-
crobeads (MCMB) graphitized powder of about 10 µm particle size is used as sacrificial tem-
plate phase, which is added to a SiC powder of 0.3 µm particle size, and to Al2O3 and Y2O3
as sintering aids. The graphite phase is removed after sintering by an oxidation treatment. In

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this work, a description of the production method is presented, as well as the properties of
the resulting SiC porous material after sintering and oxidation, like porosity, microstructure,
thermal and electrical conductivities and module of rupture (MOR). In order to discuss the
mechanisms taking place in the different processing steps, results from X-ray diffraction and
thermogravimetric analysis (TGA) are also presented. Using this production technique, dif-
ferent porous SiC materials with a wide range of porosities (≈10–70%) have been produced,
being possible to fabricate a candidate material to become the core of a SiC-sandwich FCI,
with a porosity ≈40%, a thermal conductivity at 700 °C of ≈8 W/m·K, a MOR of about 110
MPa and electrical conductivity at 550 °C well below 0.01 S/m.

372
The adsorption reaction of different shaped-alpha-bismuth oxides with
iodide ions
Tomohito Sudare1*, Yuto Kamiya2, Fumitaka Hayashi2, Katsuya Teshima1,2
1
Center for Energy and Environmental Science, Shinshu University, 4-17-1, Wakasato, Nagano-shi,
Nagano, 380-8553, Japan; *e-mail: [email protected]
2
Department of Materials Chemistry, Graduation School of Shinshu University, Nagano, Japan
Keywords: bismuth oxide, flux method, morphology control, radioiodine, adsorption

Radioiodine is an inevitable product of nuclear fission, which is highly radioactive and toxic,
and could present a health risk upon people. Iodide anion (I−) is stable over the whole pH
range. Thus, the selective capture of I− from sea or lake water is required. Although silver ox-
ide (Ag2O) is known as a high adsorption capacity and selectivity for radioactive I−, the high
costs of silver limit its practical application. Bismuth oxide (Bi2O3) is a potential adsorbent
for recovering I−. Alpha-bismuth oxide (α-Bi2O3) is known to form Bi5IO7 via I− adsorption
with morphological transformation. Previous reports say that the concentration of I− and
variety of counter cation of I− are important for adsorption reaction. However, the reaction
mechanism including crystallographic information, how I− intrude into α-Bi2O3 crystals and
are fixed in, followed by morphological transformation, are unidentified. In this study, two
kinds of shape-controlled α-Bi2O3 crystals by flux method were used for adsorption test and
the influence of exposed crystal facet on reaction pathway is revealed.
α-Bi2O3 crystals with different shapes were prepared as followed: α-Bi2O3 crystals were
grown in carbonate flux with different solute concentration by using purchased α-Bi2O3. The
kinetics of I− adsorption by α-Bi2O3 were determined using aqueous solution containing I−
with concentrations of 0.4, 0.8, and 1.2 mmol L−1 (the amount of adsorbent = 1 g L−1, solution
temperature of 10, 20, and 40 °C, pH = 6.5, stirring rate = 0, 200, and 300). The suspensions
were collected for different periods while stirring. The supernatants were separated from
solids and analyzed via ion chromatography (IC). Solids were analyzed via X-ray power
diffraction (XRD). The morphology of reacted α-Bi2O3 were characterized with scanning
electron microscopy (SEM).

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Plate-shaped α-Bi2O3 crystals were obtained in low solute concentration and in high solute
concentration, polyhedral ones were obtained. As a result of the adsorption test, only when
polyhedral-shaped α-Bi2O3 crystals were used, needle-shaped crystals were obtained after
immersed in aqueous solution containing I− for 24 h. It is found that the needle-shaped crys-
tals have Bi5IO7 composition determined by electron diffraction scattering analysis. From the
results of time-dependent analysis, α-Bi2O3 crystals changed to Bi5IO7 crystals via three-step
reaction pathways. First, partial α-Bi2O3 crystals reacts with I− to form BiI3, followed by
formation of Bi5IO7 crystals through the reaction of BiI3 with hydroxyl ions. Consequently,
further reaction of Bi5IO7 crystals with remaining α-Bi2O3 crystals and I− occurs to grow
Bi5IO7 crystals itself. From the different behaviours in adsorption reaction depending on the
crystal shape, the particular facet of α-Bi2O3 crystal which I− diffuse into should be important
to start the adsorption reaction. In addition, at equilibrium, above 80% of theoretical adsorp-
tion capacity was achieved.

Acknowledgement
This work was partly supported by a JSPS Grant-in-Aid for Scientific Research (A) 25249089.

480
Thermochemical behavior of porous SiOC/LSMO nanocomposites with
1D nanostructures for syngas production
A. Tamayo1, E. Casado2, B. Garcia3
1
Ceramics and Glass Institute, CSIC, Kelsen 5. 28049 Madrid, Spain
2
Universidad Politecnica Madrid, Spain
3
Universidad Rey Juan Carlos, Spain

Porous nanocomposites composed by a silicon oxycarbide matriz and perovskite-type oxides

have been prepared with the aim of developing ceramic supported catalysts for the thermal
decomposition of CO2 and H2O to produce CO and H2, respectively.
The materials have been prepared through the sol-gel method by the incorporation, at
different stages of the synthetic process, the precursors of La/Sr manganites (LSMO). After
pyrolysis in inert atmosphere it is obtained a glass-matrix material with high surface energy
and the presence of a well defined mesopore distribution. The inclusion of LSMO into the
glass matrix is going to be strongly affected by the synthetic procedure. These oxides possess
a hexagonal perovskite-type structure and form crystals of a few nanometer size.
The characterization of the nanocomposite material revealed the formation of 1D nano-
structures composed by a carbonaceous matrix with LSMO nanocrystals growing along in
parallel direction to the carbon fibre. Raman, FTIR and 29SiNMR spectroscopies have been
used for the structural characterization whereas textural and surface characteristics have been
analyzed by SEM, TEM and N2 adsorption techniques. Since the materials are intended to act
as catalysts, we have also studied the surface of the materials in terms of their surface energy
and fractal characteristics as well. We have compared the wettability of the as-prepared nano-
composite and the different phases taking part of the nanocomposite material.

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The suitability of the obtained materials to be employed as thermochemical catalysts

has been studied by means of thermogavimetric analysis under controlled atmosphere and
through the analysis of the gases emitted during the thermochemical reaction.

930
Terbium-doped perovskite-related proton conductors
Mateusz Tarach1,2, Konrad Świerczek, José M. Serra1*
1
Instituto de Tecnología Química (Universidad Politécnica de Valencia - Consejo Superior de
Investigaciones Científicas), Av. Naranjos s/n, E-46022 Valencia, Spain; *e-mail: [email protected]
2
AGH University of Science and Technology, Faculty of Energy and Fuels, A. Mickiewicza 30,
30-059 Krakow, Poland
Keywords: proton conductors, perovskites, phase transformation, fuel cells

High temperature proton conducting materials have unique electrochemical properties make
them suitable for numerous applications, including Protonic Ceramic Fuel Cells (PCFCs),
hydrogen sensors, gas membranes or high temperature proton conducting electrolysers
(PCECs) which, compared with oxide ion-conducting devices, offer higher fuel utilization
and an opportunity to produce dry, pressurized hydrogen. Perovskite-type and perovskite-
related materials have been widely investigated as a good oxide-ion as well as proton con-
ductors, where the transport properties are strongly dependent on the crystal structure and
particularly the defects concertation.
An evaluation of terbium content in Ruddlesden-Popper-type oxide NdBaInO4+δ and its
relation with phase composition, crystal structure and transport properties was performed. To
determine it dense pellets of Nd1-xTbxBaInO4+δ (x = 0, 0.1–1.0) with relative density above
95% were prepared via the conventional solid-state route at 1450 °C.
Structural analysis by X-ray diffraction (XRD) performed for dried, as well as hydrated
materials at room and elevated temperatures indicated that crystal structure of the studied
samples can be described as Ruddlesden-Popper-related, with structural evolution from
monoclinic to cubic symmetry observed for 50% Tb-doped material. Phase transportation
significantly promotes transport properties of investigated material. Increase of ion conduc-
tivity by two orders of magnitude with unchanged activation energy was recoded compared
with undoped sample. Electrical conductivity of the compounds conducted in dry, H2O- and
D2O-containing atmospheres as a function of oxygen partial pressure allows establishing
the H/D isotopic effect related with high temperature proton conductivity. Incorporation and
removal of water molecules were also confirmed in situ by high temperature XRD and ther-
mogravimetric techniques. Finally, in order to elucidate influence of Nd site substitution
on transport properties, also conductivity relaxation kinetics of the Tb-doped materials was
measured in different atmospheres.

Acknowledgements
Financial support by the Spanish Government (ENE2014-57651and MAT2016 Grants) and Polish
Ministry of Science and Higher Education (Diamentowy Grant D12013 003243).

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175
Optimization of (La,Sr)(Co,Fe)O3 cathodes aiming on high performance
and enhanced durability in metal-supported fuel cells
David Udomsilp1,2*, Daniel Roehrens1,2, Norbert H. Menzler2, Alexander K. Opitz1,3,
Wolfgang Schafbauer4, Olivier Guillon2,5, Martin Bram1,2
1
Christian Doppler Laboratory for Interfaces in Metal-Supported Electrochemical Energy Converters;
*
e-mail: [email protected]
2
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research – Materials Synthesis
and Processing (IEK-1), 52425 Jülich, Germany
3
TU Wien, Institute of Chemical Technologies and Analytics, Getreidemarkt 9/164-EC, 1060 Vienna,
Austria
5
PLANSEE SE, Innovation Services, Metallwerk-Plansee-Strasse 71, Reutte, Austria
5
Jülich Aachen Research Alliance: JARA-Energy
Keywords: LSCF, SOFC, metal-supported fuel cell, cathode adherence, high performance cathodes

Adapted processing of (La,Sr)(Co,Fe)O3 perovskite cathodes for metal-supported solid oxide

fuel cells (MSCs) was investigated in order to develop high performance MSCs with signifi-
cantly increased durability of the cathode structures. The activation and sintering procedure
of the cathode was optimized to overcome the main issue of insufficient cathode adherence.
Effects from different sintering approaches on the phase stability, mechanical stability, time
dependent mechanical integrity, and functionality of the cell components revealed applicable
processing strategies. These strategies include the implementation of a separate sintering
step for MSC full-cells as well as an optimization of the current state-of-the-art in-situ acti-
vation process. Both strategies lead to a substantially improved adherence of the produced
cathodes. Accordingly, electrochemical single cell measurements revealed a performance
improvement of such produced cells in comparison to state-of-the-art cells which were in-
situ activated at 850 °C during the startup procedure. In another approach the potential for
increasing the performance by applying LSC as cathode material is the focus of investigation.
The results obtained from the presented study provide the basis for further characterization of
the degradation behavior in long-term measurements.

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398
Increased Li ion conductivity of LATP ceramics by optimized powder
processing
Katja Waetzig*, Axel Rost, Jochen Schilm
Fraunhofer Institute for Ceramic Technologies and Systems, Winterbergstrasse 28, 01277 Dresden,
Germany; *e-mail: [email protected]
Keywords: Li ion conductivity, LATP, ceramic processing, separator, all-solid-state batteries

Lithium ion conducting ceramics are investigated as candidates for use as solid electrolytes
in All-Solid-State, Lithium-Sulfur and Lithium-air battery concepts. LiTi2(PO4)3 provide the
prerequisite for a high Li-ion conductivity and dense microstructures for a reliable separation
of the cathode and anode side. A partial substitution of Ti4+ by Al3+ can improve the conduc-
tivity up to 3.0.10–3 S/cm for the composition Li1.3Al0.3Ti1.7(PO4)3 (LATP). However, LATP
exhibits a high thermal expansion anisotropy and cracks are a result of grain growth during
the sintering. At least, it was described, that the formation of microcracks can be inhibited by
reducing the critical grain size (< 1.6 µm). To reduce the grain size and to achieve homog-
enous and crack free microstructures, the powder processing have to be optimized. In this
study, the LATP powders were prepared by two different pathways: (1) melting and milling
of a glass frit to a powder and (2) the wet-chemical synthesis of a calcined LATP. Both types
of powder were characterized by phase analysis (XRD), particle size and shrinkage during
sintering. The sintering was performed by SPS at temperatures between 800 and 900 °C.
The phase composition, density, porosity, ionic conductivity, He-leakage rate and grain size
of the specimens were measured. The highest density (2.82 g/cm³; 97%), ionic conductivity
(>2.10–4 S/cm) and a homogenous microstructure was achieved at 850 °C with the material
synthesized by the wet-chemical route (2). The ceramic produced from the melt of parent
glass (1) showed the formation of microcracks at Ts = 950 °C in conjunction with the appear-
ance of an AlPO4 secondary phase (caused by Li loss during the preparation). With higher
sintering temperatures coarse grains and cracks dominate the microstructure.

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373
Effect of particle size and hierarchical structuring on
the electrochemical properties of NCM-cathode materials in
lithium-ion-batteries
Amalia C. Wagner*, Nicole Bohn, Joachim R. Binder
Karlsruhe Institute of Technology, Institute for Applied Materials (IAM-KWT),
Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany;
*
e-mail: [email protected]
Keywords: microstructure-property relationship, cathode materials, lithium ion batteries (LIBs),
energy storage

In the course of energy crisis energy revolution is taking place with important changes to
renewable energy sources. In this process lithium ion batteries (LIBs) are one key technol-
ogy concerning energy storage and electromobility because of their high efficiency and their
environmental-acceptability. Nevertheless one shortcoming of this technology is generally
said the lack of long-term cyclability and poor rate capability especially at high cycling
rates. Reasons are structural changes of the active material as well as inhibited mass and
charge transport during cycling due to poor electronic conductivity. To improve latter and in-
crease the reliability of LIBs, efforts must be made by modifying the cathode design to obtain
hierarchically structured composites. Thereby nano-structuring is favoured because of the
easier manageability compared to nanoparticles and even advantageous effects like shorter
diffusion paths and improved conductivities as well as suppression of structural changes are
promoted.1
In the following the approach of hierarchically structuring of LiNi1/3Co1/3Mn1/3O2 (NCM)
cathode active material by an elaborated process of grinding, spray drying and calcination
will be presented. Here the effects of granule size and primary particle size variation by
spray drying and calcination will be presented. The relationship between process parameters,
morphology and performance of the as prepared LIBs will be given by detailed material char-
acterization in combination with electrochemical investigations. It will be shown that active
material granules between 9 and 42 µm with nanostructured morphology and defined poros-
ity have superior discharge capacities, power densities and long-term stabilities compared to
bulk NCM-material. An accurate tuning of the performance at high C-rates can be reached by
granule size optimization and adaption of calcination temperature.

Acknowledgement
This research project was supported by the Federal Ministry of Economics and Energy (BMWi), project
No. 03ET6095A.

Reference
1. Z. Chen, J. Wang, D. Chao, T. Baikie, L. Bai, S. Chen, Y. Zhao, T. C. Sum, J. Lin, Z. Shen, Scientific
reports 2016, 6, 25771.

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712
Characterization of solid oxide fuel cell sealants and anodes
Jianping Wei*, S.M. Gross-Barsnick, D. Federmann, Jürgen Malzbender
IEK-2, Forschungszentrum Jülich GmbH, Wilhelm-Johnen-Straße, 52428 Jülich, Germany;
*
e-mail: [email protected]
Keywords: solid oxide fuel cell, anode, sealant, mechanical characterization

Typically brittle sealant and anode materials are critical for the reliability of solid oxide fuel
cells (SOFCs). Hence, characterization of these failure-relevant materials is crucial for the
long term operation. In particular, the mechanical behaviour and elevated temperature sta-
bility which is strongly affected by creep has to be thoroughly understood and in terms of
property – microstructure correlation, related to the materials’ compositions, crystallization,
porosity and phase stability.
Since sealant leakage can lead to malfunction of the whole system, the structural integrity
of the sealant is a key issue for the operation of SOFC stacks and systems. Fracture properties
and elevated temperature deformation need to be assessed, particularly for partially crystal-
lized glass-ceramic sealants that might suffer from instability issues at operation relevant
temperatures due to viscoelastic deformation of the residual glass phase. In this work, a
modified sealant, which consists of a composition from the BaO-CaO-SiO2 ternary system
with Ag particles reinforcement, was characterized. Bending tests were carried out at room
temperature and typical stack operation temperatures on a head-to-head specimen geometry
in an as-sintered and annealed state, yielding average fracture stresses and apparent creep
data. Since the sealants are exposed to a complex loading state in the stack environment,
complementary torsion tests were used to investigate the shear strength. Advanced micro-
structural characterization was carried out to gain insight into the annealing and reinforce-
ment filler effects. The results are compared and discussed with respect to literature data and
their relevance for the application in SOFCs operating at different temperatures in the range
of 600 °C to 800 °C.
Typical anode substrate materials (NiO-3YSZ and NiO-8YSZ) along with their reduced
and re-oxidized state were analysed by means of fracture toughness at room temperature and
800 °C. Effects related to porosity and transformation toughening could be verified. Further-
more, creep of porous Ni-YSZ composite has been investigated under H2/Ar atmosphere at
typical operating temperatures. Ni-YSZ materials with different porosities and Ni/YSZ ratios
were tested in order to investigate material´s composition and porosity effects. Different
loading configurations such as compression, four-point bending and ring-on-ring bending
have been used to assess the differences in creep response of these materials. Interpretation
and analysis of the data were based on analytical and finite element simulation. The system-
atic comparison and discussion of the results was aided by microstructural investigations.

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454
Interfaces of CaCo- and CaMn-ceramics provide high thermoelectric
conversion efficiency
Wilfried Wunderlich1*, Helmut T. Uchida2
1
Tokai University, Fac. Eng., Material Science Department, Hiratsuka 259-1292, Kitakaname 4-1-1,
Japan; *e-mail: [email protected]
2
Tokai University, Fac. Eng., Dept. Precision Eng., Hiratsuka 259-1292, Japan
Keywords: energy Harvesting, electro-ceramics, ceramic interface, microstructure

Thermoelectric materials have the option for recovery of waste heat into electricity. CaCo-
and CaMn-oxide-ceramics1,2 show large p- and n-type Seebeck coefficients and electric pow-
er output. We prepared mixtures of CaCO3 and Mn2O3 or CoO with Co3O3, and added ZnO
and rare earth oxides (Y, Nd, Sm). After calcination, grinding and sintering at 1000 °C for 7 h,
we measured the Seebeck voltage under high temperature gradient.3 The values for Seebeck
ceoefficent (and output power) of more than -300 μV/K (8μW) for the Mn- and +200 μV/K
(10 μW) for CaCo could be improved for both materials by a certain Zn-concentration, while
the rare earth addition had not much affect.
The material compounds were characterized with SEM-EDX observations. The mapping
could clearly identify Ca-rich and Mn- or Co-rich components, which are stable in the phase
diagrams. Revising the data on a NaTaO3 / Fe3O3 compound4 showed that similar interfaces
are present, which opens the possibility for searching new similar compounds. The explana-
tion of the large effect of interfaces can be explained by the electric field at interfaces similar
as in ferrolectrics.
These oxides are easy to handle and contacting with Cu-wires is possible. Mechanical
fixation with Portland cement is also considered as an option, when the CaCo- and CaMn-
ceramics is completely dry, otherwise the thermoelectric properties deteriorate. The usage of
these oxide ceramics for functional materials in buildings as discussed.

References
1. R. Funahashi, S. Urata, J. Mater. Res. 18 [7] (2003).
2. Y.Wang, Y. Sui, W. Su, J. Appl. Phys. 104 (2008) 093703.
3. W. Wunderlich, Energy Harvest.Syst. 2 (2015) 37–46.
4. W. Wunderlich, J Nucl. Mat. 389 [1] (2009) 57–61.

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611
Designing the composite SrVO3-SrTiO3 anodes for hydrocarbon-fueled
solid oxide fuel cells
Aleksey Yaremchenko*, Javier Macías, Jorge Frade
CICECO – Aveiro Institute of Materials, Department of Materials and Ceramic Engineering,
University of Aveiro, 3810-193 Aveiro, Portugal; *e-mail: [email protected]
Keywords: perovskite, SOFC, anode, titanate, vanadate, electrical conductivity, polarization
resistance

Perovskite-type SrVO3- and SrTiO3-based phases exhibit good resistivity to sulfur poisoning
and do not catalyze carbon deposition, and are considered therefore as possible alternative
anode materials for hydrocarbon-fueled solid oxide fuel cells. SrVO3 exhibit high electronic
conductivity but also a narrow phase stability domain restricted to reducing conditions. On
the other hand, SrTiO3 demonstrates remarkable phase and dimensional stability in a wide
range of T-p(O2) conditions but rather insufficient electrical conductivity. The present work
aimed at the development of SrVO3-SrTiO3 composite anode materials with emphasis on a
compromise between dimensional/microstructural stability and electrical properties.
Initial assessment demonstrated that SrVO3 and SrTiO3 form an entire range of solid so-
lutions under reducing conditions. In all cases, exposure to air above 600–700 °C resulted
in either collapse of perovskite structure (V-rich compositions) or separation of vanadium-
containing secondary phases (Ti-rich composition). These phase transformations were ac-
companied by dimensional changes and were not reversible at temperatures below 1000 °C
(probably, due to kinetic reasons).
Instability in oxidizing atmospheres complicates the fabrication of anodes in realistic con-
ditions. Therefore, the second approach was to start from oxidized phases and to proceed via
in-situ reduction employed for Ni-YSZ cermet anodes. V5+ substituted in titanium sublattice
of SrTiO3 acts as donor-type dopant and was found to has a limited solid solubility under
reducing conditions (~30–35 at.%). In-situ reduction of oxidized SrTi1-yVyO±δ at 900 °C is
accompanied however by the reduction of vanadium cations, and the resultant conductivity
remains too low (< 0.2 S/cm) being comparable to other acceptor-doped strontium titanates.
The next approach was preparation of composite SrVO3-SrTiO3 anode materials starting
from oxidized phases. The precursors with nominal composition SrTi1-yVyO±δ (y = 0.1–0.4)
were thermally treated in air at temperatures not exceeding 1100 °C to yield equilibrated
phase mixtures comprising SrTiO3-based perovskite as a main phase and strontium orthovan-
adate Sr3(VO4)2 as a second major phase. Transformation of strontium orthovanadate on re-
duction at 900 °C into highly-conductive perovskite-type SrVO3 phase finely distributed in
the stable SrTiO3-based matrix resulted in substantial nearly instant increase of electrical
conductivity by orders of magnitude reaching 10–30 S/cm for y = 0.3–0.4. Electrochemical
activity of composite anodes applied onto yttria-stabilized zirconia solid electrolyte and infil-
trated with a fraction of Ce0.9Gd0.1O2-δ electrolyte component was evaluated by electrochemi-
cal impedance spectroscopy using symmetrical cell configuration.

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527
Fingerprinting compounds in Li2O-TiO2 phase diagram with electron
energy loss spectroscopy
Melike Mercan Yildizhan*, Mehmet Ali Gulgun
Sabanci University, Faculty of Engineering and Natural Sciences, 34956 Istanbul, Turkey;
*
e-mail: [email protected]
Keywords: Li-ion batteries, Li2Ti3O7, Li4Ti5O12, Li2TiO3, EELS, TEM

Compounds in the Li2O-TiO2 phase diagram are materials of importance for energy applica-
tions, especially in Li-ion batteries1. These applications involve complex chemical reactions.
It is crucial to be able to identify the metastable/stable phases forming that might cause
deuteriation of the efficiencies of devices2. However, detection of Li is challenging. One
of the most suitable methods is EELS, which is highly sensitive both to coordination and
chemistry of the ions. In order to identify the thermodynamically stable phases, different syn-
thesis routes were used for each compound. Solid state synthesis was utilized for Li4Ti5O12
and monoclinic Li2TiO3, air-quenching from 1200 °C was mandatory for obtaining Li2Ti3O7.
Cubic Li2TiO3 was obtained by hydrothermal method. In order to probe the fingerprints of
different compounds with unique coordination of Li and/or Ti with O, Energy Loss Near
Edge Structure (ELNES) of Li-K, Ti-L2,3 and O-K edges were determined for all compounds.
The fingerprinting studies were conducted via EELS, in STEM mode. Ti L2,3 edge showed
the least dependency on both crystallography and site symmetry. Li-K edge was effected by
the coordination number, with 4-fold coordination showing an extra structure in the near
edge. O-K edge was effected the most by site symmetry, crystallography and stoichiometry.
These fingerprints can be used as guidelines in determining the defect chemistry for energy
applications in all compounds.

References
1. T.L. Kulova, 49(1), “New Electrode Materials for Lithium–Ion Batteries (Review)”, Russ J Elec-
trochem, pp. 3–28, 2013.
2. M. Kitta, T. Akita, Y. Maeda, and M. Kohyama, “Study of Surface Reaction of Spinel Li4Ti5O12
during the First Lithium Insertion and Extraction Processes Using Atomic Force Microscopy and
Analytical Transmission Electron Microscopy”, Langmuir, 28(33), pp. 12384–12392.

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350
Preparation of alumina supports for the fabricatıon of high flux thin
membranes
A. Semih Yurttaş, H. Arda Yurtsever, Ali Altunsoy, Berna Topuz*
Department of Chemical Engineering, Ankara University, Ankara, Turkey;
*
e-mail: [email protected]
Keywords: ceramic, macroporous, supports, membrane, gas transport

Due to high energy demand in our developing world, researchers are either trying to meet this
demand in new ways or redesign existing high energy consuming systems in an economi-
cal way. Membrane based separation has superior properties like low energy consumption,
high purity separation and easy processing that makes it advantageous over other separation
techniques. Ultrathin membranes have been developed for high flux separation, nanofiltra-
tion (NF), ultrafiltration (UF), reverse osmosis (RO), gas separation and pervaporation. Sup-
ports are significant for the fabrication of thin membranes in terms of their surface rough-
ness and the flux1. Ceramic supports are mechanically/thermally/chemically stable compared
to polymeric counterpart. One major drawback of macro/mesoporous ceramic supports is
their high cost that prevents large scale deployment of thermally stable ceramic/zeolite/MOF
membranes. Silica, zirconia, titania and alumina or their composites are generally used as
the porous membrane support materials2,3. Ceramic supports supply not only thermal and
chemical stability but also good surface morphology which leads to a smooth surface for thin
membrane coating. High throughput thin membranes necessitate high flux membrane sup-
port with homogeneous surface properties and uniform pore size.
In this study, macroporous alumina supports were prepared by using vacuum assisted
filtration with different α-Al2O3 powders (Baikowski CR-6 and Sumitomo Chemical AKP-
50). Structural parameters such as pore diameter, porosity and tortuosity of the prepared
macroporous supports were estimated by using He, N2, CO2 permeance measurements. The
effect of temperature and pressure difference on the gas permeances of the prepared supports
were also investigated. Supports prepared by Baikowski powder which has a larger particle
size than AKP-50 powder exhibited a permeance of four times higher than that of AKP-50.

References
1. Gao, X., et al., The transport of gases in macroporous α-alumina supports. J. of Membrane Sci.,
409–410: p. 24–33, 2012.
2. Chang, C.H., R. Gopalan, and Y.S. Lin, A comparative study on thermal and hydrothermal stability
of alumina, titania and zirconia membranes. J. of Membrane Sci., 91(1): p. 27–45, 1994.
3. Van Gestel, T., et al., Alumina and titania multilayer membranes for nanofiltration: preparation,
characterization and chemical stability. J. of Membrane Sci., 2002. 207(1): p. 73–89.

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Poster presentations

640
Modeling of thermally induced delamination in glass/steel joints for
solid oxide cell applications
Hamid Abdoli1, Karsten Agersted2
1
Energy and Environment Center, Niroo Research Institute, Tehran, Postal Code: 1468617151, Iran
2
Department of Energy Conversion and Storage, Technical University of Denmark, Frederiksborgvej
399, 4000 Roskilde, Denmark
Keywords: solid oxide cell, interconnect steel, glass sealant, modelling, cracking

The majority of the solid oxide cell (SOC) sealants has been focusing on bonded glass seal/
steel interconnect. Glass should be prepared with match thermal expansion coefficient (α)
and low interfacial reaction with adjacent parts. Seal thickness can be also adjusted to im-
prove the interfacial mechanical characteristics. In this study an analysis was performed on
the stress situation at room temperature at where the residual thermal stress is at its maximum
level. The developed model was used to predict the crack growth condition and life time
estimation in practical situation with supports of the experimental measured data such as
Young’s modulus of glass seal (89.35 GPa) and steel interconnect (200 GPa), Critical fracture
energy of glass (Gc=6.02±0.79 J/m2) and joint couples as well as their thickness (50 and 300
μm for glass and steel, respectively). The normalized steady-state energy release rate was
considered for the analysis and modelling the crack growth of the joint. While experimental
assessments revealed that the interfacial crack deflects to the bulk glass, numerical calcula-
tions led to a diagram with
“no cracking/cracking” re-
gions. This diagram shows
the maximum allowable ∆α
to avoid crack growth. The
analysis can be regarded as
the basis step for the design
of multilayer glass/steel
frames to increase the total
resistance of the functional
sealing layer against de-
lamination. However, mul-
tilayers cannot be designed
from fracture mechanics
considerations alone. Fig. 1. Cracking diagrams showing the maximum allowable TEC mismatch
for the examined steel/glass/steel tri-layers

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T05: Ceramics for novel energy conversion, storage and use – Poster presentations

420
Ionic conductivity of Zr-rich pyrochlore Nd2Zr2O7 based system
J.C.C. Abrantes1,2, E. Gomes1, A.N. Shchegolikhin3, L.G. Shcherbakova4, A.V. Shlyakhtina4
1
UIDM, ESTG, Instituto Politécnico de Viana do Сastelo, 4901-348 Viana do Castelo, Portugal
2
Aveiro Institute of Materials – CICECO (DEMAC), University of Aveiro, 3810 Aveiro, Portugal
3
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, ul. Kosygina 4, Moscow
119991, Russia
4
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, 119991, Russia
Keywords: pyrochlore, ionic conductivity, interstitial oxygen conductor

Pyrochlore based materials, due to their high ionic conductivity, have been characterized
as potential solid electrolytes. In this paper Nd2-xZr2+xO7+x/2 pyrochlore materials (0 ≤ x ≤ 1)
were prepared by mechanical activation of the oxide mixtures, following by high temperature
sintering (1500 °C, 10 hrs) of uniaxial pressed pellets. Structure and microstructural charac-
terization of prepared ceramic samples were done by X-ray diffraction, Raman spectroscopy
and scanning electron microscopy. The behavior of their TEC (thermal expansion coefficient)
was investigated also. All Nd2-xZr2+xO7+x/2 are single phase materials with a relative density
higher than 90%.
Electrical characterization was performed by electrochemical impedance spectroscopy as
a function of temperature and oxygen partial pressure. The electrical conductivity of Zr-rich
(x > 0) compositions is more than one order of magnitude higher than the stoichiometric
composition (x = 0), with a conductivity value close to 0.03 S/cm at 1000 °C in air, and an
activation energy of 1 eV. The oxygen partial pressure dependence shows a constant conduc-
tivity value within a large oxygen partial pressure range, typical of the ionic type conductiv-
ity. The increase of the ionic conductivity for Zr-rich compositions were interpreted by the
interstitial oxygen ion formation, to compensate the Zr4+ in the Nd3+ positions. The ionic
conductivity of this material was then attributed to interstitial oxygen ions migration.

041
Effect of GD/SM co-doping on the electrical properties of ceria-based
electrolyte materials
A. Arabacı1*, M.F. Öksüzömer2
Istanbul University, Faculty of Engineering,Department of Metallurgical and Materials Engineering,
1

34320 Istanbul, Turkey; *e-mail:[email protected]

Istanbul University, Faculty of Engineering, Department of Chemical Engineering, 34320 Istanbul,
2

Turkey
Keywords: co-doped ceria, pechini method, samarium, gadolonium, solid oxide fuel cell

Ceria based materials are widely used as electrolytes for intermediate-temperature solid
oxide fuel cell (IT-SOFC). (Ce(NO3)3.6H2O, Gd(NO3)3.6H2O, Sm(NO3)3.6H2O nitrate salts
were used as the starting materials to form co-doped ceria electrolytes of Ce0.8Gd0.2-xSmxO1.90

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(0.5≤x≤0.15) using the Pechini method. The samples were characterized by means of X-
ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance
spectroscopy (EIS). XRD patterns of the all prepared compositions indicate the formation of
the cubic fluorite-type structure. The relative densities of the samples were determined above
90% after sintering at 1400 °C for 6 h. The impedance spectroscopy of the sintered pellets
was performed between 300 °C and 800 °C in air and the effects of the co-dopant on the ionic
conductivity of the ceria based electrolytes were investigated.

Acknowledgement
This work has been supported by TUBITAK project number: MAG114M238.

References
1. I. Hideaki, T. Hiroaki, Solid State Ionics, 83, pp. 1–16, 1996.
2. B.C.H. Steele, Solid State Ionics, 129, pp. 95–110, 2000.

931
Development of steam electrodes in water splitting reaction for high
temperature proton electrolysers
Nuria Bausá1, David Catalán1, Mateusz Tarach1,2, Truls Norby3, José M. Serra1*
Instituto de Tecnología Química (Universidad Politécnica de Valencia – Consejo Superior de
1

Investigaciones Científicas), Av. Naranjos s/n, E-46022 Valencia, Spain; *e-mail: [email protected]
AGH University of Science and Technology, Faculty of Energy and Fuels, A. Mickiewicza 30,
2

30-059 Krakow, Poland

UiO University of Oslo, Department of Chemistry, FERMiO, Gaustadallèen 21, NO-0349 Oslo,
3

Norway
Keywords: PCEC, electrolyser, LSM, BCZY, multitube module, catalytic promotion

High temperature electrolysis technology offers high conversion efficiency of renewable and
peak electricity to H2 and may increase performance further by utilising available sources
of heat and steam from solar, geothermal, or nuclear plant. In contrary to solid oxide elec-
trolysers (SOECs), which operate at around 800 °C and H2 is produced on the steam feed
side, proton conducting electrolysers (PCECs) generate pressurized dry H2 what significantly
enhances total efficiency.
The main objective of ELECTRA project is to develop and demonstrate scalable fabrica-
tion of tubular high temperature electrolyser (HTE) cells with proton conducting electrolyte.
In order to produce 250 Ln/h of H2 from 1 kW of electrical power, a multi-tube reactor has
been designed and built.
ELECTRA utilises a novel generic tubular module holding single-end closed tubes. The
tubular cells are mounted with patented solution allowing then to be inserted, fasted, sealed,
monitored and controlled at working conditions of individual tubes, from a cold accessible
side. High-pressure steam is fed to the outside of each tube, and pure H2 is collected inside.
The electrochemical performance and system durability have been studied by electrochemi-

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cal impedance spectroscopy (EIS) and gas chromatography methods. The measurements
were performed in the temperature range 800 600 °C and up to 30 bar of pressure of humidi-
fied air (75% of steam).
Related to the anode development, La0.8Sr0.2MnO3-δ (LSM) composite material has been
deposited on proton-conducting BaCe0.2Zr0.7Y0.1O3-δ (BCZY27) electrolyte and studied in
symmetric cells to investigate the anode microstructure and electrochemical performance.
To enhance anode kinetic reaction, the LSM/BCZY27 60/40 vol.% composite was infiltrated
with Pr, Ce, Pr-Ce 50 vol.% and Zr nanocatalysts treated at 850 °C. The Rp showed the best
results (< 0.2 Ω·cm2) applying a density current of 0.5 – 5.5 mA/cm2 range for the LSM/
BCZY27 60/40 vol.% composite infiltrated with Pr-Ce 50 vol.%
Finally, ELECTRA will demonstrate proof-of-concept CO2 and steam co-electrolysis re-
action, where compared to SOECs, pressurised steam and CO2 are fed on separate sides of the
cell in the PCEC, which may be advantageous for economical syngas production.

289
Two step sintering of spinel coatings prepared by electrophoretic
deposition method
Michal Bobruk1*, Sebastian Molin2, Peter Vang Hendriksen2, Tomasz Brylewski1
Faculty of Materials Science and Ceramics, AGH University of Science and Technology, al.
1

Mickiewicza 30, 30-059 Krakow, Poland; *e-mail: [email protected]

Department of Energy Conversion and Storage, Technical University of Denmark, Risø Campus,
2

Frederiksborgvej 399, 4000 Roskilde, Denmark

Keywords: coating, sintering, MnCo2O4, IT-SOFC

Ferritic steel Crofer 22APU is one of the possible construction materials for metallic inter-
connects for intermediate temperature solid oxide fuel cells (IT-SOFC). During the exploita-
tion of the fuel cells with metallic interconnect at 800 °C, an unavoidable phenomenon of
chromium oxide scale formation occurs. This oxide causes a substantial increase of electrical
resistance, which directly leads to higher stack losses. Another negative factor is possible
vaporization of volatile chromium compounds and contamination of the cathode electrode
which result in deterioration of the catalytic properties. In order to decrease the degradation,
a modification of the surface of the interconnect can be applied, involving the formation of a
protective and conductive manganese-cobalt spinel on the surface of the alloy. With the use
of the electrophoretic method combined with a two-step heat treatment process, dense coat-
ings can be produced, offering an effective barrier to the chromium diffusion from Crofer
22APU steel, thus substantially limiting the formation of volatile vapors from Cr scale.
In this work, a MnCo2O4 1 spinel was used to obtain a conductive-protective coating on the
interconnect made of ferritic steel Crofer 22APU. MnCo2O4 coatings, in the form of suspen-
sion, were applied on the steel surface using electrophoretic method. Deposition was per-
formed with electric field strength of 40 V/cm in acetone and isopropyl alcohol suspension in
the ratio 1:1 (v/v) and iodide. Then, a two-step heat treatment was performed. The first step

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consisted of reduction of the obtained coatings in reductive atmosphere (H2/Ar) with vari-
ous partial pressure of oxygen at 900, 1000, 1100 °C. The second step involved oxidizing of
the previously reduced coatings. The phase composition of the coatings was determined by
means of the XRD method, and microscopic observations, including the determination of the
chemical composition by means of SEM-EDS.

Acknowledgement
Participation in the conference is co-financed by the JCerS Trust.

Reference
1. M. Mirzaei, A. Simchi, M.A. Faghihi-Sani, A. Yazdanar, “Electrophoretic deposition and sintering
of nanostructured manganesecobalt spinelcoating for solid oxide fuel cell interconnects”, Ceram.
Int., 42, pp. 6648–6656, 2016.

285
Sodium and potassium based geopolymers as heterogeneous catalysts in
the production of biodiesel
Botti, R.F.1*, Innocentini, M.D.M.2, Pastore, P.3, San Gregorio, L.R.2, Colombo, P.1
1
Department of Industrial Engineering, University of Padova, Via Marzolo 9, 35131, Padova, Italy;
*
e-mail: [email protected]
2
Course of Chemical Engineering, University of Ribeirão Preto, Rua Costabile Romano 2201,
Ribeirão Preto-SP, Brazil
3
Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131, Padova, Italy
Keywords: biodiesel, geopolymer, heterogeneous catalyst

Many environment problems are caused when fossil fuels are used in engines. Thanks to its
similar properties, a promising substitute for this kind of fuel is biodiesel (fatty acid alkyl
esters), that is renewable, biodegradable and not toxic. The most used process to prepare bio-
diesel is by homogeneous transesterification of vegetable oils, despite the fact that it produces
a high concentration of impurities in the product. The use of heterogeneous catalysts is quite
attractive, their main advantage being that the purification step is minimized. Transesterifi-
cation consists of a sequence of three reversible reactions, the first step is the conversion of
triglycerides to diglycerides, followed by the conversion of diglycerides to monoglycerides,
and finally monoglycerides to glycerol, yielding one ester molecule for each glyceride at each
step.1 The reactions are reversible, although the equilibrium lies towards the production of
fatty acids monoesters and glycerol.1
In this work, we investigated the biodiesel production by transesterification of soybean
oil with methanol, using geopolymers as heterogeneous catalysts. Geopolymers were pre-
pared by mixing metakaolin with an activating alkaline solution. Two types of heterogeneous
catalysts were prepared in powder form: sodium- and potassium-based geopolymers. The
influence of geopolymer heat treatment was also evaluated. The biodiesel was obtained in
the following reaction conditions: methanol:oil ratio, 7.5:1; catalyst amount 3% of oil (w/w);

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reaction temperature, 60 °C; reaction time, 1h. The reaction yield was calculated by gas chro-
matography measurements while X-ray diffraction (XRD), thermal analysis (DTA-TGA),
and BET surface area measurements were employed to obtain more information about the
geopolymer.
The results demonstrate that both geopolymers work as catalysts, and the conversion is
higher when the potassium based geopolymer is used (~60% versus ~50%, potassium and
sodium respectively), possibly due to the higher surface area of the potassium-based geo-
polymer. Moreover, the yield of reactions seems to be dependent on the geopolymer heat
treatment. It should be noted that the biodiesel product still contains some Na or K impurities,
so a further optimization of the material and the process is required.

Reference
1. Meher LC, Sagar DV, Naik SN, “Technical aspects of biodiesel production by transesterification –
a review”, Renewable and Sustainable Energy Reviews 16, 6303–6316.

948
Synthesis, sintering, transport and thermal properties of Na2Fe2Ti6O16
freudenbergite
Cong Chen1*, Fabien Giovannelli1, Mustapha Zaghrioui1, Loïc Perriere2,
Fabian Delorme1
1
Université François Rabelais de Tours, CNRS, CEA, INSA CVL, GREMAN UMR 7347,
IUT de Blois, 15 rue de la chocolaterie, CS 2903, F-41029 Blois Cedex, France;
*
e-mail: [email protected]
2
ICMPE, 2-8 Rue Henri Dunant, 94320 Thiais, France
Keywords: freudenbergite, electrical conduction, small polaron hopping, thermal conductivity

Freudenbergite compounds have a general formula of A2B2Ti6O16, where A = Na+, and B =

Mg2+, Co2+, Ni2+, Zn2+, Al3+, Ga3+, Ti3+, Cr3+, Fe3+, etc.1 They have been widely studied as com-
ponents of synroc to immobilize radioactive waste.1–5 Among them, Na2(Al,Fe)2Ti6O16 shows
good leach resistance, reasonable radiation resistance, and could be incorporated into synroc
to immobilize nuclear waste containing a high amount of sodium. Na2Fe2Ti6O16 has also
been investigated as an ion exchanger to remove nickel from potassium solutions.6 Recently,
Na2Fe2Ti6O16 shows prospects for application as anode materials in sodium-ion batteries due
to its good cycle stability.7 The electrical and thermal transport properties of freudenbergite
have not been reported yet. Such information is required to advance its application in sodi-
um-ion batteries and other fields of research.
Na2Fe2Ti6O16 freudenbergite has been synthesized using a simple solid-state route and
conventionally sintered to reach 94% density ceramics. High temperature electrical and ther-
mal transport properties have been investigated for the first time. In the temperature range
of 468 K–1000 K, the electrical conductivity of Na2Fe2Ti6O16 can be well fitted with small
polaron hopping model. For a further verification of the model, we measured the room-tem-

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perature optical reflectivity and derived the optical conductivity (σ(ω)) with Kramers–Kronig
analysis. A mid-infrared peak in σ(ω) confirms the presence of small polarons. From 468 K
to 1000 K, Na2Fe2Ti6O16 is an n-type oxide and exhibits a temperature-independent Seebeck
coefficient (~ –590 μV.K–1), in agreement with the small polaron hopping mechanism. The
thermal conductivity decreases with increasing temperature from 16.5 W.m–1.K–1 (373 K) to
3.4 W.m–1.K–1 (1000 K). Na2Fe2Ti6O16 shows a maximum figure of merit (ZT) ~ 3 × 10–4 at
1000 K.

References
1. E.R. Vance, P.J. Angel, D.J. Cassidy, M.W.A. Stewart, M.G. Blackford, P.A. McGlinn, Freudenber-
gite: A possible synroc phase for sodium-bearing high-level waste Journal of the American Ceramic
Society 77(6) (1994) 1576–1580.
2. A.E. Ringwood, S.E. Kesson, N.G. Ware, W. Hibberson, A. Major, Immobilization of high-level
nuclear-reactor wastes in SYNROC, Nature 278(5701) (1979) 219–223.
3. S.G. Luo, L.Y. Li, B.L. Tang, D. Wang, Synroc immobilization of high level waste (HLW) bearing
a high content of sodium, Waste Management 18(1) (1998) 55–59.
4. L.Y. Li, S.G. Luo, D.X. Wang, Immobilization of sodium-bearing high-level radioactive waste
in synroc containing Na2Al2Ti6O16-type freudenbergite, Journal of the American Ceramic Society
81(7) (1998) 1938–1940.
5. K.L. Smith, M.G. Blackford, G.R. Lumpkin, N.J. Zaluzec, Ion beam-induced amorphisation of
freudenbergite, Journal of Nuclear Materials 277(2-3) (2000) 159–168.
6. M.N. Akieh, M. Lahtinen, A. Vaisanen, M. Sillanpaa, Preparation and characterization of sodium
iron titanate ion exchanger and its application in heavy metal removal from waste waters, Journal
of Hazardous Materials 152(2) (2008) 640–647.
7. J.K. Hou, Y.B. Niu, F.L. Yi, S.G. Liu, Y.T. Li, H. He, M.W. Xu, NaTi3FeO8: a novel anode material
for sodium-ion batteries, Rsc Advances 5(55) (2015) 44313–44316.

459
The effect of ceramic particles coated on the polyethylene separator
for improving the electrochemical performance and thermal stability
of lithium ion batteries
Kwon-Koo Cho*, Hoi-Jin Lee, Ji-Seub Choi, Young-Jae Shim
Department of Materials Engineering and Convergence Technology & RIGET,
Gyeongsang National University, 501 Jinju-daero Jinju-si, Korea; *e-mail: [email protected]
Keywords: ceramic-coated separator, lithium ion batteries, electrochemical performance, thermal
stability

Ceramic-coated separators are prepared by dip coating process for improving the electro-
chemical performance and thermal stability of lithium ion batteries. We coated ceramic par-
ticles (Al2O3 or Li2O-SiO2-TiO2-P2O5) slurry on polyethylene separator through dip coat-
ing process after prepared slurry with a poly (vinylidene fluoride-co-hexafluoropropylene)
(PVdF-12wt%HFP) copolymer. We investigated the physical properties of separators as a
function of coating thickness, such as thickness, weight, air permeability, electrolyte uptake,

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porosity, thermal shrinkage and morphology. Also, its electrochemical properties are per-
formed at 25 oC using a half coin cell with LiCoO2 as cathode, Li metal as anode and LiPF6
in EC/DEC as electrolyte. Compared to a pristine polyethylene, thermal stability of the all
ceramic-coated separators is improved. The cells are proven to have better capacity retention
than for cells prepared with pristine polyethylene. In particular, the separator prepared with
Li2O-SiO2-TiO2-P2O5 slurry showed the best result in capacity retention. From this study,
we supposed that the separator prepared with Li2O-SiO2-TiO2-P2O5 slurry can be potential
candidate as a separator for rechargeable lithium-ion batteries that require thermal safety and
good capacity retention.

References
1. J.A. Choi, S.H. Kim and D.W. Kim, “Enhancement of thermal stability and cycling performance in
lithium-ion cells through the use of ceramic-coated separators”, J. Power Sources, 195, pp. 6192–
6196, 2010.
2. C. Shi, P. Zhang, L. Chen, P. Yang and J. Zhao, “Effect of a thin ceramic-coating layer on ther-
mal and electrochemical properties of polyethylene separator for lithium-ion batteries”, J. Power
Sources, 270, pp. 547–553, 2014.

405
RuO2 nanoparticle passivated ZnO@MnO2 core-shell nanorod arrays
for supercapacitor application
Nilesh R. Chodankar, Do-Heyoung Kim*
School of Chemical Engineering, Chonnam National University, Gwangju 500-757, South Korea;
*
e-mail: [email protected]
Keywords: ZnO nanorods, MnO2, core/shell hybrid architecture, supercapacitors, energy storage

The nanostructured hybrids electrodes with different featured materials are promising for im-
proving the energy storing capacity of the supercapacitors. Hitherto, it is challenging for the
researcher to develop the high-performance nanohybrid electrode materials with controllable
size, composition and morphology. Here, we have prepared the ternary core–shell composed
ZnO@MnO2@RuO2 nanorod arrays on the flexible stainless steel mesh (SSM) through the
layer-by-layer process. In the first step, the ZnO nanorods are prepared on the SSM by low
temperature hydrothermal process. Later, the ZnO nanorods are decorated with the MnO2 and
RuO2 by electrodeposition and dip and dry process, respectively. The passivation of highly
conducting RuO2 nanoparticles on the surface of binary ZnO@MnO2 is allow the easy and
fast charge transfer process to further improve the electrochemical performance of the super-
capacitor. Due to enhanced electron transfer process, the charge transfer resistances of the
ZnO@MnO2@RuO2 nanorod arrays are drastically reduced. The electrochemical test for the
ZnO@MnO2@RuO2 nanorod arrays are performed in the Na2SO4 electrolyte, which gives the
ultrahigh specific capacitance (more than 1000 F/g at 5 mV/s) with excellent a capacitance
retention of 94% after 20000 CV cycles at 100 mV/s scan rate, indicating the excellent elec-
trochemical features of the ZnO@MnO2@RuO2 nanorod arrays.

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540
Creep properties of fully dense BaZr1-XYXO3-X/2 electrolyte materials
for PCFCs
Desirée Ciria1,2, Manuel Jimenez-Melendo2, Anastasia Iakovleva1, Eric Rivière3,
Véronique Aubin4, Guilhem Dezanneau1
1
Laboratoire SPMS, CentraleSupélec, CNRS, Université Paris-Saclay, 92290 Chatenay-Malabry,
France
2
Departamento de Física de la Materia Condensada and Instituto de Ciencia de Materiales, CSIC-
Universidad de Sevilla, 41080 Sevilla, Spain
3
Laboratoire de Chimie Inorganique, Université Paris-Sud, 91405 Orsay, France
4
Laboratoire MSSMAT, CentraleSupélec, CNRS, Université Paris-Saclay, 92290 Châtenay-Malabry,
France
Keywords: creep, mechanical properties, Yttrium-doped Barium Zirconate, electrolyte, PCFCs

Yttrium-doped Barium Zirconate is considered an attractive alternative to Yttria-Stabilised

Zirconia electrolyte material in Solid Oxide Fuel Cells. While numerous studies have dealt
with the preparation of dense ceramics and with the study of influence of composition on
proton conduction properties, very little is known at present about the mechanical properties
of Yttrium-doped Barium Zirconate compounds. We have thus started an exhaustive study of
the mechanical properties of high density (> 95%) sintered BaZr1-xYxO3-x/2 compounds.
Polycrystals of Yttrium doped Barium Zirconate made through conventional sintering
were prepared from nanopowders synthesized through a combustion route. The samples were
then characterized mechanically at high temperature1–3.
Compressive creep tests have been performed at constant speed and load at temperatures
ranging from 1100 to 1300 °C. The objective was determine the effective diffusion coeffi-
cient and identify the atomic mechanisms of plastic deformation and the origin of failure of
these materials at high temperature. A gradual brittle–ductile transition was observed with
increasing temperature and/or decreasing strain rate. Grain boundary sliding is the main de-
formation mechanism in the ductile region. The experimental results have been correlated
with microstructural observations by scanning and transmission electron microscopy.

References
1. Y. Li, V. Aubin, C. Rey et al. , Inter. J. Fatigue, 42, 71–81, 2012.
2. M. Oliva-Ramirez, F. Huaman-Mamani, M. Jimenez-Melendo, Fuel Processing Technology,103,
45–50, 2012.
3. M. Jimenez-Melendo, C. Vaquero-Aguilar, F. Huaman-Mamani, Fuel Processing Technology, 103,
146–150, 2012.

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877
Three phase composite PZT/Al/PU for energy storage application
Christian Courtois1, Mohamed Rguiti1, Sarah Aboubakr2, Abdelowahed Hajjaji2,
Khalil Benkhouja3
1
LMCPA, University of Valenciennes and Hainaut Cambrésis, France
2
Laboratory of Science of Engineering for Energy, National School of Applied Sciences, El Jaddida,
Morocco
3
Multidisciplinary Faculty, Chouaib Doukkali University, El Jaddida, Morocco
Keywords: dielectric, composite, energy, storage, density, efficiency

Piezoelectric composites are widely studied due to their good performances. Several kinds of
these composites have been developed for sensing and actuation applications, however, most
of them are not used for energy storage devices, because of their low dielectric properties. In
this research work, a three-phase composite was developed. This latter was obtained by add-
ing a small amount, up to 3%, of Aluminum (AL) to the PZT/PU composite. The Dielectric
constant was found to be clearly increased with the increasing volume fraction of Aluminum.
A comparison of piezo- and ferroelectric activities between aluminum doped and undoped
composites reveal a high improvement of the energy storage density, which reaches 11J/cm2.
This novel three-phase composite can be used for multifunctional embedded capacitors ap-
plications.

949
Nanostructuring of dense SnO2 ceramics by SPS
Fabian Delorme1*, Raphael Dujardin1, Frederic Schoenstein2, Bruno Pintault3,
Philippe Belleville3, Cecile Autret1, Isabelle Monot-Laffez1, Fabien Giovannelli1
1
Université François Rabelais de Tours, CNRS, INSA CVL, GREMAN UMR 7347, IUT de Blois,
15 rue de la chocolaterie, 41029 Blois Cedex, France; *e-mail: [email protected]
2
Université Paris 13, Sorbonne Paris Cite, Laboratoire des Sciences des Procédés et des Matériaux,
CNRS, UPR 3407, 99 avenue Jean Baptiste Clément, F-93430 Villetaneuse, France
3
CEA-DAM Le Ripault, 37260 Monts, France
Keywords: tin oxide, spark plasma sintering, nanostructuring

SnO2-based materials are widely used for catalytic and gas-sensing applications, as well as
electrodes.1,2 Most of these applications could benefit from nanometer-sized crystalline par-
ticles. Therefore, a new high yield (>90%) synthesis route at low temperature in aqueous
solution has been developed. The average particle size is 4–6 nm according to TEM images
and specific surface area determined by the BET method is 160 m2.g–1.
Sintering fully dense SnO2 ceramics bodies is also complicated due to the vaporization of
tin monoxide which should occur at a high rate above 1100 °C.3 Therefore, different strate-
gies such as addition of sintering agents or hot pressing have been developed.4,5 However,

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these techniques still require high temperatures and therefore, do not appear suitable for
dense nanostructured ceramics. Spark Plasma Sintering (SPS) is now a well known technique
to sinter dense ceramic bodies of oxide materials at low temperature: for instance, dense
Al-doped ZnO nanostructured ceramics have been sintered at only 500 °C.6 Therefore, the
sintering of dense SnO2 nanostructured ceramics by SPS has been studied and the key param-
eters have been determined. Densities higher than 95% have been reached with an average
grain size of circa 60 nm.

References
1. E. Comini, (2006) Metal oxide nano-crystals for gas sensing, Anal. Chim. Acta. 568 28–40.
2. T. Brousse, R. Retoux, U. Herterich, D.M. Schleich, (1998) Thin-Film Crystalline SnO2-Lithium
Electrodes, J. Electrochem. Soc. 145 1–4.
3. N. Dolet, J-M. Heintz, M. Onillon, J-P. Bonnet (1992) Densification of 0.99 SnO2-0.01 CuO mix-
ture: Evidence for liquid phase sintering. Journal of the European Ceramic Society 9, 19–25.
4. S. Zuca, M. Terzi, M. Zaharescu, K. Matisovsky (1991) Contribution to the study of SnO2-based
ceramics. Part II Effect of various oxide additives on the sintering capacity and electrical conductiv-
ity of SnO2. Journal of Materials Science 26, 1673–1676.
5. J. Park, K. Hirota, H. Yamamura, (1984) Densitication of nonadditive SnO2 by hot isostatic press-
ing, Ceramics International. 10, 116.
6. P. Diaz-Chao, F. Giovannelli, O. Lebedev, D. Chateigner, L. Lutterotti, F. Delorme, E. Guilmeau
(2014) Textured SPS Al-doped-ZnO ceramics with isotropic grains. Journal of the European
­Ceramic Society 34, 4247–4256.

907
Synthesis & characterization of Li7La3Zr2O12 solid electrolytes for all
solid-state li-ion batteries
Kamil Burak Dermenci, Servet Turan*
Department of Materials Science and Engineering, Anadolu University, Faculty of Engineering,
Iki Eylul Campus, 26555 Eskisehir, Turkey; *e-mail: [email protected]
Keywords: all solid-state Li-ion batteries, Garnet type electrolytes, Li7La3Zr2O12, EIS

All solid-state Li-ion batteries are attracted much attention for high energy density requiring
applications such as electrical vehicles since their enhanced safety compared to conventional
batteries that include liquid based organic electrolytes. Extensively studied solid electrolytes
in all solid-state Li-ion batteries are LISICON, Perovskite, LIPON and Garnet type of elec-
trolytes. Among them, Garnet type Li-ion conductors are considered as an alternative candi-
date for replacing organic liquid electrolytes1,2.
Cubic phase Li7La3Zr2O12 (LLZO) is relatively new composition3. However, low tempera-
ture stable form of LLZO is tetragonal and several attempts have been done to stabilize cubic
phase at room temperature. These are either increasing sintering temperature over 1200 °C
or adding stabilizers such as W, Ta, Ba, Y and Al4. Recently, it has been found that lowering
the cubic phase stabilization temperature below 1000 °C by using solution based synthesis
techniques is possible. But, there is a lack of systematic investigations of different precursors
on the cubic phase stabilization during LLZO synthesis. Since the crystal structure of LLZO
479 ECerS2017 / July 9–13, 2017 / Budapest, Hungary
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is similar with ZrO2, the bonding ability of Zr sources will be more important than the other
elements in the structure.
In this work, varying amounts of Al (0–40% mole) incorporated LLZO was synthesized
by using nitrate precursors of Li, La, Zr and Al. In order to investigate the effect of different
Zr precursors, oxychloride precursor was also used. The radial shrinkage was measured ac-
cording to the pellet diameter size before and after sintering. Crystal structures of calcined
powders were measured by XRD. True density and ionic conductivities of powder-bed sin-
tered pellets using cubic phase stabilized powders was measured by Archimedes Method and
AC Impedance Spectroscopy respectively. Cubic phase stabilization, types and changes of
impurity phases with different Al amounts will be discussed in terms of different Zr precur-
sors.

References
1. V. Thangadurai, S. Narayanan, and D. Pinzaru, “Garnet-type solid-state fast Li ion conductors for
Li batteries: critical review,” Chem Soc Rev, 43[13] pp. 4714–4727, 2014.
2. K. Senevirathne, C.S. Day, M.D. Gross, A. Lachgar, and N.A.W. Holzwarth, “A new crystalline
LiPON electrolyte: Synthesis, properties, and electronic structure,” Solid State Ionics, 233[0] pp.
95–101, 2013.
3. R. Murugan, V. Thangadurai, and W. Weppner, “Fast lithium ion conduction in garnet-type
Li7La3Zr2O12,” Angew Chem Int Edit, 46[41] pp. 7778–7781, 2007.
4. K.B. Dermenci, E. Cekic, and S. Turan, “Al stabilized Li7La3Zr2O12 solid electrolytes for all-solid
state Li-ion batteries,” Int J Hydrogen Energ, 41[23] pp. 9860–9867, 2016.

917
Study of optical and morphological properties of vanadium dioxide
nanofibers and thin films prepared by electrospinning and wet chemical
coating techniques
Musa Erol1, Zsolt Fogarassy3, Csaba Balázsi3, Katalin Balázsi3, Esra O. Zayim1,2*
1
Nanoscience & Nanotechnology Program, Istanbul Technical University, Maslak, Istanbul, Turkey;
*
e-mail: [email protected]
2
Istanbul Technical University, Faculty of Science and Letters, Physics Department, Istanbul, Turkey
3
Institute for Technical Physics and Materials Science, Centre for Energy Research, Budapest,
Hungary

Vanadium oxidehave many application areas such as gas sensors, photocatalysis, solar cells
thermochromics, electrochromics, optic/electronic switching devices and energy storage de-
vices due their superior chemical and physical properties. This great interest of vanadium ox-
ides is based on two main factors; range of oxidation states of vanadium and variability of the
oxygen coordination geometries. The principal oxides of vanadium occur as single valence
in oxidation states from V2+ to V5+, in the form of VO, V2O3, VO2, and V2O5. However,
the vanadium–oxygen phase diagram also includes mixed valence oxides containing two
oxidation states, such as V6O13 with V5+ and V4+ and a series of oxides between VO2 and

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V2O3 (e.g., V8O15, V7O13, V6O11, etc.) which contain V4+ and V3+ species. In an oxide,
the mixed vacancy is formed by introducing oxygen vacancy defects.
In this study, vanadium dioxide and hydrogen peroxide solutions with and without PVP
polymer were prepared as a nanofiber, nanorod and thin film on smooth surfaces by elec-
trospinning and wet chemical coating techniques respectively. Optical and morphological
properties of the oxides were investigated by TEM, TEM-EDX, XRD, SEM and UV-Vis
methods. To the best of our knowledge, this is the first time single crystalline V6O13 and
nanorods were obtained with wet chemical coating on glass and ITO-coated glass substrates.
Detail electrochemical measurement were examined of all samples on various substrates.
Composition and nanostructure of the samples affect the crystallinity, stochiometry and elec-
trochemical properties dramatically. It is worth to mention that these novel samples are good
candidates for electrode of battery, supercapacitors and sensor applications.

726
Nanocrystalline TiNb2O7: a new photocatalytic material
Gilberto S. Falk1, Mario Borlaf1, Maria J. López-Muñoz2, João B. Rodrigues Neto1,
Rodrigo Moreno3
1
Department of Mechanical Engineering, Federal University of Santa Catarina, 88040-900,
Florianópolis, SC, Brazil;
e-mails: [email protected], [email protected], [email protected]
2
Department of Chemical and Environmental Technology, Rey Juan Carlos University, 28933
Móstoles, Madrid, Spain; e-mail: [email protected]
3
Institute of Ceramics and Glass, CSIC, 28049 Madrid, Spain; e-mail: [email protected]
Keywords: TiNb2O7, sol-gel, photocatalysis, nanoparticles, TiO2, Nb2O5

A detailed study of a novel synthesis via colloidal sol–gel route for obtaining nanoparticulate
TiO2:Nb2O5 sols was performed. The H+:(Nb5+:Ti4+) molar ratio was controlled in order to
determine the best conditions of synthesis. Moreover, the combination of the data measured
with optical techniques such as laser diffraction, dynamic light scattering and multiple light
scattering with a near-infrared light allowed to follow up the evolution of the peptization pro-
cess. The obtained results indicate that the colloidal sol–gel synthesis is a good procedure for
obtaining TiO2:Nb2O5 either as stable nanoparticulate sol or as a nanosized powder. Amor-
phous nanoparticles with an average size of 10 nm were obtained by controlling the synthesis
variables. After calcination of the xerogels at temperatures between 500 ºC and 800 ºC, dif-
ferent crystalline phases were obtained, among them TiNb2O7 as the major one. Crystalline
phase composition was found to have a significant influence on the photocatalytic activity.
The best photocatalytic performance was observed for the material mainly constituted by the
monoclinic-TiNb2O7 phase.

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References
1. G. Falk, M. Borlaf, T. Bendo, A.P. Novaes de Oliveira, J.B. Rodrigues Neto, R. Moreno, Colloidal
Sol-Gel Synthesis and Photocatalytic Activity of Nanoparticulate Nb 2 O 5 Sols, J. Am. Ceram.
Soc. 99 (2016) 1968–1973.
2. M. Borlaf, R. Moreno, A.L. Ortiz, M.T. Colomer, Synthesis and photocatalytic activity of Eu 3 þ
-doped nanoparticulate TiO 2 sols and thermal stability of the resulting xerogels, Mater. Chem.
Phys. 144 (2014) 8–16.
3. M.T. Colomer, J. Guzmán, R. Moreno, Determination of peptization time of particulate sols using
optical techniques: Titania as a case study, Chem. Mater. 20 (2008) 4161–4165.
4. M. Borlaf, M.T. Colomer, F. Cabello, R. Serna, R. Moreno, Electrophoretic deposition of TiO2/
Er3+ nanoparticulate sols., J. Phys. Chem. B. 117 (2013) 1556–1562.
5. M. Borlaf, J.M. Poveda, R. Moreno, M.T. Colomer, Synthesis and characterization of TiO2/Rh3+
nanoparticulate sols, xerogels and cryogels for photocatalytic applications, J. Sol-Gel Sci. Technol.
63 (2012) 408–415.

754
Alkaline carbonates as sintering aid for Ce0.1Gd0.9O1.95
J.P.F. Grilo1*, A.P. Jamale1, A.I.B. Rondão1, R.M. Nascimento2, F.M.B. Marques1
1
Department of Materials and Ceramic Eng./CICECO, University of Aveiro, 3810-193 Aveiro,
Portugal; *e-mail: grilo.jpf @ua.pt
2
Materials Science and Eng. Postgraduate Program, UFRN, 59078-970, Natal, Brazil
Keywords: CGO, sintering aid, ionic conductivity, electronic conductivity

CGO (Gd-doped ceria) is amongst the most studied electrolyte materials for Solid Oxide Fuel
Cells (SOFC). With higher ionic conductivity when compared to zirconia-based electrolytes,
the main drawbacks of this material are the onset of electronic conductivity when exposed
to reducing conditions, and the usually demanding firing temperatures (>1400 °C) to reach
full densification. Lowering the SOFC operating temperature is the simplest solution for the
first problem. Sintering aids or chemical routes to obtain reactive powders are the best known
ways to avoid the second drawback. In this work emphasis will be in the first approach, fol-
lowing previous activity in this direction.1,2
Pellets of Ce0.9Gd0.1O1.95 (CGO) were fabricated via liquid phase assisted sintering at 900–
1100 °C by adding different contents of (Li0.52Na0.48)2CO3 (NLC) as sintering aid. The effects
of this sintering aid on the structure and microstructure were investigated by X-ray diffrac-
tion (XRD) and scanning electron microscopy (SEM), respectively. Complementary imped-
ance spectroscopy measurements performed between 200 and 750 °C included simple tests in
air or as a function of the oxygen partial pressure (pO2) down to about 10–20 atm.
XRD analysis of as-prepared powders indicates that the carbonates do not incorporate into
the cubic structure of CGO. Densification results showed that with small additions of NLC
the densification could reach 93–96% at 1000 and 1100 °C. Electron microscopy revealed
a dense well defined microstructure. A slight improvement of electrical properties was also
seen with respect to conventional CGO pellets fired at 1500 °C. A small increase in conduc-

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tivity under low pO2 also suggests that the sintering aid might partly block the electronic
conductivity of CGO. These results indicate the potential of this route to produce a competi-
tive electrolyte for low temperature.

Acknowledgements
Projects NewINDIGO /0001/2013 and CICECO - Aveiro Institute of Materials (Ref. FCT UID/
CTM/50011/2013) financed by national funds through FCT/MEC and when applicable co-financed by
FEDER under the PT2020 Partnership Agreement. This work was also developed with funding from
CNPq (Program Ciências sem Fronteira, Brazil).

References
1. J. Nicholas and L. De Jonghe, “Prediction and evaluation of sintering aids for Cerium Gadolinium
Oxide”, Solid State Ionics, 178, pp. 1187–1194, 2007.
2. A. Maheshwari and H.-D Wiemhofer, “Augmentation of grain boundary conductivity in Ca+ doped
ceria-carbonate-composite”, Acta Materialia, 103, pp. 361–369, 2016.

260
Broad band plasmonic nanomaterials included ZnO film for high
performance polymer photovoltaics
Fang-Chi Hsu
Department of Materials Science and Engineering, National United University, 2 Lienda, Miaoli,
Taiwan 360; e-mail: [email protected]
Keywords: ZnO, polymer solar cell, photovoltaic, surface plasmon, nanomaterials, composite

Metal oxides including ZnO have been commonly used as electron transport materials (ETMs)
for the fabrication of polymer photovoltaicls for their high electrical conductivity and carrier
mobility.1–3 Recently, researchers have tried to improve the light absorption capability of pho-
tovoltaics by introducing metallic nanomaterials into either electron or hole transport layer to
further raise up the power conversion efficiency (PCE) of photovoltaic devices. In this paper,
we report the use of broad band plasmonic nanomaterials to improve the electrical conductiv-
ity and carrier mobility of ZnO film as well as the light absorption efficiency of the polymer
photovoltaics. We adopt gold nanorod-in-shell (Au NR-in-shell) nanomaterials to be embed-
ded in ZnO film to serve as a new ETM in the fabrication of polythieno[3,4-b]-thiophene/
benzodithiophene:[6,6]-phenyl C71 butyric acid methyl ester (PTB7:PC71BM) photovoltaics.
In the presence of Au NR-in-shell nanomaterials, there are large improvements in the short
circuit current density (Jsc) and fill factor (FF) of devices. The enhanced Jsc and FF are at-
tributed to the combination of the enhancement in light-trapping, series resistance, carrier
lifetime, and device mobility, leading to a realization of a PCE of 9.01% from 7.94%. Our
approach shown here can pave a key step for the further development of high performance
optoelectronic devices.

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References
1. M.S. White, D.C. Olson, S.E. Shaheen, N. Kopidakis, and D.S. Ginley, “Inverted bulk-heterojunc-
tion organic photovoltaic device using a solution-derived ZnO underlayer”, Appl. Phys. Lett., 89,
pp. 143517-1–143517-3, 2006.
2. J.Y. Kim, S.H. Kim, H.H. Lee, K. Lee, W.L. Ma, X. Gong, A.J. Heeger, “New architecture for high-
efficiency polymer photovoltaic cells using solution-basedtitanium oxide as an optical spacer”,
Adv. Mater., 18, pp. 572–576, 2006.
3. A.K.K. Kyaw, X.W. Sun, C.Y. Jiang, G.Q. Lo, D.W. Zhao, D.L. Kwong, “An inverted organic solar
cell employing a sol-gel derived ZnO electron selective layer and thermal evaporated MoO3 hole
selective layer”, Appl. Phys. Lett., 93, pp. 221107-1–221107-3, 2009.

119
Material characteristics and electrochemical performance
of the Bi0.85-xCa0.15ZrxO1.5-δ electrolyte for solid oxide fuel cell
I-Ming Hung1*, Yu-Ting Chiou1, Yuan-Ting Huang1, Tai-Nan Lin2
Department of Chemical Engineering and Materials Science, Yuan Ze University, No. 135,
1

Yuan-Tung Rd., Chungli, Taoyuan 320, Taiwan; *e-mail: [email protected]

Chemical Engineering Division, Institute of Nuclear Energy Research, Atomic Energy Council,
2

Taiwan
Keywords: solid oxide fuel cell, electrolyte, bismuth oxide, solid state reaction, defect

Bismuth oxide-based materials exhibit high oxide-ion conductivity due to their high con-
centration of oxide vacancies and have been proposed as potential electrolyte materials for
SOFC and oxide sensors. In this study, Bi0.85-xCa0.15ZrxO1.5-δ (0.12 ≤ x ≤ 0.24) oxygen ion
conductors were synthesized by the solid-state reaction method. The phase, microstructure
and electrochemical performance of samples were detected by XRD, SEM, TEM and AC
impedance. Small amount of the CaZrO3 and Ca0.15Zr0.85O0.85 second phases were observed
on the grain boundary of the cubic fluorite structure Bi0.85-xCa0.15ZrxO1.5-δ matrix. The lattice
parameter a of the Bi0.85-xCa0.15ZrxO1.5-δ is in the range of 5.512~5.525 Å. Since the
ionic radius of Ca2+ (0.99 Å) and Zr4+(0.79 Å) is smaller than the ionic radius of Bi3+
(0.96 Å), therefore, the addition of CaO and ZrO2 tends to reduce the lattice parameters.
However, the lattice parameter a and unit volume of Bi0.85-xCa0.15ZrxO1.5-δ δ as x≥0.21 are ap-
parently higher than that of Bi0.85-xCa0.15ZrxO1.5-δ δ as x≤0.18. It is found that the diffraction
peaks belong to Ca0.15Zr0.85O1.85 second phase is apparently observed as x≥0.21. Therefore,
it is suggested that the doping amount of Ca2+ and Zr4+ in Bi0.85-xCa0.15ZrxO1.5-δ structure
decreased due to the formation of second phases of CaZrO3 and Ca0.15Zr0.85O1.85. The conduc-
tivity of all Bi0.85-xCa0.15ZrxO1.5-δ samples increases as the temperature increases. The
Bi0.70Ca0.15Zr0.15O1.5-δ sample has the highest conductivity of 0.05 S/cm at 750 °C. The
typical impedance spectra of Bi0.85-xCa0.15ZrxO1.5-δ samples show that the main resistance come
from the charge transfer polarization at low temperatures and the grain boundary resistance
dominated as temperature increased above 600 °C due to the second phases of CaZrO3 and
Ca0.15Zr0.85O1.85 appeared on the grain boundary. The result of Temperature-Programmed Re-
duction curves of the Bi0.85-xCa0.15ZrxO1.5-δ samples in 5% H2- 95% Ar atmosphere show that

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all Bi0.85-xCa0.15ZrxO1.5-δ reduced in the temperature range of 300–380 °C. It is still a challenge
for Bi0.85-xCa0.15ZrxO1.5-δ to be applied as the electrolyte of SOFC due to reduction problem
in low partial oxide pressure atmosphere. A high protection layer is needed if Bi2O3-based
materials used as the electrolyte of SOFC.

648
Synthesis and characterization of composite cathodes with mixed
conductivity for protonic ceramic fuel cells
Tufy Kabbas Junior1, Edson Cezar Grzebielucka1, Adriana Scoton Antonio Chinelatto1,
Glenn C. Mather2, Adilson Luiz Chinelatto1,3*
1
Departamento de Engenharia de Materiais, Universidade Estadual de Ponta Grossa, Av. Carlos
Cavalcanti 4748, 84030-900 - Ponta Grossa – Brazil - 84030-900;
*
e-mail: [email protected]
2
Instituto de Cerámica y Vidrio, CSIC, 28049 Madrid, Spain
Keywords: Solid Oxide Fuel Cells, mixed conductivity, composite

Research into clean-energy sources has grown in recent decades. Fuel cells are of particular
interest due to their high efficiency and low pollution when compared to technologies based
on fossil fuels.1 Protonic ceramic fuel cells (PCFCs) based on BaCeO3 are recognized as the
most promising for operation at intermediate temperatures (450–650 °C). Partial substitu-
tion of cerium with zirconium is one of the best ways to optimize transport and mechanical
properties, as well as improve stability in CO2 H2O, H2S and SOx-containing atmospheres.2
Composite cathodes with mixed conductivity have shown an improved performance in PCF-
Cs.3 In this work, a composite formed by BaZr0.7Ce0.2Y0.1O3-δ (BZCY72) and LaNi0.5Cr0.5O3
(LNC) was investigated. BZCY72 and LNC powders were obtained by the Pechini method
and mixed mechanically in the weight ratios of 25/75 and 50/50 BZCY72/LNC. The compo-
sitions were pressed and sintered at 1400 °C. The sintered composites were characterized by
X-ray diffraction (XRD), scanning electron microscopy/energy dispersive X-ray spectrosco-
py (SEM / EDS) and impedance spectroscopy. XRD results showed that the 25/75 and 50/50
composites presented BZCY72 and LNC phases, and a small amount of a third phase, result-
ing from the decomposition of BZCY72. The EDS mapping of the two studied compositions
showed percolation of the BZCY72 phase for two compositions studied. The conductivity
measurements in several dry gases and atmospheres humidified with H2O and D2O showed
the presence of electronic and protonic conductivity for these composites.

References
1. S. Singhal, “Solid oxide fuel cells for stationary, mobile, and military applications,” Solid State
Ionics, vol. 152–153, pp. 405–410, 2002.
2. D. Medvedev, A. Murashkina, E. Pikalova, A. Demin, A. Podias, and P. Tsiakaras, “BaCeO3: Mate-
rials development, properties and application,” Prog. Mater. Sci., vol. 60, pp. 72–129, 2014.
3. E. Fabbri, L. Bi, D. Pergolesi, and E. Traversa, “High-performance composite cathodes with tai-
lored mixed conductivity for intermediate temperature solid oxide fuel cells using proton conduct-
ing electrolytes,” Energy Environ. Sci., vol. 4, no. 12, pp. 4984, 2011.

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932
Production and characterization of waste glass based lightweight
aggregates with colemanite
Taner Kavas1,2, Utku Tiriç2, A. Doğan Soyal2
1
AKU, Faculty of Eng., Department of Material Sci. and Eng. Afyonkarahisar, Turkey
2
AKG, Gazbeton Enterprises of Ind. and Trade Inc., Department of R&D, İzmir, Turkey
Keywords: aggregates, colemanite, lightweight pellets, fluxing agent

The growing market in the building-block industry lead to an increasing demand for light-
weight aggregates. Producing lightweight aggregates reduces the bulk density and make
easier to work and transport the related products. Also, these products improve technical
specifications (e.g. good thermal and acoustic insulation, lightness of concrete).1,2 On the
other hand, lightweight aggregates are defined as materials lighter than water and distinctly
more porous than sand, gravel and ground rock, which are commonly referred to as dense
aggregates.3 In addition to that, another valuable point of producing lightweight aggregates
reduce the consuming of natural mines. In this study, the possible usability of waste glass for
the production of lightweight aggregate has been studied. To develop new receipt of light-
weight aggregate from waste glass (WG) and Colemanite (C) was added to new formulation
to form highly porous micro-structure and to achieve expending capability of aggregates
at the 750–850 oC temperature. For these purpose, different mixture and various sintering
temperature was investigated in laboratory scale. The characterization analyses of micro-
structure by electron microscope (SEM), density and mineral phase analysis (XRD) revealed
that both a glassy phase matrix on the surface and interconnected/isolated closed micropo-
rous inside the aggregates were occurred with the addition in different amount of Colemanite
which is known as a flux agent.4

References
1. T. Kavas, A. Christogerou, Y. Pontikes, T. Tunç, G.N. Angelopoulos, Production of lightweight
aggregates from different types of boron wastes, Afyon Kocatepe Univ. J. Sci. special issue, pp.
245–250, 2009.
2. T. Kavas, A. Christogerou, Y. Pontikes, G.N. Angelopoulos, Valorisation of different types of bo-
ron-containing wastes for the production of lightweight aggregates, Journal of Hazardous Materi-
als, Volume 185, Issues 2–3, 30 January 2011, Pages 1381–1389.
3. Klinefelter, T.A., Aggregates - lightweight aggregates. In: Lefond, S.J. (Ed.), Industrial Minerals
and Rocks, AIME, pp. 487–495, 1983.
4. Taner Kavas, Use of boron waste as a fluxing agent in production of red mud brick, Building and
Environment, Volume 41, Issue 12, December 2006, Pages 1779–1783.

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927
Valorisation of fired ceramic wastes as a replacement materials
in production of AAC
Taner Kavas1,2*, Aslı Tayçu2, Doğan Soyal2
1
Department of Material Science, Afyon Kocatepe University, Afyonkarahisar, Turkey;
*
e-mail: [email protected]
2
AKG Gazbeton Enterprises of Ind. and Trade Inc., Department of R&D, İzmir, Turkey

Autoclaved aerated concrete (AAC) is a highly porous and well-known walling materials
with its good fire resistance, low density, low shrinkage and low thermal conductivity when
compare with the other building materials. It usually produces by using lime, silica sand,
ordinary Portland cement, gypsum and Al metal powder (first to form hydrogen gas and after
pores inside). On the other hand, some wastes or natural raw materials like pozzolanas can
also be uses as a raw or replacement materials. This paper is focused on to study the suit-
ability of fully replacing fired ceramic sanitary ware wastes (CSW) replaced to silica sand
in standard receipt. CSW were taken from Ege Ceramic Company which was located in
Manisa/Turkey. The products produced both standard (S) and with CSW receipts were char-
acterized by thermally, mechanically and density. The result shows that CSW can easily be
used in place of silica sand in production of AAC because of similar technical properties was
observed (Table 1). In addition to that using CSW decreases both thermal conductivity and
density of the samples but compressive strength of the samples are nearly same.

Table 1. Thermal, density, compressive and A factor values of standard (G2/035) and with CSW replacing
sample of AAC

Properties S (G2/035) With CSW

Thermal conductivity (W/mK) 0.088 0.082
Density (Kg/m3) 377 373
Comprehensive strength (N/mm2) 2.15 2.09
A factor 945 939

Acknowledgments
The authors wish to express to Mr. Recep Uysal for his kind contribution.

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699
Room-temperature sodium/sulfur battery using β″ alumina
solid electrolyte
Icpyo Kim1, Ying Liu2, Hyo-Jun Ahn1, Jou-Hyeon Ahn1,2*
Department of Materials Engineering and Convergence Technology, Gyeongsang National
1

University, 501 Jinju-daero, Jinju 52828, Republic of Korea; *e-mail: [email protected]

Department of Chemical Engineering, Gyeongsang National University, 501 Jinju-daero,
2

Jinju 52828, Republic of Korea

Keywords: β″ alumina, solid electrolyte, room temperature, sodium/sulphur battery

Use of conventional energy resources such as fossil fuels has caused global environmental
pollution. To reduce this, intensive efforts have been dedicated to the development of clean
energy technologies, including solar, wind, and others. However, due to their dependence
on specific natural environments, the combination of these technologies with large-scale en-
ergy storage systems is in high demand. One of the most desired energy storage systems is
a large-scale secondary battery storage system whose secondary battery has a low cost and
high energy density. The Na/S battery is a typical secondary battery whose characteristics
are in good accordance with these requirements.1 Sodium and sulfur are highly attractive
electrode materials, with many advantages such as abundance in nature, high capacities, and
low cost. A high temperature Na/S battery has a high theoretical energy density of 760 Wh
kg-1. These advantages have led to worldwide commercialization of high temperature Na/S
batteries. However, the high temperature Na/S battery requires an operating temperature of
over 300 °C to secure liquid states for both the cathode and anode, and so a portion of the
generated electricity is continuously consumed to heat the battery, which decreases the en-
ergy efficiency of the device. In addition, physical contact between the cathode and the anode
due to failure of the solid electrolyte can cause a fire or an explosion. In order to overcome
these drawbacks, our group has investigated room temperature Na/S batteries with solid-state
electrodes, using sodium for the anode and sulfur for the cathode.2 Room temperature Na/S
batteries are safe and have a higher theoretical energy density of 1230 Wh kg-1 based on
the final discharge product Na2S. However, these Na/S batteries have a low first discharge
capacity and poor cycling properties. In this work, a room temperature Na/S battery has been
designed to improve the cycling performance using β″ alumina solid electrolyte with a S/C
composite and liquid electrolyte. The resulting Na/S battery shows a high first discharge ca-
pacity of 855 mAh g-1 and coulombic efficiency close to 100%, as well as stable cyclability.3

References
1. J.L. Sudworth and A.R. Tilley. Sodium Sulfur Battery. Chapman & Hall, New York, 1985.
2. C.W. Park, J.H. Ahn, H.S. Ryu, K.W. Kim and H.J. Ahn, “Room-Temperature Solid-State
Sodium∕Sulfur Battery”, Electrochem. Solid-State Lett., 9, pp. A123–A125, 2006.
3. I. Kim, J.Y. Park, C.H. Kim, J.W. Park, J.P. Ahn, J.H. Ahn, K.W. Kim, H.J. Ahn, “A room tempera-
ture Na/S battery using a β″ alumina solid electrolyte separator, tetraethylene glycol dimethyl ether
electrolyte, and a S/C composite cathode”, J. Power Sources, 301, pp. 332–337, 2016.

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654
Electrical characterization of Ba5(Zr,Ti)Nb4O15 hexagonal perovskites
Luiz Fernando Kultz Unti*, Adriana Scoton Antonio Chinelatto, Edson Cezar Grzebielucka,
Adilson Luiz Chinelatto
Department of Materials Engineering, State University of Ponta Grossa, Brazil.
Carlos Cavalcanti Ave. 4748, Uvaranas, Ponta Grossa/ PR, Brazil; *e-mail: [email protected]
Keywords: proton conduction, hexagonal perovskites, Pechini method, solid oxide fuel cells

Among the common materials used to produce solid oxide fuel cell’s (SOFC’s) electrolytes
and electrodes are oxides with perovskite structures. Nowadays, there are many different
studies on this field, where developing new proton conduction materials to improve SOFC’s
performance is one of them. Present work evaluated the viability of compound Ba5Nb4O15
(BNO) as a candidate to produce SOFC’s elements. This compound presents a hexagonal
perovskite structure and recent papers point that this structure can shows some indication
of proton conduction. At present study, it was evaluated BNO synthesis through an alternate
method to solid-state reaction, based on Pechini method and using different oxides as pre-
cursors. The addition effect titanium and zirconium on structure and electric properties was
also studied. Synthesized powders were pressed and sintered at temperatures of 1400 oC and
1450 oC. Sintered samples were characterized by X ray diffraction, scanning electron micros-
copy, porosity and apparent density and by electrical conductivity measurements. BNO phase
was successful obtained in all synthesis, although non-stoichiometry phases were present on
Pechini sample after calcination at 900 oC. After sintering at 1450 oC, Rietveld refinement
pointed out these phases were no longer present. To improve densification samples, the syn-
thesized powders were milled to reduce the size of agglomerates and bulk porosity achieved
after sintering was less than 5%. Electrical conductivity measurements in humid (H2O) at-
mosphere and heavy water (D2O) atmosphere of sintered samples showed an indication of
proton conduction in this structure. Addition of titanium and zirconium dopants produced
grain refinement, but it was not efficient to improving electrical conductivity.

References
1. A.L. Chinelatto et al., “Synthesis of a 12R-type hexagonal perovskite solid solution Sr3NdNb3−
xTixO12−δ and the influence of acceptor doping on electrical properties” Dalt. Trans., 44, pp. 7643–
7653, 2015.
2. C. Tabacaru et al., ‘Protonic and electronic defects in the 12R-type hexagonal perovskite Sr3LaN-
b3O12” Solid State Ionics, 253, pp. 239–246, 2013.

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376
Advanced ceramic and their composites based on zirconia for energy
application
Soukaina Lamnini1*, Katalin Balazsi2, Csaba Balazsi2
1
Obuda University, Bécsi ut 96/B, 1034 Budapest, Hungary; *e-mail: [email protected]
Hungarian Academy of Science, Centre for Energy Research, Konkoly-Thege M. str. 29-33, 1121
2

Budapest, Hungary
Keywords: advanced ceramic, yttria stabilized zirconia, porous carbon, thermo-mechanical proper-
ties, energy application

The employment of advanced ceramic materials in energy production, distribution, storage

and conversion, plays a key role in the development of sustainable and clean energy. Thus
the elaboration and exploration of ceramic matrix composites became necessary in order to
enhance the thermo-mechanical properties of ceramic, which suggest further energy applica-
tion in fuel cells, photovoltaic, wind energy, supracapacitors, hydrogen storage material, high
temperature superconductors.1 The focus consists on determining the variation of the tough-
ness, hardness, thermal conductivity, coefficient of thermal expansion and the microstructure
for yttria stabilized zirconia and zirconia matrix based composite with porous carbon, CNTs
and graphene additives. The microstructural, chemical, and thermo-mechanical behaviours
of different zirconium dioxide (ZrO2) powders have been investigated by Scanning Electron
Microscopy (SEM), X-ray diffraction (XRD), Transmission Electron Microscopy (TEM),
Energy Dispersive Spectroscopy (EDS) and X-ray Spectroscopy (XPS). Furthermore the zir-
conum dioxide (ZrO2) based powders have been sintered with sub-micro size structure by
using Spark Plasma Sintering (SPS).

Reference
1. M. Singh. R. Asthana. K. Lin. Integration challenges in alternative and renewable energy systems.
John Willey and Sons, New York, 2016, pp. 291–331 in Engineered Ceramics – Current Status and
Future Prospects ed. by T. Ohji and M. Singh, ACERS and Wiley.

682
SnSb alloys as anode materials for Li-ion and Na-ion batteries
Hyukjae Lee*, Dae Kyung Kim
School of Materials Science and Engineering, Andong National University, Andong, South Korea;
*
e-mail: [email protected]
Keywords: Li-ion batteries, Na-ion batteries, tin, antimony, anode

In recent years, Na ion battery has drawn much attention as an alternative large scale energy
storage device due to the relative abundance of sodium to lithium in earth. Sn and Sb have
been investigated as anode materials for Li-ion and Na-ion batteries in last few years, and the

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results show that Sn based anode materials demonstrate relatively high capacity, while the
Sb based anode materials present better cycling performance. SnSb alloy anode material has
also been studied, in the hope that SnSb alloy can have high capacity from Sn and high cyclic
stability from Sb. In this study, SnSb alloys with extra Sn or Sb are prepared via simple ball
milling and their Li and Na electrochemical behaviors are systematically investigated with
different starting materials and process variables. Further, the effective way to improve the Li
and Na electrochemical performance with SnSb alloy anode is also discussed.

References
1. L. Fan, J. Zhang, Y. Zhu, X. Zhu, J. Liang, L. Wang and Y. Qian, “Comparison between SnSb–C
and Sn–C composites as anode materials for lithium-ion batteries” RCS Advances, 4, pp. 62301–
62301, 2014.
2. L. Xiao, Y. Cao, J, Xiao, W. Wang, L. Kovarik, Z. Niea and J. Liu, “High capacity, reversible al-
loying reactions in SnSb C nanocomposites for Na-ion battery applications”, Chem. Commun., 48,
3321–3323, 2012.

349
IIon-exchange property of lepidocrocite-type layered titanate
Keito Makise, Nobuhiro Kumada*, Sayaka Yanagida, Takahiro Takei
Center for Crystal Science and Technology, University of Yamanashi, 7-32 Miyamae, Kofu,
Yamanashi 400-8511, Japan; *e-mail: [email protected]
Keywords: lepidocrocite-type layered titanate, ion-exchange

Ion-exchange and intercalation are low energy and eco-friendly reaction because these reac-
tions are conducted at relatively low temperatures. Layered inorganic materials can improve
ion-exchange or catalytic properties by ion-exchange, thus, layered inorganic materials have
been expected to be promising materials in chemical industry. In this study, lepidocrocite-
type layered sodium titanate (Na0.70K0.05Ti1.75Li0.25O4, Lss-Na) was prepared and its ion-ex-
change property with various cations was investigated.
Lepidcrocite-type layered potassium titanate (K0.75Ti1.75Li0.25O4, Lss) was stirred in aque-
ous NaCl solution at room temperature for 4 days to for ion-exchange of interlayer potassium
ion. After drying at room temperature for 2 days, Lss-Na was obtained. The ion-exchange
properties of Lss-Na against metal cations was examined using metal chloride under the
same conditions. The structure of the samples were estimated using XRD and DTA-TG, and
the adsorption amount of various metal cations in the samples were determined by ICP.
Fig. 1 shows the XRD patterns of Lss, Lss-Na and ion-exchanged samples. The inter-
layer space (d) increased from 0.78 nm (Lss) to 1.14 nm (Lss-Na) by ion-exchange. This
suggests that the interlayer space of Lss-Na was hydrated. Li+, Ca2+, and Ba2+ exchanged
samples shows the decreased interlayer space comparing Lss-Na. From the ICP analysis,
the chemical formula for Lss-Na is estimated to be Na0.70K0.05Ti1.75Li0.25O4. Assuming that the

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ion-exchangeable interlayer cations is Na0.70K0.05 in Lss-Na, the uptake degree of the samples
were calculated (Table 1). Lss-Na especially uptook Ca2+ ion: the 92% interlayer cations were
exchanged by Ca2+.

Table 1. The uptake degree of ion-exchanged samples

Ion Li+ K+ Rb+ Cs+ Mg2+ Ca2+ Sr2+ Ba2+

Uptake degree 24% 27% 0% 11% 17% 92% 17% 50%

892
Anode ceramic material for sodium battery
Elisa Mercadelli1, Angela Gondolini1*, Benjamin Campech2, Nicola Sangiorgi1,
Alessandra Sanson1
1
I nstitute of Science and Technology for Ceramics, National Council of Research (ISTEC-CNR),
Via Granarolo 64, 48018, Faenza, Italy; *e-mail: [email protected]
2
Chimie ParisTech - École Nationale Supérieure de Chimie de Paris, 11 Rue Pierre et Marie Curie,
75005 Paris, France
Keywords: solid state battery, sodium battery, ceramic anode

At the present times, there is an urgent need to develop high-capacity, operationally safe,
mechanically robust, and cost-effective rechargeable battery systems to enable a widespread
deployment of all-electric vehicles, renewable energy and smart grid infrastructure of our

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future. The state-of-art rechargeable batteries use two primary types of electrolyte solutions,
aqueous and organic, to support the migration of the working ion. Batteries based on aque-
ous electrolytes are safe in operation, but have low voltage and energy capacity. In contrast,
those based on organic electrolytes exhibit 2–3 times higher voltage and energy density than
the former, but are unsafe in operation, particularly at high charging/discharging rates. The
all-solid-state Li+ and Na+ rechargeable batteries have been considered the next-generation
energy storage devices because the use of solid inorganic electrolytes and electrodes exclude
leakage, volatilization, or flammability.
This work focuses on the optimization of the synthesis parameters to obtain the very
promising anode material Na2Ti3O7 (NTO) for an all sodium solid state battery. The reaction
mechanism to produce the pure phase was carefully studied. Moreover, the possibility to
combine NTO material with an electrical conductive phase to improve the electrical perfor-
mances of the anode was evaluated.

468
Microstructure and ion conducting properties of Al-substituted
Li7La3Zr2O12 ceramics sintered at high temperature
Kousuke Noi, Yuma Matsuki, Akitoshi Hayashi*, Masahiro Tatsumisago
Department of Applied Chemistry, Osaka Prefecture University, Gakuencho 1-1, Sakai, Osaka,
599-8531, Japan; *e-mail: [email protected]
Keywords: Li+ ion conductor, garnet oxide, sintering, microstructure, AC impedance measurement

Al-substituted Li7La3Zr2O12 (Al-LLZ) ceramics show high lithium ion conductivities over
10–4 S cm–1 at room temperature and chemical stability against Li metal, and thus have at-
tracted attention as solid electrolytes for all-solid-state batteries(1). Interestingly about dense
Al-LLZ ceramics (density: >90%), wide range values of the activation energy for ionic con-
duction (Ea) from from 25 kJ mol–1 (2) to over 40 kJ mol–1 (3) have been reported. However the
determining factors of Ea have remained unclear.
In this study, two dense Al-LLZ sintered ceramics with different microstructure were pre-
pared to investigate the relationship between microstructure and conducting properties. One
ceramic was composed of the grains with a few micrometers to about 20 μm and the observed
fracture mode was dominantly intergranular. The other ceramic was composed of the smaller
grains with mainly about 1 μm and the observed fracture mode was almost completely trans-
granular. In addition, SEM observation suggested that these two ceramics did not have re-
markable grain-boundary phases like an amorphous phase.
Conductivities were determined by a conventional AC impedance measurements at the
temperature range of 25–80 oC. The former ceramic with larger grains showed the total con-
ductivity of 3.6×10–4 S cm–1 and the Ea of 32 kJ mol–1. The latter with smaller grains showed
4.4×10–4 S cm–1 and 26 kJ mol–1. In other words, the ceramic in which grain growth was
suppressed and transgranular fracture occurred exhibited the low Ea even compared to many
literatures. To investigate a contribution of grain-bulk and grain-boundary resistances for this

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highly conducting Al-LLZ, AC impedances of the ceramic with Au electrodes were mea-
sured up to the higher frequencies of 100 MHz at the low temperature of –20 oC. A specially
adjusted measurement system was utilized to accurately measure small impedances at high
frequencies. As a result, one depressed inseparable arc, which was converged to the origin
at high-frequency end, and a liner spike at lower frequencies were observed. This result in-
dicates that the present Al-LLZ ceramic do not have much larger grain-boundary resistances
compared to grain-bulk one and these resistances cannot be intrinsically separated against
well densified LLZ ceramics at temperature above –20 oC.

Acknowledgements
The authors would like to thank Daiichi Kigenso Kagaku Kogyo Co., Ltd. for the supplement of pow-
der materials. We also thank Qualtec Co., Ltd. and Industrial Research Center of Shiga Prefecture for
enormous contribution to AC impedance measurements.

References
1. R. Murugan et al., Angew. Chem. Int. Ed., 46, pp. 7778–7781, 2007.
2. E. Rangasamy et al., Solid State Ionics, 206, pp. 28–32, 2012.
3. J. Sakamoto et al., Nanotechnology, 24, pp. 424005:1–8, 2013.

051
Mechanical characterization of substituted Li7La3Zr2O12 using
nano- and microindentation
Juliane F. Nonemacher1, Chih-Long Tsai2, Sven Uhlenbruck2, Jürgen Malzbender1
Institute of Energy and Climate Research, Microstructure and Properties of Materials (IEK-2),
1

Forschungszentrum Jülich GmbH, Jülich, Germany

Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1),
2

Forschungszentrum Jülich GmbH, Jülich, Germany

Keywords: solid electrolytes, battery, mechanical properties, nano and microindentation

Conventional lithium ion batteries (LIB) are based on liquid electrolytes due to their very
high ionic conductivity; however, they suffer from serious drawbacks related to their flam-
mability and leakage. Solid state Li ion conductors, such as garnet type materials, are ex-
pected to possess a higher thermal stability, larger chemical stability compared to metallic Li
anodes1 and supress detrimental dendrite formation2. Mechanical boundary conditions and
operation as an electrolyte could induce microcracking, structural and mechanical failure
that terminates the battery life. Therefore, the reliability of solid electrolytes is important to
warrant long-term reliability of solid state batteries. However, literature quoting mechanical
properties is limited, hence, studies on the relationship of mechanical behaviour and opera-
tion conditions is required.
The current work presents a mechanical assessment of Ta-substituted Li7La3Zr2O12 based
on nano- and micro-indentation characterization, yielding elastic modulus, hardness and frac-
ture toughness with their actual dependency on the apparent penetration depth. Hence, results

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are discussed with particular emphasis on the effect of local deformation behaviour of these
ceramics. The indentation tests were based on different procedures using either constant loads
or loading cycles, revealing different sensitivities for local/global behaviour related to grain,
grain boundary, pores and micro-cracks as well as softening due to surface deterioration via
the impact of environmental moisture. The interpretation of the results was also supported
by complementary optical and electron microscopy as well as roentgenographic assessment.

References
1. T. Venkataraman, N. Sumaletha and D. Pinzaru “Garnet-type solid-state fast ion conductors for Li
batteries: critical review”, Chem. Soc. Rev., 43, pp. 4714–4727, 2014.
2. C. Monroe and J. Newman, “The impact of elastic deformation on deposition kinetics at lithium/
polymer interfaces”, J. Electrochem. Soc., 152, A396–A404, 2005.

623
Facile synthesis of BiOBR/rGO composite with enhanced photocatalytic
efficiency under visible light
Prasitthikun T.1, Wu X.2, Sato T.2, Mongkolkachit C.3, Sujaridworakun P.1,4
1
Research Unit of Advanced Ceramics, Department of Materials Science, Faculty of Science,
Chulalongkorn University, Bangkok, Pathumwan, 10330, Thailand; e-mail: [email protected]
2
Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University,
Sendai, Miyagi, 980857, Japan
3
National Metal and Materials Technology Center, Pathumthani, Klong luang, 12120, Thailand
4
Center of Excellence on Petrochemical and Materials Technology, Chulalongkorn University,
Bangkok, Pathumwan, 10330, Thailand
Keywords: BiOBr, reduced graphene oxide, visible-light active photocatalyst, rhodamine B, nitrogen
gas

The high efficiency visible-light active BiOBr/rGO composite photocatalysts was success-
fully prepared via a simple precipitation method at room temperature. The precursors were
prepared by dissolving Bi)NO3(3.5H2O and KBr in glycerol and distilled water, respec-
tively. Various mounts of reduced graphene oxide )rGO; 0.1–2 wt%) were added into the
mixed solution precursors, and stirred at room temperature to get precipitated powder with-
out further heat treatment The obtained products were characterized for phase, morphology,
optical properties and surface area by X-ray diffraction, filed-emission scanning electron
microscopy, transmission electron microscopy UV-Vis diffuse reflection spectroscopy and
Brunauer–Emmett–Teller, respectively. The photocatalytic efficiency of prepared BiOBr/
rGO composites for decomposition of rhodamine B dye and nitrogen oxide gas under visible
light irradiation were examined. It was shown the enhancement in photocatalytic activity of
BiOBr by compositing with rGO, in which the highest activity for degradation of rhodamine
B and nitrogen oxide gas were obtained from samples containing 1 and 0.25 wt% of rGO,
respectively.

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References
1. Vadivel, S., et al. “Solvothermal synthesis of Sm-doped BiOBr/RGO composite as an efficient
photocatalytic material for methyl orange degradation”, Materials Letters, 128, pp. 287–290, 2014.
2. Su, B., et al. “Enhanced photocatalytic performance of ZnO/rGO composite materials prepared via
an improved two-steps method”, Ceramics International, 42(6), pp. 7632–7638, 2016.
3. Xiong, T., et al. “New insights into how RGO influences the photocatalytic performance of BiOIO3/
RGO nanocomposites under visible and UV irradiation”, J Colloid Interface Sci., 447, pp. 16–24,
2015.

926
Ceramic functionalized flow batteries electrodes for urban electric
micro-vehicles
Francisco Ramos Pérez
Francisco Albero, SAU, Barcelona, Spain; e-mail: [email protected]

In the frame of the SPECTRA (Smart Personal C02-free TRAnsport) project, which proposes
a new perspective combining electric micro-vehicle1–3, infrastructure recharge and intelligent
management of urban mobility, design and fabrication of new electrodes for flow batteries
has been developed. Economically convenient and technically competitive mobile cell stor-
age solutions must ensure not only response time and storage capacity suitable for meeting
both the generation and grid needs, but must also show mechanical instability4,5 to afford
embedding in the stack and mobile working condictions.6
In this work, the fabrication of ceramic functionalized flow batteries electrodes (CF-FBE)
has been carried out. CF-FBE based on carbon nanofibers (CNFs) provided by Grupo Antolin
and either silicon carbide (SiC) or alumina (Al2O3) has been developed to improve performance
on working conditions. Obtained results about electrode fabrication have been discussed in the
present document and related with the electrode performance and corrosion resistance.

Acknowledgment
SPECTRA is a project co-financed by the Ministry of Economy and Competitiveness, through the
CDTI, and by the European Regional Development Fund (ERDF).

References
1. Soloveichik, G.L. (2015). Flow batteries: current status and trends. Chemical reviews, 115(20),
11533–11558.
2. Patel, P. (2010). Batteries that go with the flow. IEEE Spectrum, 47(5), 18–18.
3. Rajashekara, K. (2013). Present status and future trends in electric vehicle propulsion technologies.
IEEE Journal of Emerging and Selected Topics in Power Electronics, 1(1), 3–10.
4. Parasuraman, A., Lim, T.M., Menictas, C., Skyllas-Kazacos, M. (2013). Review of material re-
search and development for vanadium redox flow battery applications. Electrochimica Acta, 101,
27–40.
5. Shin, S.H., Yun, S.H., Moon, S.H. (2013). A review of current developments in non-aqueous redox
flow batteries: characterization of their membranes for design perspective. Rsc Advances, 3(24),
9095–9116.
6. Goodenough, J.B., Kim, Y. (2011). Challenges for rechargeable batteries. Journal of Power Sourc-
es, 196(16), 6688–6694.

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751
On the electrical performance of zirconia based composite electrolytes
A.I.B. Rondão*, N.C.T. Martins, J.P. Grilo, F.M.B. Marques
Department of Materials and Ceramic Engineering, CICECO University of Aveiro, Aveiro 3810-193,
Portugal; *e-mail: [email protected]
Keywords: zirconia, composite electrolytes, alkali metal carbonates, impedance spectroscopy

Composites consisting of mixtures of oxide-ion conductors and alkaline metal carbonates are
new types of electrolytes that may find application in Low Temperature/Intermediate Tem-
perature Fuel Cells (LT/IT-SOFCs). The attention given to this class of materials is related
to their high ionic conductivity (>0.1 S/cm at T>500 °C) with respect to standard ceramic
electrolytes, allowing low operating temperatures.
Zirconia-based materials are well-known electrolytes for solid oxide fuel cells (SOFC),
although with moderate ionic conductivity. The use of such oxides as matrix of a composite
electrolyte could combine the excellent mechanical performance of zirconia with the high
ionic conductivity of the salt mixture. However, the reactivity between doped zirconia and
alkali-metal carbonates is known. Doped zirconia like PSZ (partially stabilized zirconia) or
TZP (tetragonal polycrystalline zirconia) also show a tendency to degradation, with phase
changes induced by thermal treatment and/or exposure to water vapour.
The present work aims to assess the performance of composite electrolytes based on pure
monoclinic zirconia, the stable room temperature polymorph of this oxide. This solution is
feasible since the sintering temperature can be kept below the critical monoclinic to tetrago-
nal phase change, where a large volume change is known to occur often determining the
failure of the ceramic.
In this context, zirconia-based composite electrolytes with sodium and lithium carbonates
(NLC) were prepared in a two-step method. This consists of the preparation of the ceramic
skeleton using a small amount of NLC as sintering aid, and posterior impregnation with the
carbonate mixture. The skeleton and the composite were investigated by impedance spec-
troscopy from 300 up to 600 ºC. These composite materials were also characterized by X-ray
diffraction (XRD) and scanning electron microscopy with energy dispersive spectroscopy
(SEM/EDS).
Distinct composites based on zirconia sintered under various conditions, originated a wide
range of microstructural characteristics. Impedance spectroscopy revealed a strong relation-
ship between the performance of the ceramic phase alone and after impregnation.

Acknowledgements
Projects NewINDIGO /0001/2013 and CICECO - Aveiro Institute of Materials (Ref. FCT UID/
CTM/50011/2013) financed by national funds through FCT/MEC and when applicable co-financed by
FEDER under the PT2020 Partnership Agreement.

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076
Lead free BS-PT ceramics for energy harvester applications
Dong-Jin Shin, Jung-Hyuk Koh*
School of Electrical and Electronic Engineering, Chung-Ang University, Heukseok-Dong,
Dong-Jak Gu, South Korea; *e-mail: [email protected]

Lead and lead free piezoelectric ceramics can be used for various energy related devices due
to their piezoelectric properties.1 In general piezoelectric materials were easily respond to
environmental mechanical energy. Piezoelectric materials can generate high voltages and
low currents corresponding to the mechanical energy. Also some time, lead and lead free
piezoelectric ceramics can dissipate mechanical energy by converting them to the electrical
energy. 2 As a result, piezoelectric materials can be applied to the shock absorber system or
energy harvesting system at the same time. In general, shock absorber system or energy har-
vesting system require complicate circuit to dissipate or store maximum energy. Therefore,
recently, these kinds of piezoelectric energy systems have been attracted much attention.
these kinds of converting force can be explained by the piezoelectric effects (from mechani-
cal energy to electrical energy) or inverse piezoelectric effects (from electrical energy to
mechanical energy), respectively.3
In this study, a passive damping system based on multilayer (Bi,Sc)O3–(Pb,Ti)O3 piezo-
electric ceramics was investigated by employing weight impact system. The ceramics were
prepared by employing a traditional solid-state reaction. A drop weight of 0.75 kg was ap-
plied to the area of 10×10 mm2. Furthermore, measured and simulated output energies were
compared and analyzed. The generated power was calculated through the output voltage
and current, where as the simulated power was obtained by employing the energy absorbing
impedance-matching method. Both the calcination and sintering conditions of (Bi,Sc)O3-
(Pb,Ti)O3 ceramics significantly affect the grain size and density, which effects are closely
related to the microstructure, piezoelectric, and other properties of the ceramics. Optimizing
the calcination temperature improved the piezoelectric coefficient from 388 to 440 pC/N,
while improving the relative dielectric constant at 100 Hz from 1401 to 1479. We believe
that the optimized calcination process can enhance the ezoelectric properties of (Bi,Sc)O3-
(Pb,Ti)O3 ceramics by a very large margin.

References
1. B. Jaffe, W.R. Cook, Jr., and H. Jaffe, Aca. 271 1971.
2. S.P. Beeby, M.J. Tudor, and N.M. White, Meas. Sci. Technol. 17, R175 2006.

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475
Synthesis and characterization of Pr2Ni0.9Co0.1O4+δ
Anna Theresa Strasser*, Christian Berger, Nina Schrödl, Andreas Egger, Johannes Hofer,
Edith Bucher, Werner Sitte
Chair of Physical Chemistry, Montanuniversitaet Leoben, Franz-Josef-Straße 18, Leoben, Austria;
*
e-mail: [email protected]
Keywords: rare earth nickelates, freeze drying, conductivity relaxation

Research and development in sustainable energy technologies have gained increasing im-
portance over the last years. Especially electrochemical cells and systems can be expected to
play a key role in many different fields of technologies. Rare earth nickelates with K2NiF4-
structure are among the most promising materials for many of these applications, e.g. elec-
trode materials for solid oxide fuel cells and electrolyzers, electrochemical oxygen sensors,
ceramic membranes for selective oxygen separation, or heterogeneous catalysts, because of
their favorable properties, such as high oxygen diffusivity, as well as good electronic and
significant ionic conductivity.1 Currently though, the limitation of the oxygen exchange ki-
netics by the rate of the surface exchange process represents a drawback for technological
applications.
The present work reports on the synthesis and characterization of the novel K2NiF4-type
material Pr2Ni0.9Co0.1O4+δ (PNCO). Ni in Pr2NiO4+δ is partially substituted with Co in order to
increase the surface exchange coefficient of oxygen. For the preparation of larger quantities
of chemically homogenous, single phase PNCO powder, a freeze drying method based on
aqueous acetate precursor solutions was developed. The metal cation solutions were mixed,
shock-frozen in liquid nitrogen, and freeze-dried. During a calcination step, the complex
oxide was formed. X-ray powder diffraction (XRD) and Rietveld refinement showed that
the material was single phase with K2NiF4-structure. The powder was characterized by dila-
tometry, differential scanning calorimetry (DSC), and thermogravimetriy (TG). In pure Ar,
a transition from the orthorhombic to the tetragonal structure modification occurred, which
was also reported for unsubstituted PNO.2,3 For oxygen exchange and electrical conductivity
measurements, a dense PNCO sample was obtained by sintering a pellet at 1300 °C. By this
procedure it was possible to produce a phase-pure PNCO pellet with 99% of the theoretical
density, which will be used for studies of the oxygen exchange kinetics by means of the dc-
conductivity relaxation method.

References
1. T. Ishihara. Perovskite Oxide for Solid Oxide Fuel Cells. Springer-Verlag, Berlin-Heidelberg-New
York, 2009), p. 1–16.
2. J.D. Sullivan, D.J. Buttrey, D.E. Cox, and J. Hriljac, J. Solid State Chem., 94, pp. 337–351, 1991.
3. E. Niwa, K. Wakai, T. Hori, K. Yashiro, J. Mizusaki, and T. Hashimoto, Thermochimica Acta, 575,
pp. 129–134, 2014.

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501
Hybridization of phosphate or phosphate compound and mesoporosu
silica for acid-durable adsorbent for rare earth metal cations
Takahiro Takei*, Fumitake Okabe, Sayama Yanagida, Nobuhiro Kumada
Center for Crystal Science and Technology, University of Yamanashi, 7-32 Miyamae, Kofu,
Yamanashi 400-0005, Japan; *e-mail: [email protected]

Mesoporous silica is strong candidate for adsorbent, filter, catalyst support and so on due
to its strong durability for acidic condition. Especially, mesoporous silica with hexagonal
1-dimensional pore array is an attractive material because homogeneous pore size and array
may provide possibility for molecular sieve. However, surface of mesoporous silica has low
activity for some sorts of adsorption, reaction and so on due to OH group on the silica surface
show only week acidity. Therefore, phosphate group or phosphate compounds (hydroxyapa-
tite) was hybridized with the mesoporous silica, and adsorption of rare earth metal cations
were examined under coexisting circumstance of the rare earth cations.
Typical preparation of mesoporous silica (MPS) was performed by Si(OC2H5)4,
C16H33N(CH3)3Br and C2H5NH2 with heating at 70 °C. The hybridizations of phosphate were
examined by three ways, synthesis by reflux of MPS with H3PO4 (designated as MPS-HP),
that from reflux solution of Na2SiO3 and Na2HPO4 (MPS-NaP), and that from Na2SiO3 and
PO(OC2H5)3 (MPS-EtP).
For preparation of MPS-hydroxyapatite, Ca-substituted MPS (prepared by Si(OC2H5)4 and
Ca(NO3)2·4H2O) was used for the hybridization. The Ca-substituted MPS was then put into
NH4H2PO4 aqueous solution (designated as MPS-HAp). The prepared hybrids were charac-
terized by XRD, SXRD, FT-IR, NMR, microporosimeter and XPS for structure of the hybrid,
and ICP for adsorption of rare earth metal cations.

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XRD patterns (omitted in this paper) confirm that the hexagonal structures were partial-
ly kept during the hybridization. For the hybrid with phosphate, the maximum phosphorus
amount was around 2.9 mol%. On the other hand, for MPS-HAp, the maximum amount of
HAp is around 21 mass%, which corresponds to around 8.8 mol% of phosphorus. Fig. 1
shows rare earth adsorptions under coexisting circumstance of 13 rare earth metal cations
to MPS-HAp at pH = 0. For MPS and phosphate hybrids, the adsorption amount per phos-
phorus is around 0.3, whereas approx. 0.9 for MPS-HAp. Such difference may result from
difference mechanisms for rare earth adsorption as follows, coulomb force to phosphate for
MPS-phosphate and ion exchange of Ca by rare earth for MPS-HAp. The acid durability will
be reported in the day.

940
ZnO/TiO2 nanolaminate films prepared by atomic layer deposition as
ultralong-life anode material of lithium ion batteries
Shanshan Wang, Yanqiang Cao, Xu Qian, Min Li, Wei Zhang, Aidong Li*
National Laboratory of Solid State Microstructures and Department of Materials Science and
Engineering, College of Engineering and Applied sciences, Collaborative Innovation Center of
Advanced Microstructures, Nanjing University, Nanjing 210093, People’s Republic of China;
*
e-mail: [email protected]
Keywords: atomic layer deposition, ZnO/TiO2 stacks, anode, lithium ion batteries, ultralong-life

Rechargeable lithium ion batteries hold huge potentials for energy storage due to their high
energy density and excellent cycle life. However, current commercially used graphite anode
exhibits the low theoretical capacity of 372 mAh g–1, which is unable to fill the increasing de-
mands of the ever-enlarging market. Therefore, transition metal oxides (TMOs) with higher
theoretical capacities have been widely researched as anode materials, such as Fe3O4, SnO2,
NiO, Co3O4, and ZnO. Among these oxides, ZnO has attracted a great deal of attention due
to its high theoretical capacity of 978 mAh g–1, natural abundance, easy preparation, low cost
and environmental friendliness. However, it was found that ZnO suffers from severe capac-
ity degradation and inferior rate performance, which can be attributed to the low electronic
conductivity of ZnO and the severe volumetric changes during charge/discharge. Moreover,
it has been revealed that the lithium embrittlement of ZnO is much worse than that of SnO2,
leading to the electrochemically driven solid-state amorphization and pulverization of ZnO.
Therefore, various approaches have been attempted to improve the electrochemical perfor-
mance of ZnO anode, including construction of nano-structured materials, metal doping and
decoration with highly conductive matrix.
In this work, we have designed ZnO/TiO2 nanolaminate films by atomic layer deposition
(ALD) as anode material for lithium ion batteries. ZnO/TiO2 nanolaminate films with 144 nm
thickness were fabricated on copper foils by depositing cycle unit of 5 nm ZnO/1 nm TiO2
repeatedly using ALD. The ultrathin TiO2 films inserted into ZnO films were designed to
buffer the volumetric changes during charging-discharging process. It was found that the pul-

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verization of ZnO/TiO2 has been effectively inhibited compared to the pure ZnO film anode
after cycling process. Accordingly, the electrochemical test demonstrated that the reversible
capacity and the rate performance of ZnO films anode have been greatly improved by insert-
ing TiO2 thin films, which could maintain a reversible capacity of 53.61 uAh cm–2 at 200 mA
cm–2 and 47.23 uAh cm–2 at 500 mA cm–2 after 100 cycles. Its excellent high rate capability
and long cycle stability can be attributed to the fact that TiO2 thin film can buffer the volume
change and prevent from the pulverization of ZnO. Constructing nanocomposite films might
open up new opportunities for ZnO based anode materials for lithium ion batteries.

345
Preparation and photocatalytic properties of pyrochlore-type AgMO3
(M = Nb,Ta)
Isuru Withanage, Nobuhiro Kumada*, Sayaka Yanagida, Takahiro Takei
Center for Crystal Science and Technology, University of Yamanashi, 7-32 Miyamae, Kofu,
Yamanashi 400-8511, Japan; *e-mail: [email protected]
Keywords: hydrothermal reaction, ion-exchange, photocatalytic

Pyrochlore-type oxides are formed by composing many metal element having the general
chemical formula A2B2O6O` or A2B2O7, (space group Fd-3m, No. 227) and the A and B at-
oms are generally alkaline metal, alkaline earth metal, rare-earth metal, or transition metal
elements. We attempted preparation of pyrochlore-type (K,H)MO3 ·nH2O, (M = Nb,Ta) and
ion-exchange of K+ ion with Ag+ ion. The crystal structures of the mother compound and their
ion-exchange compound were refined with Rietveld method and their photocatalytic proper-
ties were checked.
Pyrochlore-type (KH)NbO3·nH2O was synthesized by hydrothermal reaction method. The
starting compound Nb2O5 (5g), 30ml of KOH solution were put in to Teflon autoclave and
heated up to 220 °C for 2 days. In the case of (KH)TaO3·nH2O, the starting compound was
an amorphous Ta2O5 and the reaction temperature was 200°C . The ion exchange reaction
was performed with excess AgNO3 at 300 °C. The products were identified by X-ray powder
diffraction and thermal stability was checked by TG-DTA. The photocatalytic activity of the
products was checked by using phenol degradation under UV-light irradiation.
The refinement of pyrochlore-type (K,H)NbO3 ·nH2O was successful and the R factors
were Rwp = 5.27%, Rp = 2.44% and lattice parameter was a = 10.6409(2) Å. The ion-exchange
reaction of (K,H)NbO3·nH2O with excess AgNO3 was not successful and the product had flu-
orite-type structure. Structural change from fluorite-type to perovskite-type at 600°C showed
by TG-DTA. The Ag/K ratio of the fluorite-type compound was 0.53. The R factors for flu-
orite-type (K,Ag,Nb)O2-x were Rwp = 2.32% and Rp = 1.51% and the lattice parameter was a
= 5.20392(9) Å. Fig. 1 shows time dependence of phenol degradation for pyrochlore-type
(K,H)NbO3·nH2O, (K,H)TaO3 ·nH2O, AgTaO3, fluorite-type (K,Ag,Nb)O2-x , and perovskite-
type AgNbO3.

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Fig. 1. The time dependence phenol degradation for pyrochlore-type

(K,H)NbO3 ·nH2O, (K,H)TaO3 ·nH2O, AgTaO3, fluorite-type (K,Ag,Nb)O2-x
and perovskite-type AgNbO3

348
Synthesis and electrochemical properties of layered double hydroxide
film composed of period-four transition metals and its hybrid with
conductive polymer
Guoshen Yang, Takahiro Takei*, Sayaka Yanagida, Nobuhiro Kumada
Center for Crystal Science and Technology, University of Yamanashi, 7-32 Miyamae, Kofu,
Yamanashi 400-8511, Japan; *e-mail: [email protected]
Keywords: Layered Double Hydroxide, conductive polymer, electrochemical properties

Layered Double Hydroxide (LDH) is a kind of layered material composed of metal hydrox-
ide layers and intercalated anions. Generally Mg, Co, Zn and Al are used divalent and triva-
lent metal cations, which can be replaced by some transition metal. In our laboratory, metal
hydroxide-conductive polymer hybrid is gaining attention, which is beneficial to improve
the electrochemical performance of the hybrid materials by synergistic effect. In this study,
we first prepared the LDH structure with Co-Al, Ni-Al, Co-Fe and Ni-Fe composition. On
this basis, we used electrochemical method to prepare LDH–polyaniline hybrid films and its
performance were tested.
The CoAl-LDH structure were prepared by hydrothermal method (The preparation of Ni-
Al, Co-Fe and Ni-Fe were the same method). The electrodeposition was then carried out at
a constant current. The sample films were characterized by XRD, FT-IR, SXRD, FE-SEM

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and XPS. The electrochemical properties were tested by cyclic voltammetry and charge/
discharge cycles test.
Fig. 1 shows XRD patterns of Co-Al, Ni-Al, Co-Fe and Ni-Fe LDH film. In the spectrum,
we can find LDH diffraction peak. Therefore SXRD patters were measured for confirmation
of LDH formation. Fig. 2 shows SXRD patterns of formed LDH structures. From the pat-
terns, CoAl-LDH and NiAl-LDH show better crystallinity than others. The LDH composed
of Fe3+ seems to include impurity phase. By comparison to Fig. 1, the diffraction peaks of
layered structure are apparently large. Such difference may result from perpendicular orien-
tation in the film sample. Fig. 3 shows SEM images of CoAl-LDH. We find that most of the
particles seem to be vertical growth in the substrate surface and particles are roughly uniform
distribution. The result of electrochemical properties and hybridization with polyaniline will
be reported in the day.

Fig 1. XRD patterns of CoAl, CoFE, NiAl and NiFe Fig 2. SXRD patterns of CoAl, CoFe, NiAl and
NiFe

Fig 3. SEM images of CoAl-LDH

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920
Mechanical properties of LLZO solid electrolytes for battery
application
Gang Yan*, Anni Wang, Hao Zheng, Juliane Franciele Nonemacher, Martin Finsterbusch,
Jürgen Malzbender
Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research, 52425 Jülich, Germany;
*
e-mail: [email protected]
Keywords: solid electrolyte, battery, elastic modulus, strength, fracture toughness

Beneficial volumetric storage and stability aspects led to increased interest in solid state Li
based electrolyte materials are for battery application as. Especially Li7La3Zr2O12 (LLZO)
with 2 mol% Al doping, 40 mol% Ta doping is a promising material in this respect because
of its high Li-ion conductivity as well as chemical stability. Mechanical behavior is important
due to its relationship to reliability, rendering micro- as well as macromechanical behavior
into the focus of the current work. Local properties are assessed using nanoindentation yield-
ing local elastic modulus, hardness and fracture toughness, whereas the global behavior in
terms of specimens’ elastic modulus and fracture stress are characterized via ring-on-ring
tests. Fracture stresses are analyzed via Weibull statistics yielding the characteristic strength
and Weibull modulus. The aspect of environmentally assisted subcritical crack growth is dis-
cussed based on the variation of the loading rate during strength testing. Results are discussed
in terms of their relationship to microstructure and local as well as geometrical imperfections.
The interpretation of the results is supported by complementary optical and electron micros-
copy as well as roentgenographic assessment.

367
Controlled architecture of magnesium/aluminium layered double
hydroxide (LDH) crystals
Atsushi Zenzai1, Tomohito Sudare2, Fumitaka Hayashi1, Katsuya Teshima1,2
1
Department of Materials Chemistry, Graduate School of Shinshu University, 4-17-1, Wakasato,
Nagano-shi, Nagano, 380-8553, Japan; *e-mail: [email protected]
2
Center for Energy and Environmental Science, Shinshu University, Nagano, Japan
Keywords: layered double hydroxide, morphology control, intercalation, ion exchange

There have been increasing attention to layered double hydroxides (LDHs), also known as
hydrotalcite-like compounds and anionic clays. They are represented by a general formula of
[M2+1-xM3+x(OH)2]x+[Anx/n]x–mH2O consisting of octahedral brucite-like host layers (M2+/M3+:
divalent and trivalent metal cations), charge-balancing anions (An-) and interlayer water mol-
ecules. Their ion exchange properties, especially selectivity and capacity, have been widely
studied by many researchers for various combinations of metal cations. However, morphol-

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ogy control of LDHs for high ion exchange capacity has not been established. This study
report the controlled growth of three-dimensional architectures of LDHs composed of mag-
nesium and alumina in host layers (Mg/Al LDHs) by using magnesium oxide and aluminum
oxide as sources. The effects of ingredient aluminum oxide with various crystal structures
and sizes on the morphology, specific surface area and ion-exchange capacity of resulting
LDHs were investigated.
A typical synthetic procedure of LDHs with three-dimensional architectures was as fol-
lowed: aluminum oxides with amorphous phase, θ-phase or α-phase and magnesium oxide
with stoichiometric composition were immersed in an aqueous solution. These solutions were
stirred for 10 h at each temperature at 80 °C, and subsequent precipitated powders were col-
lected and filtered. After drying at 60 °C, X-ray power diffraction (XRD) analysis was carried
out and their morphologies were characterized with scanning electron microscopy (SEM).

Fig. 1. SEM image of Mg/Al LDH crystals obtained from aqueous solution
containing θ-Al2O3 and MgO as sources at 80 °C

Successful formation of Mg/Al LDHs with three-dimensional architecture was confirmed

from XRD and SEM analysis only when θ-phase aluminum oxide was used among various
ingredient aluminum oxides. With respect to the morphological feature, plate-shaped crystals
with diameter of 1.0 µm were connected to each other and construct secondary particles with
diameter of 10 µm (Fig. 1). From the time-dependent analysis, it was found that the plate-
shaped LDHs were formed on the surface of aluminum oxide through the precipitation with
magnesium ions and hydroxy ions, followed by intrusion into the center of aluminum ox-
ide. The ion exchange capacity will be discussed in comparison with conventional synthetic
LDHs.

Acknowledgement
This work was partly supported by a JSPS Grant-in-Aid for Scientific Research (A) 25249089.

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924
Enhanced visible-light photocatalytic acitivity of Fe2O3-coated TiO2
powders prepared by atomic layer deposition
Xi-Rui Zhao, Yan-Qiang Cao, Jun Chen, Lin Zhu, Xu Qian, Ai-Dong Li*, Di Wu
National Laboratory of Solid State Microstructures and Department of Materials Science and
Engineering, College of Engineering and Applied Sciences, Collaborative Innovation Center of
Advanced Microstructures, Nanjing University, Nanjing 210093, People’s Republic of China;
*
e-mail: [email protected]
Keyword: visible-light photocatalytic activity, Fe2O3 coating, commercial TiO2 powders, atomic layer
deposition

With the rapid development of modern industry, environmental pollution has become a seri-
ous issue. TiO2, as an efficient and safe photocatalytic material, can only absorb ultraviolet
light. In order to make full use of visible light, the doping and modification of commercial
TiO2 powders (P25) have drawn great concerns. Among various approaches, the semicon-
ductor/semiconductor hetero-junction is perceived as the most effective way to improve the
TiO2 visible light response. Atomic layer deposition (ALD) is a kind of novel thin film coat-
ing preparation method with large area uniformity, excellent three-dimensional conformality,
simple and precise control of film-thickness, and low processing temperature due to self-
limited surface chemisorptions mechanism.
In this work, Fe2O3-coating on commercial TiO2 powders (P25) was prepared using
Fe(Cp)2 and O3 by thermal ALD. The effect of different ALD cycles on the visible-light
photocatalytic properties of P25 has been investigated carefully. The XRD patterns indi-
cate TiO2 anatase structure without other secondary phase. The HRTEM image shows lat-
tice fringe phase of TiO2 nanocrystalline with untrathin surface disorder region, possibly
originating from the Fe2O3 or Fe-doped TiO2. XPS and ICP analyses confirm the slight Fe
amount existence in TiO2 powders. The UV-visible absorption spectra of Fe2O3 coated TiO2
indicate some absorption in the visible light region with reduced the bandgap from 3.35 eV
to 3.05 eV. Fe2O3 coated TiO2 powders exhibit significant photodegradation of methyl orange
(MO) under visible light irradiation. 400-cycle Fe2O3-coated P25 has optimal photocatalytic
acitivity with ~72% degradation of MO in half an hour. The catalyst loading amount and re-
cyclability has also been examined. The possible photocatalytic mechanism of Fe2O3-coated
TiO2 powders is proposed.

References
1. T. Tachikawa, P. Zhang, Z. Bian and T. Majima, “Efficient Charge Separation and Photooxidation
on Cobalt Phosphate –Loaded TiO2 Mesocrystal Superstructures”, Journal of Materials Chemistry
A., 2, pp. 3381–3388, 2014.
2. R.S. Sonawane, B.B. Kale and M.K. Dongare, “Preparation and Photo-catalytic Activity of Fe-TiO2
Thin Films Prepared by Sol–gel Dip Coating”, Materials Chemistry & Physics., 85, pp. 52–57,
2004.
3. M. Xu, P. Da, H. Wu, D. Zhao and G. Zheng, “Controlled Sn-doping in TiO2 Nanowire Photoanodes
with Enhanced Photoelectrochemical Conversion”, Nano Letters., 12, pp. 1503–1508, 2012.

507 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

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Invited lectures

960
Expanding applications of bioactive glasses in tissue engineering
and wound healing
Aldo R. Boccaccini
Institute of Biomaterials. University of Erlangen-Nuremberg, 91058 Erlangen, Germany;
e-mail: [email protected]
Keywords: bioactive glasses, tissue engineering, ion release, vascularization

Due to its excellent bioactivity, bioactive glasses are being highly considered for tissue engi-
neering scaffold development. Usually in combination with biopolymers, bioactive glasses
can form composites for applications in soft tissue engineering and wound healing.1 The abil-
ity of bioactive glasses to enhance vascularisation via the action of dissolution products (bio-
logically active ions) will be discussed based on in vitro and in vivo studies. 45S5 Bioglass®
scaffolds with a highly interconnected porous structure can be fabricated by the traditional
polymer replica technique. A possible disadvantage of such scaffolds is their high brittleness
and low resistance to fracture. To increase the low mechanical properties and to impart mal-
leable behaviour, scaffolds are coated with a biopolymer. In this investigation, scaffolds were
coated with gelatin by dip coating and vacuum infiltration, amongst other investigated meth-
ods. The coating and infiltration of scaffolds by biodegradable polymers will be presented as a
suitable approach to enhance the structural integrity of scaffold and to impart functionalities,
including incorporation of inorganic particles, e.g. mesoporous particles, as drug carriers.2 The
in-vitro characterisation of bioactive glass based scaffolds will be discussed highlighting the
effects of bioactive glass dissolution products (metallic ions) on cell behaviour in relation to
osteogenesis and angiogenesis.3 In-vivo investigations to determine the vascularisation poten-
tial of new bioactive glass scaffolds will be discussed in relation to the current main challenge
of tissue engineering, namely that the biomaterial construct support vascularisation. In the
emerging field of bioactive glasses for soft tissue engineering, an overview of their applica-
tions in contact with soft tissues will be presented with focus on our current work on dressings
for wound healing and on hydrogel-bioactive glass composites for biofabrication.

References
1. V. Miguez-Pacheco, et al., Bioactive glasses beyond bone and teeth: emerging applications in con-
tact with soft tissues, Acta Biomaterialia 13 (2015) 1–15.
2. E. Boccardi, et al., Uniform Surface Modification of 3D Bioglass®-Based Scaffolds with Mesoporo-
us Silica Particles (MCM-41) for Enhancing Drug Delivery Capability,  Frontiers in Bioengineer-
ing and Biotechnology 3 (2015) 177.
3. A. Hoppe, et al., A review of the biological response to ionic dissolution products from bioactive
glasses and glass-ceramics, Biomaterials 32 (2011) 2757–2774.

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370
Engineering bioactive glasses with well-balanced overall properties
José M.F. Ferreira
Department of Materials and Ceramics Engineering, University of Aveiro, CICECO,
3810-193 Aveiro, Portugal; e-mail: [email protected]
Keywords: bioactive glass, scaffolds fabrication, sintering, osteoinduction

Bioactive glasses (BGs) elicit special responses when in contact with biological fluids.1,2 The
leached ionic species exert an osteoinduction role, stimulating the recruitment of immature
cells to develop into preosteoblasts, promoting healing in bone fractures and defects filled
with BG bone grafts. The bone-like hydroxyapatite (HA) layer formed at the surface of BGs
in vivo leads to strong bonding to living tissues. Another crucial requirement for the success-
ful engineering of bone tissues is the 3D structure of bone graft (scaffold) as it provides a
suitable environment for osteogenic cells to migrate, proliferate, differentiate, and promote
new bone formation. All these relevant features strongly depend on a number of interrelated
factors that need to be well balanced, including the chemical composition and structure,
which determine the biocompatibility, the degradation rate, and the easiness of processing
(shaping and sintering) the material. BGs with high alkali contents create high pH environ-
ments, become cytotoxic and are difficult to process. This presentation deals with the devel-
opment, characterization and processing of a series of alkali-free bioactive glass composi-
tions that offer a set of well-balanced overall properties. Porous scaffold are easy to process
by additive manufacturing. BGs are biocompatible and degrade with time into non-toxic
products and exhibit fast in vitro mineralization.1 The BG compositions also foster early cel-
lular differentiation and proliferation and alleviate the oxidative stress in vitro,3 and excellent
osseointegrative and osteoconductive properties when implanted in vivo.4 These distinctive
features are very promising for demanding applications in healthcare and tissue engineering
and bone regeneration and the supporting evidences will be disclosed.

References
1. L.L. Hench, R.J. Splinter, W.C. Allen, T.K. Jr. Greenlee. “Bonding mechanisms at the interface of
ceramic prosthetic materials”, J. Biomed. Mater. Res., 2, pp. 117–41, 1971.
2. A. Goel, S. Kapoor, R.R. Rajagopal, M.J. Pascual, H.W. Kim, J.M.F. Ferreira, “Alkali-free bioac-
tive glasses for bone tissue engineering: A preliminary investigation”, Acta Biomaterialia 8, pp.
361–372, 2012.
3. A.F. Brito, B. Antunes, F. Santos, H.R. Fernandes, J.M.F. Ferreira, “Osteogenic capacity of alkali-
free bioactive glasses - In vitro studies”, J. Biomed. Mat. Res., Part B, 2016.
4. P.P. Cortez, A.F. Brito, S. Kapoor, A.F. Correia, L.M. Atayde, P.D. Pereira, A. Afonso, A. Goel,
J.M.F. Ferreira, “The in vivo performance of an alkali-free bioactive glass for bone grafting,
FastOs®BG, assessed with an ovine model. J. Biomed. Mater. Res., Part B, 2015.

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733
Resorption of calcium phosphate materials:
considerations on the in vitro evaluation
Marta Gallo, Solène Tadier, Sylvain Meille, Jérôme Chevalier
Univ. Lyon, INSA de Lyon, MATEIS UMR CNRS 5510, Bât. Blaise Pascal, 7 Av. Jean Capelle,
F-69621 Villeurbanne, France
Keywords: dissolution, precipitation, calcium phosphate, mechanics, physico-chemistry

Calcium phosphates (CaPs) are currently used as bone grafts thanks to chemical similarities
with the mineral fraction of bone. Depending on their composition and their processing route
(e.g. sintered ceramics or cements), CaPs can be more or less soluble under physiological
conditions. A deep knowledge of resorption phenomena could allow tailoring CaP based
bone graft according to the patients’ needs. Literature is quite abundant concerning the evo-
lution of calcium phosphates after immersion in model fluids. However, results vary consid-
erably according to the test conditions. A comparison of the information provided appears
therefore difficult, due to the large variability of tests performed. Thus, the present study is
aimed at underlining the importance of choosing appropriate immersion conditions and of
paying a particular attention to the influence of the set-up. The influence of the immersion
conditions is demonstrated, as well as the possible presence of artefacts induced by the ex-
perimental protocols. In addition, the interest to follow-up at the same time and at the local
scale physicochemical, microstructural and mechanical properties is discussed. For each of
the aforementioned points, evidences are provided through the results obtained by immersing
DCPD and β-TCP samples in different ‘model’ solutions (TRIS and PBS) for different times.

826
Design and processing of novel biomedical-grade nanocomposite
ceramics: tailoring composition, microstructure and properties
Paola Palmero1*, Marta Fornabaio1, Helen Reveron2, Jérôme Chevalier2,3,
Laura Montanaro1
1
Department of Applied Science and Technology, Politecnico di Torino, Corso Duca degli Abruzzi,
24, 10129 Torino, Italy; *e-mail: [email protected]
2
Université de Lyon-INSA de Lyon, MATEIS CNRS UMR 5510, 20 Avenue Albert Einstein, F-69621
Villeurbanne Cedex, France
3
Institut Universitaire de France, 103 bd Saint-Michel, 75005 Paris, France
Keywords: ceramic nanocomposites; biomedical applications, microstructural tailoring, composition-
structure-properties relationships

With the increase of life expectancy, the need for artificial biomedical devices having im-
proved performance and durability is increasing as well. This implies new challenges for the
materials used in these applications, since improved mechanical properties (strength, tough-
ness and wear behaviour) and longer term biocompatibility are required.

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In this frame, tetragonal zirconia polycrystals (TZP) and zirconia-based composites have
shown their feasibility as biomedical materials and especially oral implants, as these ceram-
ics match biocompatibility, mechanical specifications and aesthetic properties, as required
for dental applications.
However, a major concern in the processing of these composites relates to the ability of
keeping a homogeneous microstructure and a fine zirconia grain size, necessary to produce
reliable biomedical devices with the expected performances.
This work deals with a novel approach concerning both the materials design and the elabo-
ration process of nano-composite ceramics, allowing an effective tailoring of the powder
characteristics, final microstructure and properties with the aim of fabricating biomedical
devices characterized by a perfect reliability and a lifetime longer than 60 years. By this ap-
proach, a careful control and optimisation of the main ceramic processing steps is carried out,
leading to robust relationships among composition, architecture and performances in terms
of mechanical behaviour and durability. In particular, attention will be paid to the synthesis
of zirconia-based composite powders, by exploiting a simple but reliable powder coating
method, able to assure the required microstructural features in final materials. In addition,
the thermal pre-treatment of composite powders will be optimized, in order to tailor some
features (e.g. nucleation extent stage and crystallization degree) prior sintering, which will be
then carefully controlled in order to obtain fully dense materials, in which a perfect tailoring
of the microstructural parameters (grain size, distribution, morphological development of
secondary phases) will be achieved.
By this strategy, strong, tough and stable ceramics are successfully produced, making
them promising candidates for structural biomedical applications.

Acknowledgements
The research leading up to these results was undertaken in the framework of the LONGLIFE proj-
ect (www.longlife-project.eu) funded by the European Community’s Seventh Framework Program
(FP7/2007-2013) under the grant agreement n. 280741.

884
Bone in-growth: the next step in ceramic orthopedic implants
Norbert Schneider
CeramTec GmbH, Medical Products Division, Germany

Dense structural oxide ceramics are widely preferred as a favorable material in tribological
applications for arthroplasty. Their hardness, strength, wear resistance, and biocompatibility
make them suitable for artificial joints. Pure aluminum-oxide and zirconia-toughened alu-
mina (ZTA) ceramics are in use for several decades now. The most commonly used ceramic
material today is a zirconia and platelet toughened alumina (ZPTA) known under the trade
name BIOLOX®delta. Several million parts of this material have been implanted worldwide
and it has shown a significant improvement over pure alumina in terms of safety and wear.

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However, the biological and chemical “inertness” constrain the connection of the implant
to the surrounding bone. This is one of the reasons why ceramic orthopedic implants are usu-
ally backed with metal shells to facilitate fixation in the bone structure. Therefore, the aim of
today’s ceramic implant development is modifying the ceramic surface in a way that allows
direct-to-bone implantation. To omit the metal backing would allow larger bearing diameters
and wall thicknesses while at the same time saving bone substance.
In order to facilitate structural interconnection of the bone with the ceramic implant sev-
eral routes can be followed. There are additive and subtractive technologies that allow textur-
ing the surface of the ceramic body in a way that will allow mechanical interlocking with the
bone scaffold. Additionally, chemical modification of the surface can further improve bone
cell adhesion. Following the above different routes, it can be demonstrated that a material
commonly known as “bio-inert” can be bio-activated allowing osseointegration.

848
Tuning nanoceramics for angiogenesis and its potential in cancer
therapy
Sudipta Seal
Nanoscience Technology Center and Advanced Materials Processing Analysis Center, USA

Angiogenesis is the formation of new blood vessels from existing blood vessels and is critical
for many physiological and pathophysiological processes. In this study we have shown the
unique property of redox active ceramic nanoparticles (Re-NPs) to induce angiogenesis, ob-
served using both in vitro and in vivo model systems. In particular, Re-NPs trigger angiogen-
esis by modulating the intracellular oxygen environment and stabilizing hypoxia inducing
factor 1alpha endogenously. Furthermore, correlations between angiogenesis induction and
Re-NPs physicochemical properties including: surface valence state ratio, surface charge,
size, and shape were also explored. High surface area and mixed valence states make these
nanoparticles more catalytically active towards regulating intracellular oxygen, which in turn
led to more robust induction of angiogenesis. Role of these nanoceramics in potential cancer
therapy will be highlighted.

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080
The prospects for bio-glass implant coatings
George E. Stan1, Adrian-Claudiu Popa1,2, Hugo R. Fernandes3, José M.F. Ferreira3
1
National Institute of Materials Physics, 405A Atomistilor street, Magurele-Ilfov, Romania;
e-mail: [email protected]
2
Army Centre for Medical Research, Bucharest, Romania
3
Department of Materials and Ceramics Engineering, Centre for Research in Ceramics and Composite
Materials (CICECO), University of Aveiro, Aveiro, Portugal; e-mail: [email protected]
Keywords: bioactive glass, implant coatings, magnetron sputtering

The ability of certain silica-based glass formulations to bond to hard and soft tissues was
discovered in the late sixties by L.L. Hench.1 Due to their highest indices of bioactivity,
silicate bioactive glasses (SBGs) are the suitable candidates capable to stir the quest for a
new generation of osseous implants with superior functional performances. Although frantic
researches in the past were dedicated to the fulfilment of this conceptual desiderate by em-
ploying well-established and novel physical and chemical deposition technologies, reliable
metallic implants coated with SBG are not yet available for medical practice. In the recent pe-
riod, tremendous efforts have been dedicated to delineate new derivative glass formulations2
capable to expand the functionalities of SBGs to low dimensional objects for drug delivery
or regenerative bone scaffolds fabricated by additive manufacturing, robocasting or 3D print-
ing, and finally coatings for fast and safe osteointegration of metallic implants. For instance,
the ability to match the CTE values of SBG and Ti, by designed oxidic substitutions, without
affecting the osteointegration capacity, reopens the question of manufacturing durable SBG
implant coatings, capable to realize the rapid transition to real-life applications.
The presentation will provide an overview about the advantages, drawbacks and peculiari-
ties of one of the most promising technologies for functionalization of implants with SBG
coatings: radio-frequency magnetron sputtering (RF-MS). Beside its renowned remarkable
advantages (e.g., ability to generate highly adherent, pure, uniform and compact coatings, or to
enable facile engineering of coatings’ features by varying the process parameters), RF-MS is
one of the fewest deposition methods that can successfully be scaled-up to industrial level (as
demonstrated in electronics industry). The progresses achieved so far in the realm of RF-MS
SBG sputtered coatings will be reviewed to highlight the potential of this technique. Simple,
inexpensive, yet scientifically more accurate in vitro bioactivity screening tests have been used
to probe the SBG coatings performance. It is postulated that only an exigent in vitro testing
can filter the best implant solutions and boost their safe translation to clinical applications.
Furthermore, solutions to tackle the current technical obstacles will be debated, paths for po-
tentially extending the applicational range of RF-MS will be presented, whilst insights on the
chances to surpass the current knowledge boundaries in the field will be revealed and inquired.

References
1. L.L. Hench, “Bioceramics: from concept to clinic”, J. Am. Ceram. Soc., 74, pp. 1487–1510, 1991.
2. J.A. Jones, “Review of bioactive glass: from Hench to hybrids”, Acta Biomater., 9, pp. 4457–4486,
2013.

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951
Nature-inspired innovative processes to generate smart materials for
regenerative medicine
Anna Tampieri, Simone Sprio, Monica Sandri, Andrea Ruffini, Alberto Ballardini,
Monica Montesi, Silvia Panseri
Institute of Science and Technology for Ceramics, National Research Council, Via Granarolo 64,
48018 Faenza, Italy

Introduction. Tissue regeneration requires the use of scaffolds acting as an instructing guide
for cells, so that substantial mimicry of compositional, morphological and structural features
of natural tissue is highly desired. However, this target is very hard to achieve, when human
tissues with high compositional and structural complexity such as bone have to be regener-
ated. In this respect, even though hydroxyapatite (HA) is the best-in-class for bone regen-
eration, the thermal treatments compulsory for scaffold consolidation destroy all the fine
compositional and nanostructural cues triggering and directing the cell fate towards tissue
regeneration and vascularization. In this respect, nature-inspired synthesis approaches are
rapidly gaining ground in material science, for the development of biomaterials with unique
composition, structure and performance. Biomineralization and biomorphic transformation
processes1,2 are relevant examples of this concept.
Materials and methods. Biomineralization process are carried out in aqueous environment
where collagen fibrils were dispersed at body temperature in the presence of Ca, P and Mg
ions, and under pH control. The process was directed to generate bone-like and functionally
graded scaffolds with high mimicry of mineralized and non-mineralized regions present in
osteochondral tissues.
Biomorphic transformation process, starting from natural sources, such as wood, implies
a sequence of heterogeneous reactions at the interface between a natural porous template and
a reactive gas, concluded with a low temperature phosphation process that avoids the use of
sintering for physical consolidation. The 3-D structure is maintained throughout the whole
transformation process, leading to bioactive apatite with hierarchical organization.
Results and Discussion. Hybrid composites with highly porous structure and outstanding
mimicry of newly formed bone tissue are the product of biomineralization process. In par-
ticular, the heterogeneous nucleation of nearly amorphous apatitic phase occurred onto the
assembling collagen matrix, exhibiting multiple ionic substitutions and crystal orientation
inducing specific chemotactic and topotactic interaction with cells, all features at the basis of
regenerative ability demonstrated in the pre-clinical and clinical tests.
Biomorphic 3-D hierarchically organized porous ceramics consisted in highly biomimetic,
multi-substituted nanocrystalline apatite phase, directly nucleated in the 3-D state to form
a scaffold exhibiting bone-mimicking structure with open and interconnected porosity and
hierarchical organization at the multiscale. Such features determined very high mechani-
cal strength and damage-tolerant mechanical behaviour, thus resulting into high mimicry of
bone tissue. In vitro tests in static and dynamic conditions showed high biocompatibility and
bioactivity, as well as overexpression of the most relevant genes involved in bone formation.

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Conclusions. These results confirm that the adoption of nature-inspired processes is an

elective approach to obtain highly bioactive materials with innate cell-instruction ability,
thanks to biomimetic features that are not achievable by the traditional ceramic processing.
Therefore, these new approaches promise to be a breakthrough in the synthesis of bioc-
eramics with boosted bioactivity, potentially opening to frontier applications in regenerative
medicine.

References
1. Anna Tampieri, Giancarlo Celotti, Elena Landi, J. Biomed Mater Res Part A 2003 67(2), 618–625.
2. Anna Tampieri, Simone Sprio, Andrea Ruffini, J Mater Chem 2009 19 (28), 4973–4980.

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Oral presentations

338
Osteogenic differentiation of human dental pulp stem cells on
bone-apatite like coatings obtained by Pulsed Electron Deposition
Michele Bianchi1, Gianluca Carnevale2, Alessandra Pisciotta2, Laura Bertoni2,
Marco Boi1, Alessandro Gambardella1, Matteo Berni1, Gabriela Graziani1,
Gregorio Marchiori1, Alessandro Russo1, Anto De Pol2, Maurilio Marcacci1
NanoBiotechnology Laboratory, Rizzoli Orthopaedic Institute, via di Barbiano 1/10, Bologna, Italy;
1

e-mail: [email protected]
Department of Surgery, Medicine, Dentistry and Morphological Sciences, University of Modena and
2

Reggio Emilia, via del Pozzo, 71, Modena, Italy; e-mail: [email protected]
Keywords: bone apatite, hydroxyapatite, Pulsed Electron Deposition, human dental pulp stem cells

Introduction. In orthopaedics and dentistry, novel approaches for fabricating biomimetic and
mechanically robust bioactive coatings are desirable in order to further improve the clinical
results of coated implants compared to uncoated ones1. Here, we report the first deposition of
bone-apatite like (BAL) coatings directly from a biogenic apatite target, by the novel pulsed
electron deposition (PED) technique2. The osteogenic potential of BAL coatings was inves-
tigated in vitro by evaluating the adhesion, proliferation and differentiation of human dental
pulp stem cells (hDPSCs) on BAL coatings.
Experimental methods. Bovine tibial shafts were deproteinized using sodium hypochlo-
rite and machined into cylindrical targets. Sintered HA targets were used as control. BAL
and HA coatings were deposited at room temperature by PED in the Ionized Jet Deposition
(IJD) version. After deposition, part of the samples was annealed at 400 °C for 1h. Sample
composition, microstructure, morphology and mechanical properties were investigated by
SEM-EDS, ICP-OES, FT-IR, XRD, AFM, contact angle measurements and nanoindentation.
hDPSCs were plated on the samples and cultured in both osteogenic and non-osteogenic me-
dium. At day 21 the expression of typical osteogenic markers was evaluated.
Results and discussion. As deposited amorphous BAL coatings showed chemical compo-
sition very close to the one of biogenic target. Upon annealing at 400 °C, also the crystallinity
resembled that of biogenic apatite. Further, mechanical properties increased with annealing
up to value comparable with those of commercial sprayed HA coatings. hDSPCs showed a
better proliferation on BAL_400 than on other coatings. Interestingly, cells reached the os-
teogenic commitment on BAL_400 without the need of an osteogenic medium. In particular,
immunofluorescence and western blot analyses revealed the expression of typical osteogenic
markers, i.e. Runx-2, Osx, osteopontin and osteocalcin, thus suggesting that BAL_400 itself
can promote the osteogenic commitment of the cells.

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References
1. S. Lazarinis et al., “Effects of hydroxyapatite coating on survival of an uncemented femoral stem”,
Acta Orthop., 8, pp. 399–404, 2011.
2. S. Gleizer et al., “Generation of high-current electron beam in a wide-aperture open discharge”, J.
Appl. Phys., 106, p. 073301, 2009.

791
Photolymerization to prepare polymeric-ceramic composites for bone
regeneration
M. Canillas1*, T. Geever, A.H de Aza, D. Devine, M.A. Rodríguez
1
Ceramic Department, CSIC, Madrid, Spain; *e-mail: [email protected]

The life expectancy in the worldwide has been increased in the last. Consequently, traumas
and bone pathologies are frequently found in older population. For this reason, the treat-
ment and regeneration of bone defects caused by traumas, tumors, infections, disorders from
skeleton development or progressive distorting illness, is a challenge with great social and
economic impact, which the modern science have to affront.
Polymeric-ceramic composites are an encouraging suggestion. Ceramic materials such as
calcium phosphates and silicates biodegrade in Ca2+, PO43– and SiO32– ions. These ions pro-
mote bioactivity and osteinduction, which are mandatory requirements in an ideal implant
for bone regeneration. The disadvantage of ceramic materials is their brittleness. However,
these ceramics materials can be embed in a biocompatible polymer matrix which improves
their mechanical properties.
Photopolymerization has been selected to prepare these composites because it is a cost-
effective method in comparison with other techniques and allows obtaining complex struc-
tures. Moreover, photopolymerization is initiated by Ultra Violet-Visible (UV-Vis) aided by
a photoinitiator. UV-Vis aids to sterilize the composite during the synthesis process. Some
ceramics can be used as photoinitiators.
PEGDMA is an excellent candidate for photopolymerization. Moreover, has been choice
due to their mechanical properties but also because of its swelling behavior. These swelling
properties make possible PEGDMA be used as drug delivery system. For example, antibiot-
ics can be delivered in situ to avoid infections.
In this study, polymeric ceramic composites have been prepared using ceramic porous par-
ticles of β-TCP, where Ca2+ has been partially substituted with Mg2+, and wollastonite. These
particles have been embed in a PEGDMA matrix. Gel fraction, swelling and mechanical
properties of the composites have been studied. Also, in vitro studies in simulated body fluid
(SBF) have been carried. Moreover, composites have been evaluated as delivery systems to
avoid infections. Finally, ceramics have been evaluated as photointiators.

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794
Seeding of lithium disilicate glass–ceramics for enhanced fracture
toughness
Emrah Dölekçekiç1, Himmet Abdullah Çelik2, Lilian B. Romero-Sánchez3,
Aránzazu Díaz Cuenca3,4
Department of Materials Science and Engineering, Anadolu University, Yunus Emre Campus
1

Eskişehir, Turkey; e-mail: [email protected]

Department of Materials Science and Engineering, Graduate School of Sciences, Anadolu University,
2

Yunus Emre Campus Eskişehir, Turkey; e-mail: [email protected]

Materials Science Institute of Seville (ICMS), Joint CSIC- University of Seville Centre, Spain;
3

e-mail: [email protected]
Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER- BBN),
4

Spain; e-mail: [email protected]

Keywords: sol-gel, toughness, SPS, biomaterials

Lithium disilicate glass-ceramic materials are a type of glass-ceramic materials, which has
as major phase Li2O-2SiO2. Lithium disilicate glass-ceramic has been the model system of
many theoretical studies with regard to nucleation and crystallization mechanism and a nu-
cleating agent was suggested as necessary component to promote nucleation and volume
crystallization in the base glass after suitable heat treatment. Recent compositional modi-
fications to lithium disilicate base glasses have yielded translucent glass-ceramics that are
characterized by high strength, excellent chemical durability, and aesthetic appearance of
natural teeth. Therefore, these types of materials are preferred for dental applications such as
veneers, crowns, bridges and implants.
In recent years, the glasses prepared through a sol-gel route are found to have advantages
over conventional glass melting method such as: better homogeneity, higher level purity,
lower stoichiometric losses and less contamination from crucibles. On the other hand, it is
generally accepted that the sol-gel route enables to provide transparent bulk materials.1
In the present work, lithium disilicate glass–ceramics were prepared by two different
methods. The first is the conventional melting of oxide powders and heat treatment to ob-
tain final glass- ceramic material. The second method, consisted of a sol-gel process for
the preparation of crystalline lithium disilicate (Li2Si2O5) phase from tetraethylorthosilicate
(TEOS) and lithium nitrate (LiNO3) precursors. The obtained Li2Si2O5 sol-gel phase powder
was mixed in different proportions as seeding agent with the other as prepared conventional
glass powder. The aim was to obtain better mechanical properties of the final glass- ceramic
material promoting a preferential growing process of some of the lithium disilicate grains
within the composite matrix. After mixing the powders, they were pressed into pellets and
densified by Spark Plasma Sintering (SPS) method. Several heat treatment schedules were
implemented and characterization techniques as XRD, SEM and Vickers hardness test were
used to essay the final glass- ceramic samples and to reveal the effect of the seeding sol-gel
material addition. Results indicate that growing of lithium disilicate giant sized grains within
a smaller component matrix could enhance both fracture toughness and strength properties
of the material.

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Reference
1. Tohidifar, M., Alizadeh, P., Riello, P., Eftekhari-Yekta, B., & Aghaei, A. (2012). Sol–gel prepara-
tion and characterization of nano-crystalline lithium–mica glass–ceramic. Ceramics International,
38(4), 2813–2821. doi:10.1016/j.ceramint.2011.11.052

239
Spark plasma sintering of 13-93 bioglass composites reinforced with
in situ reduced graphene oxide
Siamak Eqtesadi1, Azadeh Motealleh1, Fidel H. Perrera2, Angel L. Ortiz2, Pedro Miranda2,
Antonia Pajares2, Rune Wendelbo1
1
Abalonyx AS, Oslo, Norway; e-mail: [email protected]
2
Engineering School, University of Extremadura, Spain
Keywords: 13-93 bioglass, spark plasma sintering, graphene, mechanical characterization

13-93 bioactive glass has a fairly large window between glass transition and the onset of
crystallization which greatly promotes its full densification by viscous flow sintering without
crystallization occurring. This has facilitated the fabrication of porous bioactive scaffolds
from this glass composition by a variety of shaping methods, including robocasting.1 Ro-
bocasting, also known as direct-write assembly or direct-ink writing, is an extrusion-based
additive manufacturing technique and, as such, it can produce scaffolds with customized
external shape and predefined, reproducible internal architecture.
As a consequence of this greater control over pore architecture, robocast 13-93 bioglass
scaffolds exhibit much higher mechanical strength than 13-93 scaffolds made by conven-
tional techniques.2 However, the intrinsic poor toughness of 13-93 bioglass still limits the
mechanical performance of 13-93 robocast scaffolds for load bearing applications.
Graphene, a monolayer of carbon atoms arranged in a honeycomb lattice, has shown im-
pressive thermal, mechanical, and electrical properties, and is a promising alternative as a
reinforcement to tailor the material structure at nanometre scale in order to obtain stronger
and tougher engineering ceramics.3
The current study reports the use of graphene-like nanoplatelets to enhance the fracture
toughness of 13-93 robocast bioglass scaffolds. 13-93 robocast scaffolds with a fixed three-
dimensional design and different loadings of graphene oxide (GO) were sintered by spark
plasma sintering (SPS) at a relatively low temperatures, during which in situ partial thermal
reduction of GO took place. The resulting robocast 13-93 bioglass scaffolds reinforced with
reduced graphene oxide (rGO) were subject to an ample study covering aspect of processing,
sintering, microstructural characterization, and mechanical performance.

References
1. A.M. Deliormanli, M.N. Rahaman, Direct-write assembly of silicate and borate bioactive glass
scaffolds for bone repair, J. Eur. Ceram. Soc. 32, pp. 3637–3646, 2012.
2. S. Eqtesadi, A. Motealleh, A. Pajares, P. Miranda, Effect of milling media on processing and per-
formance of 13-93 bioactive glass scaffolds fabricated by robocasting, J. Ceram. Int, 41 (1), pp.
1379–1389, 2015.
3. S. Eqtesadi , A.Motealleh, R.Wendelbo, A. L. Ortiz, P. Miranda, Reduced graphene oxide rein-
forced bioactive glass composite scaffolds fabricated by robocasting, J. Eur. Ceram. Soc, In Press.
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415
Flash sintering of TCP
Matteo Frasnelli1,3, Vincenzo Maria Sglavo2,3
Department of Industrial Engineering, University of Trento, via Sommarive 9, 38123 Trento, Italy;
1

e-mail: [email protected]
Department of Industrial Engineering, University of Trento, via Sommarive 9, 38123 Trento, Italy;
2

e-mail: [email protected]
INSTM – National Interuniversity Consortium of Materials Science and Technology, Trento
3

Research Unit, Via G. Giusti 9, Firenze 50121, Italy

Keywords: flash sintering, tricalcium phosphate, β→α phase transition, bioceramics

In this work, sintering behavior of tricalcium phosphate (TCP) ceramics under the effect of
an external electrical field (in flash sintering configuration) was analyzed to obtain dense
bio-resorbable components. The aim was to understand the physical condition leading to the
flash phenomenon and to study the effect of consequent reduction in sintering time and tem-
perature on the undesired β→α-TCP phase transition occurring at high temperature.
TCP powders were synthesized by conventional solid state reaction and then shaped into
cylindrical green body by uniaxial cold-pressing. Their sintering behavior was studied by
dilatometry under different E-field at constant rate heating. The presence of α-TCP and the
microstructure were investigated by XRD and SEM techniques.
It is shown that a flash phenomenon takes place at furnace temperature below 1000 °C.
In addition, although β→α transition occurs at ~1150 °C for pure TCP, the detection of both
polymorphs within the sintered bodies indicates that higher temperature is reached in the
material, which is very likely associated to Joule effect induced by the current flow along
the sample.

189
Translucent zirconia-silica glass ceramic for dental restoration:
structure related mechanical strength
Le Fu, Håkan Engqvist, Wei Xia*
Applied Materials Science, Department of Engineering Science, Uppsala University, Uppsala,
Sweden; *e-mail: [email protected]
Keywords: glass ceramic, ZrO2-SiO2, translucency, dental application, mechanical strength

ZrO2-based full ceramic have been widely accepted as a promising dental ceramic because
of their excellent mechanical properties and good biocompatibility. However, the aesthetics
of ZrO2-based full ceramics needs to be improved because of the opacity.1 Glass ceramic,
such as lithium disilicates, is widely used due to its excellent translucency, allowing for more
flexibility to adapt to the colour of the surrounding teeth. However, glass ceramics generally

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have flexural strength and fracture toughness, generally less than half of the full ceramics.
This limits the application of glass ceramics on long bridgeworks. Nanocrystalline materi-
als (NCM) shows significantly enhanced properties and thus have been the subject of con-
siderable research over the past three decades2. Among the different types of NCMs, tough
and high-modulus nanocrystalline glass ceramics (NCGC) has potential applications in load
bearing parts as a biomaterial. Thus, a ZrO2 based glass ceramic which possess an excellent
combination of high strength and translucency would be a promising alternative ceramic in
dentistry.
This study aims to obtain ZrO2-SiO2 glass-ceramic that possess high mechanical strength
as well as excellent translucency by controlling the content, size, and connection of nanocrys-
talline ZrO2. Toward this end, homogenous nano-powders with three different compositions
were synthesized by sol-gel method, followed by spark plasma sintering. Highly-translucent
nanocrystalline glass ceramics (NCGC) were obtained. Tetragonal ZrO2 was the only crystal-
line phase in all the glass ceramic samples. Samples with high zirconia content showed that
the structure of the skeleton was predominately built by nano-sized ellipsoidal ZrO2 particles
bonded by grain boundaries, with amorphous SiO2 filling the voids between the ZrO2 par-
ticles. One of the compositions achieved a flexural strength of 1014 MPa. To our knowledge,
1014 MPa is the highest flexural strength value of glass ceramics ever reported, which is
much higher than transparent zirconia and alumina ceramics. In conclusion, the ZrO2-SiO2
NCGC developed in this study showed promising potential for use in dental restoration.

References
1. C. Piconi and G. Maccauro. “Zirconia as a ceramic biomaterial”. Biomaterials., 20, pp. 1–25, 1999.
2. H. Gleiter, “Nanostructured materials: basic concepts and microstructure”, Acta. mater., 48, pp.
1–29, 2000.

206
Development and characterization of multi-element doped
hydroxyapatite coatings for orthopaedic applications
Monika Furko*, Csaba Balázsi
Centre for Energy Research, Hungarian Academy of Sciences, 1121, Budapest,
Konkoly-Thege Miklós út 29-33, Hungary; *e-mail: [email protected]
Keywords: bioceramic coatings, hydroxyapatite, biocompatibility, corrosion

Nowadays, intensive efforts are being made to develop such coatings that possess antimicro-
bial and biocompatible properties at the same time in order to prevent post-operative infec-
tions. These coatings can be silver (Ag), zinc (Zn), strontium (Sr) and magnesium (Mg) doped
hydroxyapatite. Among all of the antimicrobial materials, Ag is the most economic and most
effective in action against various sorts of bacteria. The main advantage of silver compared to
other antimicrobial materials is that bacteria will not become resistant to silver and the effect
of silver ions is continuous and prolonged. One major advantage of hydroxyapatite coatings

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loaded with silver and other biocompatible minerals is that they promote bone growth, accel-
erate the wound healing process owing to the Zn content, thus increasing the biocompatibility
ability of the implant materials. In our research work, the coatings were prepared by pulse
current deposition method. The hydroxyapatite layers were doped with mineral elements
either with co-deposition or with surface post-treatment with solutions c­ ontaining the neces-
sary components. The basic electrolyte solution contained Ca(NO3)2, NH4H2PO4 and H2O2 at
pH of 4.3 and the electrodeposition process was carried out at 70 °C. Since the as-deposited
calcium phosphate coating was mainly in Monetite phase, after deposition, the samples were
immersed into 1 M NaOH solution to achieve phase transformation into Hydroxyapatite.
The biodegradable properties of the layers were evaluated by electrochemical tests in simu-
lated body fluid (SBF) at temperature of 37 °C. Electrochemical Impedance Spectroscopy
(EIS) measurements were performed also to test the samples’ corrosion stability. All the
electrochemical tests were carried out using a classical three electrodes cell with platinum as
counter electrode, saturated calomel electrode SCE as reference electrode and the samples as
working electrode. The surface morphologies and grain size of samples were also observed
by SEM measurements1–3.

References
1. M. Furko, M. Lakatos-Varsányi and C. Balazsi “Complex electrochemical studies on silver coated
metallic implants for orthopaedic application” J. Solid State Electr., 20, pp. 263–271, 2016.
2. M. Furko, Y. Jiang, T.A. Wilkins and C. Balázsi “Development and characterization of silver and
zinc doped bioceramic layer on metallic implant materials for orthopaedic application” Ceram.
Internat., 42 (4) pp. 4924–4931, 2016.
3. M. Furko, Y. Jiang, T.A. Wilkins and C. Balázsi “Electrochemical and morphological investigation
of silver and zinc modified calcium phosphate bioceramic coatings on metallic implant materials”
Mat. Sci. Eng. C, 62, pp. 249–259, 2016.

624
Cleaning with photons: challenges and opportunities of photocatalytic
water and air sterilization
Endre Horváth
Laboratory of Physics of Complex Matter, Ecole Polytechnique Fédérale de Lausanne, Station 3,
CH-1015 Lausanne, Switzerland; e-mail: [email protected]
Keywords: micropollutants, ceramic filter, reactive oxygen species, advanced oxidation processes

The discovery of photocatalytic water splitting and photocatalysis dates back to the 1970s.
Since then, several semiconductor nanoparticles have been found to have remarkable pho-
tocatalytic activity to eliminate health-threatening bacteria, viruses, worms and persistent,
bioaccumulative organic water pollutants as pharmaceuticals, pesticides and endocrine dis-
ruptors. Surprisingly, despite significant research efforts, studies have mainly remained in the
stage of laboratory experiments and only a limited number of products using this technology
can be found on the market. Materials and devices with sufficient efficiency, stability and low

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cost are yet to be demonstrated. Among the known semiconductor photocatalysts, titanium
dioxide (TiO2) is the most popular owing to its excellent chemical stability, low toxicity and
low cost.

I will discuss the main technical barriers impeding the commercialization of this technol-
ogy and show several strategies as potential countermeasures to improve the photocatalytic
efficiency of titania based solar environmental purification systems. As an example, the first
prototype of a low cost, durable and easy to operate solar-thermal water purification device
will also be presented, which allows the production of bio-hazard-free drinking water from
contaminated water resources.

Acknowledgement
We gratefully acknowledge the financial support of EPFL AIT Innovation Grant and the Zeno-Karl
Schindler Foundation.

135
Novel nanocomposite ceramic scaffold fabricated via 3D printing for
cancer therapy application
Amirsalar Khandan*, Neriman Ozada
Mechanical Engineering Department, Eastern Mediterranean University, North Cyprus, Gazimağusa,
TRNC, Mersin 10, Turkey; *e-mail; [email protected]
Keywords: ceramic, magnetite, scaffold, cancer therapy, biomaterials

Cancer is the second advance cause of mortality in the world. The method approaches in-
clude surgery, radiation, and thermal therapy practiced depending on tumefaction type and
level of cancer syndrome. Through chemotherapy cases usually, encounter dangerous side

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effects due to a lack of tumor-specific uptake occurring in injury to normal organ tissues.
Magnetite ceramic is a bioresorbable material that has been widely employed in the bioma-
terials domain and cancer therapy plans. The association of nano-magnet or blending of it is
with silicate ceramics like bredigite or akermanite ceramics has allowed a variety of nano-
composite materials including significantly developed mechanical and biochemical proper-
ties before-mentioned strength, arrangement, porosity, degradation speeds, and bioactivity
that are necessary for tissue manufacturing.1,2 These features are immediately associated with
the structure and their range of porosity, as well as the dimension of their pores and their
interconnectivity.2,3 In this study, the 3D printing (3DP) stands out, where the composition
of ceramics is achieved layer by layer, according to a planned computational design which
gives a comprehensive direction of structure and scaffold geometry. The aim of this research
was to develop, for the first time, three-dimensional magnetite-bredigite scaffolds containing
various amounts of magnetite nanopowder. Morphology of bioactive surface of scaffolds was
investigated. Furthermore, the effects of scaffold composition on the bioactivity, and biode-
gradability were also evaluated. Indeed, the micro-pore size of the scaffolds decreased with
progressing bredigite content proving that the sinterability of the scaffolds was developed.
The nanocomposite scaffolds revealed higher bioactivity and biodegradability with increas-
ing magnetite content as a biological features. In this work, the optimum sample depending
on magnetite content which shows a potential candidate for bone tissue engineering.

References
1. Kazemi, A., Abdellahi, M., Khajeh-Sharafabadi, A., Khandan, A., & Ozada, N. (2017). Study of
in vitro bioactivity and mechanical properties of diopside nano-bioceramic synthesized by a facile
method using eggshell as raw material. Materials Science and Engineering: C, 71, 604–610.
2. Najafinezhad, A., Abdellahi, M., Ghayour, H., Soheily, A., Chami, A., & Khandan, A. (2017). A
comparative study on the synthesis mechanism, bioactivity and mechanical properties of three sili-
cate bioceramics. Materials Science and Engineering: C, 72, 259–267.
3. Karamian, E., Abdellahi, M., Khandan, A., & Abdellah, S. (2016). Introducing the fluorine doped
natural hydroxyapatite-titania nanobiocomposite ceramic. Journal of Alloys and Compounds, 679,
375–383.

294
Bioceramic with self-powered fluidic delivery and lubrication
Jin Ho Kim1, Ki Tae Nam2, Jimmy Xu1
School of Engineering, Brown University, 182 Hope St., Providence, RI, 02912, USA;
1

e-mail: [email protected]
Department of Materials Science and Engineering, Seoul National University, Seoul 151-744,
2

South Korea; e-mail: [email protected]

Keywords: bioceramic, hierarchically organized nanochannels, self-powered fluidic supply and
lubrication

Most living organisms are able to efficiently supply fluid and nutrients to every part of the
body by employing hierarchically organized capillaries with gradient channels. Inspired by
nature, such as bone with both sufficient mechanical strength and permeability, we developed

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a ceramic nanocomposite platform with capillary networks and capable of self-powered and
self-regulated fluidic transport. The creation of a graded micro- and nano-channel network
in hydroxyapatite bioceramic was made possible via two phase-transition mechanisms, one
being polymer-ceramic phase-segregation and the other being liquid-vapour and solid-liquid
phase transitions, both of which are pressure-temperature dependent. The pressure depen-
dences were exploited in making the gradient channels that favour directional liquid trans-
port. We directly observed cellular uptake of nutrient in this new nanostructured ceramic
material by tracing radioactive fludeoxyglucose. We also measured its mechanical strength
for load bearing and found it be similar to human bone. This approach of building into a
ceramic composite a 3D network of capillaries for self-powered and directional fluidic trans-
port opens new possibilities for ceramic applications in bone implants and in drug, lubricant,
and coolant deliveries.

792
The phase-partitioning-dependent residual stress evolution in 3Y-TZP
ceramics affecting ageing and fracture behaviour
Andraž Kocjan1*, Jasna Cotič2, Dušan Bučevac3
1
Department for Nanostructured Materials, Jožef Stefan Institute, Ljubljana, Slovenia;
*
e-mail: [email protected]
2
Department of Prosthodontics, Faculty of Medicine, University of Ljubljana, Slovenia
3
Vinca Institute of Nuclear Sciences, University of Belgrade, Serbia
Keywords: zirconia, phase transformation, X-ray diffraction, annealing, ageing, fracture

Yttria-stabilized tetragonal zirconia (3Y-TZP) is today’s ceramic material of choice in den-

tistry owing to its improved aesthetic appearance compared to metals, excellent biocom-
patibility and mechanical properties. The mechanical performance and the susceptibility to
controversial low-temperature degradation (LTD) ageing process is governed by stress- and
moisture-induced tetragonal-to-monoclinic (t–m) transformation, respectively. However, t–m
transformation not only depends on factors such as grain size and yttrium concentration/seg-
regation, but also on the internal residual stresses that evolve during sintering-related phase-
partitioning and during mechanical and thermal handling procedures.
We have investigated the influence of the phase partitioning of 3Y-TZP ceramics on the
stability and the structure of transformable yttria-lean tetragonal phase (YLZ) and un-trans-
formable yttria-rich phases (YRZ; t``– and t`–prime) and on the formation of residual stresses
in YRZ, further affecting the ageing kinetics and fracture mechanics. The results obtained,
by employing XRD (MAJ equation and Rietveld refinement), FIB-SEM, Vickers indenta-
tion and flexural strength measurements, indicate that the formed YRZ phases are under
compressive stresses in the 3Y-TZP matrix, since a systematic relaxation after ageing and/
or annealing was observed. The observed relaxation puts additional perspective on the un-
derstanding of the t–m transformation mechanism ultimately governing both the ageing and
fracture behaviour in 3Y-TZP.

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188
Micro-patterning of calcium phosphate bioceramics with femtosecond
laser
Marie Lasgorceix1, Cédric Ott1, Laurent Boilet1, Stéphane Hocquet1, Anne Leriche2,
Maria Helena Fernandes3, Fernando Jorge Mendes Monteiro4, Véronique Lardot1,
Francis Cambier1
1
Belgian Ceramic Research Centre, member of EMRA, Avenue Gouverneur Cornez, 4, B-7000 Mons,
Belgium
2
LMCPA-UVHC, Pôle Universitaire de Maubeuge, Boulevard Charles de Gaulle, 59600 Maubeuge,
France
3
Faculdade de Medicina Dentária, Rua Dr. Manuel Pereira da Silva, 4200-393 Porto, Portugal
4
Laboratorio de Biomateriais, INEB - Instituto de Engenharia Biomedica, Rua do Campo Alegre 823,
4150-180, Porto, Portugal
Keywords: CaP ceramics, laser patterning, physico-chemical surface characterization, biological
assessment

The bioactivity of synthetic bone implants is highly impacted by their surface topography,
especially by the presence of micro-patterns likely to influence cell behaviour.
In this study, laser machining technology was employed in order to produce controlled
regular micro-patterns on dense calcium phosphate surfaces, without any contamination. The
choice of the source was directed towards a femtosecond pulsed laser, with 1030 nm wave-
length and 270 fs pulse width, in order to limit the thermal impact of such a process and
thus to avoid the unwanted phase transformations potentially induced by the temperature
elevation. Beta tricalcium phosphate substrates with perfectly controlled micro-patterning
and without any secondary phase were obtained by controlling the process parameters (laser
power, scanning speed, pulse frequency). An accurate optimization of the process parameters
allowed obtaining micropatterns with several complex designs. The microstructural charac-
teristics were investigated by microscopy (optical, confocal, scanning electron) and the phase
identification was performed by X-Ray Diffraction and Raman spectroscopy. This work al-
lowed highlighting the effects of the process parameters on the patterning.
The influence of surface micro-patterning on bone marrow stem cell behaviour was high-
lighted in vitro. In particular, an elongation of the cells shape was observed along linear
grooves made by laser machining, whereas cells appeared more spread on smooth surfaces
with same chemical composition. These results show that linear patterning should promote
cell migration. The effects of the micro-patterning design and particularly the presence of
angular shapes, on cell adhesion, proliferation and differentiation are currently evaluated in
vitro.
To conclude, femtosecond laser machining technique seems to provide an interesting al-
ternative to conventional ceramic surface treatments of calcium phosphates. This technology,
which allows a minimization of the thermal impact, appears promising and can now be en-
visaged for the surface treatment of calcium phosphate ceramics or even calcium phosphate
coatings used for bone tissue engineering.

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Acknowledgements
The authors are grateful to the Walloon Region for financial support, within the “BEWARE” program
(convention n°1510392) co-funded by Wallonia and European Union (FP7 – Marie Curie Actions). All
the authors also thank the JECS Trust Action “Frontiers of Research” for the financial support facilitat-
ing the collaborative work between laboratories.

427
Evaluation of prospective perovskite mediators for magnetic fluid
hyperthermia
Katherine McBride1, Suzanne Bennington-Gray2, James Cook1,2, Lorenzo Stella1,2,
Solveig Felton2, Danai Poulidi1*
School of Chemistry and Chemical Engineering, Queen’s University Belfast, Stranmillis Road,
1

Belfast BT9 5AG, UK

School of Mathematics and Physics, Queen’s University Belfast, University Road, Belfast BT7 1NN,
2

UK; *e-mail: [email protected]

Keywords: AC magnetic field, Lanthanum strontium manganese oxide, LSMO, perovskite, peroxide
sol-gel, microwave, induction heating, magnetocaloric effect, specific absorption rate

Contemporary modalities for ‘Magnetic fluid hyperthermia’ (MFH) involve the use of a col-
loid of magnetic nanoparticles (MNPs), which in the presence of an AC magnetic field induce
a temperature increase of between 41 °C to 46 °C, selectively damaging cancerous tissue.1
The majority of materials investigated for MFH until recently were iron-based2 as they are
biocompatible with high Specific absorption rates (SARs), but, their high Curie temperatures
(Tcs) mean that an applied field may lead to overheating of local tissue. Initial research to
reduce the Tc to within the therapeutic range showed that the perovskite Lanthanum strontium
manganate (La1-xSrxMnO3, LSMO) was promising as a prospective mediator3 and is the focus
of our work. MNP clusters were synthesised and characterised via SEM, IR spectroscopy
and XRD with Rietveld analysis in order to confirm the crystalline phases, crystallite size
and morphology. The magnetic properties (magnetic susceptibility, Tc and magnetocaloric
effect (MCE) were assessed using magnetic heating experiments and the Superconducting
quantum interference device (SQUID). Initial characterisations of LSMO synthesised using
a modified peroxide sol-gel method at a range of dopant levels confirmed La0.65Sr0.35MnO3
to give the optimal induction heating results (Tc of 89 °C, Tmax of 46.7 °C and SAR of 56
W gMn−1.4 We also observed an increase in orthorhombic crystal structures with increasing
strontium dopant. Other dopants (Ba and Ca) were also evaluated, with magnetic heating
observed for materials with larger A-site dopant radii relative to La3+; and reduced magnetic
heating effects observed for smaller A-site dopant radii.5 Subsequent work has dealt with
the optimisation of LSMO (decreasing aggregate size, increasing SAR) using a variety of
synthetic approaches, including a microwave assisted method where SARs as high as 175
W g Mn–1 were achieved. The enhancement of magnetocaloric effect was ascribed to a greater
core ferromagnetic contribution as a result of the improvement in the degree of crystallinity
and magnetic susceptibility of the samples.

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References
1. Y. Fukumori and H. Ichikawa, Advanced Powder Technology, 2006, 17, 1.
2. P. Pradhan, J. Giri, G. Samanta, H.D. Sarma, K.P. Mishra, J. Bellare, R. Banerjee and D. Bahadur,
J. Biomed. Mater. Res., 2007, 81B, 12.
3. S. Vasseur, E. Duguet, J. Portier, G. Goglio, S. Mornet, E. Hadová, K. Knížek, M. Maryško, P.
Veverka and E. Pollert, J Magn Magn Mater, 2006, 302, 315.
4. K. McBride, J. Cook, S. Gray, S. Felton, L. Stella and D. Poulidi, CrystEngComm, 2016, 18, 407.
5. K. McBride, N. Partridge, S. Bennington-Gray, S. Felton, L. Stella and D. Poulidi, Mater. Res.
Bull., 2017, 88, 69–77.

449
The potential of high borate glasses for transarterial embolization
Kathleen O’Connell1, Daniel Boyd1,2
Department of Applied Oral Sciences, Dalhousie University, Halifax, Canada;
1

e-mail: [email protected]
Department of Biomedical Engineering, Dalhousie University, Halifax, Canada;
2

e-mail: [email protected]
Keywords: borate glass, gallium, therapeutic inorganic ions, transarterial embolization

Introduction: Research into borate glasses has been significantly dwarfed in comparison to
other oxides; an estimated 15.5% of oxide glass research was dedicated to borates during
1850–2013, while approximately 70% accounted for silicates1. Nonetheless, borate glasses
have (i) displayed promising therapeutic potential and (ii) the ability to modulate material
properties by compositional modifications. Within this study, a high borate glass system was
investigated as a novel resorbable material for transarterial embolization (TAE) purposes,
serving as a delivery platform for the therapeutic inorganic ion gallium, while also providing
for indication specific characteristics, i.e. a resorbable imageable material.
Materials and Method: Six glasses (70B-20Sr-10-x(Ga)Na (x = 0, 2, 4, 6, 8, 10, mol%)
were melted and processed to a particle size distribution of 45–150 μm. Structural analysis of
each composition was done via magic angle spinning nuclear magnetic resonance spectros-
copy. Glass transition temperatures (Tg) were determined by differential scanning calorim-
etry and radiopacity was verified using computed tomography at 120 kV. Ion release kinetics
for each element in each composition was determined by ICP-OES (up to 30-days). The theo-
retical mass loss was calculated from cumulate ion release and theoretical glass composition.
Results: Initial substitutions of Ga2O3:Na2O resulted in destabilization of the network.
However, at ≤6:4 Ga2O3:Na2O ratio, network stabilization occurred with an (i) increase in
Tg, (ii) a decrease in total ion release at 30-days of extraction, and (iii) a reduction in mass
loss. Maximum mass loss was observed to be 66% reducing to 39%, at the highest Ga2O3
loading. Ga release followed a similar trend with the highest release at 6:4 ratio and a de-
crease thereafter. 11B MAS NMR showed that increasing Ga2O3:Na2O caused a linear increase
of B[3] at the expense of B[4] groups. The data indicates the potential formation of GaO4–
tetrahedral, causing network stabilization to occur. Radiopacity increased from 3236 to 4943

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HU, higher than a clinically used commercial control (Contour™), which has been recorded
to be 2520 HU2.
Conclusion: A maximum mass loss of 66% was obtained and Ga ion release was main-
tained for up 30 days. A clinically relevant radiopacity was obtained, which would aid by
providing spatial and temporal distribution of materials in target tissues. All of which indicate
that borate glass systems have a very real clinical potential in TAE procedures.

References
1. J.C. Mauro, “Two Centuries of Glass Research: Historical Trends, Current Status, and Grand Chal-
lenges for the Future”, IJAGS, 5, pp. 313–327, 2014.
2. S. Kehoe, E. Tonkopi, R.J. Abraham, D. Boyd, “Predicting the thermal responses and radiopacity
of multicomponent zinc–silicate bioglasses: A focus on ZnO, La2O3, SiO2 and TiO2”, J. Non-Cryst.
Solids, 358, pp. 3388–3395, 2012.

801
Design and characterization of porous ceramic membranes for passive
sampler of water contaminants
Victor M. Orera1*, Helena Franquet-Griell2, Jorge Silva1, Víctor Pueyo2, Silvia Lacorte2
1
Instituto de Ciencia de Materiales de Aragón. CSIC-Universidad de Zaragoza. c/Pedro Cerbuna 12,
50009, Zaragoza, Spain; *e-mail: [email protected]
2
Department of Environmental Chemistry, IDAEA-CSIC. c/Jordi Girona 18, 08034 Barcelona, Spain
Keywords: passive sampler, ceramic membrane, flow rate, diffusion coefficient

The increasing presence of “emerging contaminants” in wastewaters represents a potential

environmental risk. However, very little is known about the incidence and real dangers in-
volved due in part to analytical complications. In order to properly formulate preservation
regulation more information about the impact of presence of these contaminants in environ-
ment is necessary. Environmental monitoring tools require the use of efficient and reliable
sampling and analytical techniques. Currently, grab sampling is the most common way to
monitor surface waters although it might not be completely representative if contamination
fluctuates with time. Alternatively to active sampling, passive or diffusive samplers (PS)
offer information on average pollution levels over several hours or days. PS devices allow
the free flow of contaminants from the media to the receiving phase due to the difference
in chemical potentials between the external and internal area of the sampler. Organic com-
pounds are retained inside the sampler and its efficiency and performance depends on the
design of the membrane as well as the polarity and solubility of the contaminants, the nature
of the sampled water and properties of the receiving phase. The aim of this study was to
develop and characterize macroporous ceramic membranes for passive samplers (MCPS)
for the analysis of water contaminants. The MCPS’s designed consist in an alumina porous
ceramic tube in which the pore morphology and membrane thickness were varied to achieve
for different sampling rates of organic compounds. In this study we used methylene blue as
test compound, which can be measured by spectrophotometry to evaluate the diffusion dy-

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namics of the ceramic membranes. This study also compiles the evaluation of the diffusion
coefficients, membrane geometrical factor, tortuosity factor and sampling rate of the ceramic
membranes. Three different membrane configurations were prepared by slip casting using
different pore former, cornstarch and graphite, and membrane thickness. Membranes with
34.5% and 36.9% connected porosity and 1.5 mm thick and with 39.6% open porosity and
1.1 mm thickness were prepared. The pore configuration is bimodal with pores of 80–200
nm diameter. The systems herein proposed represent a new, robust and effective sampling
devices to determine water contaminants as allow a high flux of contaminants through the
ceramic membrane and a high accumulation potential in the receiving phase.

291
Influence of carbonate groups on the low-temperature consolidation by
spark plasma sintering of phosphocalcic bioceramics
Camille Ortali1*, Christophe Drouet2, Isabelle Julien1, Éric Champion1
1
SPCTS, Université de Limoges, CNRS, ENSCI, 12 rue Atlantis, 87068 Limoges, France
2
CIRIMAT, Université de Toulouse, CNRS, INPT, UPS, ENSIACET, 31030 Toulouse, France
Keywords: bioceramics, carbonated apatites, Spark Plasma Sintering, low-temperature sintering

Carbonated hydroxyapatites (CHA) have crystal structure and chemical composition

(Ca10x(PO4)6-x(HPO4,CO3)x(OH)2-x-2y(CO3)y) close to the mineral part of bone. In contrast to
the stoichiometric calcium phosphate hydroxyapatite conventionally used to manufacture
implants for bone replacement, they are expected to exhibit better biological properties in
terms of dissolution and resorbability. However the main drawback of CHA is to get de-
carbonated at low temperature, which makes the consolidation of ceramic parts difficult by
conventional sintering.1 Previous studies have shown that it was possible to consolidate at
low temperature biomimetic nanocrystalline apatite at low temperature (T<300 °C) using
Spark Plasma Sintering (SPS).2 The challenge of our study was to consolidate CHA ceramics
at low temperature by SPS in order to retain the carbonates in the apatite structure as well as
a low crystallinity: the objective being to produce a sintered ceramic material with chemical
characteristics approaching those of the bone mineral.
The study showed that consolidation at very low temperature (150 °C) by SPS to produce
carbonated apatite ceramics was possible provided that the initial powder, synthesized by
aqueous precipitation, was amorphous. Conversely, crystallized powders did not consolidate
in the experimental SPS conditions tested. This consolidation occurred in the same time as
the crystallization of the amorphous compound into apatite. The ceramics obtained were low-
crystalline, microporous, non-stoichiometric carbonated apatites having grains of nanometric
size and presented advantageous mechanical properties (biaxial flexural strength of 18 MPa).
A thorough investigation of this material was carried out by Fourier Transform Infrared
Spectroscopy (FTIR). The distribution of labile (surface) and bulk carbonate species in the
A or B sites of the apatite was evaluated, using spectral decomposition and analysis of the

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vibration bands of the PO43– and CO32– groups, in order to refine the composition of the sin-
tered material.
For more investigation of the phenomena observed during SPS, calcium phosphate pow-
ders of variable chemical composition and crystallinity were also carbonated by surface ion
exchange. Then, they were heat-treated by SPS. This method of powder carbonation was set
up in order to determine if only the carbonation of calcium phosphate particles surface could
be sufficient to obtain consolidated carbonated apatite ceramics after SPS. The characteriza-
tion of these powders and ceramics using complementary techniques (X-Ray Diffraction,
FTIR spectroscopy) helped to specify the evolution of the chemical composition, stoichiom-
etry and crystal structure of materials during the elaboration process.

References
1. J.P. Lafon et al., J. Eur. Ceram. Soc., 2008.
2. D. Grossin et al., Acta Biomater., 2010.

798
Sol-gel derived mesoporous glasses with high surface area and good
bioactivity
Franziska Schmidt*, Fabian Zemke, Valerie Schölch, Maged Bekheet, Aleksander Gurlo
Fachgebiet Keramische Werkstoffe / Chair of Advanced Ceramic Materials, Institut für
Werkstoffwissenschaften und –technologien, Technische Universitaet Berlin, Hardenbergstrasse 40,
10623 Berlin, Germany; *e-mail: [email protected]
Keywords: sol-gel synthesis, bioactive glasses, high surface area, biomaterials

Sol-gel derived mesoporous materials are of big interest in the biomedical field. Mesoporous
and ordered mesoporous silica has been investigated as a drug delivery material, due to its
high specific surface area, high pore volume and high amount of silanol groups on the sur-
face. Based on this approach mesoporous glasses have been developed with different ions
incorporated into the silica network. By incorporating CaO and P2O5 bioactive properties can
be achieved, that are similar to the well-known bioactive glasses such as 45S5 Bioglass®.
Sol-gel is a low temperature approach that allows for a variety in compositions and shapes.
We have produced bioactive glasses in the SiO2-P2O5-CaO system by sol-gel synthesis
with high specific surface area of up to 300 m²/g, pore radius of 4 nm. We were able to in-
fluence the particle properties through varying synthesis parameters to achieve microscale
powders with spherical morphology. The resulting microspheres are promising materials for
a variety of life sciences applications, as further processing e.g. granulation, is unnecessary.
Microspheres can be applied as materials for powder based additive manufacturing, or in
stable suspensions for drug release, in bone cements or fillers.

References
1. S.M. Sze. Physics of Semiconductor Devices. John Willey and Sons, New York, 1981.
2. J. Nishizawa and K. Suto, “Semiconductor Raman laser”, J. Appl. Phys., 51, pp. 2429–2431, 1980.

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101
Phosphate based glass/ceramic coatings for therapeutic ion leaching in
orthopaedic applications
Bryan W. Stuart*, Miquel Gimeno-Fabra, Joel Segal, Ifty Ahmed, David M. Grant
Department of Mechanical, Materials and Manufacturing Engineering (Advanced Materials Research
Group), University of Nottingham, UK; *e-mail: [email protected]
Keywords: phosphate glass ceramics, heat treatment, therapeutic ions, PVD

Phosphate based glasses (PBG) are fulfilling biomaterials applications from the fibre rein-
forcement of resorbable polymeric matrices to carriers for therapeutic drug delivery. Vapour
deposition has shown its ability to condense tailorable compositions of glasses, maintaining
their amorphous tetrahedral structures.1,2 Post deposition heat treatment has been used to
relieve internal stresses in glasses, or to nucleate and grow crystals to initiate the formation
of ceramic phases, therefore stabilising their dissolution properties.3 Coatings of up to 2.7
μm thick have demonstrated linear ion release capabilities and the ability to accommodate a
vast array of potentially therapeutic ions to promote osteogenic or antimicrobial capabilities.4
Quinternary, P, Na, Mg, Ca and Fe containing coatings were deposited amorphous onto
Ti6Al4V substrates and were subsequently heat treated at 500610 °C to observe the effects
on structure and dissolution properties. Similar structural changes were observed for two
treatments at 500 °C, associated with the formation of Fe2O3 hematite crystals whilst XPS
showed a reduction of phosphorous from (21.6–1.3) at%, coupled with an increase in iron
from (1.4–22.8) at% within the surface layers. Heat treatment at 550 and 610 °C led to the
formation of multiple crystalline phases.
As deposited and heat treated coatings at 500 °C were degraded in water for up to 96 h
and assessed for ion release in ultrapure water up to 48 h whilst coatings treated at 550 °C
and 610 °C were continued up to 28 d. Heat treatment improved the durability of coatings by
diminishing the initial exponential solubility profile in the first 2 h of submersion and reduced
linear degradation rates by factors of 2.44–4.55 ± 0.35 from 500 °C–610 °C. Similarly this
was coupled with a reduction in ion release rates by maximum factors of 3.9, 4.0, 4.3, 3.4
and 7.7 for P, Na, Mg, Ca and Fe respectively. Release rates ranged from 0.39–0.05 ppm h–1,
0.01–0.02 ppm h–1 and 0.01–0.02 ppm h–1 for the as deposited, HT 500 °C, 30 min and HT
500 °C, 120 min coatings respectively.

References
1. Stuart, B., et al., Preferential Sputtering in Phosphate Glass Systems for the Processing of Bioactive
Coatings. Thin Solid Films, 2015.
2. Stuart, B.W., et al., Insights into structural characterisation and thermal properties of composition-
ally equivalent vapour-condensed and melt quenched glasses. Materials & Design, 2016.
3. Bio-Glasses: An Introduction, ed. J. Jones and A. Clare. 2012: John Wileys and Sons Ltd.
4. Stuart, B.W., et al., Degradation and Characterization of Resorbable Phosphate-Based Glass Thin-
Film Coatings Applied by Radio-Frequency Magnetron Sputtering. ACS applied materials & inter-
faces, 2015. 7(49): p. 27362–27372.

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410
Study of effective parameters on crystallization behaviour
in the erbium-doped SiO2-Al2O3-PbF2 glass ceramic system for
Ir-Vis up-conversion applications
Pooya Torab-Ahmadi, Bijan Eftekhari-Yekta*, Farhad Golestani-Fard
Ceramic Division, Department of Materials, Iran University of Science and Technology (IUST),
Narmak, Tehran, 16846, Iran; *e-mail: [email protected]
Keywords: oxy-fluoride glass ceramic, PbF2 nanocrystal, up-conversion, luminescence, rare earth
ions

Recently, up-conversion materials are presented as a new candidate for specific Biomedi-
cal, photovoltaic and optical applications1. Oxy-fluoride glass ceramics can be considered as
an appropriate host for rare earth ions in optical applications rather than expensive fluoride
single-crystals2. To the best of our knowledge, glass technological topics have been neglected
in favour of optical properties in previous studies.
In this research, optimal procedures were utilized to develop SiO2-PbF2-Al2O3-ErF3 glass
and glass-ceramic samples by conventional melting method with appropriate microstructure
and optical properties. Many techniques were used to adjust melting and forming methods
such as changing mold design, controlling heat tolerance during glass melting and decreasing
fluorine loss. The thermal parameters of non-heat treated glasses with various compounds
were investigated by DTA /TG. Also, innovative thermal setup was designed to find out glass
thermal behaviour visually. According to thermal analysis results, precursor glass samples
were heat treated. The heat treated samples phase transition, microstructure and absorption-
transmission spectra were identified by XRD, SEM/FESEM and UV-VIS double beam Spec-
trophotometer, respectively. Moreover, the effects of Er3+ doping and increasing Al2O3 con-
tent on Glass-making capabilities, fluorine loss, phase separation mechanism, crystallization
behaviour and optical properties were studied.
Increasing 10mol% Al2O3 content in glass compound played key role in decreasing evapo-
ration rate during melting (near 8wt%), increasing Ir-Vis transparency (about 20%), improv-
ing the crystallization stability more than 100 oC, preventing uncontrollable and extensive
phase separation in glasses; Although Al2O3 addition disturbed single phase crystallization
of PbF2. Results distinctly showed that the presence of Er3+ ions in composition had signifi-
cant effect on phase separation, β-PbF2 single phase crystallization and crystallite size and
distribution. In addition, Er3+ ions created specific absorption peaks in transmission spectra
(400–1100 nm) which are appropriate for up-conversion process. Green and red up-conver-
sion luminescence emissions were observed after 980nm laser excitation. This phenomenon
demonstrated β-PbF2:Er3+ formation. Furthermore, β-PbF2:Er3+ lattice parameter shrinkage
was observed with increasing Al2O3 content, which represented increasing Er3+ ions dissolu-
tion in β-PbF2 crystalline structure.

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References
1. J. Zhou, Q. Liu, W. Feng, Y. Sun and F. Li, “Upconversion Luminescent Materials: Advances and
Applications”, Chem. Rev, 115, pp. 395–65, 2015.
2. M.H. Imanieh, I.R. Martin, B.E. Yekta, J. Gonzalez-Platas and A.H. Creus, “Investigation on Crys-
tallization and Optical Properties of Ca1–xLaxF2+x Glass-Ceramics”, Am. Ceram, 97, pp. 782–788,
2014.

670
Cancer diagnosis & therapy using functionalized inkjet-printed
mesoporous silica microdots
R. Trihan1,4, A. Noureddine1, J. Graffion1, O. De Los Cobos1, M. Lejeune1, A. Aimable1,
F. Rossignol1, N. Vedrenne2, L. Micallef2, H. Akil2, F. Lalloué2, O. Baudet3, J. Desroches3,
T. Mansuryan3, C. Enguehard4, X. Cattoën5
1
Science of Ceramic Processing & Surface Treatments laboratory (SPCTS), UMR CNRS 7315,
Limoges, France
2
Cellular Homeostasis and Diseases (HCP), EA 3842, Limoges, France
3
Kamax Innovative System, 12 rue Gemini, 87280 Limoges, France
4
Dyameo, Avrul Dept Incubateur, 1 avenue Ester, 87100 Limoges France
5
Néel Institute, UPR 2940 CNRS/UJF, Grenoble, France
Keywords: mesoporous silica, Inkjet Printing (IJP), Evaporation-Induced Self-Assembly (EISA),
click chemistry, FRET

Early detection of tumors is advantageous for treatments efficiency. Studies carried out by
SPCTS and HCP laboratories have led to a patent in 2013 related to the development of an
endoscopic probe suitable for in situ early detection and local treatment of tumors1. The main
advantages of this device are to be local and non-invasive in terms of diagnosis and therapy
of cancers compared to current techniques. At first, this device is to be used for head and neck
tumors, and for breast and prostate cancers with time.
The Inkjet Printing (IJP) process allows to build 3D structures of various materials (met-
al, ceramic or polymer) with a high definition, accuracy, flexibility and on industrial scale.
Combined with Evaporation-Induced Self-Assembly (EISA) mechanism, 3D IJP allows the
deposition on the probe surface, of mesoporous silica multilayer microdots arrays2 that can
be further specifically functionalized by click chemistry3.
For the diagnosis, bioreceptors are labeled with appropriate fluorophores and anchored
to the microdots surface. When interacting with the specific cancerous biomarkers on tumor
cells, a conformation change of the bioreceptors occurs, and the fluorophores get closer.
Consequently, a Fluorescence Resonance Energy Transfer (FRET) occurs and is spectrally
detected by confocal laser microscopy or using the endoscopic device.
Once the diagnosis is effective, this device can be upgraded with therapy function. On that
purpose, Photodynamic Therapy (PDT) is used to produce singlet oxygen that leads to cells
apoptosis.

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References
1. O. De Los Cobos, M. Lejeune, F. Rossignol, J. Graffion, P. Faugeras, J. Vincent, F. Lalloué, H.
Akil, Dispositif photoactif permettant la détection et la transformation d’éléments chimiques à son
contact, French Patent N°13/01417.
2. B. Fousseret, M. Lejeune et al., Chem. Mater., 2010, 22 (13), pp. 3875–3883.
3. O. De Los Cobos, M. Lejeune et al, Chem. Mater., 2012, 24 (22), pp. 4337–4342.

114
Progress in calcium-magnesium phospho-silicate hydraulic bio-cements
for dentistry and orthopedics
T. Troczynski
Materials Engineering, University of British Columbia, Vancouver B.C., Canada

The novel Calcium Phosphate Silicate Cement (CPSC) combines the best biological and
structural properties of Calcium Phosphate Cement (CPC) and of Calcium Silicate Cement
(CSC). The resulting CPSC is relatively stronger than CPC and has extended and controlled
degradability time range, as compared with CPC. The current FDA-approved applications
of CPSC include dental root sealers and root repair materials. The materials are distribut-
ed worldwide by Vancouver BC Canada company Innovative BioCeramix Inc (IBC), and
through the associated network of distributors including Brasseler USA Inc. and Henry
Schein Inc.
One area of active CPSC research for orthopedics concerns its setting time, as the cur-
rently known CPSC variants set within ~1 hr after water contact. There is a desire to shorten
this time to < 10 min for certain dental and orthopaedic applications. One approach includes
admixture of biocompatible/biodegradable and fast-setting Mg compounds to CPSC, render-
ing it now Calcium-Magnesium Phosphate Silicate Cement (CMPSC).
This work reviews our research progress on these novel, faster-setting bio-cements, in-
cluding both CPSC, and the effects of Ca/Mg on the properties of CMPSC after hydration
(setting) at 37 ºC for various length of time, and its final properties (variation of pH, compres-
sive and 3-point bending strength, in vitro bioactivity). The phase transformations in CMPSC
during setting show that calcium hydroxide, produced during the hydration of calcium sili-
cates, reacts with the phosphate additives to form hydroxyapatite. The in-situ formation of
a nanocomposite from the hydroxyapatite and calcium silicate hydrates appears responsible
for the significant enhancement in CMPSC strength, bioactivity, and biocompatibility, as
compared to pure CSC.

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269
Diopside-tricalcium phosphate bioactive ceramics
Sari Vanhatupa1, Pilar Pena1, Carmen Baudín2*
1
Faculty of Medical and Life Sciences (MED), BioMediTech, University of Tampere, Finland
2
Instituto de Cerámica y Vidrio, CSIC, Madrid, Spain; *e-mail: [email protected]
Keywords: diopside, tricalcium phosphate, composites, microstructure, mechanical behaviour, bioac-
tivity

Bioactive ceramics of nominal compositions x Ca3(PO4)2 – (1-x) CaMg(SiO3)2 x = 100, 40

and 20 wt.%), were obtained by solid state sintering of mixtures of a fine synthetic precursor
of Ca3(PO4)2 and synthetic CaMg(SiO3)2 powders. Mixing was done by attrition milling us-
ing ZrO2 balls and the dried and sieved powders were shaped into discs by uniaxial pressing.
Sintering was performed at 1225 ºC during 2 h using 10 ºC/min as heating and cooling rates.
Final specimens were discs of about 7.7 and 3.3 mm of diameter and thickness, respectively.
Complete microstructural analysis of the sintered materials, including X-ray diffraction and
field emission scanning electron microscopy with microanalysis (FE-SEM-EDS), was per-
formed. The single phase material (TCP) was β-Ca3(PO4)2 and the composites (60D-40TCP
and 80D-20TCP) were mainly constituted of CaMg(SiO3)2 and β-Ca3(PO4)2; a small amount
of CaSiO3 (≈ 3 wt.%) was also homogeneously distributed in the microstructure. Mechanical
characterisation was performed in terms of the Weibull distribution of tensile strength deter-
mined by the Diametrical Compression of Discs Test (DCDT). Alkaline phosphatase activity
(ALP) assay of mesenchymal stem cells was performed in order to evaluate bioactivity.

Acknowledgements
Work performed in the frame of Cost action MP1301, NEWGEN and projects MAT2013-48426-C2-
1-R and PIE 20160E097 (Spain) and Jane and Aatos Erkko foundation (Finland).

805
Dental restorative ceramics: balance between aesthetics, mechanical
properties and long-term stability
Fei Zhang1,2,3, Bart Van Meerbeek2, Jef Vleugels3, Jérôme Chevalier1
1
University of Lyon, UMR CNRS 5510 (MATEIS), INSA de Lyon, France
KU Leuven (University of Leuven) & Dentistry, BIOMAT, Department of Oral Health Sciences,
2

University Hospitals Leuven, Belgium

KU Leuven (University of Leuven), Department of Materials Engineering, Belgium;
3

*
e-mail: [email protected]
Keywords: dental ceramics, translucency, mechanical properties, stability

The continuous quest for dental materials that offer adequate translucency (aesthetics) com-
bined with superior mechanical properties is driving materials science towards development
of innovative tooth-restoration concepts. Today, dentists favour all-ceramic restorations, as
they are more biocompatible (metal-free) and can provide more natural appearance.1

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In this work, yttria-stabilized zirconia ceramics with various levels of translucency were
studied. Classical 3 mol% yttria-stabilized zirconia with 0.25 wt.% alumina addition had
limited translucency. Reducing the alumina content increased the translucency but slightly
compromised the hydrothermal-aging stability. Here we show that engineering the grain
boundary of zirconia ceramics allows obtaining a better balance between the translucency,
aging-stability and mechanical properties including crack resistance and flexural strength.2,3
On the other hand, increasing the yttria content to 5 mol% resulted in high-translucent zir-
conia even for the use in front region with high aesthetic demands, but this material could
no more benefit from the transformation toughening effect of tetragonal zirconia. 5 mol%
yttria-stabilized zirconia had at the end rather similar crack resistance as lithium-disilicate
glass-ceramic for which excellent aesthetic results have been documented.4,5

References
1. I. Denry and J.R. Kelly, J. Dent. Res., 2014, 93, 1235–1242.
2. F. Zhang, M. Inokoshi, M. Batuk, J. Hadermann, I. Naert, B. Van Meerbeek and J. Vleugels, Dent.
Mater., 2016, 32, e327–e337.
3. F. Zhang, K. Vanmeensel, M. Batuk, J. Hadermann, M. Inokoshi, B. Van Meerbeek, I. Naert and J.
Vleugels, Acta Biomater., 2015, 16, 215–222.
4. P. Baldissara, A. Llukacej, L. Ciocca, F.L. Valandro and R. Scotti, The Journal of Prosthetic Den-
tistry, 2010, 104, 6–12.
5. A. Vichi, M. Carrabba, R. Paravina and M. Ferrari, Journal of Esthetic and Restorative Dentistry,
2014, 26, 224–231.

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Poster presentations

677
Morphology of hydroxyapatite crystals obtained through
the hydrothermal method
André Vitor Chaves de Andrade1*, Geovana Stafin2, Eliane Leal de Lara2,
Liziane Antunes2, Eder Carlos Ferreira de Souza2 , Christiane Philippini Ferreira Borges2,
Sandra Regina Masetto Antunes2
Department of Physics, State University of Ponta Grossa, 4748 Carlos Cavalcanti Avenue,
1

Ponta Grossa, Paraná, Brazil; *e-mail: [email protected]

Department of Chemistry, State University of Ponta Grossa, 4748 Carlos Cavalcanti Avenue,
2

Ponta Grossa, Paraná, Brazil

Keywords: biomaterial, hydroxyapatite, hydrothermal

Hydroxyapatite (HA) has been used in many areas of medicine and dentistry due to its
biocompatible character. Crystallographic and chemical studies evidence the similarity of
the synthetic material to the natural HA. This work focuses on the hydrothermal synthe-
sis method, which enables the control of the parameters associated to the synthesis.1,2 The
products obtained with this method present different morphologies and sizes. The samples
were obtained using calcium and phosphorus ion precursors respecting the 1.67 Ca/P relation
with the addition of organic additives (glycol ethylene and glycerin) to the reaction medium.
Among the characterization analyses performed, the scanning electronic microscopy allowed
the observation of the influence of the additives in the formation of crystals. The crystals kept
a hexagonal rod with different sizes and thickness. The increase in the additive concentra-
tion favored the increase in the crystal size in the direction [00l]. The crystals obtained us-
ing ethylene glycol or glycerin presented the same change patterns. The samples Ca/P ratio
was determined using energy dispersive spectroscopy which, for the synthesized samples,
remained 1.67. X-ray diffraction identified the majoritarian phase as Ca5(PO4)3OH, Space
Group P 63/m. Small amounts of calcium phosphate phases were observed in some samples.
Larger peaks observed when the additive was increased indicated reduction in the samples
crystallinity. FTIR results revealed the formation of carbonated HA. The method used in this
work resulted in the formation of crystals with different morphologies (from the prism like
format with hexagonal base to the plate format).

Acknowledgments
Authors are thankful to UEPG/CLABMU, and the financial support of CAPES, CNPq and Fundação
Araucária.

Reference
1. M. Sadat-ShojaI, et al. “Synthesis methods for nanosized hydroxyapatite with diverse structures”.
Acta Biomaterialia, 9, pp. 7591–7621, 2013.

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643
Hydroxyapatite as a system of amoxicillin controlled release
Sandra Regina Masetto Antunes1*, Rafael Eiji Saito1, Liziane Antunes1,
André Vitor Chaves de Andrade1, Christiane Philippini F. Borges1,
Jesiane Stefânia da Silva Batista3, Eder Carlos Ferreira de Souza1
1
Department of Chemistry; *e-mail: [email protected]
2
Department of Physics, Department of Structural Molecular and Genetics Biology
3
State University of Ponta Grossa, 4748 Carlos Cavalcanti Avenue, Ponta Grossa, Paraná, Brazil
Keywords: biomaterial, hydrothermal synthesis, amoxicillin

Hydroxyapatite (HA), Ca10(PO4)6(OH)2, is a biomaterial used in dentistry and medicine for

implants, due to its biocompatibility and bioactivity. HA can be associated to different types
of materials, for example, antibiotics aiming at releasing the drug directly into the damaged
tissue, reducing the risk of infection in the implant. However, the use of HA as drug release
system is dependent on its structural and morphological properties.1 Several synthesis meth-
ods are found for the production of HA, such as, precipitation, sol-gel and hydrothermal.2 In
this work a study was carried out to obtain HA through the hydrothermal and microwave as-
sisted hydrothermal methods with morphologic characteristics suitable to be used as a system
of drug controlled release. The HA samples were obtained using citric acid as complexing
agent. The samples were characterized using vibrational absorption spectroscopy in the infra-
red region by Fourier transform (FTIR) and scanning electron microscopy effect field (SEM
/ EGF) with accessory coupling spectroscopy energy dispersive (EDS). SEM results revealed
that samples obtained are HA nanoparticles with spherical agglomerates. FTIR results indi-
cated that the method enabled the formation of carbonated HA. After characterization, the
powders were associated to amoxicillin and microbiological tests in vitro were carried out.
HA associated to the antibiotic was seen to inhibit bacterial growth with the maximum re-
lease time of 72 hours. Other tests were employed to prove the controlled release profile of
HA associated to amoxicillin.

Acknowledgments
Authors are thankful to UEPG/CLABMU, and the financial support of CAPES/PNPD, CNPq and
Fundação Araucária.

References
1. F. Zheng, et al. “Characterization and antibacterial activity of amoxicillin-loaded electrospun nano-
hydroxyapatite/poly (lactic-co-glycolic acid) composite nanofibers”. Biomaterials, 34, pp. 1402–
1412, 2013.
2. M. Sadat-ShojaI, et al. “Synthesis methods for nanosized hydroxyapatite with diverse structures”.
Acta Biomaterialia, 9, pp. 7591–7621, 2013.

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531
Role of calcium aluminate phases on the apatite forming ability
Eva Bartonickova*, Jan Vojtisek, Jiri Masilko, Jaromir Porizka, Lukas Kalina,
Juliana Drabikova, Lucie Galvankova
Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkynova
464/118, 612 00 Brno, Czech Republic; *e-mail: [email protected]
Keywords: in situ foaming, hydroxyapatite-alumina composite, calcium aluminate phases, in vitro
apatite forming ability

The demands on the properties of materials that are appropriate to bone tissue replacement
are steadily growing. The reinforced HA composites belongs to ceramics with desirable os-
teoconductive and osteointegrating properties and also exhibit relatively matched mechanical
stability under the body simulated conditions1,2.
Hydroxyapatite scaffold reinforced by alumina (1 to 10 wt. %) was prepared by in situ
foaming process with the final total porosity of sintered product up to 70% t. d. The presence
of formed calcium aluminate structures were studied by in situ X-Ray diffraction analysis
from 25 °C to 1300 °C and verified by Raman spectroscopy. Phase’s morphology was ob-
served by scanning electron microscopy. The apatite forming ability was performed on the
scaffolds sintered at different temperatures with different alumina content immersed in the
simulated body fluid. The newly formed apatites were studied in order to identify their struc-
ture by X-Ray photoelectron spectroscopy and Raman microscopy. The time dependence of
released or consumed Ca2+, Al3+ and PO43– cations content in applied simulated body fluid
was monitored. The paper deals the formation of intermediate and stable phases during ther-
mal treatment of hydroxyapatite- alumina composite foams and their impact on the surface
reactions lead to newly apatite species formation.

References
1. I. Sopyan, A. Fadli, M. Mel, Effect of hydroxyapatite and tricalcium phosphate addition on protein
foaming-consolidation porous alumina, J. Porous Mater. 19 (5), pp.733–743, 2012.
2. S.M.H. Ghazanfari, A. Zamanian, Phase transformation, microstructural and mechanical properties
of hydroxyapatite/alumina nanocomposite scaffolds produced by freeze casting, Ceram. Int. 39 (8),
pp. 9835–9844, 2013.

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881
Pressureless spark plasma-sintered Bioglass® 45S5 with enhanced
mechanical properties and stress-induced new phase formation
Luca Bertolla1, Ivo Dlouhý1, Peter Tatarko2,3, Alberto Viani4, Amit Mahajan2,
Zdeněk Chlup1, Michael J. Reece1, Aldo R. Boccaccini5
1
Institute of Physics of Materials ASCR, CEITEC IPM, Zizkova 22, 61662 Brno, Czechia
2
Nanoforce Technology Limited, Queen Mary University of London, London E1 4NS,
United Kingdom
3
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 84536,
Bratislava 45, Slovakia
4
Centre of Excellence, Telˇc Batelovská 485-6588 56 Telˇc, Czechia
5
Institute of Biomaterials, Department of Materials Science and Engineering,
University of Erlangen-Nuremberg, 91058 Erlangen, Germany

Commercial Bioglass® 45S5 powder was sintered using spark plasma sintering (SPS) tech-
nique without the assistance of mechanical pressure with heating and cooling rate of 100 °C/
min, dwell temperature of 1050 °C and dwell time of 30 min. Such route enabled the produc-
tion of samples exhibiting superior mechanical properties in comparison with Bioglass® sin-
tered in furnace. In particular, flexural strength and fracture toughness reached values close
to those of apatite-wollastonite bioceramics, already widely used in clinical applications.
The residual stresses implemented by indentation promoted the formation of a new phase in
samples sintered by SPS. Complementary use of Raman and energy dispersive spectroscopy
(EDS) indicated the phase as sodium carbide and a formation mechanism was proposed.

343
Design and 3D printing of novel PCL/Bioactive glass scaffolds for bone
tissue regeneration
Michele Bianchi1, Mauro Petretta2, Chiara Gualandi3, Devis Bellucci4,
Gregorio Marchiori1, Matteo Berni1, Marco Boi1, Carola Cavallo2, Valeria Cannillo4,
Maria Letizia Focarete3, Brunella Grigolo2, Maurilio Marcacci1
NanoBiotechnology Laboratory, Rizzoli Orthopaedic Institute, via di Barbiano 1/10, Bologna, Italy;
1

e-mail: [email protected]
Laboratory of preclinical studies for regenerative medicine of the musculoskeletal system,
2

Rizzoli Orthopaedic Institute, via di Barbiano 1/10, Bologna, Italy; e-mail: [email protected]
Department of Chemistry “Giacomo Ciamician”, “Alma Mater Studiorum” University of Bologna,
3

via Zamboni 33, Bologna, Italy; e-mail: [email protected]

Department of Engineering “Enzo Ferrari”, University of Modena and Reggio Emilia, via del Pozzo,
4

71, Modena, Italy; e-mail: [email protected]

Keywords: polycaprolacton, Bioactive glass, 3D printing, Finite Element Analysis

Introduction. In this study we investigated the correlation between the mechanical proper-
ties of novel polycaprolactone (PCL)/Bioactive glass constructs and the overall compressive
strength of 3D printed PCL/Bioactive glass scaffolds. By Finite Element Analysis (FEA), it

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was possible to efficiently optimize the scaffold geometry in terms of compressive perfor-
mance for bone substitution and regeneration.
Experimental methods. The PCL/Bioactive glass composite material was realized by mix-
ing PCL pellets and bioactive glass powders with innovative formulation (BGMIX_Mg1, size
< 20 μm) containing from 0 to 50 wt.% of bioglass. Thermal analysis was conducted on PCL/
bioglass composites by DSC and TGA. The mechanical characteristics of the composites
were obtained by nano-indentation and used as input parameters for the FEA optimization
of the scaffold architecture, together with fibre and pore size, fibre orientation and layer
offset. Scaffold mechanical performance was measured in terms of compressive modulus
and maximal internal strain. To validate the FEA analysis, 3D PCL/Bioactive glass scaffolds
were printed by Fused Deposition Modeling (FDM) and compression tests were performed
on them according to ISO 844.
Results and discussion. The elastic modulus and hardness of the PCL/Bioactive glass con-
structs were ~ 0.3 GPa and ~ 19 MPa, respectively, for the 10 wt.% composite and ~ 0.6 GPa
and ~ 45 MPa, respectively, for the 30 wt.% composite. Using these values as input data,
FEA analysis showed that scaffolds with suitable geometry and composition PCL/Bioac-
tive glass 70/30 wt.%, exhibited a compressive modulus falling in the range of interest for
trabecular bone2. This approach, combining FEA and experimental tests, provided scaffolds
with strength suitable to withstand physiological loads when used as bone substituted in the
trabecular bone.

References
1. D. Bellucci et al., “Role of Magnesium Oxide and Strontium Oxide as Modifiers in Silicate-Based
Bioactive Glasses: Effects on Thermal Behaviour, Mechanical Properties and In-Vitro Bioactivity”,
Mater. Sci. Eng. C., 72, pp. 566–575, 2017.
2. P. Feng et al., “Characterization of mechanical and biological properties of 3-D scaffolds reinforced
with zinc oxide for bone tissue engineering”, Plos One, 9, p. e87755, 2014.

890
Injectable bone cement based on α-tricalcium phosphate
Daniela Brazete, Paula M.C. Torres, José M. Ferreira*
Department of Materials and Ceramic Engineering, CICECO, University of Aveiro, 3810-193 Aveiro,
Portugal; *e-mail: [email protected]
Keywords: injectable bone cements, apatite, β↔α-TCP transformation, injectability

The main objective of this work was the development of injectable apatitic calcium phos-
phate cements with mechanical properties suitable for orthopaedic applications. The initial
tricalcium phosphate powders used in this study were produced by the wet chemical precipi-
tation process, followed by heat treatment in order to obtain the desired phases (β-TCP and/
or α-TCP). The results demonstrated that the allotropic β↔α-TCP phase transformations are
noticeably affected by other experimental factors such as the cooling rate and the presence of
secondary phases of calcium pyrophosphate or hydroxyapatite.

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The calcium phosphate (CPC) bone cement pastes were prepared by mixing the pure α-TCP
powders with reactive aqueous solutions of different concentrations of sodium hydrogen
phosphate as a setting accelerator. To some aqueous solutions, additives (Aristoflex®TAC,
polyethylene glycol 600) were further added with the deliberate intention of improving the
rheological behaviour of the cementitious pastes during extrusion. However, during the in-
jectability tests, these additives were found to lower the percentage of extruded paste. It has
also been found that the particle size distribution is a crucial factor in determining the rheo-
logical behaviour of cementitious pastes.
The combination of α-TCP powder with 2.5 wt% sodium hydrogen phosphate as setting
liquid resulted in apatite cements with interesting properties from the point of view of the
injectability, microstructure, porosity, mechanical strength and crystalline phases formed.

708
Effect of hydrogen dioxide treatment on the osteogenic potential
of duck-beak bone derived natural bioceramic microparticles
Seok Hwa Choi
ChungBuk National University, Cheongju, South Korea; e-mail: [email protected]
Keywords: duck-beak, bone, osteogenic, potential, hydrogen dioxide

As an alternative material to the autogenous bone, duck-beak bone particles for bone sub-
stitute has been attracting great attention due to its biological properties. To deliver the most
favorable outcome of the medical treatment, it is essential to study the effect of various pro-
cessing methods of the duck-beak bone. In this study, we compared the two deproteinizing
agents for manufacturing duck-beak bone. Group 1 was treated by conventional chemical
agent (ethylenediamine), and Group 2 was treated by hydrogen dioxide (H2O2). In vitro and
in vivo experiments were conducted parallel to compare the cytocompatibility and osteogenic
capability between two processing methods. For in vitro tests, human adipose-derived mes-
enchymal stem cells were planted onto each sample, and their attachment and growing were
evaluated. For in vivo biocompatibility and osteogenic properties, the samples were applied
on the critical sized calvarial bone defect of the rats. Group 2 showed significantly higher cell
attachment, but Group1 showed slightly higher cell proliferation. In in vivo test, all groups
have shown biocompatibility and increased level of osteogenic potential. However, Group 2
had significantly higher bone regeneration (p < 0.05). This experiment confirmed that H2O2
can be an optimal processing method for duck-beak bone particle.

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869
Microstructure and properties of bioactive glass-ceramics
Annamária Dobrádi*, Margit Enisz-Bódogh, Kristóf Kovács
University of Pannonia (Institute of Materials Engineering, Veszprém, Hungary H-8200;
*
e-mail: [email protected]
Keywords: apatite, glass ceramics, implants, bioactive

Meat processing facilities produce significant amount of raw animal bone waste represent-
ing a serious biohazard. For this reason the safe deposition of these bones is of utmost im-
portance. The main mineral constituent of these bones is calcium phosphate, therefore they
can be used as a precursor for production of bioactive glass-ceramics. A process was devel-
oped to convert animal bones into a valuable secondary raw material of calcium phosphate
based glass-ceramics for bone replacement, tissue repair, and augmentation. Bioactive glass-
ceramics containing β-whitlockite/α-whitlockite and wollastonite were manufactured from
chemically and heat treated, protein-free bovine bone as well as a base glass prepared by
melt quenching. Body fluids (similar to the blood plasma) enhance apatite formation on the
surface of calcium phosphate based bioceramic implants, which in turn improve the bone-
binding strength of such devices. A systematic investigation of hydroxyapatite formation on
the surface of bioactive glass ceramics immersed into simulated body fluids (SBF) was there-
fore conducted on glass ceramic samples produced from high temperature sintered animal
bones. Significant changes of phase composition, microstructure, as well as microhardness of
surface prior to and after SBF-treatment were observed. Open porosity correlates with other
results. Dissolved constituents (Ca and P) of bioactive glass ceramics were quantified by X-
ray fluorescence analysis of SBF. Optimum conditions were determined by using microhard-
ness, porosity, and dissolved Ca as independent variables.1

Reference
1. T. Kokubo, H. Kushitani, C. Ohtsuki, S. Sakka and T. Yamamuro, Chemical reaction of bioactive
glass and glass-ceramics with a simulated body fliud, J. Mater. Sci.: Mater. Med., 3 (1992) 79–83.

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548
Simple and reinforced biological-derived hydroxyapatite coatings for
metallic implants
L. Duta1*, G.E. Stan2, A.C. Popescu1, P.E. Florian3, G. Popescu-Pelin1, V. Grumezescu1,
A. Achim4, M. Enculescu2, I. Zgura2, F.N. Oktar5,6, A. Roseanu3
1
National Institute for Lasers, Plasma and Radiation Physics, Magurele, Romania;
*
e-mail: [email protected]
2
National Institute of Materials Physics, Magurele, Romania
3
Institute of Biochemistry of the Romanian Academy, Bucharest, Romania
4
Center for Advanced Laser Technologies (CETAL), Magurele, Romania
5
Department of Bioengineering, Faculty of Engineering, University of Marmara, Istanbul, Turkey
6
Advanced Nanomaterials Research Laboratory (ANRL), University of Marmara, Istanbul, Turkey
Keywords: reinforced biological-derived hydroxyapatite, high adherence, in vitro tests, pulsed laser
deposition

We report on simple and reinforced hydroxyapatite (HA) thin films synthesized by Pulsed
Laser Deposition from sustainable resources (bovine and ovine bones) onto medical grade
Ti discs. The role of reinforcement agents (e.g., Li2O, Li2CO3, Li3PO4) on the morphology,
structure, bonding strength and cytocompatibility of the films was investigated by Scanning
Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), X-Ray Diffrac-
tion (XRD), Fourier Transformed Infrared (FT-IR) Spectroscopy, surface energy measure-
ments, pull-out and in vitro tests (bioactivity in simulated body fluid, SBF, and cytocompat-
ibility in human mesenchymal stem cells, hMSC).
SEM investigations evidenced that the morphology of the surfaces consisted of particu-
lates with mean diameters in the range of (2‒3) µm. FT-IR and XRD analyses demonstrat-
ed that the synthesized structures consisted of a pure HA phase, with different degrees of
crystallinity mainly influenced by the reinforcement agents. A quasi-stoichiometric target-
to-substrate transfer was inferred from EDS analyses, with a Ca/P ratio corresponding to a
biological apatite. For all synthesized structures, a hydrophilic behaviour was evidenced,
which is known in the literature to be related to an improved surface attachment of osteoblast
cells. The pull-out measurements have indicated adherence values superior to the threshold
imposed by International Standards, the highest values being determined in the case of rein-
forced structures. After only three days of immersion in SBF, FT-IR spectra corresponding
to all synthesized structures showed a remarkable growth of a biomimetic HA layer which
demonstrated the excellent bioactivity of the films. In vitro viability tests revealed that high
concentrations of Li2O within HA thin films were cytotoxic for hMSC, whilst incorporation
if Li2CO3 and Li3PO4 in HA promoted cells harmonious growth on film surfaces.
Due to proven physical-chemical characteristics and superior cytocompatibility, along
with the low fabrication cost from sustainable resources, these reinforced biological-derived
materials should be considered as a prospective solution for future progress of metallic im-
plants field.

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Acknowledgements
LD, ACP, GPP and PEF acknowledge with thanks the support of the Romanian National Authority for
Scientific Research and Innovation, CNCS-UEFISCDI, under project number PN-II-RU-TE-2014-1570
(TE 108/2015) and Core Programme – Contract 4N/2016.

693
Open-celled glass-ceramic foams from alkali activation
and sinter-crystallization of bioglasses
Hamada Elsayed1, Acacio Rincón Romero1, Chiara Vitale-Brovarone2, Enrico Bernardo1*
1
Dipartimento di Ingegneria Industriale. Università degli Studi di Padova, Italy;
*
e-mail: [email protected]
2
Dipartimento Scienza Applicata e Tecnologia. Politecnico di Torino, Torino, Italy
Keywords: alkali activation, gel casting, bioactivity, wollastonite, diopside, glass-ceramics

Highly porous wollastonite (CaSiO3)-diopside (CaMgSi2O6) glass-ceramics have been suc-

cessfully obtained by a new gel-casting technique. The gelation of an aqueous slurry of glass
powders was not achieved according to the polymerisation of an organic monomer, but as the
result of alkali activation. The alkali activation of a Ca-Mg silicate glass (with a composi-
tion close to 50 mol% wollastonite – 50 mol% diopside, with minor amounts of Na2O and
P2O5) allowed for the obtainment of well-dispersed concentrated suspensions, undergoing
progressive hardening by treatment at low temperature (80 °C), owing to the formation of
C-S-H (calcium silicate hydrate) gel. An extensive direct foaming was achieved by vigorous
mechanical stirring of partially gelified suspensions, comprising also a surfactant. The open-
celled structure resulting from mechanical foaming could be ‘freezed’ by the subsequent
sintering treatment, at 800–900 °C, causing a substantial crystallization. A total porosity
exceeding 85%, comprising both well-interconnected macro-pores and micro-pores on cell
walls, was accompanied by an excellent compressive strength, above 3 MPa. An extension of
the approach to another Ca-Mg bioglass (CEL2, richer in Na2O and P2O5), will be presented
as well.

References
1. A. Rincón, G. Giacomello, M. Pasetto and E. Bernardo, “Novel ‘inorganic gel casting’ process for
the manufacturing of glass foams”, J. Eur. Ceram. Soc., 37, pp. 2227–2234, 2017.
2. H. Elsayed, A. Rincón Romero, L. Ferroni, C. Gardin, B. Zavan and E. Bernardo, “Bioactive Glass-
Ceramic Scaffolds from Novel ‘Inorganic Gel Casting’ and Sinter-Crystallization”, Materials 10(2),
171, 2017.

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639
Influence of plasma treatments on the surface of Al2O3-5vol%ZrO2
nanocomposites in the formation of calcium phosphate phases
Julieta A. Ferreira1, Kátia H. Santos1, Denise Osiro1, Luiz A. Colnago2,
Clodomiro Alves Junior3, Eliria M.J.A. Pallone1*
1
Department of Biosystems Engineering, Sao Paulo University, Pirassununga, SP, Brazil;
*
e-mail: [email protected]
2
Brazilian Agricultural Research Corporation (Embrapa) Instrumentation, São Carlos, SP, Brazil
3
Federal Rural University of Semi-Arid, Mossoró, RN, Brazil
Keywords: nanocomposites, calcium phosphate, plasma surface treatments, biomimetic coating,
alumina-zirconia

The bioinert nature of the Al2O3-ZrO2 nanocomposites has stimulated the development of
techniques to make the biological performance of these ceramics more suitable.1 For this
purpose, the biomimetic coating has been used to promote the deposition of different calcium
phosphate phases2 onto theirs surfaces, improving the bioactivity of the Al2O3-ZrO2. Besides,
the surface treatment prior to the biomimetic coating could favor the formation of a particular
calcium phosphate phase, determining the successful implementation of an implant as well
as the influence host tissue response. Therefore, the objective of this study is to evaluate
the influence of different plasma surface treatments in the formation of calcium phosphate
phases on the surface of Al2O3-5vol%ZrO2 nanocomposites. To do so, Al2O3-5vol%ZrO2
samples were shaped, calcined at 400 °C, sintered at 1500 °C, subjected to different plasma
surface treatments (20%N2-80%H2, 40%N2-60%H2, 40%N2-40%H2-20%O2, 30%N2-50%H2-
20%O2, 100%N2 and 100%O2) and biomimetically coated. The surface characterization was
performed by atomic force microscopy, confocal microscopy, X-ray diffraction, and infrared
spectroscopy. The plasma treatments influenced the chemical and physical characteristics
of the surfaces of the nanocomposites, especially for the follow plasma compositions of
N2-H2-O2. For these conditions, the content of calcium phosphates formed was significantly
higher than for the nanocomposites treated by others plasma compositions as well as for un-
treated nanocomposites. It was also observed that the preliminary plasma surface treatment
favored much more the formation of hydroxyapatite phase than the formation of alpha-trical-
cium phosphate and beta-tricalcium phosphate phases. These differences among the content
formed phases affected the homogeneity of calcium phosphate distribution on the treated sur-
face of the nanocomposites. Thus, the plasma surface treatments that the Al2O3-5vol%ZrO2
nanocomposites undergo prior to the biomimetic coating are believed to effectively contrib-
ute to the adhesion, proliferation and biofixation of the desired cell type on bone implants.

Acknowledgement
This work has been financially supported by different Brazilian projects: FAPESP (process no
2014/11100-9), CNPq (process no 306114/2013-5) and CAPES (process no 23038.009604/2013-12).

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References
1. Y. Abe, T. Kokubo, T. Yamamuro, “Apatite coating on ceramics, metals and polymers utilizing a
biological process”, J. Mater. Sci. Mater. Med., l, pp. 233–238, 1990.
2. K.L. Santos, J.A. Ferreira, D. Osiro, G.J.A. Conceição, R. Bernardes Filho, L.A. Colnago, E.M.J.A.
Pallone, “Influence of different chemical treatments on the surface of Al2O3/ZrO2 nanocomposites
during biomimetic coating”, Ceram. Int., 43, pp. 4272–4279, 2017.

630
Characterization and SBF evaluation of neat and heat treated SiC
fibers-containing polycaprolactone composites
Yaser E. Greish, Maryam S. AlNehayan
Department of Chemistry, College of Science, United Arab Emirates University, Al Ain, UAE
Keywords: polycaprolactone, silicone carbide, thermal treatment, bioactivity, SBF media

Polycaprolactone (PCL) has been in use as a biodegradable polymer for tissue engineering
and drug delivery applications. Its application in the treatment of defective bone is based on
its integration with ceramic reinforcements to improve their mechanical properties. Among
these reinforcements, ceramic fibers provide, not only mechanical support, but may also
enhance the bioactivity of the polymer if it has its built-in bioactivity characteristics. Sili-
con carbide (SiC) is classified as a structural ceramic with superior mechanical properties.
SiC is also classified as a bioinert material. In the current study, SiC ceramic fibers, both as
received (SiC) and after heat treatment at 950 oC (TSiC), were mixed with PCL solutions in
CHCl3 in percentages up to 6 wt%. Suspensions were casted and dried at room temperature.
Composites prepared thereafter, were characterized for their composition by XRD, FTIR and
TGA techniques and for their microstructure using SEM technique. Composites were also
subjected to measurement of their tensile strength using a Schimadzu mechanical testing
machine and were evaluated for their preliminary in vitro characteristics by soaking in SBF
media for up to 14 days at 37 oC. Results showed formation of a thin layer of SiO2 onto the
surfaces of the SiC fibers. SiC and TSiC were homogeneously distributed within the PCL
polymeric matrix, as revealed by SEM investigation. Mechanical properties and SBF char-
acteristics were both shown to depend on the type and concentration of the reinforcing fibers
in the polymer matrix.

Reference
1. M.A. Woodruff, D.W. Hutmacher. The return of a forgotten polymer- Polycaprolactone in the 21st
century. Progress in Polymer science. 35, pp. 1217–1256, 2010.

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602
Preparation and characterization of HAp-wollastonite composites
and their performance in SBF media at 37 oC
Yaser E. Greish, Sulafa S. Abdel Halim, Anood M. Al Saedi, Aysha A. Al Kaabi
Department of Chemistry, College of Science, United Arab Emirates University, Al Ain, UAE
Keywords: hydroxyapatite, wollastonite, chemical synthesis, bioactivity, SBF media

Hard tissues, such as bone and teeth, are natural composites of hydroxyapatite (HAp) nano-
crystallites and collagen nanofibrils.1 The unique properties of natural bone stems from the
mechanical interlocking between these ingredients. Bone-like implants of various composi-
tions have been prepared for total or partial fixation of defective bone. In the current study,
bone-like HAp was prepared in the presence of various percentages of bioactive highly crys-
talline calcium silicate (wollastonite) fibers at 70 oC and pH 10–11. Prepared composite pow-
ders were heat treated at 800 oC. As-prepared and heat treated powder composites were char-
acterized for their composition by XRD, FTIR, TGA and for their morphology using SEM
techniques. Powders were further aged in SBF media and maintained at 37 oC for up to 14
days. Results showed the dependence of the HAp structure and crystallinity on the type and
concentration of wollastonite fibers. Moreover, and after evaluation in SBF media, wollas-
tonite fibers were shown to provide sites for the precipitation of bone-like HAp crystallites,
indicating the preliminary bioactivity of the prepared composites powders.

Reference
1. R. Müller. Hierarchical microimaging of bone structure and function. Nat. Rev. Rheumatol. 5, pp.
373–381, 2009.

060
Preparation and application of silica-coated maghemite in the isolation
of plasmid DNA
Gye Seok An, Jae Uk Hur, Dong Ho Chae, Hyeon Seung Lee, Sung-Churl Choi
Division of Materials Science and Engineering, Hanyang University, Seoul, 04763, Korea;
e-mail: [email protected]
Keywords: surface treatment, superparamagnetic nanoparticle, maghemite, plasmid DNA

The aim of this study was to prepare the magnetic bead for purification plasmid DNA using
low cost γ-Fe2O3 phase nanoparticle on behalf of Fe3O4 phase nanoparticle with limited pro-
ductivity. As the technology of separation and purification biomolecule using magnetic bead
is based on the superparamagnetic property, the magnetic property of γ-Fe2O3 phase could
replace the intrinsic property of Fe3O4 phase. However, it has relatively low surface charge
for bonding SiO2 layers for selective bonding with plasmid DNA. In this study, for that rea-

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son, surface of the γ-Fe2O3 nanoparticles were modified with hydrogen chloride or ammonia,
which are acid and base, to secure a surface state for forming the SiO2 layer on its surface.
In addition, the dispersibility in the aqueous solution was improved by the modified surface
characteristic, and it could be provided an environment in which a single layer can coated on
its single particle. Surface modified the γ-Fe2O3 nanoparticles were successfully coated SiO2
layer through Stöber process. Morphology of prepared γ-Fe2O3@SiO2 nanoparticle were ob-
served by FE-SEM, and TEM. Moreover, the behavior of changes of surface properties were
measured by FT-IR, and Zeta-potential. Particle size distribution data as well as Zeta-poten-
tial value was understood tendency of dispersion force in the suspension. Magnetization of
the specimens were estimated by VSM. The performance evaluation of magnetic purification
of plasmid DNA analyzed directly by agarose gel electrophoresis and UV spectroscopy.

References
1. C.-L. Chiang, C.-S. Sung, and C.-Y. Chen, “Application of silica-magentite nanocomposites to the
isolation of ultrapure plamid DNA from bacterial cells”, J. Magn. Magn. Mater., 305, pp. 483–490,
2006.
2. Z. Zhang, L. Zhang, L. Chen, L. Chen and Q.-H. Wan, “Synthesis of novel porous magnetic silica
microspheres as adsorbents for isolation of genomic DNA”, Biotechnol. Prog., 22, pp. 514–518,
2006.
3. C. Wang, L. Yin, L. Zhang, L. Kang, X. Wang, and R. Gao, “Magnetic (γ-Fe2O3@SiO2)n@TiO2
Functional Hybrid Nanoparticles with Actived Photocatalytic Ability”, J. Phys. Chem. C., 113, pp.
4008–4011, 2009.

500
Customized ceramic implants made by additive manufacturing
Johannes Homa*, Daniel Bomze, Martin Schwentenwein
Lithoz GmbH, Mollardgasse 85a/2/64-68, 1060 Vienna, Austria; *e-mail: [email protected]
Keywords: additive manufacturing, implants, bioceramics, tricalcium phosphate, alumina, zirconia

Lithography-based additive manufacturing (AM) technologies based on photopolymeriza-

tion have gained increasing interest for biomedical applications because of their high preci-
sion and resolution. This contribution focuses on ceramics made by lithography-based ce-
ramic manufacturing (LCM) for two main application areas: permanent implants on the basis
of zirconia and alumina ceramics as possible substitutes for titanium implants in cranio-max-
illofacial surgery or for blood pumps, and resorbable ceramics such as tricalcium phosphate
(TCP) or hydroxyapatite as scaffolds in regenerative medicine.
For permanent implants the main advantage of printed ceramics is the possibility of easily
making tailor-made designs based on patient-specific CT data. Showcases include plates and
screws for fixation devices but also implantable blood pumps.
On the other hand, printed compounds based on bioresorbable ceramic materials such as
TCP would be ideal candidates for temporary bone substitute materials in tissue engineering
due to the similarity to native bone tissue.

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This work presents the results regarding the shaping of TCP by means of LCM. The layer-
by-layer principle of this method enables the fabrication of highly intricate structures with
virtually no limitations regarding geometrical complexity. Scaffolds, cellular structures or
parts with defined macroporosity can be shaped using LCM to provide environments for cells
to adhere, migrate and proliferate throughout the structure.
For in vivo experiments printed TCP scaffolds were implanted into New Zealand white
rabbits. The results based on histological sections showed excellent results in terms of defect
bridging and the area of regrown bone compared to titanium. Especially in presence of bone
morphogenetic protein-2 significant improvements could be measured indicating the suit-
ability of these printed scaffolds as bone substitute material.

657
Colored powders for bioceramics based on calcium phosphates
Gilyana Kazakova1*, Tatyana Safronova2, Valery Putlayev2,1, Pavel Evdokimov1
1
Department of Materials Science, Lomonosov Moscow State University, Russia;
*
e-mail: [email protected]
2
Department of Chemistry, Lomonosov Moscow State University, Russia
Keywords: bioceramics, calcium phosphate, 3D-printing, stereolithography, osteoconductivity

Composite materials containing phases of tricalcium phosphate Ca3(PO4)2 (TCP) and/or hy-
droxyapatite Ca10(PO4)6(OH)2 (HA) have been approved and authorized for clinical use in the
most countries of the world. The main advantages of these materials include good biocompat-
ibility and osteoconductivity in vivo. Chemical composition of ceramic materials based on HA
and TCP are very similar to those of bones of animals and humans. These materials are not
toxic and they do not cause allergic reactions. However, they have the following disadvantag-
es: low speed of bioresorption, weak stimulatory effect on the growth of new bone tissue (os-
teoinduction), low fracture toughness and low fatigue strength under physiological conditions.
The selection of various calcium salts as initial ingredients allowed us to control a prede-
termined pH level in the reaction zone. Nanosized calcium phosphate powder synthesized
from 0.5 M solutions of calcium acetates/saccarate and ammonium hydrophosphate con-
tained a significant amount (64%) of sucrose as the reaction by-product. A microporous ce-
ramic with a pore size from 1 to 6 μm and a relative density of 56% was obtained on the basis
of calcium phosphate powder synthesized from aqueous solutions of monocalcium saccha-
rate and ammonium hydrophosphate. A significant linear shrinkage of powder workpieces
after calcination (up to 40% after calcination at 1200 °C) indicates a high activity of the syn-
thesized powder with respect to sintering. The phase composition of the ceramic represented
by β-TCP and HAP allows one to consider the synthesized powder to be acceptable for the
manufacture of bone implants. Ceramic composites containing these phases are widely used
as materials for bone implants.

Acknowledgement
The authors would like to thank the Russian Science Foundation (Grant No. 15-19-00103) for provid-
ing financial support to this project.

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402
Al2O3–ZrO2–TiO2 nanocomposites for dental applications
Amani Khaskhoussi1,2, Luigi Calabrese1, Jamel Bouaziz2, Edoardo Proverbio1
Department of Engineering, University of Messina, Contrada di Dio Sant’Agata 98166 Messina,
1

Italy; e-mails: [email protected], [email protected], [email protected]

Laboratory of Industrial Chemistry, University of Sfax, National School of Engineering 1173-3038
2

Sfax, Tunisia
Keywords: dental bioceramics, alumina, zirconia, titania, mechanical properties, microstructure

Alumina and Zirconia based ceramics are preferred over metallic biomaterials in orthopaedic
and dental applications. Their widespread use is due to their good biocompatibility, aesthet-
ics (dental restoration), good mechanical properties (high hardness, low rates of friction) and
chemical resistance.1 However individual Al2O3 applications suffered for failure problems
due to alumina intrinsic low toughness,2 while a major drawback of zirconia ceramics are the
in vivo ageing related defects due to the martensitic phase transformation, from tetragonal to
monoclinic structure, when in contact with physiological fluids.3 Alumina-zirconia compos-
ites which combine the high alumina hardness with the fracture resistance of zirconia is an al-
ternative choice. Several studies on Al2O3/ZrO2 composites are indeed reported in literature.
Moreover, the addition of small amount of different metal oxide such as TiO2 have been
proposed to promote the sintering behaviour, customize the microstructure and improve the
mechanical properties.4 There are some publications in literature about the effect of titania on
Zirconia Toughened Alumina (ZTA) but no study on sintered ternary ceramic composites of
Al2O3–ZrO2–TiO2 has been carried out yet specifically related to dental applications.
The main purpose of the present study is the development of Al2O3–ZrO2–TiO2 nanocom-
posite ceramics targeted to dental applications. Al2O3, ZrO2 and TiO2 powders were mixed,
uniaxially pressed and sintered at 1400 °C to obtain the desired composites. Microstructure
and phase composition of the sintered ceramic composites were studied using X-ray dif-
fraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer
(EDS). The mechanical properties: Vickers hardness, Young’s Modulus and strength were
also examined. The results revealed that the Al2O3–ZrO2–TiO2 system could offer different
promising composite materials for a wide range of dental applications.

References
1. S. Sequeira, M.H. Fernandes, N. Neves, M.M. Almeida, “Development and characterization of
zirconia-alumina composites for orthopedic implants”, Ceram. Int., 43, pp. 693–703, 2017.
2. A. De Aza, J. Chevalier, G. Fantozzi, “Crack growth resistance of alumina, zirconia and zirconia
toughened alumina ceramics for joint prostheses”, Biomaterials, 23 pp. 937–945, 2002.
3. J. Wang, R. Stevens, “Surface toughening of TZP ceramics by low temperature ageing”, Ceram.
Int., 15, pp. 15–21, 1989.
4. C.J. Wang, C.Y. Huang, “Effect of TiO2 addition on the sintering behavior, hardness and fracture
toughness of an ultrafine alumina”, Mater. Sci. Eng. A, 492, pp. 306–310, 2008.

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972
Functionally graded porous Si3N4 ceramics produced by tape casting
and sintered in nitrogen
Ayşen Kılıç1*, Yasemin Tabak1, Bayise Kavaklı Vatansever1, Hakan Ünsal1, Şeyda Polat2
1
TUBITAK MRC Materials Institute, Gebze, Kocaeli, Turkey; *e-mail: [email protected]
2
Kocaeli University, Department of Metallurgical and Materials Engineering, Kocaeli, Turkey
Keywords: tape casting, silicon nitride, porous, functionally graded materials

Porous Si3N4 ceramics have recently acquired great interest and been studied intensively due
to their superior mechanical, physical and chemical performances. They have been widely
applied in the fields of environmental protection, chemical industry, aviation, biomaterials,
etc.1–4
Thin layers of ceramics can be produced by tape casting to be used as single layers or to
be stacked and laminated into multi-layered structures. Various types of pore formers are
being used for the fabrication of ceramics with controlled porosity. Porous silicon nitride
ceramics having properties similar to the human bone are sintered and characterized in order
to develop a material applicable as bone substitute.
In this study a process for the tape casting of silicon nitride ceramics has been developed
and comparison is made between different sintering temperatures. For this purpose, silicon
nitride functionally graded ceramic layers were sintered at different temperatures via nitro-
gen gas sintering. A slurry, consisting of the silicon nitride powder in a solvent with addi-
tives like dispersants, binders and plasticizers was cast on a stationary surface. In the study,
non-aqueous-based tape casting of Si3N4 was carried out in a non-continuous single blade
tape casting machine. The green tapes were then dried, laminated and mechanical pressing
by cold isostatic pressing (CIP) was carried out. After pressing they were sintered to obtain a
functionally graded ceramic. Porous silicon nitride (Si3N4) ceramics were sintered in nitrogen
atmosphere graphite element furnace between 1650 °C–1750 °C and 1850 °C with sintering
additives like Al2O3 and Y2O3. The sintered layered material was characterized using SEM
and XRD.

References
1. M. Chen, H. Wang, H. Jin, X. Pan, Z. Jin, Effect of pores on crack propagation behavior for porous
Si3N4 ceramics, Ceramic International, 42 (2016), 5642–5649.
2. L. Tiantian, J. Cuifeng, G. Wei, Effect of CeO2 on low temperature pressureless sintering of porous
Si3N4 ceramics, Journal of Rare Earths, 35 (2017), 172–176.
3. H. Liang, Y. Zeng, K. Zuo, X. Xia, D. Yao, J. Yin, The effect of oxidation on the mechanical proper-
ties and dielectric properties of porous Si3N4 ceramics, Ceramics International, Available online 15
January 2017, In Press, Corrected Proof.
4. X. Hou, E. Wang, B. Li, J. Chen, K.C. Chou, Corrosion behavior of porous silicon nitride ceramics
in different atmospheres, Ceramics International, 43 (2017), 4344–4352.

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875
Apparatus for treatment of skin and subcutaneous cancer diseases by
hyperthermic methods
Z. Kovziridze1*, G. Menteshashvili1, Kh. Bluashvili2
1
Georgian Technical University (GTU) 1Department of Chemical and Biological Technology,
Technical University of Georgia 69, Kostava str., Tbilisi 0175, Georgia; *e-mail: [email protected]
2
Institute of Clinical Oncology, 5, Lublyana str., Tbilisi, 1059, Georgia
Keywords: controlled local hyperthermia, necrosis, ulceration, metastasis

To develop mono-therapeutic effect of hyperthermia against cancer diseases, on the basis of

experimental material, a laboratory device “Lezi”, was used which was created in Georgia
at the Bionanoceramic and Nanocomposite Materials Science Center of Georgian Technical
University (National Center of Intellectual property of Georgia “Georgian Patent”, Certifi-
cate of Deposition # 5054. “Controlled local hyperthermia for treatment of cancer diseases”).
In all animals (albino rat, 3 month age mice) inhibition of cancer disease and development
of intra-tumor necrosis were fixed. After 7–10 sessions tumor was ulcerated, that refers to ir-
reversibility of the process and the efficiency of the applied method of hyperthermia (Conclu-
sion of Laboratory of Morbid Anatomy “PathGeo”. Examination # 3119012, Tbilisi, Geor-
gia).
On the basis of results of morphological study it was proved that liver and lungs (main
target bodies) are intact; secondary tumor injuries are not fixed.
Thus, we can conclude, that during cancer mass lysis that is conditioned by local hyper-
thermia, matastasis in bodies does not take place. Clinical device was created for controlled
local hyperthermia to treat surface diseases.

References
1. Certificate of Deposition “Controlled local hyperthermia for treatment of cancer diseases”. Printed.
National Intellectual Property Center of Georgia, “Georgian Patent”, Certificate of deposition #
5054.
2. Z. Kovziridze, J. Heinrich, R. Goerke, G. Mamniashvili, Z. Chachkhiani, N. Mitskevich, G. Don-
adze. Production of superparamagnetic nanospheres for hyperthermic therapy of surface (skin)
cancer diseases. 3rd International congress on Ceramics, November 14-18, 2010, Osaka, Japan.
IOP Conference Series: Materials Science and Engineering, 2010. ICC 3 Proceedings, Innovative
Technologies and Future Outlook for Ceramics, The Ceramic Society of Japan. P.p. 1536–1539.
3. M. Kawashita, Y. Iwahashi, T. Kokubo, T. Yao, S. Hamada, and T. Shinjo, “Preparation of Glass–
Ceramics Containing Ferrimagnetic Zinc-Iron Ferrite for the Hyperthermal Treatment of Cancer,”
J. Ceram. Soc. Jpn., 112 373–379 (2004).

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170
Cerium-doped bioactive 45S5 glasses: spectroscopic, redox, bioactivity
and biocatalitic properties
Gigliola Lusvardi1, Gianluca Malavasi1, Ledi Menabue1,
Valentina Nicolini1 Francesco Benedetti2,3, Paola Luches3, Sergio Valeri2,3
1
Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia,
via Campi 103, 41125 Modena, Italy
2
Department of Physics, Informatics and Mathematics, University of Modena and Reggio
Emilia, via Campi 213/a, 41125 Modena, Italy
3
Istituto Nanoscienze-CNR, via Campi 213/a, 41125 Modena, Italy
Keywords: cerium, bioactive glasses, catalase mimetic activity, superoxide dismutase mimetic activ-
ity, FTIR, XRD, XPS

The ability of Ce-containing bioactive glasses, based on 45S5 Bioglass®, to inhibit oxidative
stress in terms of reduction of hydrogen peroxide and superoxide, by mimicking the catalase
and superoxide dismutase activity is reported in this work. The best catalyst activities were
obtained for the glass with the higher content of cerium (H_5.3 = 5.3% mol of CeO2 in the
nominal glass composition). Moreover, the detailed study of the surface during the mimic
enzymatic activity tests shows the formation on the glass surface of a Ca-P rich layer where
the presence of Ce ions favours the formation of CePO4. The formation of CePO4 inhibits the
formation of hydroxyapatite decreasing the bioactivity of the glass with higher % of CeO2
in the glass composition. This study allows also to find the best Ce3+/Ce4+ ratio in order to
optimize the catalytic activity toward the decomposition of hydrogen peroxide

References
1. Hench LL (1993) An Introduction to Bioceramics. World Scientific.
2. Hoppe A, Güldal NS, Boccaccini AR (2011) A review of the biological response to ionic dissolution
products from bioactive glasses and glass-ceramics. Biomaterials 32:2757–2774.
3. Nicolini V, Varini E, Malavasi G, et al. (2016) The effect of composition on structural, thermal,
redox and bioactive properties of Ce-containing glasses. Mater Des 97:73–85.

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132
Synthesis, characterization, redox properties and in-vitro bioactivity of
glasses coated by alginate
G. Malavasi, G. Lusvardi, L. Menabue, V. Nicolini, M. Abati
Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia,
Via Campi 103, 41125 Modena, Italy
Keywords: Ce-containing bioactive glasses, alginate coating, catalase mimetic activity

Alginate is a polymer widely applied in the pharmaceutical industry (e.g. excipient for drugs,
dental impression material, and a wound dressing). As a biomaterial, alginate has a number
of advantageous features including biocompatibility and nonimmunogenicity and they are
likely related to its hydrophilicity. The gentle gelling behavior of alginate allows encapsula-
tion of various substances with minimal trauma. A chemically modified alginate is currently
used clinically as a drug delivery vehicle for proteins that promote regeneration of mineral-
ized tissue and as a carrier for transplanted cells.1 The addition of Ca ions into a solution of
Na-alginate causes a cross linkage forming Ca-alginate system. The Ca-alginate is insoluble
in aqueous solution and culture medium. This enables it to remain as supporting structure for
the seeded cells when it is used as a scaffold both in vitro and in vivo.
Bioglasses are the most preferred bioactive fillers that form a bond to both hard and soft;
this is due to formation of hydroxyl-carbonated apatite (HCA) layer on their surface in physi-
ological fluid. The addition of bioactive glass particles into scaffold material not only im-
proves the biomineralization capability of the composite scaffolds but also increases the stiff-
ness of the scaffold material and the surface adsorption of proteins.
In this paper we report the preparation of scaffold (beads) formed by bioactive glasses
and calcium alginate, their solid state characterization and the effect of alginate coating on
the bioactivity and the catalase mimetic activity of Cerium-containing glasses.2 The inves-
tigated glasses are obtained by melting method: 45S5 Bioglass® (H) and 50S25N25C (K)
glasses and sol-gel coupled EISA method: mesoporous bioactive glasses (MBG) and the
same glasses doped with CeO2 up to 5.3%mol: H 5.3Ce_alg, K 3.6Ce_alg, MBG 5.3Ce_alg;
the mean experimental wt % composition of beads is 60% glass, 40% alginate. The results
indicate that i) all Ce-containing beads maintain catalase mimetic activity that varies in the
order: MBG 5.3Ce_alg >> H 5.3Ce_alg > K 3.6Ce_alg; ii) catalase mimetic activity is ob-
served also for the beads of undoped glasses, iii) the amount of H2O2 decomposed varies
with the glass composition, iv) the absence of a mutual influence of alginate and cerium on
samples behavior. The hydroxyapatite formation is observed only for MBG 5.3_alg in view
of its high surface area.

References
1. Augts A.D Kong H.J., Mooney D.J. Macromol. Biosci. 6, 623–633, 2006.
2. Nicolini V., Varini E., Malavasi G. et all. Materials and Design 97, 73–85, 2016.

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675
Calcium phosphate ceramics from hydroxyapatite suspensions
containing sucrose and diammonium phosphate aqueous solutions
Konstantine Malyutin, Egor Mukhin1*, Tatiana Safronova1, Valery Putlyaev2,
Yaroslav Filippov2
Faculty of Materials Science, Lomonosov Moscow State University, Leninskie gory 1, Building 73,
1

119991 Moscow, Russia; *e-mail: [email protected]

Department of Chemistry, Lomonosov Moscow State University, Leninskie gory 1, Building 3,
2

119991 Moscow, Russia

Keywords: calcium phosphates, calcium polyphosphate, calcium pyrophosphate, calcium orthophos-
phate

One of the most important development directions of modern medical materials science is
the creation of inorganic materials for artificial bone implants. The regenerative medicine
development requires the creation of resorbable materials based on calcium phosphates in
which the Ca/P ratio is smaller than in the main inorganic component of the bone – hydroxy-
apatite (HA, Ca/P = 1.67). Creation of such materials requires the development in methods
for synthesis of calcium phosphates with Ca/P ratio = 1.5; 1.0; 0.5. The composite materials
containing phase of calcium polyphosphate (Ca/P = 0.5) have the highest solubility. The pur-
pose of the present work is to obtain ceramic materials containing calcium polyphosphate,
calcium pyrophosphate and calcium orthophosphate phases.
We assume that depending on the components ratio, various bioresorbable phases are
formed via following reactions during the heat treatment.
3Ca10(PO4)6(OH)2 + 2(NH4)2HPO4 = 10Ca3(PO4)2 + 4NH3 + 6H2O
Ca10(PO4)6(OH)2 + 4(NH4)2HPO4 = 5Ca2P2O7 + 8NH3 + 7H2O
Ca10(PO4)6(OH)2 + 14(NH4)2HPO4 = 10Ca(PO3)2 + 28NH3 + 22H2O
The ceramic materials were obtained from highly concentrated hydroxyapatite suspen-
sions in an environment of sucrose and diammonium phosphate aqueous solutions. Cord-
shaped samples were formed via 2 mm diameter plastic injectors. The ability to form homo-
geneous paste layers and stable multi-layer constructions was studied. The most reassuring
results were given by suspensions with HA/sucrose solution ratio of 0.8 g/ml and sucrose
aqueous solution concentration of 0.5M.
After molding the samples were sintered in the range of temperatures from 900 °C to 1100
°C depending on the target phase. Phase composition of the sintered samples is presented
below. The properties of ceramic materials obtained were also studied with thermal analysis
(TA), mass spectrometry (MS) and scanning electron microscopy (SEM).

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Target phase Ca/P ratio Sintering temperature Phase composition

β-Ca3(PO4)2 1.5 1100 °C β-Ca3(PO4)2
β-Ca2P2O7 1.0 1100 °C β-Ca2P2O7, β-Ca3(PO4)2
β-Ca(PO3)2 0.5 900 °C β-Ca(PO3)2

Acknowledgments
The authors would like to thank the Russian Foundation for Basic Research (Grants No. 16-53-00154,
16-08-01172, 15-03-09387) for providing financial support to the project.

922
One-pot sol-gel synthesis of scaffolds for biomedical applications
Margarida S.M.S. Nabiça, José Carlos Almeida1*, Maria Helena F.V. Fernandes,
Isabel M.M. Salvado
Department of Materials and Ceramic Engineering, CICECO- Aveiro Institute of Materials,
1

University of Aveiro, Aveiro, Portugal; *e-mail: [email protected]

The development of three-dimensional porous structures (scaffolds) with ability to interact

with the body leading to the formation of new bone at a rate equal to its own degradation rate
has become a major challenge in tissue engineering.
In the present study the scaffolds for bone regeneration applications were developed,
within the glass systems SiO2-CaO-TiO2 and SiO2-CaO-ZrO2 produced by one-pot sol-gel
method using two types of surfactants (sodium lauryl sulphate, SLS, and polyethylene oxide,
PEO) as porogenic agent. The study was focused on the influence of the type and amount of
surfactant used, the introduction of alkoxides of zirconium and titanium, and the potential
bioactivity of the scaffolds.
The use of a nonionic surfactant (PEO) as a porogenic agent, allowed the production
of monolithic scaffolds with morphological characteristics more interesting that the ones
produced by the introduction of an anionic surfactant (SLS). The former showed a homoge-
neous network of macropores interconnected and with larger macropores (> 50μm) as well
as higher values of surface area (262m2 / g). In addition, it was also found that the scaffolds
of the system SiO2-CaO-ZrO2 showed significantly greater surface areas than the scaffolds
produced from the system SiO2-CaO-TiO2, showing therefore a greater ability to interact
with the surrounding medium and form an apatitic surface layer.
The bioactivity tests showed that all scaffolds exhibited the formation of a layer of calcium
phosphate on their surface, and a constant degradation rate, thus showing the high potential
of applying these materials in the field of bone regeneration.

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230
Mechanical characterization and corrosion behavior of protective
TiC/amorphous C nanocomposite coating as surface thin film
Nikolett Oláh1*, Mónika Furkó1, Zoltán May2, Attila Sulyok1, Katalin Balázsi1
Thin Film Physics Department, Institute for Technical Physics and Materials Science,
1

Centre for Energy Research, Hungarian Academy of Sciences, Konkoly-Thege M. str. 29-33,
1121 Budapest, Hungary; *e-mail: [email protected]
Plasma Chemistry Research Group, Institute of Materials and Environmental Chemistry,
2

Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar tudósok körútja 2,
1117 Budapest, Hungary
Keywords: TiC/a:C protective coating, potentiodynamic polarization method, mechanical properties,
SBF, ICP-OES

The long-term performance of surgical implants is often limited by their surface properties
(such as poor tribological property). There are a colorful range of the various developments,
so, using different nanocomposite coatings in order to improve the mechanical properties are
widespread. Ceramic titanium carbide/amorphous carbon (TiC/a:C) protective nanocompos-
ite thin film may be a potential candidate for such a surface protection coating to the different
implant materials which serves as barrier layer. The main goal of my research work is to
study the influence of TiC/a:C protective thin film on the corrosion, mechanical and tribologi-
cal properties of sandblasted/polished Ti and TiAl6V4 substrates. For these purpose, the coat-
ings were developed by simultaneously depositing Ti and C on the mentioned wafers using
DC magnetron sputtering system in argon (0.25 Pa) at room temperature. The X-ray Photo-
electron Spectroscopy (XPS) and Scanning Electron Microscopy (SEM) were used to study
and compare the chemical compositions and morphologies of the deposited TiC/a:C protec-
tive thin films. The mechanical characteristics of the films were investigated by nanoindenta-
tion technique while the tribological behavior of them was examined by a ball-on-disk tester
(CSM tribometer). The electrochemical corrosion behaviors of the samples were investigated
in simulated body fluid (SBF) by potentiodynamic polarization and electrochemical imped-
ance spectroscopy (EIS) techniques at 7.4 pH and 37 °C. Besides the electrochemical tech-
niques, metal ion release has been quantified by inductively coupled plasma optical emission
spectroscopy (ICP-OES). The experimental results obtained from different electrochemical
methods, ICP-OES and SEM showed that the TiC/a:C protective coating on sandblasted im-
plant device improve the corrosion properties of the implant material and it is able to control
the metal ion release. So, it is also proved that the roughening the surface by sandblasting can
enhance the corrosion resistance. However, the presence of V was detectable in each case, the
Al and Ti ions have been detained by the TiC/a:C thin film coated s.b. TiAl6V4. It was also
shown, that the hardness and tribological property of the bare implant materials are improv-
ing by four orders of magnitude with the TiC/a:C nanocomposite coating beside a moderate
elastic modulus value. The highest hardness (H) of ~ 28 GPa ± 3 with friction coefficient of
~ 0.20 ± 0.07 was observed in case of the film prepared at ~ 40 at% Ti content. The main
conclusion of my research is that a ceramic TiC/a:C thin film with ~ 20 at% a:C and ~40 at%
Ti contents would be a suitable choice for a protective nanocomposite coating.

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621
Bioceramics based on CaKxNa1-xPO4 (x = 0÷1)
Orlov N.K.1*, Evdokimov P.V.1, Putlayev V.I.1, Garshev A.V.1, Günster J.2, Dagmar N.2
Department of Material Science, Lomonosov Moscow State University, Leninskie gory 1,
1

Building 73, Moscow, Russia; *e-mail: [email protected]

Division of Ceramic Processing and Biomaterials, Bundesanstalt für Materialforschung und -prüfung
2

(BAM), Unter den Eichen 44-46, Berlin, Germany

Keywords: bioceramics, phase diagram, rhenanite, bone implants

Nowadays, calcium phosphate bone implants are of great interest bearing in mind their prin-
cipal biocompatibility and well-elaborated processing routes. Such materials should be, at
least, rather resorbable and facilitate newly bone ingrowth (osteoconductivity). At present,
hydroxyapatite (Ca10(PO4)6(OH)2) and tricalcium phosphate (Ca3(PO4)2), the former is less
resorbable, are used to treat the damaged bones. Low resorption rate of hydroxyapatite means
that an implant cannot dissolve in time and a bone de-novo grows up on implant surface
leading to increase of probability of fracture. One of the way to increase resorption rate
(that means to increase solubility) of the implant is to enlarge its molar volume (in fact, cell
volume of materials lattice). From this viewpoint, a replacement of a part of calcium ions
in tricalcium phosphate lattice to sodium or/and potassium one follows such a strategy very
well. In this case, Ca3-x(KyNa1-y)2x(PO4)2 can be regarded as almost ideal composition for such
an intent.
In this study we determined phase relationships in the system of CaKPO4 - CaNaPO4 and
described an intermediate phase noted us as X, having a range of its homogeneity and the
temperature of its phase transition about 657 °C. As revealed by SEM, ceramics based on
these compositions demonstrated domain-like microstructure resulted from phase transfor-
mation of complex nature.
Strength properties of the ceramics under study was measured by B3B method. Decrease
of strength value for x = 0.5-0.7 was attributed to phase transformation accompanied by
volume changes.
Dissolution behavior of the CaKxNa1-xPO4 ceramics in model solutions at constant pH was
studied and compared with other calcium phosphates as well as thermodynamic predictions.

Acknowledgment
The work of Russian part of the team was supported by RSCF, grants #14-19- 00752.

References
1. Evdokimov P.V., Putlyaev V.I., Ivanov V.K., Garshev A.V., Shatalova T.B., Orlov N.K., Klimashina
E.S., Safronova T.V.. Phase Equilibria in the Tricalcium Phosphate-Mixed Calcium Sodium (Potas-
sium) Phosphate Systems. Russian Journal of Inorganic Chemistry, 59, №11, 1219–1227, 2014.
2. G. Berger, R. Gildenhaar und U. Ploska. Rapid resorbable, glassy crystalline materials on the basis
of calcium alkali orthophosphates. Biomaterials, 16, pp. 1241–1248, 1995.

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627
Mechanical properties of aging resistant coated 3Y-TZP
R.S.F. Pereira1,2*, C.G. Moura2, B. Henriques1,2, F.S. Silva2, M.C. Fredel1
1
Ceramics and Composites Materials Research Center (CERMAT)-UFSC, Campus de Florianópolis,
88040-900, Florianópolis-SC, Brasil; *e-mail: [email protected]
2
CMEMS-UMinho, Universidade do Minho, Campus de Azurém, 4800-058, Guimarães, Portugal
Keywords: zirconia, dip coating, aging, B3B, LTD

Since Garvie1 first publication on zirconia phase transformation, which occurs in the pres-
ence of mechanical stresses, a lot of studies lead to improvement of this material properties.
Bending strength, for example, was reported for him to be in the order of 650 MPa, while
nowadays this number is easily found above 1 GPa.2,3 Despite great advances, when stabi-
lized by yttria (Y-TZP), water molecules diffusion can promote phase transformation without
mechanical stress, reducing material strength in a phenomenon called Low Thermal Degra-
dation (LTD) or aging.4 Because yttrium is a trivalent metal, when bonded with oxygen, and
zirconium is tetravalent, when the former is used to stabilize zirconia tetragonal phase an ox-
ygen unbalancing is promoted and vacancies are generated. These vacancies are reported as
the reason for tetragonal phase stabilization, even for low yttria content added, but they also
make, allied to the metastability of the phase, Y-TZP susceptible to aging.5,6 However, other
oxides as magnesium, calcium and cerium, can be also used to stabilize tetragonal phases
with the advantage to not generate a significant amount of oxygen vacancies, and, therefore,
showing almost no aging.5,7 Ceria, for instance, stabilizes the tetragonal phase of zirconia
with really appreciated fracture toughness and having a strong aging resistance.5–7 The dis-
advantage is that mechanical strength achieved by using different yttrium oxide contents,
to stabilize cubic phase, or other stabilizers is substantially lower. In this work, mechanical
properties of 3Y-TZP and aging resistance of 12Ce-TZP and Y-PSZ were combined. To reach
this objective, 3Y-TZP disks were pressed and subsequently dip coated, as green bodies,
in suspension containing 12Ce-TZP or Y-PSZ. Co-sinterization was performed in air for 2
hours at 1400 and 1500 ºC, depending of coating. Suspensions and process were optimized
to obtain the thinner and denser layer as possible. Aging was evaluated for coatings and bulk
showing that produced layers are able to protect the bulk. B3B and micro indentation tests
were performed to evaluate the influence of layers in flexural and Young modulus of coated
samples.

References
1. R.C. Garvie, R.H. Hannink, R.T. Pascoe, Ceramic steel?, Nature. 258 (1975) 703–704.
doi:10.1038/258703a0.
2. E. Camposilvan, F.G. Marro, A. Mestra, M. Anglada, Enhanced reliability of yttria-stabilized zir-
conia for dental applications, Acta Biomater. 17 (2015) 36–46. doi:10.1016/j.actbio.2015.01.023.
3. G.K.R. Pereira, C. Muller, V.F. Wandscher, M.P. Rippe, C.J. Kleverlaan, L.F. Valandro, Compari-
son of different low-temperature aging protocols: Its effects on the mechanical behavior of Y-TZP
ceramics, J. Mech. Behav. Biomed. Mater. 60 (2016) 324–330. doi:10.1016/j.jmbbm.2016.02.017.

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4. M. Inokoshi, F. Zhang, J. De Munck, S. Minakuchi, I. Naert, J. Vleugels, B. Van Meerbeek, K.

Vanmeensel, Influence of sintering conditions on low-temperature degradation of dental zirconia,
Dent. Mater. 30 (2014) 669–678. doi:10.1016/j.dental.2014.03.005.
5. J. Chevalier, What future for zirconia as a biomaterial?, Biomaterials. 27 (2006) 535–543.
doi:10.1016/j.biomaterials.2005.07.034.
6. P. Palmero, P. Torino, L. Montanaro, P. Torino, H. Reveron, Towards long lasting zirconia-based
composites for dental implants . Part I : Innovative synthesis , microstructural characterization and
in vitro stability, Biomaterials. 50 (2015) 38–46. doi:10.1016/j.biomaterials.2015.01.018.
7. M. Fornabaio, P. Palmero, R. Traverso, C. Esnouf, H. Reveron, J. Chevalier, L. Montanaro, Zirco-
nia-based composites for biomedical applications: Role of second phases on composition, micro-
structure and zirconia transformability, J. Eur. Ceram. Soc. 35 (2015) 4039–4049. doi:10.1016/j.
jeurceramsoc.2015.04.027.

608
Acceleration of the conversion of HA to TCP by the densification
process
M.J. Pomeroy*, F. Cox
University of Limerick, Limerick, Ireland; *e-mail: [email protected]
Keywords: HA, TCP, HA decomposition, densification and grain growth grain growth

Hydroxyapatyite (HA) powder samples and disc samples, pressed from the same powder
type, have been heated to temperatures in the range 1200 to 1300 °C. Subsequent X-ray dif-
fraction analysis showed that the powder samples underwent far less transformation to tri-cal-
cium phosphate (TCP) than the pressed discs, which also underwent densification and grain
growth. Further analysis of sintered disc materials showed a definite correlation between HA
to TCP conversion and grain size with the volume fraction of TCP increasing with grain size.
The data is discussed in terms of material degradation mechanisms and material transport
mechanisms during sintering and it is concluded that the enhanced degradation rates during
densification are due to grain boundary material transport, which involves decomposition of
hydroxyapatite to constituent ions or sub-assemblies. In contrast the decomposition of the
powdered material is solely dependant on dehydroxylation of surface layers and subsequent
equilibration of the resultant reaction products with the underlying hydroxyapatite.

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711
Antibacterial efficiency of alkali-free biocompatible glasses additivated
with ZnO and/or SrO active agents
Adrian-Claudiu Popa1,2, George E. Stan1, C. Besleaga1, M. Necsulescu2,
Hugo R. Fernandes3, José M.F. Ferreira3
1
National Institute of Materials Physics, 405A Atomistilor street, Magurele-Ilfov, Romania;
e-mail: [email protected], [email protected]
2
Army Centre for Medical Research, Bucharest, Romania
3
Department of Materials and Ceramics Engineering, Centre for Research in Ceramics and Composite
Materials (CICECO), University of Aveiro, Aveiro, Portugal; e-mail: [email protected]
Keywords: biocompatible glass, alkali-free, antimicrobial, implant coatings, magnetron sputtering

Bioactive glasses (BG) are a remarkable class of materials based on oxides, which possess
the highest index of bioactivity, reflected in their ability to form a strong bond with the liv-
ing tissues (both hard and soft) in a very short period.1,2 Such properties make them ideal
candidates for the biofunctionalization of titanium (Ti) implants in view of boosting their
osseointegration. However, the significant mismatch in the thermal expansion coefficients
(CTE) of the classical BG systems (~15–17×10–6/°C) and Ti (~9.2×10–6/°C), impeded the
successful use of BGs as implant coatings, thus limiting for the moment the applicability of
these osteoproductive materials only to applications bearing low biomechanical loads.
On the other hand, the microbial contamination with extremely resistant and adaptive
strains is one of the major issues in osseous surgery. Furthermore, in dental surgery one can-
not obtain the aseptic conditions achieved in the current general or orthopaedics surgery. The
impossibility to attain aseptic conditions, but only to limit contamination, demand implant
surfaces that do not permit colonization with commensal bacteria, or even enable bacterio-
static or bactericidal effect.
Thereby, in this study series of innovative alkali-free BG formulations (SiO2-CaO-MgO-
P2O5) with ZnO and/or SrO antimicrobial agents are introduced and thoroughly studied, from
physical-chemical and biological points of view, in both bulk and thin film form. The concur-
ring action of combined antimicrobial agents are surveyed in the search of the most effective
ratios, capable to simultaneously enable reduced CTEs and prevent the adaptability/resis-
tance of microorganisms, with the aim of delineating the best dental implant coating design.

References
1. L.L. Hench, “Bioceramics: from concept to clinic”, J. Am. Ceram. Soc., 74, pp. 1487–1510, 1991.
2. J.A. Jones, “Review of bioactive glass: from Hench to hybrids”, Acta Biomater., 9, pp. 4457–4486,
2013.

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408
Macroporous composite scaffold (HA/TiO2) with enhanced mechanical
properties
Lorenzo Preti*, Silvia Panseri, Alberto Ballardini, Anna Tampieri, Simone Sprio
Institute of Science and Technology for Ceramics, National Research Council, Via Granarolo 64,
Italy; *e-mail: [email protected]
Keywords: scaffold, bone, hydroxyapatite, titanium dioxide, macroporous, ceramic, foam

In the field of bone surgery, the development of bone substitutes for load-bearing bone parts
represents one of the most challenging applications, especially due to the difficulty of ex-
pressing high bioactivity and bone-like mechanical properties simultaneously1. The present
work proposes a modified foaming process2 to produce porous HA and composite TCP/TiO2
scaffolds in relatively short time, where the pore extent and organization can be tailored in
a reliable and repeatable manner to offer wide, pervious pathways to cells and fluids, in as-
sociation with high mechanical strength, to meet specific demands in bone surgery.
HA powder was calcined and sieved under 150 µm, and used to prepare HA scaffolds or
to be mixed with TiO2 nanoparticles to obtain, after sintering, TCP/TiO2 scaffolds. A high-
energy ball milling process was used to prepare ceramic suspensions for the foaming process.
Then, the foamed suspensions were poured in paper moulds and dried at room temperature
to obtain stable ceramic foams. HA and TCP/TiO2 scaffolds with different porosity were
prepared by varying the air volume into the jar before the last stirring. Finally, a high-temper-
ature thermal treatment was used to consolidate the green bodies.
The XRD patterns revealed that, whereas HA scaffolds maintained phase purity after sin-
tering, the composite scaffolds were made of TCP, TiO2 and small amount of calcium titanate
(CaTiO3). The reduction in the porosity extent led to a remarkable and significant increase of
both compressive strength and Young’s modulus. Cell tests carried out by using MG-63 hu-
man osteoblast-like cells, reported very good cytocompatibility and cell viability, with very
good cell morphology in contact with the porous scaffolds. The obtained results suggested
that the use of a direct foaming method and planetary ball milling, can result in a simple and
quick approach to generate porous bioactive scaffolds with improved mechanical perfor-
mance.
The statistical evaluation of the mechanical properties enabled to validate the proposed
synthesis method in respect to repeatable and reliable production of highly porous bone scaf-
folds. A simple model of the process parameters also pointed out the feasibility of flexible
design of porous scaffolds even for load-bearing applications, thus opening to new personal-
ized therapies.

References
1. Shackelford JF, Bioceramics, Taylor & Francis, 2003.
2. Dapporto M et al., J Eur Ceram Soc, 36: 2383–2388, 2015.

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387
3D cellular silicon nitride structures and their in vitro viability for bone
regeneration
M.A. Sainz*, B. Román-Manso, S. Serena, M. Belmonte, M.I. Osendi, P. Miranzo
Department of Ceramics, Institute of Ceramics and Glass (ICV-CSIC), Kelsen 5, Madrid, Spain;
*
e-mail: [email protected]
Keywords: silicon nitride, cellular, robocasting, bioactivity

Highly porous cellular ceramics are commonly employed in applications where conditions of
high temperatures, extensive wear and corrosion media exist (like filters, catalyst supports,
heat sinks...)1. However, one of the most challenging uses is as biomaterial for bone replace-
ment or regeneration. On the other hand, Robocasting2, a filament-based printing method that
requires concentrated shear thinning colloidal inks to extrude continuous filaments, arises as
a promising additive manufacturing technique to produce cellular ceramic scaffolds. In fact,
biomaterials such as hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP), have been
printed by this method3, although the main problem for application of these macroporous
scaffolds still lies in the poor mechanical resistance associated with their composition and
porosity. Silicon nitride (Si3N4) has shown to be a biocompatible material4. Additionally, due
to its high strength and toughness, it could be a great candidate to fabricate scaffolds for
custom orthopedic applications.
In the present work, Si3N4 structures with sintering aids were 3D printed by Robocast-
ing with a pattern of macroporous cavities of 400–600 µm. The optimization of the ceramic
inks favoured the controlled extrusion through the fine nozzle (330 µm) while avoided sag-
ging. The inks had a total solids volume fraction of 0.40 and a content of organic additives
≈10–12 wt.% that imparted a pseudoplastic behaviour with yield stress rheology. After print-
ing, drying and calcining processes, the 3D-structures were sintered either in a conventional
graphite furnace or by spark plasma sintering technique, under controlled N2 atmosphere
and low-pressure in both cases. These sintered cellular 3D-structures displayed densities
above ≥ 96–99% of the theoretical value and ~18–22% of linear shrinkage. Results on the
densification, weight loss, linear shrinkage, semi-quantitative analysis of crystalline phases,
microstructure analysis and the mechanical properties of these structures are comparatively
discussed. In addition, the bioactivity and ion release rate in simulated body fluid (SBF) of
these 3D-structures as well as their influence on protein adsorption (Bovine Serum Albumin)
were evaluated for its potential application in bone regeneration.

References
1. A. Studart, U.T. Gonzenbach, E. Tervoort, J. Ludwig and J. Gauckler,”Processing Routes to Ma-
croporous Ceramics: A Review”, J. Am. Ceram. Soc., 89 [6] pp 1771–1789, 2006.
2. J.E. Smay, J. Cesarano III and J.A. Lewis, “Colloidal Inks for Directed Assembly of 3-D Periodic
Structures” Langmuir, 18, pp 5429–5437, 2002.

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3. M. Miranda, A. Fernández, E. Saiz, A. Tomsia, R. Torrecillas, “Application of new forming and sin-
tering techniques to obtain hydroxyapatite and β-TCP nanostructured composites” Inter. J. Mater.
Res., 101(1), pp 117–121, 2010.
4. R. Kue, A. Sohrabi, D. Nagle, C. Frondoza, D. Hungerford, ”Enhanced proliferation and osteocal-
cin production by human osteoblast-like MG63 cells on silicon nitride ceramic discs”, Biomateri-
als, 20, (13), pp 1195–1201 July 1999.

740
Functionally graded porous Si3N4 ceramics produced by tape casting
and sintered in air
Yasemin Tabak1*, Ayşen Kılıç1, Şeyda Polat2, Hakan Ünsal1, Bayise Kavaklı Vatansever1
1
TUBITAK MRC Materials Institute, Gebze, Kocaeli-Turkey; *e-mail: [email protected]
2
Kocaeli University, Department of Metallurgical and Materials Engineering, Kocaeli-Turkey
Keywords: tape casting, silicon nitride, porous, functionally graded materials

Silicon nitride (Si3N4) is a synthetic non-oxide ceramic that is used in many industrial ap-
plications, and has been investigated or adapted as a biomedical material since 1989. Porous
silicon nitride ceramics having properties similar to human bone have been sintered and
characterized with a primary purpose to develop a material to be used as bone substitute.
Functional grade materials are preferred to represent the human bone. Tape casting provides
a good grading of this type of material.
The aim of this work was to evaluate the effect of sintering temperature on silicon nitride
functionally graded ceramic layers sintered at different temperatures via air sintering. A slur-
ry, consisting of silicon nitride powder in a solvent with additives like dispersants, binders
and plasticizers was cast on a stationary surface. The green tapes were then dried laminated
(including different amount of porosifier) and mechanically pressed at 3 different pressures
(100 MPa, 200 MPa and 300 MPa) by cold isostatic pressing (CIP), then finally sintered to
obtain a functionally graded porous ceramic.
Porous silicon nitride (Si3N4) ceramics were sintered in air atmosphere tube furnace at
temperatures between 1300 °C to 1600 °C with sintering additives Al2O3 and Y2O3. In the
study, non-aqueous-based tape casting of Si3N4 was carried out in a non-continuous single
blade tape casting machine. The sintered layered material was characterized using stereo
microscope, SEM and XRD.

References
1. T.J. Webster, A.A. Patel, M.N. Rahaman, B. Sonny Bal, Anti-infective and osteointegration prop-
erties of silicon nitride, poly(ether ether ketone), and titanium implants, Acta Biomaterials 2014
Mar;10(3):1485–1486.
2. K. Bodisova, M. Kasiarova, M. Domanicka, M. Hnatko, Z. Lences, Z. Novakova, J. Vojtassak, S.
Gromosova, P. Sajgalik, Porous silicon nitride ceramics designed for bone substitute applications,
Ceramics International 39 (2013) 8355–8362.
3. S. Liu, Q. Shen, G. Luo, M. Li and L. Zhang, Calculation of Tape Thickness for Ceramic Tape Cast-
ing, Key Engineering Materials, ISSN: 1662-9795, Vols. 512–515, pp 328–333.

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390
Surface functionalization of novel silicate bioactive glass by bioinspired
coating
Rocío Tejido-Rastrilla1,2*, Giovanni Baldi1, Aldo R. Boccaccini2
1
Centro Ricerche Colorobbia Consulting s.r.l, Sovigliana-Vinci, Italy; *e-mail: [email protected]
Institute of Biomaterials, Department of Materials Science and Engineering, University of Erlangen-
2

Nuremberg, Germany
Keywords: bioactive glass, polydopamine, silver nanoparticles, surface functionalization

Bioactive glasses are widely considered in bone tissue engineering applications1. These ap-
plications involve dental and orthopaedic implants fields. Surface functionalization offers the
possibility of modifying the properties of the surface of the substrate without changing the
bulk properties. Polydopamine is a bioinspired polymer whose extraordinary properties were
discovered in 2007. Among the outstanding properties of polydopamine, it offers a platform
for post-modification (i.e.: electroless deposition of metal particles)2. In this work, we have
synthesized a new silicate bioactive glass. The novel bioactive glass (so-called BG1) was
fully characterized by DSC/TGA, hot stage microscopy, XRD, XRF and SEM techniques.
The sintering behaviour of the substrate was studied and BG1 powder was sintered into 1
cm disks of 3 mm thickness. In a second step, surface of BG1 was modified by coating with
polydopamine. Afterwards, we deposited silver nanoparticles onto the surface of the bioac-
tive glass in order to confer an antimicrobial behaviour to the samples. The biomineralization
ability of the samples was tested by soaking them in simulated body fluid (SBF). Formation
of an hydroxyapatite layer on the surface was assessed by SEM, ICP-OES and XRD. Results
show the successful achievement of both polydopamine and silver nanoparticles deposition
on the bioactive glass surface. In addition, the formation of an hydroxycarbonate apatite layer
on the surface of the samples after soaking them in SBF was confirmed. These results will be
compared with standard Bioglass 45S5®.

Acknowledgement
The project leading to this presentation has received funding from the European Union’s Horizon 2020
research and innovation programme under the Marie Skłodowska-Curie grant agreement No 642557
(CoACH-ETN).

References
1. Gerhardt L-C, Boccaccini AR. Bioactive Glass and Glass-Ceramic Scaffolds for Bone Tissue Engi-
neering. Materials (Basel). 2010;3(7):3867–3910. doi:10.3390/ma3073867.
2. Lee H, Dellatore SM, Miller WM, Messersmith PB. Mussel-inspired surface chemistry for multi-
functional coatings. Science. 2007;318(5849):426–430. doi:10.1126/science.1147241.

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604
Sintering, mechanical and in vitro behaviour of wollastonite-diopside
and wollastonite-tricalcium phosphate ceramic foams for bone
regeneration
I. Torres, E. Garijo, A. Caballero, S. Serena, M.A. Sainz*
Department of Ceramics, Institute of Ceramics and Glass (ICV-CSIC), Kelsen 5, Madrid, Spain;
*
e-mail: [email protected]
Keywords: wollastonite, diopside, TCP, scaffolds

Ceramic foams are a class of high porosity materials that are used for a wide range of tech-
nological applications1. In the present work highly porous ceramics foams for bone regenera-
tion or replacement were prepared.
The study was focused on the design, obtention and characterization of highly porous
scaffolds of CaSiO3-CaMgSi2O6 (W-D) and CaSiO3-Ca3(PO4)2 (W-TCP) bioceramics. Poly-
meric sponge replication method2 by impregnating with concentrated ceramic slurries was
employed to synthesize the ceramics foams.
In this process, commercial polymeric sponges were impregnated employing well-dis-
persed concentrated slurries with a low content of organic additives. For the replication tech-
nique polyurethane sponges with dimensions 40×20×10 mm³ were used as templates. The
coated polymers were dried and carefully heating for burning-out the polymer. Later the
optimized porous scaffolds were sintered in air at high temperature (1300–1450 °C). A com-
parative study of the different compositions scaffolds was made. Size, morphology, micro-
structure, crystalline and glassy phases, micro and macro-porosity, compressive strengths
and elastic modulus were determined and discussed. In addition, bioactivity and ion release
rate were assessed in simulated body fluid (SBF).
It was found that the physico-chemical parameters of slurries (concentration, viscos-
ity, pH, etc.) are relevant for generating a stable and self-supporting ceramics scaffold and
achieve appropriate green bodies. The apparent density of all cellular structures obtained cor-
respond to 98–99% of the theoretical density, with a total macroporosity between 60–85%.
To point out, scaffolds become denser as the slurries density increases. The SEM studies
showed that highly porous structures with completely interconnected macropores (200–600
μm) and different size of micropores were obtained. The interconnect porosity, mechanical
strength and bioactivity of the scaffold make them suitable for bone regeneration in non-load
bearing sites.

References
1. L. Montanaro, Y. Jorand, G. Fantozzi, A. Negro, “Ceramic foams by powder processing” J. Eur.
Ceram. Soc., 18(9), pp 1339–1350, 1998.
2. M.A. Muhamad Nor, L.C Hong, Z. Arifin Ahmad, H. Md Akil, “Preparation and characterization
of ceramic foam produced via polymeric foam replication method”, J. Mater. Proc. Tech. 207(1–3),
pp 235–239, 2008.

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876
A critical analysis of the strength evaluation of Ce-TZP composites for
dental applications
Imane Touaiher1, Malika Saâdaoui1, Jérôme Chevalier2, Helen Reveron2
1
Université Mohamed V de Rabat, EMI, LERSIM, Avenue Ibn Sina, 10000 Rabat, Morocco
2
Université de Lyon, INSA de Lyon, MATEIS CNRS UMR 5510, 20 Avenue Albert Einstein,
F-69621 Villeurbanne Cedex, France
Keywords: biaxial flexural strength, zirconia composites, phase transformation

Zirconia based ceramics have proven to be successfully and widely used for biomedical ap-
plications due to their excellent mechanical properties, resulting from the stress induced te-
tragonal to monoclinic phase transformation occurring in this materials. Besides the compre-
hension of this transformation toughening mechanism, there have been a significant advances
in the design and control of the microstructure of zirconia based ceramics and composites.
Recent studies have shown that CeO2-stabilized tetragonal zirconia (Ce-TZP) based compos-
ites are promising for dental applications due to their high toughness and resistance to aging.
Biaxial flexural tests are increasingly used to evaluate the fracture strength of bioceram-
ics, due to the simple preparation of required samples. In particular, the piston-on-3-balls
(P3B) test is used to the certification of ceramic materials in dentistry (ISO 6872-2008). In
this study, the validity of this test to evaluate the fracture strength of Ce-TZP composites is
discussed. Its results are compared to those of the common 4-point bending test for Ce-TZP/
Al2O3 composites with in-situ formed platelets of strontium and lanthanum hexa-aluminates.
The results show that the P3B test drastically overestimates the strength values of these ma-
terials. This can be related to the extensive transformation zones and the resulting substantial
compressive residual stresses in the biaxial configuration, compared to the uniaxial one. This
aspect should therefore be integrated when designing a component from such transformable
ceramics.

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217
Hydrothermal deposition of biocompatible ferroelectric BaTiO3
coatings for bone implants
Přemysl Vaněk1*, Elena Buixaderas1, Jan Drahokoupil1, Zdeněk Tolde2,
Marta Vandrovcová3, Václav Nehasil4, Fedir Borodavka1, Radmila Krupková1, Jan Petzelt1
1
Department of Dielectrics, Institute of Physics CAS, Na Slovance 2, CZ-18221 Prague,
Czech Republic; *e-mail: [email protected]
2
Faculty of Mechanical Engineering, Czech Technical University, Prague, Czech Republic
3
Institute of Physiology CAS, Czech Republic
4
Faculty of Mathematics and Physics, Charles University, Prague, Czech Republic
Keywords: ferroelectrics, hydrothermal synthesis, biocompatibility, bone implants

Our paper1 showed that surface charge due to ferroelectric polarization influences the electric
double layer and diffusion layer in a liquid at the surface. We also proved that surface charge
of ferroelectrics promotes bone cell growth and proliferation, but the sign of the charge does
not play important role.1,2 Therefore coating of bone implants by electrically active ferroelec-
tric materials could be advantageous for healing.
We tested various techniques for coating of Ti39%Nb substrates (the alloy suitable for
bone implants construction) by ferroelectric BaTiO3. Pure Ti was also used for comparison.
Hydrothermal synthesis was found as a suitable one, it can be used for curved surfaces, it
is relatively cheap and can be extended from laboratory preparation to a larger-scale pro-
duction. At first, the substrates were cleaned and annealed in oxygen at 500 °C for 24 hr to
form TiO2 layer. BaCl2 and NaOH were dissolved in reboiled deionized water under argon
atmosphere to prevent BaCO3 formation, potential BaCO3 precipitates were removed by a
single-use syringe filter. Formed Ba(OH)2 reacted with TiO2 to BaTiO3, the hydrothermal
synthesis was performed in an autoclave with a 50 ml Teflon insert at 250 °C for 6 weeks.
XRD detected nanocrystalline BaTiO3 (crystallite size ~40 nm from Rietveld refinement) to-
gether with about 35% of TiO2 and TiNb substrate. SEM also showed nano-size grains. Micro
Raman spectra detected BaTiO3 and TiO2 (rutile), the small Raman peak near 300 cm–1 of B1
symmetry indicated the presence of tetragonal ferroelectric phase of BaTiO3. PFM indicated
random orientation of grains and electric dipoles. XPS detected nearly stoichiometric Ba:Ti
ratio in the surface layer. Bone cell growth was enhanced on BaTiO3/Ti39%Nb surfaces.
Detailed biologic experiments are in progress.

References
1. P. Vaněk, Z. Kolská, T. Luxbacher, J.A.L. García, M. Lehocký, M. Vandrovcová, L. Bačáková, and
J. Petzelt, “Electrical activity of ferroelectric biomaterials and its effects on the adhesion, growth
and enzymatic activity of human osteoblast-like cells”, J. Phys. D: Appl. Phys., 49, pp. 175403(1)–
175403(12), (2016).
2. M. Vandrovcová, L. Bačáková, P. Vaněk and J. Petzelt, “Adhesion, growth and osteogenic dif-
ferentiation of human bone marrow mesenchymal stem cells on positively and negatively charged
and uncharged ferroelectric crystal surfaces”, Engineering of Biomaterials, 135, pp. 2–7, (2016).

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977
Wet chemically precipitated porous hydroxyapatite powders
Azade Yelten, Suat Yilmaz
Department of Metallurgical and Materials Engineering, Istanbul University, 34320 Avcilar, Istanbul,
Turkey; e-mails: [email protected], [email protected]
Keywords: hydroxyapatite, wet chemical precipitation technique, apparent porosity

Bioactive ceramics are important for forming biochemical bonds with the body tissues. They
are widely used in several orthopaedic and dentistry applications. Hydroxyapatite (HA) is a
member of this class and already found in human hard tissues such as bone and dentin as the
mineral component.1 Wet chemical precipitation technique is a feasible way to produce HA
powders in large quantities economically and practically. In this study, porous HA powders
were obtained by using calcium hydroxide (Ca(OH)2, ACS Reagent ≥95%, Sigma-Aldrich)
and phosphoric acid (H3PO4, ACS Reagent, ≥85% wt. in H2O, Sigma-Aldrich) as the calcium
and phosphorus precursors.2 Wet synthesis methods can be influenced by various parameters
such as the reaction temperature of the starting materials, pH of the reaction system, reactant
addition rate, etc. This research concentrates on the HA powders obtained by considering
the reaction temperature (50 °C and 85 °C) and acid addition rate (slow-5.5 ml/min and
rapid-1.5 ml/min) as the process parameters. Cconcentrations of the Ca(OH)2 suspension
and the H3PO4 solution were arranged according to the (Ca/P) molar ratio which is 1.67 for
stoichiometric HA. After the acid-alkaline reaction, the suspension was ripened for 7 days.
At the end of the aging period, decantation was carried out to separate the precipitate and the
supernatant. The wet precipitate was dried for 7 h at 110 °C and then the dried precipitate was
heat-treated at 1250 °C for 2 h. The hard structures obtained as the result of heat treatment
were ground by employing a mortar grinder. The ground powders were formed into cylindri-
cal pellets with the (h/d) ratio set as 1.5 utilizing a uni-axial hydraulic press and stainless steel
molds. These prepared green pellets were sintered at 1250 °C for 1 h.3 Bulk density and %
apparent porosity measurements of the sintered HA pellets were realized depending on the
well-known Archimede’s Principle. X-Ray Diffraction (XRD), Fourier Transform Infrared
Spectroscopy (FTIR) and Scanning Electron Microscopy-Energy Dispersive Spectroscopy
(SEM-EDS) analyses were performed to characterize the chemical, molecular bonding, mi-
crostructural and elemental properties of the synthesized HA powders.

References
1. B.D. Ratner, A.S. Hoffman, F.J. Schoen, J.E. Lemons. Biomaterials Science An Introduction to
Materials in Medicine. 2nd ed. Elsevier Academic Press, New York-London, 2004.
2. K. Salma, L. Berzina-Cimdina, N. Borodajenko, “Calcium Phosphate Bioceramics Prepared from
Wet Chemically Precipitated Powders”, Process. Appl. Ceram., 4(1), pp. 45–51, 2010.
3. A. Yelten. Production and Characterisation of Bioceramic Composite Powder for Three Dimen-
sional Printers. PhD Thesis, Istanbul University, continuing.

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T07: Challenges and opportunities
in industrial ceramics
Invited lectures

851
A personal perspective of ceramic research collaborations with industry
W.E. (Bill) Lee
Dept. of Materials, Imperial College London, UK

This talk will describe personal experience over the last 35 years of working with industry
on ceramic research in the refractories, glass, electroceramics, nuclear, whitewares and engi-
neering ceramics areas. Key benefits and drawbacks of such collaborations will be discussed.

818
New challenges in occupational health
in the European ceramic industry
Eliseo Monfort
Instituto de Tecnología Cerámica (ITC), University Jaume I, 12006, Castellón, Spain
Keywords: nanoparticles (NPs), respirable crystalline silica (RCS), indoor air, occupational exposure,
ceramic industry

It is well known that one of the most important health risk in the ceramics industries is the
respiratory exposure to chemical agents, usually in particulate form. In this regard, a lot of
attention has traditionally been paid to the exposure, effects and control measures to micro-
sized fractions of dust, especially those containing respirable crystalline silica (RCS) and
lead, since a significant number of workplaces in the ceramic industry have been and are
potentially affected by these pollutants. Even though, the epidemiological data suggests that
the European ceramic industry has suffered a relatively limited number of workplace dis-
eases linked to these pollutants, the new development in ceramic materials (e.g.: nano-sized
materials) and processing (e.g.: ink-jet printing) as well as the new findings in toxicology
(e.g.: nano-particle health effects) and new legal requirements (e.g.: classification of RCS as
carcinogen) are opening new challenges, and opportunities, in occupational health.
This talk is focused on the recent advances of the author’s research group in two of these
new challenges: i) exposure to airborne nano-sized particles in the ceramic industry, and. ii)
development of processes for detoxifying raw materials containing RCS.
Nanoparticles (NPS) may be generated in industrial processes either when engineered
nanoparticles are handled or when processes involving high-energy (mainly thermal or me-

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chanical) are developed. Therefore, industrial ceramic processes which usually include high-
energy stages, have a significant potential for producing unintentional NPs release. In this
work, the developed methodology for adequately monitoring the NPs in industrial settings,
and, the monitoring NPs release results obtained in several industrial ceramic processes are
presented. The research line includes the study of thermal (such as thermal plasma spraying
or conventional firing) and mechanical processes (such as milling or mechanical treatments).
The results obtained so far evidenced the significant emissions and impact on workplaces
exposure of several of the studied processes, especially thermal processes. The developed
methodology has also allowed the efficiency of some of the proposed control measures to be
quantified.
In a previous project an effective RCS detoxification process was carried out and imple-
mented at industrial scale in traditional ceramic manufacturing, but the developed process
implies a chemical reaction in an aqueous media (wet process). Based on the promising re-
sults obtained in that project, a new detoxification treatment without the need of an aqueous
step (dry process) is currently being developed (SILIFE project). The applicability is also
foreseen to be tested at industrial scale in different processes and products and not limited
to ceramic material. In this talk the preliminary results of the dry RCS treatment at lab scale
will be presented, as well as, the new legal requirements established by the European Union
for industries potentially exposed to RCS.
In summary, this communication tackles two of the most important challenges in occupa-
tional health in the coming years for the European ceramic industry: nanoparticles and RCS
exposure. These examples show the need to perform research studies at industrial scale, in
order to establish adequate protocols to minimise occupational exposure in real conditions
and at affordable costs.

Acknowledgement
The results presented in this communication are mainly supported by ERANET-SIINN, project
CERASAFE (PCIN-2015-173-CO2-02) and LIFE+ programme, SILIFE project (LIFE 14ENV/
ES/000238).

858
Industrial materials: the challenges for smart coatings
Mariarosa Raimondo
Institute of Science and Technology for Ceramics, ISTEC CNR, Faenza, Italy;
e-mail: [email protected]
Keywords: smart surfaces, wettability, amphiphobicity, durability

Today, many different industries need of innovative solutions allowing to make of the same
bulk material a new multifunctional one with improved added value, to be easily integrated
at a larger scale. Wettability is a fundamental property of a solid surface, whose control plays
a key role in industrial sectors such as ceramic and glass ones, aerospace, naval or maritime,
electronic and mechanical, and so on. The assessment of the criteria to modulate wetting –

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which depends in a complex way on surface chemistry and microstructure interacting with
the working environment and on the contact fluids – is among the biggest challenges of in-
novation in materials’ science.
In the last ten years, a lot of studies tried to mimick the outstanding ability of living organ-
isms to repel water and/or oily substances thanks to their perfectly, mostly hierarchically,
organized structures and controlled chemistry, and to replicate it on synthetic materials. Cur-
rent knowledge highlights that high contact angle (CA>150°), CA hysteresis lower than 5°
in dynamic phenomena and an extremely reduced surface energy are required to produce
i.e. self-cleaning materials, de-icing, anti-fouling, low friction components as well, etc. This
lecture focuses on the design of amphiphobic glasses and ceramics, metals and alloys, whose
surface behaves simoultaneously as superhydrophobic and oleophobic. Nano-oxides suspen-
sions with an average particle size of less than 30 nm, eventually coupled with perfluorinated,
lubricant compounds, have been used to modify the material surfaces giving rise to solid-
liquid-air working interfaces or, alternatively, to solid-liquid-liquid ones. Dip coating, auto-
mated spraying or roller printing were selected as deposition techniques thanks to their high
industrial feasibility. Optically transparent, homogeneous, nanostructured organic/inorganic
hybrid coatings, with a thickness commonly in the 200–300 nm range that, if any, can be im-
plemented up to some microns, have been generated by sol-gel method, followed by thermal
processing and introduction of low energy elements. Static contact angles with water as high
as 178°±1° were obtained, the same materials presenting excellent de-wetting phenomena,
with CA hysteresis lower than 5°±1°. A full characterization of the surface chemistry was
undertaken by XPS analyses, while FESEM observations allowed to estimate the coating’s
thickness (300–400 nm) and the different structural features (flower-like lamellas, agglomera-
tion of spherical nanoparticles, etc). The potential applications of amphiphobic materials still
clamp on durability under different conditions (i.e. chemically aggressive environments, pres-
ence of mechanical stresses, friction effects, etc), so that materials’ scientists are even more
asked to design lasting products able to keep unchanged their performances over the time.
Good mechanical resistance and durability to wearing phenomena, anti-frost performances
and resistance to chemical attacks of properly designed functional surfaces will be presented,
according to different scenarios. The obtained results encourage to think that durable smart
materials can be planned, bringing great convenience in many strategic industrial processes.

702
Pathway towards high recycled content traditional ceramics
Elisa Rambaldi
Centro Ceramico Bologna, via Martelli 26, Bologna, Italy
Keywords: ceramic tiles, secondary raw materials, circular economy, sustainability

Nowadays plenty is already known about traditional ceramic tiles. More than one hundred
scientific works dealing with waste recycling in porcelain stoneware mixes are available in
literature and over twenty research results have been patented. Until about 2005, the research

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demonstrated just a limited substitution of waste, such as scrap glass, in traditional tile mixes
(up to 10% of packaging glass and up to 5% of cathode ray tube glass). The main technologi-
cal risk inhibiting a significant industrial production was the low stability during firing (high
pyroplastic deformation) of tiles.
Recently, the European Commission published several communications focusing on en-
ergy recovery from waste1 and greater recycling and reuse2 able to bring benefits for both the
environment and the economy. The revised legislative proposals on waste set clear targets for
reduction on waste (i.e. recycling of 75% of packaging waste by 2030) and establish ambi-
tious and credible long-term path for waste management and recycling. In this frame, Ceram-
Unie stressed that resource efficiency requires an LCA approach, highlighting that social and
economic aspects of sustainability should always be considered in the EU legislation.
With the target to demonstrate a reduction of the environmental impact and a significant
reuse of end of waste materials, a new concept of traditional ceramic was developed in the
last years. At least 60% of natural raw materials are replaced by (i) new glassy raw materials
coming from vitrification of different waste able to crystallize during firing or (ii) different
type of waste opportunely balanced allowing a “waste synergy” during firing. In both cases,
the innovative ceramic mixes are mainly constitute by secondary raw materials able to crys-
tallize during firing. It allows to obtain products with good stability during firing, overcoming
the technological risk linked to the pyroplastic deformation.
Industrial production of these kind of innovative tiles has been already demonstrated with-
in the European founded project WINCER,3 in which ceramic tiles (25×25 cm and 30×60
cm) containing 85–95%% of secondary raw materials were obtained by sintering about 150–
200 °C lower respect traditional tiles. Beyond the social and environmental benefits for the
sustainability of waste management, about 25% of industrial costs abatement can be reached
due to the lower expenses for raw materials, lower energy and methane consumption.

References
1. The role of waste-to-energy in the circular economy, COM(2017) 34 final.
2. Closing the loop - An EU action plan for the circular economy, COM(2015) 614 final.
3. WINCER project, ECO/13/630426, Co-founded by the Eco-innovation Initiative of the European
Union, www.wincer-project.eu.

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Oral presentations

584
Mechanical reinforcement of traditional ceramics by incorporating
glass-fibres
Philippe Aubry1*, Sophie André1, Xavier Buttol1, Jérôme Goffin2, Oleksandr Trefilov2,
Véronique Lardot1, Francis Cambier1
1
BCRC (Belgian Ceramic Research Centre), Avenue du Gouverneur Cornez, 4, B-7000 Mons,
Belgium; *e-mail: [email protected]
2
3B-Fibreglass Company, B-4651 Battice, Belgium
Keywords: glass fibres, bricks, compressive strength

Nowadays bricks are manufactured with a very mature process in terms of technology and
energy efficiency. But recently, new challenges are appearing with environmental issues de-
fined by European policy and regulation.1 A key innovation concerns the energy recovery for
new efficient building, implying the development of new types of bricks with always higher
compressive strength and thinner walls and/or combining isolation materials. It also concerns
the refurbishment of existing building: the external walls insulation from the outside requires
thinner bricks to maintain building dimensions.
Reinforcement of building materials with glass fibres has been already studied at room
temperature into concretes. This works aims at introducing glass fibres into bricks. Glass was
chosen because of its chemical composition quite close to bricks. But during processing at
quite high temperature, specific glass is required in order not to denature the fibres. That’s
why E-CR glass from 3B-Fibreglass Company2 were used.
Several Belgian clays or mixtures were used as hosts of glass fibres. Bricks were processed
in different ways and characterized according to standards specifications. It was shown that
fibre addition does not change the visual aspect of bricks. The comparison between bricks
without and with glass fibres shows no differences on main properties – density, porosity,
water absorption after immersion, capillarity – except for compressive strength: the addition
of 5 to 10%wt of glass fibres increases hugely the mechanical resistance for molded bricks.

Acknowledgement
The DGO6 of Wallonia is acknowledged for the financial support (project n°1510586).

References
1. http://ec.europa.eu/research/industrial_technologies/energy-efficient-buildings_en.html
2. http://www.3b-fibreglass.com/

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009
Chemical strengthening of industrial glazes suitable for ceramic tile
Silvia Barbi, Paola Miselli, Paolo Veronesi, Cristina Siligardi
University of Modena and Reggio Emilia, Department of Engineering Enzo Ferrari, 41125, Modena,
Italy
Keywords: glaze, strengthening, hardness

Glazed ceramic tiles are used principally for wall and floor covering because of high re-
sistance to chemical attack, even if the mechanical resistance is typical of fragile material.
To improve the mechanical resistance of fragile inorganic materials ion exchange processes
are industrially applied with good results, since many years1. The purpose of this study was
to verify the applicability of a well-known glass hardening process to glazed ceramic tiles.
Moreover also coloration of glazed ceramic tile through ion exchange was investigated.
Materials and Method. Microstructural and mechanical properties of the glazes were de-
termined before and after different ion exchange processes on three different types of com-
mercial ceramic glazes and on other three new glazes (not commercial available). The mi-
crostructure was investigated through scanning electron microscopy (SEM) in conjunction
with energy dispersive spectrometry (EDS). In particular, the distribution of ions before and
after the ion exchange was determined with these techniques. Also the hardness of the glazes
was investigated through micro Vickers Hardness on different loads, in order to correlate the
ions distributions with the hardness and to evaluate the glaze most suitable for this process.
Finally L* a* b* coordinates and ΔE parameter were measured in order to identify any varia-
tion in colour.
Results. Only one of the commercial glazes was suitable to ion exchange process, thanks
to its high Na2O content, with the respect of the majority of the glazes nowadays on the
market of ceramic tile production. The other three new glazes, were B2O3, Na2O Li2O and
P2O5 contents were modified, give interesting results also in terms of mechanical properties.
In fact, under certain conditions of ion exchange, an increment of +25% of hardness was
observed. Finally a coloration of the glaze was observed employing Co(NO2)3 as melted salt,
together with KNO3.
Conclusion. The results suggest that ion-exchange process is positively affected by an
appropriate combination of ions in the glaze formulation and a low amount of commercial
ceramic glazes are nowadays suitable for ion exchange.

Reference
1. A.K. Varshneya, Chemical Strengthening of Glass: Lessons Learned and Yet To Be Learned, Int. J.
Appl. Glass Science, 2, pp. 131–14, 2010.

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565
Performance of lightweight coated oxide ceramic composites for
industrial high speed wood cutting tools: a step closer to market
Gurdial Blugan1*, Claudia Strehler1, Marc Vetterli2, Bruno Ehrle3, Roland Duttlinger4,
Peter Blösch4, Jakob Kuebler1
1
Empa, Swiss Federal Laboratories for Material Science and Technology, Laboratory for High
Performance Ceramics, Ueberlandstrasse 129, 8600 Duebendorf, Switzerland;
*
e-mail: [email protected]
2
Inspire AG, icams, Lerchenfeldstrasse 5, 9014 St.Gallen, Switzerland
3
OERTLI Werkzeuge AG, Hoftstrasse 1, 8181 Höri bei Bülach, Switzerland
4
Blösch AG, Moosstrasse 68-78, 2540 Grenchen, Switzlerand

The introduction of lightweight cutting tips in industrial wood machining could lead to ma-
chining at much higher speeds and thus greatly increase efficiency. One possible way to
achieve this is through lightweight ceramic composites. An Al2O3 ceramic matrix was se-
lected and reinforced with particles resulting in a density of approximately one quarter of the
currently used heavy tungsten carbide tools (density of > 15 g/cm3). Furthermore, a coating
was applied to the ceramic cutting tools in order to increase the stability of the cutting edge.
A combination of reduced coefficient of friction, frictional forces and a resulting decrease in
temperature can lead to a reduction in chipping at the cutting tip. Chipping has always been
the major drawback of ceramic cutting tools for industrial wood cutting. A ceramic compos-
ite containing 25 vol.% of submicron and nano sized SiC particles shows good mechanical
properties with HV2 = 21.5 GPa and KIc = 4.5 MPa m1/2. This composition performed very
well in industrial cutting trials on laminated beech. The cutting performance was increased
further by use of an industrially available coating on the tools. The quality of the cut wood
surface has always been difficult to characterize when comparing cutting tool materials and is
often performed qualitatively by experienced carpenters by touch. The surface quality of the
machined laminated beech was for the first time quantitatively characterized using Gelsight
2.5D tactile sensing.

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502
Influence of oil shale ash addition on thermophysical processes
in an illitic clay during heating
Štefan Csáki1,2*, Tiit Kaljuvee3, Igor Štubňa1, Patrik Dobroň2, Libor Vozár1
1
Department of Physics, Constantine the Philosopher University, A. Hlinku 1, 949 74 Nitra, Slovakia;
*
e-mail: [email protected]
2
Department of Physics of Materials, Charles University, Ke Karlovu 5, 121 16 Prague 2,
Czech Republic
3
Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia
Keywords: illite, oil shale ash, thermal analyses, mass spectrometry

As a base material, illitic clay (containing 80% of illite) originated in Miskolc region, Hun-
gary was used. The clay was crushed, milled and sieved to obtain particles < 100 µm. Esto-
nian oil shale (EOS) ash was prepared by dry milling to obtain a powder with homogenous
particle size distribution. Clay and EOS ash mixtures were prepared with 4 different ratios of
EOS ashes (from 10 to 40 wt.%). To the as-prepared clay and EOS ash dry mixtures distilled
water was added to obtain a plastic mass from which samples of rectangular shape were
made. The samples were dried freely on air for 72 h.
Differential thermal analysis (DTA) and thermogravimetry (TG) methods with simultane-
ous mass spectrometry analysis of evolved gases were used to characterize the processes
taken place at thermal treatment of samples. To avoid the temperature shifts of the processes
investigated in different measurement equipment, the all thermal analyses were conducted
with the heating rate of 5 °C/min up to 1000 °C.
Structural analyses of samples were performed using X-ray diffraction (XRD) and scan-
ning electron microscopy (SEM). In addition, the specific surface area (SSA) and porosity of
samples were also determined.
Several thermally induced processes take place in illite-EOS mixtures during heating.
Firstly, the physically bound water is removed (< 350 °C). Dehydroxylation of illite starts at
450 °C and continues up to 700 °C, between 350-500 °C takes place the decomposition of
Ca(OH)2. As the amount of the EOS ash increases, the thermal effect of the dehydroxylation
decreases, but considering the content of Ca(OH)2 in the mixtures the total mass loss in this
temperature range increases. At temperatures above 600 °C the carbonates, contained in EOS
ashes, start to decompose performing completely at 850–900 °C.
The results reveal a possible utilization of oil shale ashes in the manufacturing of indus-
trial ceramics by reducing the amount of the clay needed.

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616
Differences in mullite crystal growth in triaxial ceramics containing
K- and/or Na- feldspar
Marek Grandys*, Janusz Partyka, Jerzy Lis, Szymon Ryba, Katarzyna Pasiut
Faculty of Material Science and Ceramisc, AGH University of Science and Technology, al.
A. Mickiewicza 30, 30-059 Kraków, Poland; *e-mail: [email protected]
Keywords: mullite, cristalization, porcelain, feldspar, X-ray difraction, SEM

The triaxial vitreous ceramics are containing in majority the glassy phase (50–70%), com-
monly 2 crystal phases can be observed: (1) quartz (and, or cristobalite) and (2) mullite. The
second one can be found as primary (flat, disk shape) and secondary mullite (needle shape).
Some authors say that secondary mullite is represented by large needles and they also define
third type as small needles. Crystals of needle mullite have large influence in mechanical
properties of triaxial vitreous ceramics. Those crystals are crystallizing in clay - feldspar en-
vironment in temperatures above 1200 oC. Triaxial bodies were prepared employing different
feldspars. Mixtures were sintered in different viscosities of melt which were controlled by
temperature. Influence of soaking from 30 to 180 min was checked. Received samples were
checked with X-rays phase analysis and Scanning electron microscopy. The authors focused
mainly on mullite’s shape parameters and its content.

References
1. K. Schuller. Reactions between mullite and the glassy phase in porcelain. Trans. Brit. Ceram. Soc.,
1964, No. 2, pp. 103–117.
2. M. Tuttle, R. Cook, Fundamental study of crystalline and glassy phases in whiteware bodies, J. Am.
Cer. Soc., 1949.
3. S. Kr. Das, K. Dana, Differences in densification behaviour of K- and Na- feldspar-containing por-
celain bodies, Thermochimicha Acta 406 , pp. 199–206, 2003.
4. W.E. Lee, G.P. Souza, C.J. McConvielle, T. Tarvornpanich, Y. Iqbal, Mullite formation in clays and
clay-derived vitreous ceramics, J. Eur. Cer. Soc. 28, pp. 465–471, 2008.

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698
Improvement of enamel coatings used as food contact materials
in industrial applications
Meltem Ipekci1, Kagan Benzesik1, Filiz Cinar Sahin1, Onuralp Yucel1*, Alper Yesilcubuk2
1
Department of Metallurgical and Materials Engineering, Istanbul Technical University, Chemistry
and Metallurgy Faculty, Metallurgical and Materials Engineering Department, 34469, Maslak,
Istanbul, Turkey; *e-mail: [email protected]
2
Arcelik A.S., Istanbul, Turkey
Keywords: enamel, migration, food contact materials

Chemical bonding is one of the mechanisms providing the holding ability of enamel on sub-
strate. Diffusion of FeO from the substrate to the enamel, and NiO and CoO from enamel to
the substrate is the basis of the chemical bonding.1–3
In this study, we used different frits containing different amounts of NiO and CoO to
investigate the effects of these metal oxides on the holding ability of enamel coating. Firing
temperatures for enamel were kept stable at 810, 830 and 850 °C for the different experimen-
tal sets, and firing times were 2 and 6 min for 810 and 850 °C, 4 and 5 for 830 °C, thus we
could observe the effect of firing time and temperature for the different compositions of frit.
After the experiments, we performed SEM and EDX analysis to investigate the holding
mechanism between enamel and substrate materials. By linear analysis and linear mapping,
we could observe the elemental diffusion from substrate to enamel, and from enamel to sub-
strate. In addition to this, we performed migration tests and ICP MS analysis to determine
the amount of the Ni and Co which can migrate from the enamel to food. Furthermore, we
performed impact tests to determine the holding abilities of enamel in terms of composition
of frit, firing time and temperature.

References
1. A.H. Dietzel, Emaillierung: Wissenschaftliche Grundlagen und Grundzüge der Technologie.
Springer-Verlag. [2013].
2. B.W. King, H.P. Tripp, W.H. Duckworth, J Am Ceram Soc, Nature of adherence of porcelain enam-
els to metals, 42(11), 504–525. [1959].
3. D.G. Moore, J.W. Pitts, J.C. Richmond, W.N. Harrison, J Am Ceram Soc, The galvanic corrosion
theory for adherence of porcelain enamel ground coats to steel, Volume 37, Issue-1, pp. 1–6. [1954].

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377
Ceramic tile surfaces: cleanability and durability performances
Beatrice Lucchese1*, Elisa Rambaldi2, Marcel Engels3, Miriam Miehling3,
Maria Chiara Bignozzi1,2
1
Department of Civil, Chemical, Environmental and Materials Engineering, University of Bologna,
via Terracini 28, Bologna, Italy; *e-mail: [email protected]
2
Centro Ceramico, via Martelli 26, Bologna, Italy
3
Forschungsinstitut für Anorganische Werkstoffe Glas/Keramik GmbH, Heinrich-Meister-Str. 2,
Höhr-Grenzhausen, Germany
Keywords: durability, cleanability, accelerated aging, ceramic tiles

In recent years, the durability concept of ceramic surfaces has become a key factor during de-
sign process. A deep knowledge of product performances is essential to select suitable product
for any environment or use. However, standard procedures to evaluate and assess the durabil-
ity performances still lack. It is due to the fact that it is rather hard to keep under control a wide
range of factors causing deterioration (environmental conditions, chemical agents, weather-
ing, mechanical stresses). In any case it is possible setting-up a method by focusing only on
few factors related to one aspect of the performance under a well-defined set of conditions,
thus simplifying the procedure. The aim of this work is to evaluate the durability of ceramic
tile surfaces by focusing on their cleanability. Surface cleanability, i.e. the facility and ef-
ficiency of dirt and stain removal, is an essential technological feature for ceramic tiles, even
if little is known about the durability of this characteristic.1 Among ceramic tiles, porcelain
stoneware is the most performing product due to high density, surface hardness, abrasion and
stain resistance. However, to attain aesthetic characteristics, porcelain stoneware tiles are of-
ten lapped to increase their gloss. Removing a fine layer of glaze, the lapping process induces
several changes in the surface microstructure (micro-cracks and flaws formation, opening of
pores). This may compromise the cleanability performance of tiles2 and it can be improved
by using commercial protective treatments able to fill up pores and holes, thus preventing the
penetration of dirt and staining agents. Many of the surface treatments are generally subjected
to ageing and weathering, so a stable performance over time cannot be ensured. In this work,
commercial lapped porcelain stoneware tiles with and without protective treatment were in-
vestigated. Comprehensive sets of both accelerated and natural ageing tests have been carried
out and compared. Accelerated ageing was performed by applying optimized soiling mixtures
on tile surfaces to reproduce chemical and mechanical actions simulating the working condi-
tions and traditional cleaning operations. Durability test was also performed by fixing tiles on
floor after 3 and 6 months of natural ageing. Surface characteristics (microstructure, topogra-
phy, roughness) were analyzed before and after cleanability and durability tests. Correlation of
the results allowed to set-up a protocol for durability performance of lapped tile.

References
1. Esposito L., Tucci A., Porcelain stoneware tile surfaces. Am. Ceram. Soc. Bull.,79(5), 59–63, 2000.
2. Dondi M., Ercolani G., Guarini G., Melandri C., Raimondo M., Rocha E. Almendra E., Tenorio
Cavalcante P.M., The role of surface microstructure on the resistance to stain of porcelain stone-
ware tiles. J. Eur. Ceram. Soc., 25(4), 357–365, 2005.

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718
The significance of Okpella granite in ceramic glaze formulae
Otimeyin Pius, Osariyekemwen Daniel
Department of Ceramics Auchi Polytechnic, PMB 13. Auchi, Edo State, Nigeria;
e-mails: [email protected], [email protected]

On the northern part of Edo State Nigeria is Auchi, the administrative headquarters of Etsako
Local Government Area with Okpella in Etsako East from where huge mountain of mineral
Granite abound. It was from a part of these mountains that samples of Granite pieces were
collected, milled and analyzed. The Mini pal 4 version with PW 4030 series of the X-ray
Spectrometer, which is an energy dispersive microprocessor controlled equipment of the
Centre for Energy Research and Training (CERT) Ahmadu Bello University, Zaria was were
the Granite sample was analized. It was this analytical instrument designed for the detection
and measurement of elements present in soil mineral sample that revealed the ceramic poten-
tials of the Okpella Granite in glaze composition.

615
The effect of addition of alkali metals oxide on selected parameters
of the ceramic glazes
Janusz Partyka*, Katarzyna Pasiut, Magdalena Leśniak, Marcin Gajek, Jarzy Lis,
Mirosław Bućko, Maciej Sitarz
AHG University of Science and Technology, Faculty of Material Science and Ceramic, Kraków,
Poland; *e-mail: [email protected]
Keywords: ceramic glaze, alkali metals oxygen, glaze structure, physicochemical properties

In the scientific literature there are two ideas concerning the behavior of alkali oxides in
ceramic glazes. First, that sodium and potassium oxides have almost the same influence on
the properties of ceramic glazes. Due to this fact, in the Seger formulas summary molar con-
tent of alkali oxides are often found (Na2O+K2O or R2O). In the second case, the prevailing
opinion is, that these oxides differ in functionality due to different behavior during thermal
treatment and the impact on structure of internal network of glassy phase of glazes. The ar-
ticle presents the results of selected physicochemical parameters of ceramic glazes the glazes
from SiO2-Al2O3-CaO-MgO-R2O in the presence of various alkali metal oxides (R = Na, K,
Li). Additionally, the presentation shows some conclusions of the influence of alkali metal
oxides on the internal structure of the glazes.

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642
The structure of raw porcelain glazes modified by the zirconium oxide
addition
Katarzyna Pasiut1*, Janusz Partyka1, Mirosław Bućko1, Magdalena Leśniak1,
Maciej Sitarz1, Zbigniew Olejniczak2
1
Department of Ceramics and Refractories, Faculty of Materials Science and Ceramics,
AGH University of Science and Technology, al. Mickiewicza 30, Kraków, Poland;
*
e-mail: [email protected]
2
Institute of Nuclear Physics, Polish Academy of Science, ul. Radzikowskiego 152, Kraków, Poland
Keywords: glazes, zirconium oxide, IR, NMR, Raman spectroscopy

The growing demands for the ceramic glazes creates the necessity for more detailed research
on the influence of oxides on the properties of ready-prepared glazes. The complexity of
multi oxides systems of glazes causes difficulties in analyzed this system and make some
problems to describe the influence of adding oxides on the glazes. The interaction between
the single oxides included in the composition of glaze should also be analyzed. The pres-
ence of each oxides, even in small amounts, could have a significant impact on properties of
obtained glaze.
The objective of this study was determining the effect of addition of zirconium oxide on
the structure of ceramic glazes, for firing process at 1230 oC. The glass-ceramic materials
from SiO2-Al2O3-Na2O-K2O-CaO-MgO system were examined. The zirconium oxide was
added in five different amounts (1,5; 3; 6; 12; 24 wt.%). In addition the sample without zirco-
nium oxide as the reference sample were prepared. The structure of this glazes was described
based on the results from Infrared Spectroscopy (IR), Raman spectroscopy and spectroscopy
of Nuclear Magnetic Resonance (NMR). This data were linked with the results from X-ray
diffraction (XRD) and Scanning Electron Microscopy (SEM) with microanalyzer (EDS). All
of obtained results create a lot of interesting dependences, which are the consequences of the
addition of the zirconium oxide to this glass-crystalline materials.

Acknowledgments
This work was carried out thanks to support from NCBiR grant number PBS1/B5/17/2012.

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356
Glass-ceramic foams from ‘inorganic gel casting’
and sinter-crystallization of waste glass mixtures
Patricia Rabelo Monich, Acacio Rincon Romero, Enrico Bernardo*
Dipartimento di Ingegneria Industriale, Università degli Studi di Padova, Via Marzolo 9, 35131,
Padova, Italy; *e-mail: [email protected]
Keywords: gel casting, alkali activation, waste-derived glass-ceramic foams

Highly porous open-celled glass-ceramics have been successfully obtained by a new gel-
casting technique. The gelation of an aqueous slurry of glass powders was not achieved
according to the polymerisation of an organic monomer, but as the result of alkali activation
of fine glass powders1. The alkali activation of a Ca-rich glasses, consisting of common
soda-lime glass and glass from the plasma processing of municipal solid waste (‘Plasma­
stone’)2 allowed for the obtainment of well-dispersed concentrated suspensions, undergoing
progressive hardening by treatment at low temperature (75 °C), owing to the formation of
C-S-H (calcium silicate hydrate) gels. An extensive direct foaming was achieved by vigorous
mechanical stirring of partially gelified suspensions, comprising also a surfactant. The open-
celled structure resulting from mechanical foaming could be ‘freezed’ by the subsequent
sintering treatment, causing a substantial crystallization of Ca-Fe silicates. Viscous flow sin-
tering and crystallization could be tuned depending on the firing temperature (from 800 to
1000 °C) and balance between soda-lime glass and waste-derived glass. For optimized foams
(20 wt% soda-lime glass – 80 wt% Plasmastone, fired at 1000 °C), a total porosity exceeding
80% was obtained, comprising both well-interconnected macro-pores and micro-pores on
cell walls, being accompanied by good compressive strength, above 1 MPa. Owing to the
open-celled morphology the obtained glass-ceramic foams could be applied as filters as well
as catalytic supports.

Acknowledgement
This project has received funding from the European Union’s EU Framework Programme for Research
and Innovation Horizon 2020 under Grant Agreement No 721185.

References
1. A. Rincón, G. Giacomello, M. Pasetto and E. Bernardo. “Novel ‘inorganic gel casting’ process for
the manufacturing of glass foams”, J. Eur. Ceram. Soc., 37, pp. 2227–2234, 2017.
2. L. Machiels, L. Arnout, P. Yan, P.T. Jones, B. Blanpain and Y. Pontikes, “Transforming Enhanced
Landfill Mining Derived Gasification/Vitrification Glass into Low-Carbon Inorganic Polymer
Binders and Building Products”, J. Sustain. Metall., pp. 1–11, 2016.

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228
Mullite foams from engineered alkali activated suspensions
Acacio Rincón Romero, Enrico Bernardo*
Department of Industrial Engineering, University of Padova, Via Marzolo 9, 35131 Padova, Italy;
*
e-mail: [email protected]
Keywords: gel casting, alkali activation, cellular ceramics, mullite

The progressive hardening of suspensions associated with inorganic polymerization has been
already shown to offer interesting possibilities for the development of highly porous foams.
In fact, air may be easily incorporated by vigorous mechanical stirring, with the help of
surfactants. The cellular structure is stabilised by the increase of viscosity caused by the
same curing reactions, configuring an ‘inorganic gel casting’.1,2 The present paper is aimed
at extending the approach to mullite foams, obtained by the thermal treatment of engineered
alkali activated suspensions. ‘Green’ foams were first obtained by gel casting of a suspension
for Na-geopolymer enriched with reactive γ-Al2O3 powders. Sodium was later extracted by
ionic exchange with ammonium salts. In particular, both removal of Na+ ions and retention
of the cellular structure were achieved by immersion in ammonium nitrate solution (at 60 °C,
overnight). Finally, the ion-exchanged foams were successfully converted into pure mullite
foams by application of a firing treatment at 1300 °C, for 1 h.

References
1. A. Rincón, G. Giacomello, M. Pasetto and E. Bernardo, “Novel ‘inorganic gel casting’ process for
the manufacturing of glass foams” J. Eur. Ceram. Soc., 37(5), pp. 2227–2234, 2017.
2. M. Strozi Cilla, P. Colombo, and M. Raymundo Morelli, (2014). “Geopolymer foams by gelcast-
ing”. Ceram. Inter., 40(4), pp. 5723–5730, 2014.

163
Powder rheology and compaction behavior of spray dried bodies for
porcelain stoneware slabs
Roberto Soldati1*, Chiara Zanelli1, Guia Guarini1, Sandra Fazio2, Maria Chiara Bignozzi2,
Michele Dondi1
1
CNR-ISTEC, via Granarolo 64, Faenza, Italy; *e-mail: [email protected]
2
Centro Ceramico, Bologna, Italy
Keywords: compaction, porcelain stoneware, powder rheology, spray dried bodies

The technological behavior of porcelain stoneware bodies strongly depends on the rheologi-
cal properties and response to compaction of spray-dried powders during the deposition and
pressing stages, particularly in the case of large slabs. Even the firing behavior betrays the
features of powder compacts, especially in terms of shrinkage and densification kinetics.
Although the literature offers some insights into the characteristics of spray dried powders

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for ceramic tiles, both red stoneware and porcelain stoneware, no data are available on bodies
currently utilized to manufacture large slabs (>4 m2) by novel technologies.1,2 In order to fill
this gap, a systematic approach to properties and behavior of spray dried powders for por-
celain stoneware large slabs was carried out within the IPERCER project.3 For this purpose,
nine industrially-manufactured spray dried bodies were characterized for particle size and
agglomerate size distribution; shape, moisture and internal porosity in function of agglomer-
ate size; rheological properties of powders (flowability, static and dynamic angles of repose,
poured and tapped densities); compaction behavior (curves of bulk density, intergranular and
intragranular porosity in function of applied load); firing behavior (effect of green porosity
and density on firing shrinkage, bulk density, open and closed porosity, phase composition).
The aim is to gather the information necessary to model the behavior during deposition (in
mould or on tape) and pressing. Results reveal the occurrence of two types of spray dried
powders in terms of agglomerate size distribution, even though most physical properties are
similar. This has a significant effect on some rheological properties (flowability and tapped
density, but not angles of repose), leading to some differences in the features of compacted
bodies. The features of green compacts are somehow inherited by the fired bodies, even
though the starting differences are damped in the fired bodies. In conclusion, there is room to
improve the performance of spray dried bodies by pointing out a compromise between pow-
ders flowability, compaction and densification during firing. The challenge is to transfer this
progress to the management of industrial spray driers, at present focused on energy efficiency
and constancy in the moisture content.

References
1. M. Raimondo, M. Dondi, C. Zanelli, G. Guarini, A. Gozzi, F. Marani and L. Fossa, “Processing and
properties of large-sized ceramic slabs”, Boletín de la Sociedad Española de Cerámica y Vidrio, 49
(4), pp. 289–295, 2010.
2. A. Bresciani and C. Ricci, “Technologie de pressage Continua®”, L'Industrie Céram. & Verrière,
1016, pp. 24–28, 2008.
3. IPERCER, Process innovation for the sustainable ceramic tile chain, www.ipercer.it.

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641
Comparative analysis of surface properties for assessing slip resistance
of glazed ceramic tiles
Anita Terjék1, Zsuzsanna Józsa2
Material Testing Laboratory, ÉMI Nonprofit Llc., H-2000 Szentendre, Dózsa Gy. út 26., Hungary;
1

e-mail: [email protected]
Department of Construction Materials and Techologies, Faculty of Civil Engineering, Budapest
2

University of Technology and Economics, H-1111 Budapest, Műegyetem rkp. 3., Hungary;
e-mail: [email protected]
Keywords: ceramic tile, slip resistance, slipperiness, Pendulum Test Value, surface roughness

Ceramic tiles, playing a major role in the performance of flooring, have to meet many require-
ments at the same time according to EN 14411. As far as application of these materials is
concerned there is a great importance of defining precisely the slip-resistant ability, the most
controversial feature of a floor in service. Slipperiness of tiles is usually interpreted relatively.
In some areas there is an increased risk of slipping that depends not only on interaction with
slippery materials, but pedestrian behaviour and type of footwear also. Furthermore surface
texture should be considered to have a great influence. Taking into account the presence of a
contaminant on the surface, which can cause a walking person to lose footing, loss of traction
can be predicted. Measurements of frictional properties of floor coverings is essential in risk
assessment of slip and fall accidents. For determining friction a precise examination is neces-
sary, which approximately simulates the physical forces of walking and can be repeated at any
time under the same conditions. The objective of this study was to determine and to assess the
affecting factors that can possibly change slipperiness of coverings. In the research 8 different
types of glazed ceramic tiles were chosen. Firing time and temperature were key variables
during manufacturing and there was also difference in glazing operation and decoration ap-
plication. Laboratory slip resistance tests were conducted using Skid Resistance Tester, where
Pendulum Test Value (PTV) was measured under dry and wet conditions. The results of PTV
measurements showed that the variation in surface structure determined slipperiness of glazed
ceramic tiles. Surface roughness, an important contributor to slip resistance, was significant
due to the fact that production technology defines the surface quality of a flooring material.
Arithmetical mean deviation (Ra) and maximum height of the assessed profile (Rz) were mea-
sured using a profilometer according to EN ISO 4288. With the quantification of roughness
parameters diversity in the characteristics of the surface was evaluated.

References
1. W.R. Chang, I.J. Kim, D. Manning, Y. Bunterngchit, “The role of surface roughness in the measure-
ment of slipperiness”, Ergonomics 44 (13), 1200–1216, 2001.
2. A. Terjék, “Multiple aspects of comparing surface properties of ceramic tiles regarding slip resist-
ance”, Applied Mechanics and Materials, 861, 129–136, 2016.
3. Z. Karaca, S. Gürcan, M.V. Gökçe, O. Sivrikaya, “Assessment of the results of the pendulum fric-
tion tester (EN 14231) for natural building stones used as floor-coverings”, Construction and Build-
ing Materials, 47, 1182–1187, 2013.
4. B.S. Parra, M.R. de Freitas, F.G. Melchiades, A.O. Boschi, “Alternatives to increase the spread-
ability of glazes and reduce the surface roughness of ceramic tiles”, Qualicer2008.

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901
Exploring waste-based body formulations for porcelain stoneware tiles
produced at lower sintering temperatures
Chiara Zanelli1*, Roberto Soldati1, Guia Guarini1, Elisa Rambaldi2,
Maria Chiara Bignozzi2, Michele Dondi1
1
CNR-ISTEC, via Granarolo 64, Faenza, Italy; *e-mail: [email protected]
2
Centro Ceramico, Bologna, Italy
Keywords: waste recycling, porcelain stoneware, ceramic tiles

Waste recycling in vitrified ceramic bodies is getting a growing concern in the literature,
where a wide range of residues have been proposed as raw materials for porcelain stoneware
tiles, with promising results in terms of base properties.1 However, drawbacks arose about
technological behavior of waste-bearing bodies and actual cases of transfer to the tile-making
industry seem to be limited to cannibalization of residues of the ceramic process itself.2,5 The
target of introducing high amounts of end-of-life residues is particularly challenging because
of the fast innovation rate in the tile industry, that is shifting current expectations towards
large ceramic slabs. The present contribution relates preliminary results of the MATER_SOS
project6 which is aimed at testing the chances for an actual industrial symbiosis involving the
recycling chain in the Emilia-Romagna region, Italy, where the Sassuolo-Scandiano ceramic
district is situated. The analysis of regional waste flows led to select various typologies of
wastes which for characteristics and amounts appear to be potentially suitable as ceramic
raw materials, mostly glasses, ashes and sludges, some well-known (e.g. soda-lime glasses,
rice husk ash) and others less investigated (e.g. wood combustion ash). A dozen samples of
residues were characterized (chemical and phase composition, particle size distribution, ther-
mal properties) and used as fluxes in replacement of feldspathic raw materials (from 20% to
60%) in a standard porcelain stoneware batch. Bodies underwent a laboratory simulation of
the industrial tile-making processing in order to test their technological behavior in milling,
pressing and firing stages. Every waste has been classified through a technological profile
summarizing compositional features and effects on grindability, compressibility and sinter-
ing by means of variation indexes based on particle size distribution, bulk density, firing
shrinkage and water absorption. The main advantages achievable with waste-bearing batches
is about the temperature of maximum densification that can be reduced of tenths degrees
depending on the residue. General drawbacks are the tendency to have lower bulk density
(symptom of close porosity) and a darker color after firing. Deviation from the tolerable
range in the industrial practice may occur in specific cases (e.g., excessive slip viscosity with
combustion ashes). Nevertheless, technological properties usually do not scale linearly with
the waste percentage and frequently escape from the additivity rule, thus making every waste
type a case-study and suggesting caution in batch design.

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References
1. F. Andreola, L. Barbieri, I. Lancellotti, C. Leonelli, T. Manfredini. “Recycling of industrial wastes
in ceramic manufacturing: State of art and glass case studies.” C. Intern. 42, pp. 13333–13338,
2016.
2. Á. Guzmán, M. Gordillo, S. Delvasto, A. Quereda, V.Sánchez. “Optimization of the technological
properties of porcelain tile bodies containing rice straw ash using the design of experiments meth-
odology.” C. Intern. 42, pp. 15383–15396, 2016.
3. Á. Guzmán, J. Torres, L. M. Cedeño, S.Delvasto, A.Vicente, V. Sánchez. “Stoneware tile manu-
facturing using rice straw ash as feldspar replacement.” B. de la Soc. Espan. de Cer. y Vidrio, 52
(6), pp. 283–290. 2013.
4. E. Bernardo, L.Esposito, S. Hreglich, E. Rambaldi, G. Timeillini, A. Tucci. “Tailored waste based
glasses as secondary raw materials for porcelain stoneware.” Advan. in Ap. Ceram., 107 (6), pp.
322–328. 2008.
5. F. Andreola, L. Barbieri, E. Karamanova, I. Lancellotti, M. Pelino, “Recycling of CRT panel glass
as fluxing agent in the porcelain stoneware tile production.” C. Intern., 34 (5), pp. 1289–1295. 2008.
6. MATER_SOS, Sustainable materials for restoration and construction of new buildings, www.ma-
tersos.it

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Poster presentations

273
Effects of hollow micro glass sphere materials for developing
lightweight porcelain tile
Umit Engin Anil1, Ferhat Kara2
1
Kaleseramik Canakkale Kalebodur Seramik San. A.S., Can, Turkey
2
Materials Science and Engineering Department, Anadolu University, Eskisehir, Turkey

In building materials market, there is a growing trend for lightweight products recently. Por-
celain tile has many superior properties but its high density limits the usage of it as façade
cladding material especially for large sizes. This study aims to decrease the density of por-
celain tile by occurring of closed porosity using hollow micro glass spheres (HMGS) with
different particle size. After preparing the samples, sintering behaviour was simulated by
contactless optical dilatometer in order to obtain information about expansion characteristics.
Microstructural evolution (pore formation, morphology and size etc.) of the body were inves-
tigated by SEM for all the particle sizes. Results show that it is possible to obtain porcelain
tile body less dense by 25% with appropriate water absorption, strength and deformation
according to the standard product.

071
Alumina coatings on C35 steel: a numerical modelling of the interface
Al2O3/steel for characterizing the coating adherence
Réda Berkouch*, Stéphane Valette, Joseph Absi, Pierre Lefort
SPCTS - European Ceramic Center – 12 Rue Atlantis – 87068 LIMOGES Cedex – France;
*
e-mail: [email protected]
Keywords: numerical simulation, FEM, tensile adhesion test, fracture mechanics, alumina coating,
steel

The C35 steel substrates used were alumina-coated via thermal plasma spraying. Before coat-
ing, the steel surface was pre-oxidized in CO2. The pre-oxidized samples exhibited coatings
adhesions of 82 ± 7 MPa. This good result was attributed to the “crystallographic bonding”,
which is characterized by the structural continuity of the chain: steel/α-Fe/wüstite/magnetite/
γ-Al2O3/α-Al2O3. The adhesion measurements were obtained utilizing the new technique of
the “silver print test” that consists in the painting of a part of the samples surface with a silver
paint, before coating. The rupture of the coatings occurred at the surface of the substrates, or
inside the wüstite layer.1
A numerical approach using the finite element method is investigated in order to optimise
junction parameters. First, a multi-layered system is defined in the elastic domain for very

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small strain, as seen in Fig. 1. Three layers are superimposed with successively the alumina
top coat (300 µm depth), the wüstite grains (2 µm depth) and the C35 steel substrate (1 mm
depth). The shape of the included wüstite grains allowed the study the effect of the roughness
at the wüstite/steel interface, on the energy release rate and on the stress intensity factors.
Then the preferential crack trajectory is chosen, based on the experimental observations (the
cracks appeared both at the alumina/wüstite boundary and at the steel/wüstite one). Where-
upon, a thermo-mechanical approach based on the same model including the influence of
internal stress appearing during cooling or thermal cycling, wüstite growth, and creep on the
stress concentration, is considered.
Finally, the use of the pre-programmed subroutine called “DEBOND” permits to study the
influence of the fracture criterion on the crack trajectory. This modelling allows to highlight
the main parameters influencing the stresses of the interfacial zone, in order to minimize
them.

Fig.1. TEM micrograph of the interfacial zone alumina/wüstite/C35 steel (a) and corresponding numerical
modeling (b), from Ref. 1

Reference
1. R. Bernardie, S. Valette, J. Absi, P. Lefort, Surface & Coating Technology 276 (2015) 677–685.

149
Influence of the ZrSiO4 and ZnO on the whiteness and
physical-mechanical properties of industrial ceramic sanitary-ware
K. Boudeghdegh1*, S. Benkacem1, M. Ferkhi2, R. Aguib1, H. Laggoun1
1
LEAM, Faculty of Sciences and Technology, University of Jijel, B.P 98 Ouled Aissa, 18000 Jijel,
Algeria; *e-mail: [email protected]
2
LIME, University of Jijel, B.P 98 Ouled Aissa, 18000 Jijel, Algeria
Keywords: physical-mechanical properties, whiteness, FTIR, SEM, DTA/TG, ceramic sanitary-ware

The object of this study is to improve the whiteness and physical-mechanical characteris-
tics of sanitary glazes. The glazes were prepared using the traditional ceramic substrate by
spraying and then thermally treated in industrial tunnel kiln at temperature of 1250 °C. The
obtained glazes were characterized by FTIR spectra and were observed by SEM to study

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microstructure the glaze-ceramic. The whiteness characteristics of the glazes obtained by

instrument Micro color colorimeter data station. The important phase for sanitary ware is the
mechanism of interaction body-glaze, this mechanism determines the physical-mechanical
and aesthetic properties of the products ceramics sanitary-ware for this study we used DTA/
TG.
The chemical durability of glazes was evaluated in acidic C6H8O7, Hydrogen peroxide and
Potassium permanganate KMnO4 solutions. The results showed the improvement possibility
of the whiteness (up to 87%) and flexural strength (55.06 MPa).

779
Effect of WC grain morphology on the diamond coating adhesion
in tungsten carbide tool
K.W. Chae*, J.W. Rhyu, D.B. Lee
Research and Development Division, Precision Diamond Co. Ltd., Republic of Korea;
*
e-mail: [email protected]
Keywords: diamond coating, grain morphology, adhesive strength, tungsten carbide, mechanical
interlocking

CFRP (carbon fiber reinforced plastics) have been used as the composite materials with a
very high strength-to-weight ratio and rigidity, which properties are required in aerospace
and automotive parts. Special cutting tools are necessary to process the CFRP-composites
into the final shape parts efficiently. It is widely believed that the diamond coating tool is the
most suitable for them. The most critical problem for the application of CVD diamond tool
is the adhesion strength between the diamond film and tungsten carbide. Various techniques
for controlling and improving the adhesion have been reported, including chemical etching,
sandblasting and thermal treatment. Although a rough and corrugated WC-Co surface con-
tributes to enhancing the adhesive strength by mechanical interlocking, the diamond cutting
tools produced by this technique is still not satisfactory for cutting CFRP.
In this study, we focused on the evolution of each WC grain morphology instead of the
surface roughness of the pre-treated WC-Co substrate. The shape of WC grains after pre-
treatments (multi-steps etching) was observed by using SEM and the hot filament CVD was
employed to deposit nanocrystalline and micron-size diamond films. The adhesion strength
of diamond films was estimated by sandblast peeling. In order to investigate the cutting
performance of the diamond coating tools, cutting tests were conducted on as-deposited dia-
mond coated drills with a work-piece of CFRP plate. The tool-life and adhesion of deposited
diamond film on the WC-Co tools appear to be critically dependent on the WC grain mor-
phology.

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Fig. 1. WC grain morphologies of the pre-treated tungsten carbide tools

190
An industry-oriented classification of fluxes for ceramic tiles
Michele Dondi
CNR-ISTEC, via Granarolo 64, 48018 Faenza, Italy; e-mail: [email protected]
Keywords: ceramic tiles, feldspar, flux, technological classification

Fluxes are fundamental ingredients of bodies and glazes used to manufacture ceramic tiles.
They play a primary role during firing, giving rise by melting to the vitreous phase that gov-
erns the viscous flow sintering process. Feldspars and feldspathoids are quintessentially the
most common ceramic fluxes, even though a much wider range of minerals (e.g., talc, wol-
lastonite, sericite, dolomite) is utilized as flux in highly vitrified bodies (porcelain stoneware)
vitrified and semi-semivitrified bodies (stoneware) up to porous bodies.
The main problem in planning mining activities and correctly evaluate the present market
and future demand of ceramic fluxes is the lack of a clear identification of what is needed by
the tilemaking industry. In fact, there is no standard definition and classification of ceramic
fluxes. Current terminology in the field of ceramic tiles encompasses commercial definitions,
local terms, and rock names, not always referred to the international geological nomencla-
ture. Therefore, there are often ambiguities when linking a given flux name with a certain
composition. Thus, no univocal correspondence exists, in general, between common flux
terms and actual chemical and mineralogical composition.
The igneous, sedimentary and metamorphic rocks, which are the sources of ceramic flux-
es, are classified according to geological schemes based on mineralogical (modal) analysis
or chemical features. However, these classifications have little technological significance and
no way to be systematically applied in the ceramic sector. On the market, feldspathic fluxes
are roughly distinguished in sodic, potassic and mixed feldspars. Nepheline syenite and feld-
spathic sands are often considered in separate classes. Further fluxes are commonly referred

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to a given commodity (e.g., talc, wollastonite, basalt, pumice) even though these names are
not always correct under the geological and petrographic viewpoints.
In order to overcome the limits of current terminology, a new, industry-oriented clas-
sification is here proposed and applied to the wide range of fluxes utilized in the production
of ceramic tiles. The main goal of this general classification of ceramic fluxes is to unam-
biguously describing any flux by a simple coding, based on the chemical composition only,
which should have technological and commercial significance. This classification makes use
of a few parameters able to discriminate between alkaline fluxes (based on feldspars and
felspathoids), alkaline-earth fluxes (prevalently consisting of Mg and Ca silicates and car-
bonates) and special fluxes (containing significant amount of lithium, boron, phosphorus or
fluorine). The alkaline fluxes are classified, by the equivalent amount of feldspars and the
alkali ratio, in: foid-bearing, feldspathic, quartz-feldspathic and feldspar-bearing fluxes. The
alkaline earth fluxes are classified, based on their alumina content and the alkaline earth ratio,
in magnesian, magnesio-calcian, calcio-magnesian and calcian fluxes. Examples of classifi-
cation of industrial minerals, representative of different geological sources and used by the
ceramic industry in various countries, are given for both alkaline and alkaline earth fluxes.

811
A study for glass-ceramic glaze modified by brass powder waste to
obtain metallic effect
Fatma Duman*, Tugce Yagyemez, Ayse Tunali, Neslihan Tamsu Selli
Eczacibasi Building Product Cooperation-Vitra Innovation Center, Bilecik, Turkey;
*
e-mail: [email protected]
Keywords: brass waste, glass-ceramic glaze, metallic effect

Ceramic products have good technical properties such as thermal and acoustic insulation,
scratch resistance besides inert to weather conditions as well as. In other words, corrosion
of metals due to weather conditions (air, water, steam, ice) is not observed in ceramic parts.
In addition, numerous decorative techniques can be applied to ceramics when compared to
metal plates. On the other hand, unique metallic reflections of metals increase aesthetic per-
ception. For this reason, different compositions and techniques have been developed to create
products with superior properties by combining the aesthetic qualities felt by metals such as
metallic reflection-luminescence, and other advantages of ceramic products. In the related
study, methods have been developed to separate the brass powder which is formed during the
sanding of brass parts formed by casting method, to evaluate it for decorative purpose in the
production of ceramic tile.

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762
Usage of bandirma colemanite wastes in the production of matte
opaque frits and glossy opaque glaze
Fatma Duman1, Tugce Yagyemez1, Emirhan Karadagli2, Ayse Tunali1,
Neslihan Tamsu Selli1, Emre Talsik1, Bugra Cicek2
Eczacibasi Building Product Cooperation - Vitra Innovation Center, Bilecik, Turkey;
1

e-mail: [email protected]
Department of Metallurgy and Material, Yildiz Technical University, Davutpasa Campus Esenler
2

Istanbul, Turkey
Keywords: colemanite waste, frit, glaze

Every year large quantities of wastes are formed during the productions of boron compounds
by the Eti Mine Boron Company of Turkey. The disposal of wastes cause economical loss,
some technical and environmental problems. In the present study, Bandirma colemanite
enrichment wastes (the rich B2O3 content of the waste) were employed as a raw material
into the production of matte opaque frits. The objective of the study was to reduce boric
acid consumption and to substitute the wastes with the B2O3 present in frit composition, not
only for developing a sustainable production but also providing an economical benefit. Frit
is the main component of the glaze, which highly used in numerous applications such as;
tiles, sanitaryware products, enamels, kitchenwares and so on. Laboratory scale production
is carried out according to the basic principles of producing frit. Frits is subjected to various
characterization tests which can be arrayed as; mineralogical, microstructural and thermal
analysis. The result of frits showed that usage of wastes does not affect the crystallization and
microstructure of the frits. Even though there have been increases in the brightness values,
decreases in the surface roughness and whiteness values of the frits, these differences do not
have a negative effect on usage of frit. Besides that newly produced frits used in a glossy
opaque glaze recipes. The final product, in this study; new glazes tested EN ISO 10545 tests
includes surface abrasion, chemical resistance, resistance to thermal shock and stains. When
compare the results of the analysis of glazes with the standard glaze, it can be show that there
is no differences with the standart test results. By this study, it can be seen that frits prepared
with colemanite wastes can be easily used in glossy opaque glaze recipe without leading to
any surface failure or fault and can be adopted into the current industrial production.

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767
Increasing casting rate by increasing gel buildup
Pervin Gencoglu1, Nimet Ozen2, Baran Tarhan3, Alpagut Kara1, Kagan Kayaci3
1
Ceramic Research Center, Eskisehir, Turkey
2
Eczacıbası Yapı Gerecleri Seramik San. Tic. A.S., Bilecik, Turkey
3
Kale Seeramik Canakkale Kalebodur Seramik San. Tic. A.S., Canakkale, Turkey
Keywords: sanitaryeare, gel buildup, casting rate

Slip casting method is used in sanitaryware production and it is known to be a suitable and in-
expensive shaping process to produce material with high green densities and micro structural
homogeneity, even for complex geometries. One of most important manufacturing measure
is cast rate, which is the thickness of the cast achieved during a specified time in the plaster or
polymer mold. A higher cast rate results in quicker casts and it means more efficient produc-
tion. Many of the parameters affect the casting rate like particle size, density and thixotroph
of the slurry and properties of molds. In this work, thixotrophy of slurry increased as adding
bivalent cations like salts (CaCl2 and MgSO4) with constant of other paramters.
Rate of buildup is measured for determine the casting rate. Because, rate of buildup is a
measure of the speed at which the viscosity increases and is therefore also a measure of the
rate at which the colloids are immobilized within the gel structure. Bivalent cations were add-
ed in the slurry as increasing rate and rheological properties were measured with Brookfield
viscosimeter. According to the measuring results of rate of buildup and casting rate, CaCl2
salt is more effective agent for increasing thickness of products because of high thixotropy. It
is observed that casting rate increased 30% according to the standard slurry.

330
Enhanced catalytic activity of CeO2-V2O5-ZrO2/WO3-TiO2 based for
De-NOX catalyst
Bora Jeong1, Bora Ye1,2, Eok-Soo Kim1, Hong-Dae Kim1*
Green Manufacturing 3Rs R&D Group, Korea institute of industrial technology, Ulsan, 44413,
1

Korea; *e-mail: [email protected]

School of Mechanical and Advanced Materials Engineering, Ulsan National Institute of Science and
2

Technology (UNIST), Ulsan, 44919, Korea

Nitrogen oxide (NOX) are generated (emission) from high temperature combustion gases
such as thermal power plants and ships, it cause various environmental pollution problems
such as greenhouse effect and smog. The selective catalytic reduction (SCR) is the most ef-
fective NOX control system. The commercial catalyst was consist of anatase TiO2 as mono-
liths, V2O5 and WO3 as active component. However, this type is applied a narrow temperature
area of 300–400 oC. Therefore, we studied to synthesis the catalyst using for wide tempera-
ture window by addition of ceria and zirconium.

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In this present study, synthesis of catalyst were performed by hydrothermal and impreg-
nation method. And, using the carbon material to improvement the catalyst component dis-
persion. We confirmed the promotion effect of catalyst according to dispersion of catalyst
component.
The catalyst was characterized by scanning electron microscopy (SEM) and Transmission
electron microscopy (TEM), X-ray diffractometer (XRD), X-ray fluorescence (XRF) in order
to analyze the surface and components, the physical-chemical characteristics about measure-
ment of specific area were by Brunauer–Emmett–Teller (BET). Also, the De-NOx activities
were measured by Fixed-bed Reactor.

472
Amorphization and valence state of tungsten doped ceria/titania
Soonok Kim1, Seung-hyeon Jo1, Jinsun Cha2, Minchul Shin2, Heesoo Lee1*
1
Department of Materials Science and Engineering, Pusan national University,
Busandaehak-ro 63beon-gil 2, Geumjeong-gu, Busan 609-705, Republic of Korea;
*
e-mail: [email protected]
2
Material & Components Technology Center, Korea Testing Laboratory, Seoul 08389, Korea
Keywords: thermal stability, interstitial tungsten, local atomic structure, non-stoichiometry,
NOx conversion

Tungsten (W) has received attention as a co-catalyst with CeO2 for improving the catalytic
activities of TiO2 based catalysts. Chen et al. reported that tungsten could be a solid solution
with CeO2, resulting in a higher NOx conversion property.1 We examined the solid solution
behavior of W in CeO2/TiO2 catalyst in terms of local atomic structure. The Ce-L3 and W-L3
edges were analyzed by extended x-ray absorption fine structure (EXAFS) spectroscopy.
Tungsten ion should be in an interstitial site of CeO2 since a bond distance between W and
Ce was about 1.4Å. The inter planar spacing of ceria (111) in tungsten doped CeO2/TiO2 was
expanded about 5.7% compared with CeO2/TiO2. The interstitial tungsten has affected in
amorphization of the ceria nanoparticles because tungsten and cerium have a large amount
of difference in ionic radii, which occurred severe lattice distortion. Interstitial tungsten also
enhanced the thermal stability of ceria, which was confirmed by TEM_EDS mapping. We
investigated the increase of Ce3+ ratio on the surface of the catalyst resulted from tungsten
addition. Since the Ce3+ ratio is a major factor affecting the catalytic activity in SCR reaction,
the increase of Ce3+ ions have influenced on NOx conversion as one of chemical changes in
company with the structural changes such as amorphization of ceria.

Reference
1. Y. Jiang and Z. Xing, “Activity and characterization of a Ce-W-Ti oxide catalyst prepared by single
step sol-gel method for selective catalytic reduction of NO with NH3”, Fuel, 151, pp.124–129,
2015.

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225
Investigation of thermal expansion mismatches in fine fire clay ceramic
sanitaryware
Nazım Kunduracı*, Engin Kocaman, Irem Nur Gamze Şimşek
Department of Metallurgical and Materials Engineering, Bulent Ecevit University, Farabi Campus,
Zonguldak, Turkey; *e-mail: [email protected]
Keywords: thermal expansion, ffc, ceramics, chamotte

Vitreous ceramics are the materials consist of clay, kaolin, feldspar and quartz, are sintered
with a glazed surface at around 1250 °C. These ceramics are commonly called as sanitary-
ware and they are used in hygienic parts of everyday life such as closets, washbasins, shower
stalls, urinals. Two different slips are used in the production of ceramic sanitaryware. One of
them is a slip of fine fire clay (FFC) while the other is vitreous slip. Large size products are
usually produced with FFC sludge, which generally require less deformation behaviour. The
most important reason is use of chamotte material, which is actually sintered clay, it provides
low deformation during sintering. In this study, thermal expansion behaviour was investigat-
ed depending on the amount of chamotte material. The main purpose of such a study is to re-
duce the gap of glaze-body expansion in the production of FFC. The value of body and glaze
expansions were measured by using dilatometer. It was observed that expansion difference
was high enough to cause crack formation. One of the ways to prevent crack formation is to
increase the thermal coefficient of glaze. However, this solution may degrade the quality and
brightness of surface as well as water absorption properties. Instead, the thermal coeffient of
body was reduced and this method has been seen as a more seamless application. For this
reason, the thermal expansion behaviour of new recipes have been investigated by reducing
the amount of chamotte in the FFC slip. It was observed that the expansion value of body is
decreased with decreasing chamotte amount. In contrast with this finding, deformation value
of the body has started to increase with chamotte addition.

684
Preparation of copper-plated graphite powder, and the sintering
behavior of its composite with copper
Hyukjae Lee
School of Materials Science and Engineering, Andong National University, Andong, South Korea;
e-mail: [email protected]
Keywords: DC-motor brush, electroless plating, copper, graphite, sintering, composites

To reduce the inhomogeneity from density difference in copper-graphite composite, which is

a material system for DC-motor brushes, copper is deposited on graphite surface via electro-
less plating, and then the copper-plated graphite mixed with pure copper powders is pressed

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and sintered to produce a final compact. Here, we identified the optimum electroless plating
condition for a large amount of copper deposition, and used it to prepare composite powders
with pure copper. We compared the sintering behavior of the copper-plated graphite/copper
composite powder with that of pure graphite/copper composite powder. The results show that
the copper-plated graphite/copper composite significantly enhanced the sinterability of the
composite powder, along with the homogeneity of the sintered compact.

References
1. J. Pyrhonen, T. Jokinen, and V. Hrabovcova, in“Design of Rotating Electrical Machines, second
edition” (Wiley-VCH, 2013) p. 1.
2. M. Schlesinger and M. Paunovic, in “ Modern Electroplating, Fifth edition” (John Wiley & Sons,
2010) p. 433.

849
Model to predict dustiness of ceramic raw materials
A. López-Lilao, A. Escrig, G. Mallol, E. Monfort
ITC- AICE, Universitat Jaume I, 12006, Castellón, Spain
Keywords: particulate matter, dustiness measurement, minerals, prediction model

A wide variety of raw materials employed in the ceramic industry were selected and charac-
terised, including more than twenty samples of quartzes, feldspars, nephelines, carbonates,
dolomites, sands, zircons and alumina. The dustiness of these samples, ergo their tendency
to generate dust when they are handled, was determined using the continuous drop method.
This study presents a physical characterisation of these samples and an assessment of the
influence of some material parameters on its dustiness. In this regard, the obtained results
show that dustiness may significantly be affected by particle size distribution.
Moreover, a model to predict dustiness has been developed. This model is based on the
hypothesis that, for a given test (i.e. the energy applied to the powder remains constant),
dustiness depends on the fraction of particles in the bulk material which can be emitted, and
the ability to release these particles.
In this regard, dustiness is defined as the ratio between the mass of generated dust with
a specific size and the mass of tested material. Meanwhile, relative emission can be defined
as the ratio between the mass of generated dust with a specific size and the mass of particles
with this size in the bulk material. The introduction of the relative emission instead of the
dustiness as an adjustment parameter in the proposed model has allowed not only a better
goodness of the obtained fits but also a better comprehension of the apparently contradictory
results reported in previous studies.
These finding suggest that these discrepancies could be due to the fact that the relative
emission is directly related with the easiness of the material to release dust (bulk material
parameters) and energy applied (device and parameters of dustiness test), whilst dustiness
also depends on the fraction of particles susceptible to be emitted.

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The developed model let to estimate dustiness from only particle size distribution data.
The goodness of the fit is quite good and the fact that only particle size distribution data is
required is an important advantage regarding its applicability because it does not require ad-
ditional or sophisticated tests (these data are commonly known by the raw materials suppliers
and users).
This information is deemed essential for establishing the most efficient preventive and/
or corrective measures to reduce the generation of fugitive emissions of particulate matter
during powders processing, both into the outside atmosphere (air pollution) and inside the
facilities (occupational health).

Acknowledgement
This study has been financially supported by the Spanish Ministry of Science and Innovation (MINE-
CO) through the research project PREDEXPIN (reference CGL2015-66777-C2-2).

772
High feed rate suspension plasma spraying of ceramic materials using
water stabilised plasma
Jan Medricky1*, Radek Musalek1, Frantisek Lukac1, Tomas Tesar2
Department of Materials Engineering, Institute of Plasma Physics of the CAS, Za Slovankou 1782/3,
1

182 00 Prague 8, Czech Republic; *e-mail: [email protected]

Department of Materials, Faculty of Nuclear Sciences and Physical Engineering, Czech Technical
2

University, Czech Republic

Keywords: air plasma spraying, water stabilised plasma, suspension

Plasma spraying is a well-established technology for preparation of unique protective and

functional coatings. Various materials such as metals, cermets, and ceramics may be depos-
ited. Standard approach of plasma spraying is based on introduction of powder material into
the plasma jet, where the powder is melted and then deposited onto the coated part, where it
forms continuous coating. Alternatively, it is possible to use suspensions of fine particles dis-
persed in appropriate liquid (e.g. water or ethanol) as a feedstock, rather than using dry coarse
powders. Such coatings prepared by suspension plasma spraying often exceed coatings pre-
pared by standard plasma spraying and have high potential in various industrial applications.
When using standard APS torches with typical power 40–60 kW, the suspension federate
is limited to small amounts of liquid (about 30 ml/min), since additional heat is required to
process the liquid carrier decreasing the heat available to melt the powder particles.1 As an
alternative to standard gas-stabilised APS torches, we present in this study suspension depo-
sition with high-enthalpy hybrid water stabilised plasma torch (WSP-H) which combines of
water stabilisation and gas stabilisation principles, bringing along high power of the torch,
up to 160 kW.2 Suspension plasma spraying using WSP-H torch allows us to use consider-
ably higher feed rates (more than 100 ml/min) and therefore thick coatings may be formed
in much shorter time than in the case of low feed rates. Deposition of coatings using WSP-
H suspension plasma spraying can be achieved from various feedstock materials and the

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coating microstructures can be tailored to fulfil the needs of various applications by choice
of deposition conditions; from dense coatings suitable for wear protection to porous coat-
ings with low thermal conductivity and high thermal shock resistance.3 The coatings from
selected materials, such as Al2O3, TiO2, Cr2O3 and YSZ, were deposited on rotating carousel
with integrated temperature monitoring which enabled effective cooling and repeatability of
the spraying process. The obtained coatings were analysed by means of SEM, XRD and their
microstructures and mechanical properties are discussed to demonstrate the viability of the
newly developed process.

References
1. P. Fauchais, M. Vardelle, A. Vardelle and S. Goutier: “What Do We Know, What Are the Current
Limitations of Suspension Plasma Spraying?”, J Therm Spray Tech, 24(7), pp. 1120–1129, 2015.
2. M. Hrabovsky, “Thermal Plasma Generation with Water Stabilised Arc” Open Plasma Phys J., 2(1),
pp. 99–104, 2009.
3. R. Musalek and J. Medricky and T. Tesar and J. kotlan and Z.Pala and F. Lukac and T. Chraska and
N. Curry: “Suspension Plasma Spraying of Ceramics with Hybrid Water sma Technology”.J Therm
Spray Tech, 26, pp. 37–46, 2017.

025
Thermomechanical properties and fracture of resin-bonded-sand cores.
experimental study and application in aluminium foundry
Claire Menet1*, Pascal Reynaud1, Gilbert Fantozzi1, Adrien Laforêt2, Delphine Thibault3
1
MATEIS, INSA Lyon, 7 avenue Jean Capelle 69621 Villeurbanne, France;
*
e-mail: [email protected]
2
MONTUPET, rue Champollion 36130 Diors, France
3
MONTUPET, rue de Nogent 60290 Laigneville, France
Keywords: granular materials, mechanical properties, fracture, sand-core, foundry, thermal degrada-
tion

Sand cores are used to produce internal cavities of metallic cast parts with complex shapes
like automotive cylinder heads. Foundry cores are granular materials made of sand grains
aggregated with binder bridges. In the cold box coring process, the binder is a polyurethane
resin. It is noteworthy that during the casting of the liquid metal, the polymer binder is seri-
ously damaged. This kind of materials has been poorly investigated so far. This study aims
for a better understanding of the mechanical behaviour and fracture of cores subjected to
various loads and thermal ageing. Particularly, the focus is on the decoring step, which con-
sists in removing the sand by hammering and vibration of the metallic part after casting. This
major project, generated from the collaboration of the aluminum casting company Montupet,
and two laboratories Centre des Matériaux (CdM) and MATEIS, includes both experimental
and numerical activities in order to model the decoring step of cylinder heads based on em-
piric data. Here, the experimental part of the work is presented.

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This presentation will deal with the experimental characterization of sand cores, especially
the links between the thermal degradation of the binder, the microstructure and the mechani-
cal properties will be pointed out. The damage and breaking mechanisms depending on the
kind of loads get also our interest. The influence of the binder is primordial and though
modifications in its nature, proportion or intrinsic properties will change deeply the behavior
of the material.
Various cycled or monotonous mechanical tests have been performed on as-received and
heat-treated materials for this purpose in order to examine the response of the material sub-
ject to compressive, bending or shear stress. A decrease of these mechanical properties has
been observed at room temperature after a heat-treatment at temperatures higher than 200 °C,
in relationship with the binder degradation during such heating. A particular attention has
been paid to crack propagation. In particular, some compressive tests have been followed in-
situ by X-ray tomography, permitting to determine the evolution of the strain field during the
test. All these information will nourish a finite element model of the decoring step.

064
Flame resistant composite panels processed from preceramic prepregs
C. Mingazzini1, M. Scafè1, F. Mazzanti1, F. Bezzi1, L. Giorgin2,3, G. Zattini2,3, E. D’Angelo2,3,
L. Laghi4, G. De Aloysio4
1
ENEA SSPT/PROMAS TEMAF via Ravegnana 186, Faenza (Ra), Italy
2
Dep. of Industrial Chemistry 'Toso Montanari', University of Bologna, V.le Risorgimento 4,
Bologna, Italy
3
Interdepartmental Center for Industrial Research on Advanced Applications in Mechanical
Engineering and Materials Technology, CIRI-MAM, University of Bologna, Viale Risorgimento 2,
Bologna, Italy
4
CertiMaC, Via Granarolo 62, Faenza (Ra), Italy
Keywords: preceramic prepregs, pyrolysis, Basalt reinforced Ceramic Matrix Composites (CMC),
Continuous Fiber Ceramic Composite (CFCC), laser flash analysis (LFA), cone calorimetry

The objective of EEE-CFCC project (www.eee-cfcc.it) is the development and characteriza-

tion of low cost Basalt reinforced Ceramic Matrix Composites1 (CMC) for flame resistant
panels, heat shields and complex shaped for thermostructural applications in transports up to
600 °C. In particular, thermoplastic polysiloxane mixtures were used to produce compara-
tively cheap basalt-based preceramic prepregs, which can be shaped using standard proce-
dure employed for polymeric matrix composites (PMC) and may then be cured and pyrolysed
in inert atmosphere (24 h at 700 °C). The composite material can withstand his own weight
up to 1200 °C, although basalt fibers loose most of their mechanical properties beyond 600
°C. Laser flash analysis (LFA), providing direct measure of thermal diffusivity up to 1250
°C and, indirectly, specific heat and thermal conductivity, according to the cogent European
harmonised Standards2,3, was employed to evaluate achievable fire resistant ratings. These
data are crucial for further dynamic modelling activities aiming at simulating fire scenarios

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and thermal behaviour of the whole ceramic structure. TG-DTA, XRD and SEM were used
to study weight and phase changes upon heating. In some cases, the composite material in the
cured state is even more interesting, being flame retardant and superior to pyrolysed material
in term of room temperature mechanical strength. This uncured state was studied by cone
calorimetry and 4 point flexural strength measurements. The application of an 80 µm electro-
spun Nomex® layer was tested to achieve additional flame resistance. The ignition delay of
the different solutions was compared according to test conditions EN 13501.

Acknowledgement
These activities and the project EEE-CFCC (2016-2018) are cofunded by the POR-FESR 2014-2020,
Asse 1, Azione 1.2.2 of Emilia Romagna Region.

References
1. PCT WO201698022 A1 “A method to manufacture an article made of a fibre-reinforced thermo-
structural composite”, C. Mingazzini.
2. EN 821-2: Advanced technical ceramics – Monolithic ceramics – Thermo-physical properties –
Part 2: Determination of thermal diffusivity by the laser flash (or heat pulse) method.
3. ISO 18755: Fine ceramics (advanced ceramics, advanced technical ceramics) – Determination of
thermal diffusivity of monolithic ceramics by laser flash method.

768
Innovative ceramic tiles to enhance buildings energy efficiency
Rui M. Novais*, G. Ascensão, M.P. Seabra, J.A. Labrincha
Department of Materials and Ceramic Engineering/CICECO- Aveiro Institute of Materials,
University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal;
*
e-mail: [email protected]
Keywords: ceramic tiles, phase change material, energy efficiency

To face the overwhelming increase on the CO2 emission levels demanding directives have
been implemented by the European Commission limiting the Union’s energy consumption.1
To cope with these directives new and exciting building components must be developed,
since buildings are responsible for nearly 40% of the energy consumption in the Europe-
an Community. One very exciting approach is the incorporation of phase change materials
(PCMs), which can store and release energy. Ceramic tiles are an extensively used material
in construction yet PCMs incorporation into tiles is uncommon. In this investigation PCMs
were directly incorporated into lightweight ceramic tiles2 and then their thermal performance
was evaluated. Results demonstrate that this innovative material present improved thermal
performance in comparison with conventional ceramic tiles, mitigating the energy consump-
tion inside buildings by decreasing the operation time of cooling/heating devices.

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Fig. 1. Temperature evolution for the different tiles heated in a hot plate:
without PCM (reference) and with 8 wt.% PCM content

References
1. Directive 2010/31/EU of the European parliament and of the council of 19 May 2010 on the en-
ergy performance of buildings (Document: 32010L0031). Official Journal of the European Union,
L153/13-L153/35.
2. R.M. Novais, M.P. Seabra and J.A. Labrincha, “Wood waste incorporation for lightweight porcelain
stoneware tiles with tailored thermal conductivity”, Journal of Cleaner Production, 90, pp. 66–72,
2015.

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579
Modelling powder distribution of powder injection molded green bodies
Leslie Poh1,2, Christian Della2, Shengjie Ying1, Cindy Goh2, Yun Li2
1
Dou Yee Technologies Pte Ltd, 113 Defu Lane 10, Singapore 539227
2
School of Engineering, University of Glasgow, Oakfield Avenue, Glasgow G12 8LT, UK
Keywords: segregation, powder injection molding (PIM), thermogravimetric analysis (TGA),
differential scanning calorimetry (DSC), numerical simulation

Powder injection moulding (PIM) is a set of process that combines the shape forming process
of plastic injection moulding with powder metallurgy. Most commercial injection mould-
ing software focuses on plastic injection moulding simulation. A few have progressed to al-
low powder injection moulding (PIM) simulations to be carried out. These software enables
the visualization of shear rate and powder concentration distribution to predict the potential
moulding defects. These defects are caused by the segregation between powder and binder
during moulding which leads to inhomogeneity in the green bodies. A numerical model has
been developed using a commercial software, Moldex3D, to simulate the injection stage of
silicon nitride-based ceramics. The Cross-WLF model based on experimental data of the
feedstock is employed in the numerical model. Simulated results from the numerical model
have been compared with experimental results. The powder distribution results from the
simulation is compared with powder distribution analysis of green bodies using thermogravi-
metric analysis and differential scanning calorimetry.

863
Geopolymers incorporating silicate waste
Nicoletta Toniolo1, Acacio Rincon Romero2, Piero Ercole3, Enrico Bernardo2,
Aldo R. Boccaccini1
1
Institute of Biomaterials, University of Erlangen-Nuremberg, Cauerstraße 6, 91058 Erlangen,
Germany
2
Department of Industrial Engineering, University of Padova, Italy
3
Sasil S.p.a. Brusnengo, Italy
Keywords: geopolymers, waste, fly ash, red mud, waste glass

Geopolymers are being primarily developed for the construction industry as a substitute for
traditional Portland cement, which requires extremely high temperatures during manufactur-
ing, with consequent high energy dispersion and emissions.1
Geopolymer technology enables not only the reduction of CO2 emissions within the ce-
ment industry, but also to use waste materials that are not currently deployed in other fields
but are abundant and urgent to dispose of.

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Working towards this purpose, fly ash, a residue generated during coal combustion in
thermal power plants, and red mud, a by-product in the aluminum production, are used as
aluminosilicate source.
The innovation of this work lies in the use of soda lime waste glasses, in addition to fly ash
and red mud, in order to substitute relatively expensive chemical reagents such as like water
glass and sodium hydroxide that are generally employed in geopolymerization reaction.
The red mud and fly ash based geopolymers were prepared with different amounts of glass
and different NaOH molarity. The mechanical resistance of the new materials was assessed
by compressive strength test after 28 days of air cooling. Spectra have been acquired through
Fourier transform infrared spectroscopy (FTIR) and crystalline phases have been detected by
X-ray diffraction (XRD) analysis. Helium pycnometry and microstructural characterization,
including pore size and crack distribution analyses by scanning electron microscopy (SEM),
were carried out. Moreover leaching tests were conducted to assess the stability and sustain-
ability of the geopolymers.
The performance comparisons were made between the new compositions, and geopoly-
mers made using commercial sodium silicate and traditional construction materials.

Reference
1. F.N. Okoye, J. Durgaprasad, and N.B. Singh, Effect of silica fume on the mechanical properties of
fly ash based-geopolymer concrete. Ceram. Int., Vol 42, No 2, pp. 1–7, 2015.

679
Development of continuous self-cleaning enamel using slag as raw
materials
Maria Nalu Verona1, Dalmarino Setti1, Sandra Regina Masetto Antunes2,
Silvana Patrícia Verona1
Department of Mechanical Engineering, Federal Technological University of Paraná, Pato Branco
1

85503-390, Brazil
Department of Chemistry, State University of Ponta Grossa, 4748 Carlos Cavalcanti Avenue,
2

Ponta Grossa, Paraná, Brazil; e-mail: [email protected]

Keywords: enamel, slag, self-cleaning, domestic ovens

One kind of enamel that has been developed for domestic ovens is the self-cleaning one. The
systems of continuous self-cleaning are layers of porous silica applied to metallic materials
which absorb the splashed grease marks that are produced in the utilization of roast food
in the oven, which are decomposed afterwards by the action of oxide catalytes and by the
temperature rise. This research carried out a study about the utilization of iron cast slag in
the cupola oven for the production of self-cleaning enamels, which will be applied to ovens
in domestic stoves. Thus, there would be a raw-material cost reduction and, consequently, an
environmetal impact decrease caused by the slag waste. The formulations used consisted of
a blend of commercial self-cleaning enamels (X e Y) and slag enamel ranging at the rate of

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20% to 80% of the slag enamel (EE). The samples were based on: chemical analysis, X-ray
diffractometry, X-ray fluorescence, optical microscopy, and sweeping. In the enamel prepara-
tion, the size and distribution of particles, viscosity, and, density were controlled. The final
product was analysed considering its resistance to abrasion and impact. The self-cleaning
property was assesed by determining the oil absorption. By using a self-cleaning enamel
layer of 250 µm to 300 µm with 40% of slag enamel (EE), it is possible to obtain 5 self-
cleaning cycles of second degree according to the ISO STANDARD.

Acknowledgment
Authors are thankful to UTFPR/DAMEC, UEPG/CLABMU and the financial support of Atlas Eletro-
domestics, CAPES/PNPD and CNPq.

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simulation and in-situ experimentation
Invited lectures

676
In situ observation of the heat-induced phase transformation of 3D
hierarchical niobium oxide nanostructures with atomic resolution
Sophia B. Betzler1,2
1
Max Planck Institut für Festkörperforschung, Heisenbergstraße 1, 70569 Stuttgart, Germany
2
Ludwig-Maximilians-University, Butenandtstraße 5-13, 81377 München, Germany

Nb3O7(OH) nanostructures, which captivate due to their complex morphology consisting of

highly-ordered nanowire networks, are attractive candidates for green energy applications
such as solar-driven hydrogen production and solar cells. Their structural and morphological
stability at elevated temperatures is crucial for their application and therefore studied at the
atomic scale as a function of atmosphere.
The study reveals a strong effect of the presence of oxygen on the phase transformation,
which reflects the ability of niobium oxide to form suboxides and accommodate oxygen de-
ficiency via structural strain. In situ heating experiments in the transmission electron micro-
scope are used to study the thermal and structural stability of the Nb3O7(OH) nanostructures
in the absence of oxygen. The initial Nb3O7(OH) nanowires exhibit a defective region in
their interior which develops during the synthesis to compensate for the off-stoichiometric
chemical composition. This region serves as origin for the formation of dislocations observed
at 450 °C which move through the crystal lattice towards the surface of the nanowire with
a speed of 5.9 ± 1.3 nm/min. The in situ phase transformation starts at 750 °C featuring the
formation of pores in the nanowires to compensate for the volume difference of the initial
Nb3O7(OH) crystal phase and the formed oxygen-deficient niobium oxide phase. In the pres-
ence of oxygen no pores are observed in the ex situ calcined sample which was identified as
monoclinic Nb2O5. Independent of the atmospheric conditions the Nb3O7(OH) nanostructures
demonstrate a surprisingly high thermal stability of their crystal structure as well as their
complex morphology which is preserved up to 850 °C.

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083
Ab initio modelling of structure and properties of cements
Wai-Yim Ching
Department of Physics and Astronomy, University of Missouri-Kansas City, Kansas City, MO, USA;
e-mail: [email protected]
Keywords: cements, CSH crystals, ab initio calculations, electronic structures

Cement and concrete are among the most important materials throughout the human his-
tory. They possess extremely complex composition and structure at various spatial scales.
Realistic structural models, especially at the atomic-scale are much needed to understand
from bottom-up building block level on how the cementitious materials perform. We have
been investigating the electronic structure and bonding of a large number of calcium silicate
hydrates (CSH) mineral crystals using ab initio method.1 Our results reveal a wide range of
intricate bonding types (covalent, ionic and hydrogen bonding), which is pivotal for critical
analysis of spectroscopic measurements and construction of realistic C-S-H models at larger
scale. We advocate the use of the total bond order density (TBOD) as the ideal quantum
mechanical metric for assessing crystal cohesion of cements and should replace the conven-
tional criterion such as the Ca/Si ratio.2 A rarely known orthorhombic CSH phase Suolunite is
found to have higher cohesion (TBOD) than Jennite and Tobermorite, which are traditionally
considered to be the backbone of hydrated Portland cement. We have now extended our ab
initio modeling to Al-substituted crystals (CASH models) for a more complete description
for cements at nanoscale.

References
1. Ching, W.Y. and P. Rulis, Electronic Structure Methods for Complex Materials: The orthogonalized
linear combination of atomic orbitals 2012: Oxford University Press, USA.
2. Dharmawardhana, C.C., A. Misra, and W.Y. Ching, Quantum Mechanical Metric for Internal Cohe-
sion in Cement Crystals. Scientific reports, 2014. 4: p. 7332.

886
Importance of soft processing (= low-energy production) of advanced
ceramic materials for sustainable society
Masahiro Yoshimura1,2
Distinguished Chair Professor & Director, Promotion Center for Global Materials Research,
1

Dept of Mater., Sci. and Eng., National Cheng Kung University, Tainan, Taiwan
Prof. Emeritus. Tokyo Institute of Technology, Japan;
2

e-mails: [email protected], [email protected]

As well as organic and/or bio- materials, advanced inorganic materials, most of metallurgical
materials, semiconductors and ceramic materials have been used in wide area of applica-
tions like structural, mechanical, chemical, electrical, electronic, optical, photonic, biologi-

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cal, medical, etc. Most of them except for bio-minerals have never been produced in natural
processes via biological systems. Thus they have generally been fabricated artificially and/or
industrially by so-called high-technology, where high temperature, high pressure, vacuum,
molecule, atom, ion, plasma, etc. have been used for their fabrications, then consumed huge
amount of resources and energies thus exhausted huge amounts of wastes: materials, heats
and entropy.
Considering the lowering of total energy consumption, we have challenged to fabricate
those advanced inorganic materials with desired shape/size/location, etc. directly in low ener-
getic routes using aqueous solutions since 1989 when we found a method to fabricate BaTiO3
film on Ti substrate in a Ba(OH)2 solution by Hydrothermal Electrochemical[HEC] method
at low temperatures of 60–200 C. We proposed in 1995 an innovative concept and technol-
ogy, “Soft Processing” or “Soft Solution Processing,” which aims low energetic (= envi-
ronmentally friendly) fabrication of shaped, sized, located, and oriented inorganic materials
in/from solutions. It can be regarded as one of bio-inspired processing, green processing,
or eco-processing. When we have activated/stimulated interfacial reactions locally and/or
moved the reaction point dynamically, we can get patterned ceramic films directly in solution
without any firing, masking nor etching. Direct Patterning of CdS, PbS and CaWO4 on papers
by Ink-Jet Reaction method and LiCoO2 by electrochemically activated interfacial reactions.
Furthermore, we have succeeded to fabricate BaTiO3 patterns on Ti by a laser beam scanning
and carbon patterns on Si by plasma using a needle electrode scanning directly in solutions.
Successes in TiO2 and CeO2 patterns by Ink-Jet Deposition, where nano-particles are nucle-
ated and grown successively on the surface of substrate thus become dense even below 300
C will be presented. Nano-structured films will be also talked. A recent novel subject, Soft
Processing for various nano-carbons including Graphene and functionalized Graphene, will
be introduced. Where we have succeeded to prepare functionalized Graphene Ink via succes-
sive processes under ambient temperature and pressure conditions.3–6

References
1. MRS Bulletin, 25[9], Sept. issue 2000, special issue for Soft Processing of Advanced Inorganic
Materials, Guest Editor: M. Yoshimura and J. Livage.
2. Yoshimura, M., J. Mater. Sci., 41 [5], 1299–1306 (2006), 43[7] 2085–2103(2008).
3. J. Senthilnathan, M.Yoshimura et al., J. Mater Chem A, (2014) 2, 3332–3337 (2015).
4. Sanjeeva Rao, K and Yoshimura, M et al. Adv. Funct. Mater., 25, 298–305.
5. Senthil Nathan J. et al. , J. Mater. Chem A, 3, 3035 (2015).
6. Elumalai Satheeshkumar,Taron Makaron,Yury Gogotsi,M. Yoshimura, Sci, Repts, Aug. 30, (2016).

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846
Bio-inspired functional materials converted from nature species
Di Zhang*, Wang Zhang, Jiajun Gu, Qinglei Liu, Shenming Zhu, Huilan Su
State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dong Chuan Road,
Shanghai, 200240, China; *e-mail: [email protected]
Keywords: bio-inspired materials, bio-templates, butterfly, wood, agricultural wastes

Biological materials naturally display an astonishing variety of sophisticated nanostructures

that are difficult to obtain even with the most technologically advanced synthetic methodolo-
gies. Inspired from nature materials with hierarchical structures, many functional materials
are developed based on the templating synthesis method. This review will introduce the way
to fabricate novel functional materials based on nature bio-structures with a great diversity of
morphologies, in State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University
in near five years. We focused on replicating the morphological characteristics and the func-
tionality of a biological species (e.g. wood, agriculture castoff, butterfly wings). We change
their original components into our desired materials with original morphologies faithfully
kept. Properties of the obtained materials are studied in details. Based on these results, we
discuss the possibility of using these materials in photonic control, solar cells, electromag-
netic shielding, energy harvesting, and gas sensitive devices, et al. In addition, the fabrication
method could be applied to other nature substrate template and inorganic systems that could
eventually lead to the production of optical, magnetic, or electric devices or components as
building blocks for nanoelectronic, magnetic, or photonic integrated systems. These bio-
inspired functional materials with improved performance characteristics are becoming in-
creasing important, which will have great values on the development on structural function
materials in the near future.

References
1. Zhang D, et al. Progress in Materials Science. 68, pp. 67–96, 2015.
2. Zhang D, et al. Advanced Materials. 27, pp. 464–478, 2015.
3. Zhang D, et al. Advanced Materials. 26, pp. 1229–1234, 2014.

968
Bioinspired optical structure for enhancement infrared absorption
Wang Zhang*, Junlong Tian, Jiajun Gu, Qinglei Liu, Di Zhang
State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dong Chuan Road,
Shanghai, 200240 China; *e-mail: [email protected]

Recently, an increasing number of researchers have directed their attention to the wings of
lepidopterans (butterflies and moths) because of their dazzling colors. According to one pre-
vious study, these iridescent colors are caused by periodic structures on the scales that make

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up the surfaces of these wings. These materials have recently become a focus of multidis-
cipline research because of their promising applications in the display of structural colors,
advanced sensors, and solar cells. This work will provide a broad overview of the research
into these wings. Specifically, the review focuses on characterization and simulation of bio-
inspired optical materials templated from lepidopteran wings scales.

Fig. 1. The Model and Angular dependence of the reflection intensities. (a) the Parameters of model (b) 2D
β-Reflectance line plot under the wavelength of 450 nm (c) field maps (d) 2D β-wavelength filled contour
plot of angular dependence of the reflection intensities

References
1. Zhang W, et al. Progress in Materials Science 2015 68, 67–96.
2. Zhang W, et al. Adv. Mater. 2015 27, 464–478.
3. Zhang W, et al. Phys Chem Chem Phys 2015 16, 19767–19780.

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Oral presentations

019
In situ HT-ESEM observation of sintering first stage
of MO2 (M = Ce, Th, U) microspheres
Nicolas Clavier1*, Galy Ingrid Nkou Bouala1, Jacques Léchelle2, Renaud Podor1
1
ICSM, UMR 5257 CEA/CNRS/ENSCM/Univ. Montpellier, Site de Marcoule, BP 17171,
30207 Bagnols/Cèze, France; *e-mail: [email protected]
2
CEA/DEN/DEC/SESC/LLCC, Site de Cadarache, 13108 St-Paul lez Durance, France
Keywords: HT-ESEM, sintering, modelling, oxides, actinides

As a key-step in the elaboration of numerous ceramic materials over a wide range of appli-
cations, sintering of oxide compounds has been studied for years. If grain growth processes
were investigated thanks to experimental works and calculations, the elaboration of necks
during the first step of sintering was generally assessed only through numerical models, fre-
quently based on simple configurations (two spherical single crystals in contact). In order
to complement such numerical approaches, the elaboration of necks during the sintering of
MO2 microspheres (with M = Ce, Th and U), herein used as model compounds of nuclear
fuels, was experimentally observed by High Temperature Environmental Scanning Electron
Microscopy (HT-ESEM).
In a first step, the study of the morphological modifications occurring within a single grain
during heat treatment at high temperature (typically in the 1000–1300 °C range) led to deter-
mine the variation of the number of crystallites included in the polycristalline microspheres
and the attached mechanisms1. Mechanical rearrangement of the crystallites was generally
pointed out for short heating times and associated to low values of activation energies, while
solid-state diffusion was found to occur for longer durations. In parallel, the conditions re-
quired to reach spherical single crystals grain were evaluated.
The kinetics associated to the evolution of neck, contact angles and centers displacement
during the sintering of two microspheres were then evaluated2,3. In this case, the evolution of
polycrystalline assemblies and of single crystals was studied in parallel and led to determine
the driving diffusion mechanism. The comparison of the results with that supplied by the
SALAMMBO model then allowed us to estimate the bias associated to the polycristallinity
of the powders or to the existence of mesoporosity within the microspheres.

References
1. G.I. Nkou Bouala, N. Clavier, J. Léchelle, A. Mesbah, N. Dacheux, R. Podor, “In situ HT-ESEM
study of CeO2 nano-ripening : toward a control of nanostructure”, Ceram. Intern., 41, pp. 14703–
14711, 2015.
2. G.I. Nkou Bouala, N. Clavier, S. Martin, J. Léchelle, N. Dacheux, J. Favrichon, H.P. Brau, R.
Podor, “From in situ HT-ESEM observations to simulation: how does polycristallinity affects the
sintering of CeO2 microspheres”, J. Phys. Chem. C, 120, pp. 386–395, 2016.
3. G.I. Nkou Bouala, N. Clavier, J. Léchelle, J. Monnier, Ch. Ricolleau, N. Dacheux, R. Podor, “High-
temperature electron microscopy study of ThO2 microspheres sintering”, J. Europ. Ceram. Soc., 27,
pp. 727–738, 2017.
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328
High temperature characterization using novel thermo-optical
measuring devices
Holger Friedrich*, Friedrich Raether
Fraunhofer-Center HTL, Gottlieb-Keim Str. 62, 95448 Bayreuth, Germany;
*
e-mail: [email protected]
Keywords: in-situ characterization, thermo-optical measurement TOM, high temperature materials,
refractories

Predictable and reliable high temperature performance is critical for materials like refrac-
tories, kiln furniture, heat exchangers etc. In order to minimize energy consumption, main-
tenance or damages the best available material has to be chosen. In order to gain better and
more realistic data the Fraunhofer-Center HTL has developed Thermo-Optical Measuring
(TOM) devices for more than 20 years. The TOM method is based on advanced sensor tech-
nique which is applied in well-defined and controlled temperature fields and combined with
specific software tools for data evaluation. Recent developments are driven by higher resolu-
tion, larger samples sizes and additional measurands.1–3 Two new TOM devices, TOM_wave
and TOM_air, will be presented which allow the in-situ measurement during thermal cycling,
creep or sintering as well as characterization of high temperature properties.
TOM_wave is a combination of a 1750 °C high temperature furnace and a 600 W CO2-
laser with variable light paths. It allows for different laser heatings of samples which are
customarily pre-heated in the furnace: one and two side sample irradiation, variable laser fo-
cus and power. TOM_wave measures thermo-physical properties like thermal conductivity,
thermal cycling behavior and hot thermal shock resistance. The so-called hot thermal shock
by laser heating is better defined than the customary quenching of hot samples in cold liquids
or gases. Sample damage is monitored in situ during thermal cycling using sound emission
analysis. Thermal conductivity is obtained using the laser flash method. Based on laser and
pyrometer characteristics samples can be measured without coating. Large samples can be
measured by using inverse FE-simulations of the 3-dimensional heat propagation.
TOM_air is designed for precise measurements of sample deformation during sintering,
uniaxial loading or due to inhomogeneous green-bodies, temperature fields or interaction
with support material. Thermo-mechanical properties like uniaxial viscosity and viscous
Poisson ratio can be measured in load and temperature controlled experiments.
Latest developments will be presented by current data on thermal conductivity, thermal
shock as well as creep behaviour of ceramics.

References
1. Raether, F.: Current State of In Situ Measuring Methods for the Control of Firing Processes; Journal
of the American Ceramic Society 92 (2009) 146–152.
2. Raether, F.; Klimera, A.; Baber, J.: In situ measurement and simulation of temperature and stress
gradients during sintering of large ceramic components; Ceramics International 34 (2008) 385–389.
3. Raether, F.: The kinetic field – a versatile tool for prediction and analysis of heating processes; High
Temperatures-High Pressures 42 (2013) 303–319.

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384
In situ study of the oxidation of ZrB2 and HfB2-based ceramics through
laser-induced fluorescence from BO2
Vincent Guérineau1*, Aurélie Julian-Jankowiak1, Gautier Vilmart2, Nelly Dorval2
1
ONERA – The French Aerospace Lab, F-92322 Châtillon, France;
*
e-mail: [email protected]
2
ONERA – The French Aerospace Lab, F-91761 Palaiseau, France
Keywords: UHTC, LIF, ZrB2, HfB2, BO2

The Ultra-High Temperature Ceramics (UHTC) are a class of materials of growing inter-
est. For applications like hypersonic flights, re-entry vehicles or propulsion, these materials
are expected to sustain very high temperatures (>2000 °C) in very corrosive and oxidizing
atmospheres. The most promising materials are ZrB2 and HfB2-based composites. When SiC
is added to the diboride, the material develops a multi-oxide scale composed of a MeO2 skel-
eton and a glassy borosilicate layer at high temperatures. Stability of this glassy borosilicate
layer is the key in ensuring the protection of the underlying materials. Most of the studies
dealing with UHTC oxidation are post-mortem studies, meaning that characterization of the
sample is performed after the oxidation test. Very few in situ studies are published, some
authors use high-temperature X-Ray diffraction1 or optical emission spectroscopy2. In this
study, the laser-induced fluorescence (LIF) technique is used to probe BO2 radicals in the
gas phase above the heated sample in air atmosphere. This provides an in situ and real-time
monitoring UHTC thermal oxidation.
Various sample compositions (ZrB2, ZrB2-20 vol % SiC, HfB2-20 vol % SiC and HfB2-20
vol % SiC-3 vol % Y2O3) are heated with a 2 kW CO2 laser, in a custom-made chamber. The
sample surface temperature is measured using an optical pyrometer. Samples are heated up
to 1650 °C in air flow at 1 bar. The chamber is equipped with fused silica windows for laser
diagnostics.
LIF of BO2 is performed in the A2Пu - X2Пg electronic system with laser excitation at 547
nm and detection of the fluorescence at 580 nm. A tunable dye laser pumped by a frequency
doubled pulsed Nd:YAG laser is used to promote BO2 in the A2Пu excited state. Monitoring
BO2 fluorescence signal throughout the heating ramp gives insights on the thermal stability
of the boria glassy phase (at low temperatures, when SiC is not oxidized) and then of the
borosilicate layer. This signal is first correlated with the reaction of B2O3 with air, and then
to the external borosilicate layer. These in situ diagnostics allow us to propose more precise
oxidation mechanisms with temperature. Afterwards, samples are characterized with SEM/
EDS to confirm the oxidation mechanisms.

References
1. Sarin P., Driemeyer P.M., Kim D.-K. et al., “In situ studies of ZrB2 and ZrB2-SiC composites at high
temperatures”, J. Eur. Ceram. Soc., 30, pp. 2375–2386, 2010.
2. Playez M. et al., “Optical emission spectroscopy during plasmatron testing of ZrB2-SiC ultra-high-
temperature ceramic composites”, J. Thermophysics and Heat Transfer 23 (2), 279–285 (2009).

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610
Identification of mechanical properties of perovskite membranes of
type La(1-x)Sr(x)Fe(1-y)Ga(y)O(3- δ) versus temperature and oxygen partial
pressure by inverse method
Selom Kaligora1*, Jean Gillibert1, Eric Blond1, Laure Guironnet2, Pierre-Marie Geoffrey2,
Nicolas Richet3
1
Univ. Orléans, PRISME, EA 4229, 45072 Orléans, France;
*
e-mail: [email protected]
2
SPCTS, UMR CNRS 7315, ENSCI, Université de Limoges, CEC, 12 Rue Atlantis, 87068 Limoges,
France
3
Air Liquide, CRCD, Jouy en Josas 78350, France
Keywords: mechanical properties, MIEC, creep, I-DIC

Among materials proposed in the literature for oxygen transport membranes, La(1-x)Sr(x)Fe(1-y)
Ga(y)O(3-δ) perovskites are some of the most promising materials.1 In service, these materials
are exposed to high temperature and oxygen partial pressure gradients that are at the origin of
their thermal and chemical expansion. To ensure mechanical reliability and avoid membrane
breakage induced by mechanical constraints, it is then important to characterize the me-
chanical properties of these materials from room temperature to service temperature and for
different atmospheres.2,3 Recently, a set of experimental protocol using I-DICs methods was
proposed to determine elastic properties in air at room and high temperature (900 °C).4 In this
study the mechanical characterization set-up and the I-DIC routine has been enhanced to per-
formed test for different atmospheres and to identify creep properties. The present routines
are based on home-made subroutines and a coupling between finite elements methods and
the DIC program. The optimisation algorithm for the parameters identification is a modified
Levenberg-Marquardt.5 Then, the Young modulus, the poison’s ratio and tensile strength of
La(1-x)Sr(x)Fe(1-y)Ga(y)O(3-δ) perovskite materials were determined at 1000 °C in air, nitrogen and
argon gas firstly. Secondly, creep parameters were determined in air at 1000 °C from a power
law creep model. To consider the influence of oxygen partial pressure at high temperature,
the creep model proposed by Bretheau6 is investigated.

References
1. J.P.M. Geffroy et al., “Identification of the rate-determining step in oxygen transport through La(1-x)
SrxFe(1-y)GayO3-δ perovskite membranes”, J. Mem. Sc., 476, pp. 340–347, 2015.
2. J. Wei et al., “Review of mechanical characterization methods for ceramics used in energy tech-
nologies”, Ceram. Int. 40 (2014), pp. 15371–15380.
3. E. Blond, N. Richet, “Thermomechanical modelling of ion-conducting membrane for oxygen sepa-
ration”, J. Eur Ceram. Soc., 28 (4) (2008), pp. 793–801.
4. C. Gazeau et al., “Experimental set up for the mechanical characterization of plane ITM membrane
at high temperature”, J. Eur. Cera Soc 35 (2015) 3853–3861.
5. D.W. Marquardt, “An algorithm for least-square estimation non-linear parameters”, J. Soc. Indust.
Appl. Math. 11 (1963) pp. 37–42.
6. T. Bretheau at al., Adv in Phys., 28, 836–104 (1979).

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371
Experiment-based, predictive simulation of ceramic high-temperature
processes
Gerhard Seifert*, Heiko Ziebold, Friedrich Raether
Fraunhofer-Center for High Temperature Materials and Design HTL, Gottlieb-Keim Str. 62,
95448 Bayreuth, Germany; *e-mail: [email protected]
Keywords: high temperature processes, process simulation, in-situ characterization

The quality and reliability of ceramic parts is strongly related to the thermal processing condi-
tions a material is exposed to on its way from green body to dense sintered product. A merely
empirical optimization of temperature profile and other processing parameters is usually very
time-consuming, and often ends up with thermal cycles which consume significantly more
time and energy than optimally required. Most existing approaches to do these optimizations
by numerical simulations suffer from the need for one or more adjustable parameters within
the models used.
To overcome these limitations and enable reliable quantitative predictions, the Fraunhofer
HTL has developed an approach to model the behaviour of ceramics during thermal pro-
cesses on the basis of precise in-situ measurements of the relevant process kinetics. The
in-situ data are obtained using specialized thermo-optical measuring (TOM) systems1; the
data are then used in the form of a kinetic field2 as input for finite element simulations. These
simulations can, for instance, provide predictions of sinter shrinkage and possible final shape
distortion as a function of applied time-temperature cycle. This knowledge is particularly
helpful for the design and processing of additively manufactured ceramic parts, whose final
shapes cannot be corrected by machining.
In this contribution, the quality of the simulation approach is demonstrated on the sintering
of pure alumina ceramics. The finite element sintering model uses TOM in-situ results ob-
tained by special optical dilatometry and cyclic loading dilatometry, and can predict stresses
and sinter shrinkage during any time-temperature cycle which is in the range of the measured
kinetic field. As well, the expected final 3D geometrical shape of an arbitrary ceramic part
can be calculated. In addition, it will be shown that this modeling concept can successfully
be transferred to other thermal processes like debinding or dehydroxilation, where besides a
kinetic field for the rate of weight loss further experimental input like knowledge about exo-
or endothermic processes is required.
Altogether, the method of thermal process simulation presented here enables a compre-
hensive optimization of ceramic production processes with respect to energy efficiency, pro-
cessing time and product quality.

References
1. F. Raether: Current State of In Situ Measuring Methods for the Control of Firing Processes; Journal
of the American Ceramic Society 92 (2009) 146–152.
2. F. Raether: The kinetic field - a versatile tool for prediction and analysis of heating processes; High
Temperatures-High Pressures 42 (2013) 303–319.

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447
Theoretical modeling the magnetic properties of (Cr2/3M1/3)3AX2
(M = Ti, V, A = Al, Si, P, S, Ge, Ga, X = C, N) tailored by chemical
compositions
Jiemin Wang*, Jingyang Wang
High performance Ceramics Division, Institute of Metal Research, Chinese Academy of Sciences,
Wenhua Road 72#, Shenyang, Liaoning, China; *e-mail: [email protected]
Keywords: MAX phases, magnetic properties, first principles

Please note that the whole text should fit to this single page Mn+1AXn (MAX) phases belong
to a group of nanolaminated ceramics, which have the unique layered crystal structure. The
Cr or Mn containing MAX phases were found to be magnetic materials, attracting great
interests due to the combination of nanolaminated structure and magnetic properties, which
has promising functional application in spintronics or as the self-monitoring smart coating.
Most of the discussed magnetic MAX phases are belong to the group of M2AX. However,
Cr2TiAlC2 is recently reported as magnetic materials and been synthesized experimentally.
Previous studies also show the solid solution method is a strong tool to develop new MAX
phase from the pure MAX phases which are considered to not exist before. In this work, the
magnetic properties of Cr containing (Cr2/3M1/3)3AX2 solid solutions were studied from first
principles. The results show that magnetic moments of the solid solutions are mainly con-
tributed from the Cr atoms. The chemical compositions strongly effected the local magnetic
moments of Cr atoms due to changing the number of valence electrons and the Cr-Cr atomic
plane separations. This result can provide an insight on tailoring magnetic properties of MAX
phases by tuning the chemical compositions through solid solution method.

References
1. Zhimou Liu, Erdong Wu, Jiemin Wang, Yuhai Qian, Huimin Xiang, Xichao Li, Qianqian Jin, Guan-
gai Sun, Xiping Chen, Jingyang Wang, Meishuan Li, “Crystal structure and formation mechanism
of (Cr2/3Ti1/3)3AlC2 MAX phase”, Acta Materialia 73, pp. 186–193, 2014.
2. Jiemin Wang, Zhimou Liu, Haibin Zhang, and Jingyang Wang, “Tailoring Magnetic Properties of
MAX Phases, a Theoretical Investigation of (Cr2Ti)AlC2 and Cr2AlC”, J. Am. Ceram. Soc., 99, pp.
3371–3375, 2016.

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Poster presentations

552
Modeling of functional properties of microwave dielectric ceramics:
study-adapted materials informatics approach
Natalia Kireeva1,2*, Vladislav S. Pervov3
Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Sciences,
1

Leninsky prospect, 31a, 119071, Moscow, Russia; *e-mail: [email protected]

Moscow Institute of Physics and Technology (State University), Institutsky per., 9, 141700,
2

Dolgoprudny, Russia
Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences,
3

Leninsky prospect, 31a, 119071, Moscow, Russia

Keywords: microwave dielectric properties, materials informatics, machine learning, quantitative
composition-structure-property relationship, data curation, miltitask learning, relative permittivity,
temperature coefficient of resonant frequency

During the past decades the hurtling growth of technologies related to wireless communica-
tion resulted in the development of wide spectra of new dielectric materials for microwave
applications. These inorganic materials have to meet three main requirements: high permit-
tivity for possible device miniaturization, high quality factor (low loss) for frequency selec-
tivity and near zero temperature coefficient of resonant frequency for temperature stability.
Ceramics related to different structure-types are widely investigated in this concern as the
candidates for the components of communication systems because of their attractive mi-
crowave properties. This study encompasses the information on the compounds related to
complex perovskites, wolframites, columbites, ixiolites, aeschynites, and euxenites as the
data basis for the development of predictive quantitative models establishing the chemical
composition-structure-microwave dielectric property relationships.
The data curation procedure is considered in this study as one of the key aspects of the
model development, where two conceptually different approaches are represented in order to
aid the expert decision for the cases where different data is published for the same compound.
Another feature of this study is the attempt to adopt the idea of multitask learning in order
to share the information gained from one structure-type among the other ones as well as to
assist the compromise solution in reaching the balance between the contradictory microwave
properties for new compounds. Both approaches are intended to demonstrate the possibilities
of machine learning in speeding-up the process of the development of new compounds with
tailored properties as well as the assisting the experimental data analysis.

Acknowledgement
Authors thank Russian Foundation for Basic Research (Project No.15-29-09075) for the support.

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324
FEM of the factors affecting nanoindentation in the coated systems
D. Németh, F. Lofaj
Institute of Materials Research of the Slovak Academy of Sciences, Watsonova 47, Košice, Slovakia

The factors affecting nanoindentation were studied experimentally and by finite element
method (FEM) on around 1 um thin hard W-C coatings deposited by High Power Impulse
Magnetron Sputtering (HiPIMS) technique on softer steel (12050) substrate. Nanoindenta-
tion was performed by Berkovich indenters with three different tip radii in continuous stiff-
ness measurement (CSM) mode and the indents were observed by scanning electron micros-
copy, atomic force microscopy and focus ion beam. The nanoindentation was simulated by
2D axisymmetric FEM model using sharp tip and experimental tip radii. The experimental
and FEM results showed that the hardness and modulus depth profiles of hard coating/soft
substrate system strongly depend on the radius of the indenter tip, ratio of the tip radius to
coating thickness (R/t) and on the ratio of the yield strengths of coating/substrate (σc/σs).
The correct measurement of nanohardness and indentation modulus of thin hard coatings on
softer substrates requires the limits for the ratios R/t and σc/σs are fulfilled. The determination
of these limits is a valuable contribution to the standardization of CSM method for nanoin-
dentation on coated systems.

545
Microstructure characterization of silicon carbide/boron nitride
composite by precession electron diffraction technique in transmission
electron microscope
Umut Savacı1*, Yilmaz Zuhal2, Nuran Ay1, Servet Turan1
1
Materials Science and Engineering Department, Anadolu University, Eskisehir, Turkey;
*
e-mail: [email protected]
2
Bilecik SeyhEdebali Universitesi, SMYO, Bilecik, Turkey
Keywords: precession, electron diffraction, silicon carbide, boron nitride, TEM

Structure property relationship has significant importance in materials science, especially the
orientation between the phases present in the structure. Electron backscattered diffraction
(EBSD) technique in scanning electron microscope (SEM) is widely used for characteriza-
tion and visualization of orientation difference between the grains. To overcome the limita-
tions of EBSD, especially the resolution, transmission electron microscope (TEM) based
techniques like precession electron diffraction (PED) had been developed.1 This technique
involves a scanning of nearly parallel nano probe over the specimen and at each point diffrac-
tion spots are collected while the probe is tilted away from the optical axis in order to mini-
mize the dynamical diffraction. This movement of the beam is created by the scan generator

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(DigiSTAR™ P1000, NanoMEGAS) and collected electron diffractions by the external CCD
then indexed through template matching algorithm with theoretical patterns in a software
(ASTAR™).2,3
In the present work, SiC with 7 wt% h-BN additive composite material produced by spark
plasma sintering (SPS) method is characterized by TEM/STEM and precession electron dif-
fraction (PED) techniques. Transmission electron microscopy sample is prepared by conven-
tional mechanical polishing followed by Ar-ion beam milling. Electron transparent sample is
examined by using 200 keV field emission TEM (JEOL-JEM2100F) equipped with STEM
high angle annular dark field (HAADF) detector (Fischione-Model 3000) and energy disper-
sive X-ray (EDX) spectrometer (JEOL-JED2300T). The TEM phase and orientation map-
ping results are obtained at NBD mode 0.5 nm and the probe is scanned in a user specified
area over the sample up to 0.7° of precession angle and obtained diffraction patterns are
analyzed with software (ASTAR™ V2).
TEM and STEM-HAADF results showed that microstructure of the composite system has
micron sized SiC and h-BN grains with an amorphous phase that contains yttrium, aluminum
and oxygen elements. Due to the mass difference, there is a sharp contrast change between
the present phases in TEM and STEM-HAADF results and EDX results confirms the con-
trast difference in TEM and STEM-HAADF images. TEM and STEM results also showed
that, liquid phase that is formed during SPS process is present between not all SiC particles
but some of them and this result is concluded as the selective wetting of liquid phase on SiC
surfaces.
In this study, apart from the crystallographic orientation and phase maps of the composite
structure, the crystallographic relationship between SiC and BN particles during synthesis
and wetting behavior of liquid phase around SiC particles are investigated by the application
of PED technique at different precession angles (from 0° to 0.7°). It is also important to em-
phasize that indexing parameters have a great influence on the orientation mapping results.
Thus, in this study it is also tried to find out the optimum indexing parameters to have the best
indexing results which is quantified by the index and reliability values.

Acknowledgements
The authors would like to acknowledge the financial support from the Scientific Research Project Com-
mission of Anadolu University (grant no: 1504F168) and The Scientific and Technological Research
Council of Turkey (TUBITAK) 2211 scholarship programme.

References
1. Brons, J.G. and G.B. Thompson, Orientation Mapping via Precession-Enhanced Electron Diffrac-
tion and Its Applications in Materials Science. Jom, 2013. 66(1): p. 165–170.
2. Rauch, E.F. and A. Duft, Orientation Maps Derived from TEM Diffraction Patterns Collected with
an External CCD Camera. Materials Science Forum, 2005. 495–497: p. 197–202.
3. NanoMEGAS. Available from: http://www.nanomegas.com/.

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828
Correlation composition-processing conditions to optimize cement
clinker quality
Adrian Volceanov1, Zeno Ghizdăveț1, Mihai Eftimie1, Daniela Năstac2, Sabina Socoteanu1
1
University POLITEHNICA Bucharest, Splaiul Independentei Street, No. 313, Bucharest, Romania;
e-mail: [email protected]
2
CEPROCIM S.A, Preciziei Street, Sector 6, Bucharest, Romania; e-mail: [email protected]

Nowadays challenges in ceramic materials processing are closely related to the integration
of all factors contributing to process efficiency. Practically, efficiency could be expressed as
obtaining the best quality for the material with a minimum expenditure of materials, energy,
fuels and manpower, thus lessening the costs and the imprint on the environment. When deal-
ing with industrial processes with outcomes of up to 10000 t/day – such as clinker process-
ing – the efficiency level becomes highly significant.
The solution to this challenges is to consider an integrated approach that can involve
most – if not all – of the contributing factors, thus minimizing loss by accurately correlating
these factors. In this work, two leading selections for a cement plant, i.e. raw materials and
thermal processing conditions are being included into an integrated approach, that translates
into: selecting the most appropriate thermal history and the best corresponding raw materials
from available ones.
The aim of this research is to find out the exact influence of these two factors that affect
clinker quality. It has to be found, also, whether all these factors do affect not only the clinker
quality but also microstructural features, such as grains size and shape, and minerals propor-
tions in clinker. A total of 9 series (3×3) of combinations of materials composition – process-
ing conditions were used.
Clinkers were analyzed by using various methods such as: Scanning Electron Microscopy
(SEM), Optical Microscopy, X-Ray powder diffraction (XRD). Free CaO was measured as
an indicator of the clinker quality.
Experimental showed that free CaO and clinker mineral composition clearly depends on
both materials composition and thermal histories. Optimal combination of factors within the
available possibilities has been clearly identified, with reasonably small efforts. Although the
numbers (resulted values) are not universally applicable, given the specificity of each cement
plant’s features, our findings can be used as a roadmap procedure to select the best combina-
tion possible.

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265
The effects of tin bath entrance design on molten glass flow during
float process
Zhong-Xi You, Huey-Jiuan Lin*
Department of Materials Science and Engineering, National United University, No.1 Lien-Da Rd.
MiaoLi, Taiwan; *e-mail: [email protected]
Keywords: float process, tin bath, multiphase modeling

One of the most widely employed procedures for flat glass manufacture is float process,
proposed by Pilkington. Nowadays, there is great demand for thinner float glass of high opti-
cal quality. In the float process, the molten glass moves out of the melting furnace and flows
into an enclosed bath of molten tin through its canal and spout, spreads out on the surface of
the molten tin incessantly. The forming of the glass ribbon takes place during passage of the
glass through tin bath, where the glass is stretched to achieve the required size and cooled
down until the surfaces are hard enough. The most important stage of float process is the
glass forming in tin bath.
When the molten glass flows into the tin bath from spout, most of the glass flows forward
in the direction of the float bath outlet, but a small amount flows backward. The part of the
float tank in which the glass flows backward is called wet back region. The glass appearing
in the wet back region can cause defects in the glass and need lead to the sidewall of tin bath.
In this study, a multiphase flow model including molten glass, tin bath and protective at-
mosphere was established using the FLUENT software. The flow phenomena of molten glass
when spouted over a lip onto the tin bath under protective atmosphere were simulated and
analysed. The influence of wet back tile and restrictor tile design on flow behaviour of wet
back flow was investigated. Simulation indicates that the molten glass in the wet back region
flows outward into the extreme edges of the glass ribbon and depends on the length of wet
back tile and angle of restrictor tile.

References
1. L.A.B. Pilkington, “Review Lecture. The Float Glass Process,” Proc. R. Soc. Lond. A Math. Phys.
Sci., 314 [1516] 1–25 (1969).
2. Z. Xing, S. Xu, Y. Li, and S. Liu, “Simulation of Molten-glass Evolution from Spout Lip to Tin
Bath.” International Journal of Applied Glass Science, 1–11 (2015).
3. J. M. Fernández Oro, K. M. Argüelles Díaz, C. Santolaria Morros, “Multiphase Modelling of Pour-
ing Glass Over the Spout Lip of an Industrial Float in the Flat Glass Forming Process”, Int. J.
Numer. Meth. Fluids. 58 (2008) 1147–1177.

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T09: Boron-based ceramics
Invited lectures

462
Preparation of boride-based eutectic composite by melt-solidification
Takashi Goto*, Hirokazu Katsui, Kishin Morita
Institute for Materials Research, Tohoku University, 2-1-1 Katahira Aoba-ku Sendai Miyagi, Japan;
*
e-mail: [email protected]
Keywords: boride, SiC, eutectic, one directionally solidification, laser

Since borides have high melting temperature, high mechanical strength and stability at high
temperature, they are promising structural materials. Various boride-based composites have
been fabricated by solid-state sintering such as hot press and spark plasma sintering.1 How-
ever, fully dense composites are often difficult to fabricate due to low diffusion coefficient
and covalent nature. It was also too hard to melt because of their high melting temperature
often more than ~3000 K. On the other hand, laser or electron-beam technology is develop-
ing, and the high-temperature can be easily produced by laser. Boride-based composites can
be fabricated by melt-solidification using laser. By scanning laser and sequential powder
loading, melting and solidification, additive production or 3D printing of ceramic materials
can be realized. One-directionally solidification is particularly useful to control microstruc-
ture of ceramic composites improving mechanical properties.2 Borides are often corroded in
oxidizing atmosphere at high temperature forming volatile B2O3, while silicon carbide (SiC)
is not oxidized due to protective SiO2 formation. Therefore, boride-SiC eutectic composite
can be promising high temperature structural materials. In this study, we will present several
boride-SiC eutectic composites by melt-solidification using laser and arc melting. VB2-SiC is
a quasi-binary eutectic system, whose eutectic composition is 55 mass%VB2. By arc melting,
SiC phase dispersed in VB2 matrix with labyrinth-like lamellar structure. The SiC and VB2
phases have a relationship of SiC(111)//VB2(1-210) and SiC[01-1]//VB2[0001]. The Vickers
hardness show the maximum of 22.2 GPa (load: 9.8 N) at the eutectic composition. CrB2-SiC
is also quasi-binary eutectic system, whose eutectic composition is 80 mass% CrB2. At the
eutectic composition, thin lamellar SiC phase dispersed in a CB2 matrix. The eutectic tem-
perature of the CrB2-SiC system could be relatively lower than other boride-SiC system, and
thus CrB2-SiC eutectic composite was melted by laser (Nd:YAG laser, 180 W). By scanning
laser, CrB2-SiC eutectic composite was easily melted and solidified one-directionally along
the scanning direction. CrB2(0001) was perpendicular to the scanning direction.

References
1. M. Kitiwan, A. Iti, T. Goto, J. Euro. Ceram. Soc., 34, pp. 197–203, 2014.
2. W-T. Chen, R.M. White, T. Goto, E.C. Dickey, J. Am. Ceram. Soc., 99, pp. 1837–1851, 2016.

625 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T09: Boron-based ceramics – Invited lectures

790
Correlation between microstructure and mechanical properties of
boron suboxide B6O ceramics; a TEM study
Hans-Joachim Kleebe1, Mathias Herrmann2
1
Director, Applied Geosciences, Technische Universität Darmstadt, 64287 Darmstadt, Germany
2
Researcher, Fraunhofer-Institut für Keramische Technologien und Systeme IKTS, 01277 Dresden,
Germany

B6O is a potential candidate for superhard materials with a hardness of 45 GPa measured
on single crystals. In recent studies it was found that mixtures of Al2O3/Y2O3 can be utilized
as an effective sintering aid. Therefore, liquid phase sintering of B6O can be achieved with
such oxide additives. Microstructure evolution as a function of additive composition dur-
ing SPS/FAST processing and resulting mechanical properties were investigated in detail.
A strong dependence of the resulting microstructure and the corresponding mechanical re-
sponse was found. The material revealed characteristic triple junctions filled with amorphous
residue composed of B2O3, Al2O3 and Y2O3, while no clear evidence of grain-boundary films
was observed along internal interfaces. Mechanical testing revealed on average a hardness
of 33 GPa, a fracture toughness of approximately 4.5 MPa(m)1/2 and a strength value of
520 MPa. Scanning electron microscopy (SEM) and conventional as well as high-resolution
transmission electron microscopy (TEM) analysis allowed for the correlation of the intrinsic
microstructure and local distribution of sintering additives with the measured mechanical
properties, in particular, with the fact that, independent of additive composition and volume
fraction, no further increase in fracture toughness could be achieved.

082
Combustion synthesis of refractory ceramics
Alexander S. Mukasyan1,2
1
Department of Chemical and Biomolecular Engineering, University of Notre Dame, IN, USA, 46556
2
National University of Science and Technology MISiS, Moscow, Russia, 119049
Keywords: combustion synthesis, high-propagation high temperature synthesis, ceramics, boron
nitride, boron carbide, silicon nitride, silicon carbide

Combustion synthesis (CS) or self-propagating high-temperature synthesis (SHS) is an at-

tractive technique to fabricate a wide variety of advanced compounds in forms of powders,
bulk materials and near-net shape articles.1 The characteristic feature of the CS approach is
the self-sustained propagation of a chemical reaction through the heterogeneous mixture of
the precursors. The temperature in the combustion front can reach quite high values (2000–
4000 K) and the velocity of its propagation typically in the range 0.1–10 cm/s. Ceramics
were among the first materials produced by SHS.2 They include boron and silicon nitrides
(BN, Si3N3), boron and silicon carbides (B4C, SiC).3 Recently cubic modification of boron

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 T09: Boron-based ceramics – Invited lectures

nitride (c-BN) was produced by combination of CS and shock-wave. The goal of this review
is summarized and critically discussed the results for direct CS of these ceramics, including
synthesis conditions, mechanisms of microstructure formation, as well as material’s proper-
ties. It is also an attempt to prove that combustion-based approach provide unique efficient
routes for production of these refractory compounds.

References
1. A.S. Rogachev and A.S. Mukasyan, Combustion for Materials Synthesis, CRC Press, Taylor &
Francis, Boca Raton, London, New York, 2015.
2. A.G. Merzhanov and I.P. Borovinskaya, “Self-propagating high-temperature synthesis of refractory
inorganic compounds”, Dokl. Chem., 204:429–431, 1972.
3. Combustion Synthesis and Applications, Editors: AA. Gromov, L. Chukhlomina, Wiley, VCH,
2014.

419
PCBN – supermaterial for abrasive and non-abrasive applications
Serdar Ozbayraktar
Global Innovation Centre, Element Six, Oxfordshire, UK; e-mail: [email protected]

Since its first synthesis 40 years ago Polycrystalline Cubic Boron Nitride has established it-
self as a unique cutting tool material for machining of hard ferrous materials. High Pressures
(4 to 6 GPa) and relatively high temperatures (1400 °C to 1600 °C) are required to sinter typi-
cal grades. Complex ceramic binder structures form the matrix around cBN grains of various
sizes. These binders present challenges and opportunities for the product, process design and
applications. This paper will give an overview of the history of PcBN synthesis and sintering,
typical structures, material classifications, properties and a couple of case studies of abrasive
applications. Hardened Steel and Gray Cast Iron Machining will be described to highlight
critical and interesting tool-workpiece interactions. The final section includes discussion on
the opportunities for PcBN outside of cutting; for example Friction Stir Welding and PcBN
as a functional High Voltage Insulator material.

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T09: Boron-based ceramics – Invited lectures

857
B4C based ceramic composites prepared by spark plasma sintering
F. Sahin1, B. Apak1, M. Cengiz1, B. Yavaş1, S.C. Özer2, G. Göller1, O. Yücel1, S. Turan2,
K. Balazsi3
1
Istanbul Technical University, Dept.of Metallurgical & Materials Eng., 34485, Maslak, İstanbul,
Turkey
2
Anadolu University, Dept. of Materials Sci. & Eng., İki Eylül Kampüsü, 26555, Eskişehir, Turkey
3
Centre for Energy Research Hungarian Academy of Sciences, Institute for Technical Physics and
Materials Science, Thin Film Physics Department, Konkoly-Thege M. 29-33, 1121 Budapest,
Hungary

Boron carbide ceramics posses low density, high hardness, high wear resistance, high neutron
absoption cross section, high melting temperature and high corrosion resistance to chemical
attack. Due to these outstanding properties, they found wide application in industry such as
cutting tools, blasting nozzles, armor materials, nuclear reaction control rods. However low
self diffusivity of constituent elements of B4C and high melting temperature make difficult
to obtain fully densified B4C ceramics. Beside poor sinterability, another major drawback of
B4C is its brittle feature. To overcome these problems many studies have been attempted by
using various sintering techniques and additive materials.
In this talk, we will discuss the effect of various additives such as metals (Al, Si, W),
­oxides (Al2O3, SiO2, TiO2, Y2O3,), carbide (SiC), boride (TiB2) and carbon nanotubes on sin-
terability and some properties on spark plasma sintered B4C ceramics.

144
Processing and properties of B4C-based systems combined with
TiB2 and SiC
D. Sciti, S. Failla, L. Zoli
ISTEC-CNR, Institute of Science and Technology of Ceramics, I-48018 Faenza (RA), Italy

Boron carbide is one of the lightest and hardest ceramics. Properties such as high melting
point, high elastic modulus, high corrosion resistance to chemical agents and high neutron
absorption cross section have generated a great interest in B4C – based ceramics. As a result,
this carbide is currently used in many advanced application fields, including cutting tools,
high temperature thermoelectricity conversion, armor materials and nuclear industry. In spite
of that, B4C is not exploited to its full potential mainly due to its brittleness and extremely
poor sinterability. As many other covalent type carbide ceramics, temperature in excess of
2000 °C and/or pressure assisted techniques are required to obtain the full densification.
In this talk, we first explore different approaches to the processing and sintering of B4C
with the aim to enhance the densification. Then we focus on the B4C – TiB2 system that is par-
ticularly attractive because the addition of TiB2 allows not only an improvement of fracture

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 T09: Boron-based ceramics – Invited lectures

toughness and strength, but also a better machinability, thanks to the possibility of using the
EDM technique. We analyze the effects of: -different TiB2 content on the composite proper-
ties, -further secondary phases used to improve either sinterability (such as WC), or high
temperature properties/oxidation behavior (such as SiC). Finally, we compare the properties
of these materials with reference B4C-based materials, discussing advantages/drawbacks of
different processes.

668
Thermoablative resistance of ZrB2-SiC-WC ceramics at 2400 oC
Ji Zou, Jon Binner
School of Metallurgy and Materials, University of Birmingham, B15 2TT, Birmingham, UK;
e-mails: [email protected], [email protected]
Keywords: borides, UHTCs, microstructure, oxidation

Although ZrB2-SiC ceramics have been extensively researched for applications at ultra-high
temperatures (>2000 oC), it is well known that at these temperatures the SiC oxidises actively
yielding a gaseous sub-oxide, SiO, rather than the protective, passive oxide product, SiO2.
This limits the high-temperature range of SiC-bearing ceramics for ultra-high temperature
applications. In this presentation, dense ZrB2-20vol%SiC ceramics with and without 5 vol%
WC additions have been consolidated by spark plasma sintering at 1950 oC under an axial
pressure of 60MPa. Apart from the mechanical properties, the presentation will focus on the
thermoablative resistance of sintered ceramics at ultra-high temperatures. Results show that
the addition of 5 vol% WC has been shown to effectively eliminate the active oxidation of
SiC in ZrB2-SiC ceramics, even when exposed to an oxyacetylene flame at 2400 oC. In con-
trast to the porous and fragmentary surface observed with ZrB2-SiC ceramics tested under the
same conditions, a dense oxide surface layer was observed that is believed to have resulted
in decreasing pO2 in the layers beneath. This had the effect of changing the chemistry of the
system and hence the composition of the phases produced. Clear evidence of the presence
of SiO2 was observed, thus indicating that the oxidation of the SiC had been passive rather
than active. A full volatility diagram for WB at 2400 oC was derived, and existing volatility
diagrams for ZrB2 and SiC were extended to the same temperature, in order to develop a theo-
retical understanding the active mechanism. The significantly improved ablation resistance
of ZrB2-SiC-WC is consequently mainly attributed to a competitor transition from tungsten
boride (WB) to metallic tungsten in the oxygen partial pressure range 10–8 Pa to 10–3 Pa,
which retards the occurrence of the active oxidation of the SiC phase.

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T09: Boron-based ceramics

Oral presentations

975
In-situ formation of VB2/VC composite powders from oxide raw
materials via powder metallurgy processes
Duygu Ağaoğulları1*, Sıddıka Mertdinç1, Emre Tekoğlu1, Özge Balcı2, M. Lütfi Öveçoğlu1
1
Istanbul Technical University, Chemical and Metallurgical Engineering Faculty, Metallurgical
and Materials Engineering Department, Particulate Materials Laboratories (PML), 34469 Maslak,
Istanbul, Turkey; *e-mail: [email protected]
2
Koç University, Department of Chemistry, Rumelifeneri Yolu, 34450 Sarıyer, Istanbul, Turkey
Keywords: vanadium boride/vanadium carbide, milling, annealing, composite powders

Vanadium borides have superior properties such as high melting point, high hardness, high
wear resistance and good chemical stability. They are generally used as materials in high
temperature applications due to their advanced thermal and mechanical properties.1–3 Not
only vanadium borides, but also vanadium carbides are also attractive for many industrial
applications related with the high hardness, high temperature strength and excellent thermal
stability at high temperatures.4,5 In ceramic materials, addition of a second phase developed
the fracture toughness and strength of a single phase ceramic material.6 Also, boride/carbide
hybrid ceramics can exhibit improved mechanical properties than those of individual char-
acteristics.7
The aim of the present study is the in-situ synthesis of vanadium boride and vanadium
carbide composite powders by using powder metallurgy routes. VB2/VC composite powders
were synthesized from the V2O5, B2O3 and C powder blends via the carbothermal reduction
which were assisted by mechanical milling. Powders blends prepared in the stoichiometric
amounts were milled up to 5 h in a high energy ball mill (1200 rpm) by using hardened steel
vials and balls with 10/1 ball-to-powder weight ratio. Milling step reduced the crystallite
size, increased the uniformity of the distribution and increased the reactivity of the starting
powders. Mechanically milled and also activated powders were annealed at different tem-
peratures in a tube furnace under Ar atmosphere for 12 h to produce single phase VB2 and VC
powders. Annealing temperatures were determined as 1400, 1450 and 1500 °C with 10 °C/
min heating and cooling rates. Annealed powders were characterized by X-ray diffractometer
(XRD) to determine the yielded phases and phase transformations. In the case of using an-
nealing temperature of 1400 °C, VB2-V3B4-V2B3/VC hybrid powders were obtained. Besides,
Rietveld analyses were performed in regard of the XRD patterns to determine the approxi-
mate percentages of the phases. However, annealing temperature of 1400 °C is not enough to
the formation of the most stable VB2 as a single phase in the structure in addition to the VC.
Also, morphologies of the synthesized powders were investigated by using scanning electron
microscope/energy dispersive spectrometer (SEM/EDS). Also, particle size distributions of
the synthesized composite powders were measured by using of laser diffraction technique.

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References
1. S.A. Hassanzadeh-Tabrizian, D. Davoodi, A. Asghar Beykzadeh, S. Salahshour, “Fast mechano-
chemical combustion synthesis of nanostructured vanadium boride by a magnesiothermic reac-
tion”, Ceram. Int., 42, pp. 1812–1816, 2016.
2. L. Shi, Y. Gu, L. Chen, Z. Yang, J. Ma, Y. Qian, “Low-temperature synthesis of nanocrystalline
vanadium diboride”, Mater. Lett., 58, pp. 2890–2892, 2004.
3. N. Gidikova, “Vanadium boride coatings on steel”, Mater. Sci. Eng. A, 278, pp. 181–186, 2000.
4. B. Zhang, Z.Q. Li, “Synthesis of vanadium carbide by mechanical alloying”, J. Alloys Compd., 39,
pp. 183–186, 2005.
5. Y. Wu, G. Zhang , K. Chou, “A novel method to synthesize submicrometer vanadium carbide by
temperature programmed reaction from vanadium pentoxide and phenolic resin”, Int. J. Refract.
Metal. H. Mater., 62, pp. 64–69, 2017.
6. F. de Mestral, F. Thevenot, Boride-Carbide Composites: TiB2-TiC-SiC, The Physics and Chemistry
of Carbides, Nitrides and Borides, 185 of the NATO ASI Series, pp. 457–481, 1990.
7. Ö. Balcı, D. Ağaoğulları, D. Ovalı, M.L. Öveçoğlu, İ. Duman, “In situ synthesis of NbB2–NbC
composite powders by milling-assisted carbothermal reduction of oxide raw materials”, Adv. Pow-
der Technol., 26, pp. 1200–1209, 2015.

058
Effect of titanium diboride on properties of functionally graded boron
carbide-titanium diboride-aluminium composites
Gürsoy Arslan*, Betül Kaytaz
Department of Materials Science and Engineering, Anadolu University, Faculty of Engineering,
Iki Eylül Campus, 26555 Eskisehir, Turkey; *e-mail: [email protected]
Keywords: functionally graded materials, spark plasma sintering, infiltration, mechanical properties,
ceramic-metal composites

In this study, the effect of titanium diboride on the properties of functionally graded boron
carbide-titanium diboride-aluminium composites was investigated. Boron carbide-titanium
diboride powder mixtures containing 0 to 30 weight % titanium diboride were partially sin-
tered at 1700 oC for 5 minutes by spark plasma sintering.
Functionally graded materials were designed by considering the porosity content of the
boron carbide-titanium diboride pellets after partial sintering, and their titanium diboride con-
tent. An aluminium-12 weight % silicon alloy was then infiltrated into the partially sintered
functionally graded preforms at 1200 oC for 10 minutes via pressureless melt infiltration.
Phase analysis of the functionally graded composite layers were characterized by x-ray dif-
fraction, and their microstructure was investigated by using a scanning electron microscope
attached with an energy dispersive x-ray spectrometer. Hardness and compressive strength
values, and densities of the functionally graded composite layer were measured.
Results obtained indicate that titanium diboride addition has a positive effect on both the
sintering behavior of boron carbide, and the hardness and compressive strength of the produced
boron carbide-titanium diboride-aluminium functionally graded composite layers. Furthermore,
it was determined that the amount of residual porosity in the produced functionally graded com-
posite layers was always well below 1%. Hardness and compressive strength values changed
gradually in moving from front to rear surface of the functional graded composite materials.

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369
Sintering and properties of AlB12C2 – based materials
Pavlo Barvitskiy1*, Tatiana Prikhna1, Valeriy Muratov2, Vladimir Sverdun1, Sergey Dub1,
Viktor Moshchil1, Myroslav Karpets2, Artem Kozyrev1, Valeriy Kovylaev2
Institute for Superhard Materials of the National Academy of Sciences of Ukraine,
1

Avtozavodskaya Street, Kiev, 04074, Ukraine; *e-mail: [email protected]

Institute for Problems in Material Science, NAS Ukraine, 3 Krzhizhanovsky Str., 03680, Kiev,
2

Ukraine
Keywords: aluminum dodecaboride-based materials, hardness, fracture toughness, bending strength,
compressive strength, structure

This article focuses on the formation of AlB12C2 – based ceramics from the submicron α-AlB12
powder with C and TiC additions under hot pressure (30 МPа) and high quasihydrostatic
pressure (2 GPа) conditions at 1200–2100 ºС. The interrelations between materials properties
and structures are under the consideration.
The results of the present study allowed us to conclude that the fracture toughness of
α-AlB12 (98 wt.%, porosity 1.59%, density 2.58 g/cm3) was lower than that of the AlB12C2 –
based composites (AlB12C2 = 70 wt.% BN = 14 wt.% Al2O3 = 16 wt.%, porosity 5%, density
2.42 g/cm3) prepared by hot pressing (at 30 MPa). The fracture toughness (estimated under
49 N-load) of AlB12C2 – based composite was 7.6 MPа·m0.5 and the material Vickers hardness
was about 20.1 GPа while the fracture toughness of α-AlB12 prepared under the same condi-
tions was K1C = 4.2±0.5 MPа·m0.5 and hardness HV = 24.1 GPа (at 49 N-load). The fracture
toughness of α-AlB12 sintered under high pressure (2 GPa) conditions was as well lower than
that of AlB12C2. Addition of carbon (17 wt.%) to α-AlB12 and hot pressure synthesis leads to
the formation of the composite material (AlB12C2 = 86 wt.% and AlN_H = 14 wt.%, porosity
0.13%, density 2.7 g/cm3) with K1C = 5.9±1.4 MPа·m0.5 and Vickers hardness HV = 23.6±2.8
GPа (at 49 N-load).
The results of SEM studies showed that the main matrix phase of the AlB12C2 – based
material (sintered at 1950 ºC, 30 MPa and which demonstrated high mechanical characteris-
tics) high deficit of Al and some deficit of boron as compare to AlB12C2 stoichiometry, while
boron in rather high amount was present in the secondary phase having Al2O3 structure. The
increase of concentration of Al-B-O-based phase with Al2O3 structure up to 5 wt.% (accord-
ing with the results of Rietveld refinement of the X-ray pattern) in AlB12C2 – based material
correlated with the higher fracture toughness (4.2±1.3 МPа·m0.5). The material synthesized
from α-AlB12 and 20% TiC at 1950 °C contained after synthesis 74% AlB12C2, 22% TiB2 and
4% Al2O3, its hardness was HV = 28.9 GPa, fracture toughness K1C (49 N) = 5.2 MPа·m0.5,
bending Rbs = 633 MPa and compressive Rcs = 640 MPa strengths, density ρ = 3.2 g/cm3.

Acknowledgement
The work was performed in the framework of the NATO Science for Peace G7050 project.

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534
Novel catalytic synthesis of boron nitride nanotubes at low
temperatures
Mustafa Baysal1*, Kaan Bilge1, Yelda Yorulmaz1, Melike Mercan Yildizhan1, Çinar Oncel2,
Melih Papila1, Yuda Yurum1
Sabanci University, Faculty of Engineering and Natural Sciences, Tuzla 34956, İstanbul, Turkey;
1

*
e-mail: [email protected]
Muğla Sıtkı Kocaman University, Faculty of Engineering, Metallurgical and Materials Engineering
2

Department, B Building Kötekli Campus 48000, Muğla, Turkey

Keywords: BNNT, catalyst, CVD

Boron Nitride Nanotubes (BNNT) have been the most popular inorganic nanotubes for the
last 20 years, after carbon nanotubes. BNNTs are structurally analogous to carbon nano-
tubes. However, their chemical difference to carbon nanotubes makes them more advan-
tageous on many aspects such as chemical stability, thermal stability (oxidation resistance
up to 1100 oC), piezoelectricity, neutron screening, and super hydrophobicity. Moreover, as
opposed to the semiconducting or metallic carbon nanotubes, BNNTs, owing to the par-
tially ionic character of their bond structure, are wide bandgap (5–6 eV) insulating materials.
Because of all those unique properties, BNNTs are candidate materials for nanoelectronics
(nano insulating material, nanosensors), optical applications (Deep-blue and infrared lasers),
magnetic applications (targeted drug delivery), biomedical applications (biosensors, tissue
scaffold), energy applications (hydrogen storage), ceramic-glass composites and polymeric
nanocomposites. However, the most important drawback of BNNTs lie in the challenges of
synthesizing them with high purity and amount. Chemical Vapor Deposition (CVD) tech-
nique is advantageous in the sense that it is possible to produce high amounts of material
with high purity. Hence, CVD is a technique of importance in industrialization of BNNTs,
and is considered as the primary technique in BNNT synthesis. However, the catalysts used
in BNNT production only function at temperatures at and above 1100 oC.1,2 Here, a novel al-
kali based catalyst is produced and used in vapor trap CVD synthesis of BNNTs. The catalyst
works at temperatures as low as 750 oC. The catalyst is characterized via XRD. The structural
characterization of BNNTs were conducted by XRD and Raman Spectroscopies, the size of
the nanotubes were determined with SEM, wall structure was determined with TEM and
chemical composition analysis was carried out with EELS measurements.

References
1. C.H. Lee, M. Xie, V. Kayastha, J. Wang and Y.K. Yap, Patterned growth of boron nitride nanotubes
by catalytic chemical vapor deposition, Chem. Mater., 2010, 22, 1782–1787.
2. A. Pakdel, C. Zhi, Y. Bando, T. Nakayama and D. Golberg, A comprehensive analysis of the CVD
growth of boron nitride nanotubes, Nanotechnology, 2012, 23, 215601.

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202
SHS of TiB2-B4C powder mıxtures
Mehmet Buğdaycı1,2, Kağan Benzeşik1, Ahmet Turan2, Onuralp Yücel1
İstanbul Technical University, Metallurgy and Materials Engineering, Maslak, Istanbul, 34469,
1

Turkey
Yalova University, Chemical and Process Engineering Department, Yalova, 77100, Turkey;
2

e-mails: [email protected], [email protected], [email protected], [email protected]

Titanium-diboride (TiB2) is an important and promising transition metal boride with its
unique properties such as high strength, hardness, durability, melting point, wear resistance,
thermal conductivity and low electric resistivity. Boron Carbide (B4C) is one of the hardest
materials known, ranking third behind diamond and cubic boron nitride. It is the hardest ma-
terial produced in tonnage quantities. Originally discovered in mid-19th century as a by-prod-
uct in the production of metal borides, boron carbide was only studied in detail since 1930.
TiB2 and B4C are are being used in various industrial areas from space technology to nuclear
industry owing to combination of their unique properties. Present study was conducted in two
main stages: Self-propagating high-temperature synthesis (SHS) reactions and leaching. TiO,
Carbon black, B2O3 were used as starting material to produce TiB2-B4C powders by SHS. The
metal oxide powders have over 97% purity and 150 µm average grain sizes. For thermody-
namic analysis of system Fact sage 6.4 software was used, in order to determine probable
phases at different temperatures. The reaction mixtures were weighted on a precision scale
and mixed thoroughly 15 minutes in a turbula mixer and powder mixtures (approximately
150 g) were charged into Cu crucible and compacted. W (tungsten) wire was placed at the
top of copper crucible and the reaction realized by passing current through the wire. After
initiation, a highly exothermic reaction became in a self-sustaining mode and propagated
throughout the SHS mixture. The obtained SHS products were discharged from the crucible
after cooling. At the end of the SHS process leaching step was applied to eliminate undesired
Mg based phases. The hydrochloric acid solution was prepared with TiB2-B4C SHS powders.
The samples were characterized by using Atomic Absorbsion Spectrometer, X-Ray Diffrac-
tion, X-Ray Fluorescence, Scanning Electron Microscope and EDS techniques.

References
1. A. Turan, M. Bugdayci and O. Yucel, High Temp. Mater. Proc., 34(2) (2015) 185–193.
2. Alkan M., Sonmez M. S., Derin B., Yucel O. “Purification Attempts of B4C Powders Produced by
Metallothermic Process” Proceedings of the 11th ECERS Conference, Krakow, (2009) 1003–1005.

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207
Production of IV-B group boride composite ceramics via SHS
Mehmet Buğdaycı1,2, Ahmet Turan2, Kağan Benzeşik1, Onuralp Yücel1
Istanbul Technical University, Metallurgy and Materials Engineering, Maslak, Istanbul, 34469,
1

Turkey
Yalova University, Chemical and Process Engineering Department, Yalova, 77100, Turkey;
2

e-mails: [email protected], [email protected], [email protected], [email protected]

TiB2 and ZrB2 are important metal borides. They are being used in various industrial areas
such as space technology, nuclear industry owing to their unique physical properties such
as high thermal/electrical conductivity, high melting point and low density. In the SHS ex-
periments, a mixture of ZrO2, TiO2, B2O3 and Mg powders were used in order to produce
advanced ZrB2-TiB2 composite ceramic powders. The metal oxide powders have over 97%
purity and 150 µm average grain sizes. In the experimental set TiB2-ZrB2 composite powders
produced by SHS and leaching processes. In this experiment set TiB2 and ZrB2 ratio changed
and optimum conditions determined, initial conditions and results of these series present in
Table 1.

Table 1. Initial conditions of ZrB2-TiB2 SHS experiments

No Zr/Ti ZrO2 (g) TiO2 (g) B2O3 (g) Mg (g) SHS Product(g)
1 90/10 23.20 2.96 41.90 31.92 90.00
2 80/20 20.64 5.92 40.12 33.33 90.30
3 70/30 18.04 8.89 38.32 34.31 71.90
4 60/40 15.46 11.85 36.53 36.14 71.80
5 50/50 12.89 14.82 34.74 37.54 91.20
6 40/60 10.31 17.78 32.94 38.95 94.90
7 30/70 7.73 20.74 31.20 40.40 57.00
8 20/80 5.15 23.71 29.30 41.72 97.50
9 10/90 2.57 26.67 27.57 43.16 60.30

After the SHS experiment again leaching process made, Fig. 1 indicates leached and un-
leached products of ZrB2-TiB2 composite powders.

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A%40 ZrB2 %60 TiB2 – B%50 ZrB2 %50 TiB2 – C%60 ZrB2 %40 TiB2

Fig. 1. XRD Graphs of Unleached and leached ZrB2-TiB2

397
A study of novel PcBN tool materials in interrupted machining
applications
Antionette Can1*, Robert Lyons2, John J. Barry1, Alexandre Thomasson1,
Myriam Motchelaho1
1
Element Six Global Innovation Centre, Oxfordshire, United Kingdom;
*
e-mail: [email protected]
2
School of Mechanical and Materials Engineering, University College Dublin, Ireland
Keywords: polycrystalline cubic boron nitride, PcBN, interrupted machining, properties, tool life

Polycrystalline cubic Boron Nitride (PcBN) materials are increasingly being used to make
tools for high speed machining of various alloys, including hardened steels. Next generation
PcBN materials need to out-perform existing PcBN materials as well as ceramic and coated
carbide grades in terms of tool life and predictability of performance. In the quest for next
generation PcBN tool materials, different materials processing technologies are employed to
manufacture novel grades. Testing of these materials in application tests is costly and time
consuming. This study presents novel PcBN materials, with performance superior to cur-
rent commercially available grades in interrupted applications. This paper also presents an
observed correlation between Vickers micro-indenter crack length distributions and tool life

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of these variants in moderately interrupted applications. This work has resulted in new PcBN
tool material solutions, as well as a significant saving in cost and time for screening of new
PcBN variants in moderately interrupted machining applications.

586
Effect of calcium carbonate addition on the gel precursor synthesize of
boron carbide
Özge Gündüz1, Duygu Yılmaz1*, Nurşen Koç1, Servet Turan2
1
Metallurgy and Materials Engineering, Eskisehir Osmangazi University, Eskisehir, Turkey;
*
e-mail: [email protected]
2
Materials Science and Engineering, Anadolu University, Eskisehir, Turkey
Keywords: carbothermic reduction, boron carbide, gel precursor

Boron carbide (B4C) is an expensive material, commercially synthesized by the carbother-

mal reduction at high temperature. However, this technique results in excessive free carbon
residue in the final product due to the boron loss. To minimize boron loss during synthesis,
additional assistive compounds can be added into the system and afterwards these additives
are easily removed to obtain purified end-product. Citric acid (CA) has frequently used as a
carbon source to synthesize B4C but studies showed that despite the high synthesising tem-
peratures, high amount of residual carbon still exist in the system.1–3
In this study, B4C was synthesized with using of gel precursor technique that was prepared
in a single step process and by the carbothermic reduction via reaction of boron oxide from
boric acid (H3BO3) and carbon from citric acid (C6H8O7). Effect of calcium carbonate addi-
tion and its optimum amount on the residual carbon content have been investigated system-
atically.
The gel product was characterized by means of Fourier Transform Infrared Spectroscopy
(FTIR) and Thermal Analysis (TG/DTA) to prove of gel formation. X-ray diffractometry
(XRD) and scanning electron microscopy (SEM) have been used to analyse phase formation
and morphology of the synthesized powders. It was found that Ca3B2O6, CaB2O4 phases were
formed as transitional phases and all of them were easily removed via acid leaching from the
end product. The optimum synthesis conditions for the formation of B4C without free carbon
residue were determined as 1400 °C for 10 h in an argon flow and the ratio of CaO:B2O3=1:3.

References
1. S. Corradetti, S. Carturan, L. Biasetto, A. Andrighetto, P. Colombo, Boron carbide as a target for the
SPES project, J. Nucl. Mater., 432, pp. 212–221, 2013.
2. A.M. Hadian, J.A. Bigdeloo, The Effect of Time, Temperature and Composition on Boron Carbide
Synthesis by Sol-gel Method, J. Mater. Eng. Perform., 17, pp. 44–49, 2008.
3. Sinha, T. Mahata, B.P. Sharma, Carbothermal route for preparation of boron carbide powder from
boric acid–citric acid gel precursor, J. Nucl. Mater., 301, pp. 165–169, 2002.

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457
Modification of B4C ceramics surface by the intense electron beam
and ion plasma sputtering
Oleg Khasanov1*, Yurii Ivanov1,2, Maria Petyukevich1, Oleg Tolkachev1, Anton Teresov2,
Zulfa Bikbaeva1, Valentina Polisadova1
1
Department of Nanomaterials, Tomsk Polytechnic University, 30, Lenin Ave., Tomsk, 634050,
Russia; *e-mail: [email protected]
2
Institute of High Current Electronics SB RAS, 2/3 Akademichesky Ave., Tomsk, 634055, Russia
Keywords: boron carbide ceramics, spark plasma sintering, intense pulsed electron beam, metalliza-
tion, microhardness, fracture toughness

B4C ceramics has been sintered by SPS technique using powder mixture of two fractions: 90
wt% of submicrometer fraction (average size of B4C particles 0.55 microns, JSC Uralinvest,
Russia) and 10 wt% of nano-scaled one (average size of B4C particles 46 nm, Plasmachem
GmbH, Germany). Relative density of sintered ceramics was 99.2%; microhardness 36.5
GPa (Vickers pyramid indentation using the microhardness tester PMT-3M LOMO); fracture
toughness 5.6 MPa*m1/2 by Niihara’s formula.1 Ceramic samples were irradiated with a low-
energy intense pulsed electron beam (IPEB, energy 15 keV, energy density 5–30 J/cm2, pulse
duration 100 µs, pulse frequency 0.3 s–1,) in residual argon atmosphere (10–2 Pa). TEM (JEM-
2100F JEOL), SEM (SEM-7500F JEOL) analysis showed that the irradiation caused the
formation of a full-dense surface layer (thickness of 15 microns) with microstructure having
micro-twins and nanoscale interlayers along the boron carbide crystalline interfaces. Fatigue
tests were performed before and after irradiation using ultra-microhardness tester DUH-211S
Shimadzu (up to 50 loading cycles by 10 mN indentation load with 5 s time exposure; size
of loading pyramid tip was 10 nm). After 10 loading cycles surface of the irradiated ceramics
had microhardness of 27 GPa while non-irradiated one showed microhardness decreasing up
to 17 GPa. So the surface layer hardening of the irradiated ceramics has been shown.
Ti film (thickness of 0.5 micron) was deposited on the B4C ceramics by the ion-plasma
sputtering.2 It was found that irradiation of Ti film/B4C substrate by the IPEB lead to forma-
tion of metal-enriched mixed system (α-Ti)+TiB2 in the surface layer (thickness of 5–7 mi-
crons) having improved plastic properties. The irradiated metallized Ti/B4C surface was not
fractured under Vickers pyramid indentation at load of 1.96 N while at the same testing the
initial B4C ceramics showed the cracks and had fracture toughness of 5.4 MPa*m1/2.

References
1. K. Niihara, R. Morena and D.P.H. Hasselman, “Evaluation of KIc of brittle solids by the indentation
method with low crack-to-indent ratios”, J. Mater. Sci. Lett., 1, pp. 13–16, 1982.
2. Yu.F. Ivanov, O.L. Khasanov, Z.G. Bikbaeva, M.S. Petyukevich, A.D. Teresov, V.V. Shugurov,
O.V. Ivanova, and A.A. Klopotov, “Structural and phase transformations in Ti-B4C system formed
when melting the composition film/substrate by an intense electron beam”, Key Eng. Mat., 712,
pp. 76–80, 2016.

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982
Design-synthesis-evaluation of hard coatings for industrial applications
Kwang Ho Kim
School of Materials Science and Engineering, Pusan National University, Global Frontier R&D
Center for Hybrid Interface-based Future Materials, Busan 609-735, South Korea

Hard-phase films have been extensively applied in various parts with superior mechanical
properties like high hardness, wear resistance, low friction, etc. for the applications in ma-
chining, die-casting processes. Recently, the electrochemical applications of DLC, diamond
films are spotlighted for waste-water treatments.
(1) Nanocomposite films: Various new materials for the multi-function are designed. For
example, various ternary, quaternary, and quinary nano-structured films in the (Ti, Cr, Mo,
Al, Si)-(B, C, N) system are compared in sense of not only hardness but also other properties
of corrosion, oxidation, friction etc. for the structural applications.
(2) DLC and BDD films for the waste-water treatment: Diamond- like carbon (DLC)
and boron-doped diamond (BDD) films have superior chemical stability and electrochemical
properties. For the applications of waste-water treatment, the hard layers should have ideal
interlayer structure and those multi-layered structure must show the excellent properties such
as mechanical stability and electrochemical properties.

518
Preparation and characterization of oxidation behavior of YB4-SiC
ceramics
Z. Kováčová1,2, Ľ. Bača1, E. Neubauer2, M. Kitzmantel2
1
Institute of Inorganic Chemistry, Technology and Materials, Faculty of Chemical and Food
Technology, Slovak University of Technology, Radlinského 9, 812 37 Bratislava
2
RHP-Technology GmbH, Forschungs- und Technologiezentrum, A-2444 Seibersdorf, Austria
Keywords: YB4, synthesis, oxidation

Yttrium tetraboride (YB4) powders were synthetized via four reactions including: direct syn-
thesis from elements (1), reduction of yttrium oxide with boron (2), boron carbide reduction
method (3) and combined boron carbide/carbothermal reduction (4) at 1500 °C, 1700 °C and
1900 °C for 2 hours in vacuum. Powders were characterized by X-ray diffraction analysis
and scanning electron microscopy. Pure YB4 was successfully synthetized using combined
boron carbide/carbothermal reduction method. Secondary phases, especially Y2O3, YB2 or
YBO3, were found in powders prepared using other three methods.
YB4 powder synthetized via reaction (4) was used for preparation of composites with 20,
30 and 40 wt% of SiC. YB4-SiC composites were densified using hot-pressing technique and
subjected to oxidation test up to 1650 °C. Weight changes after oxidation were measured and

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the thickness of formed oxide layer was evaluated by scanning electron microscopy. Electron
dispersive spectroscopy and X-ray phase analysis was used to identify the phase composition
of samples after oxidation.

466
Reactive spark plasma sintering of boron carbide nanostructured
ceramics
Dmitry Moskovskikh1*, Alexander Mukasyan2
National University of Science and Technology MISiS, Moscow, Russia, 119049;
1

*
e-mail: [email protected]
Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame,
2

USA, 46556
Keywords: ceramics, boron carbide, high-energy ball milling, mechanical activation, reactive sinter-
ing, spark plasma sintering

Boron carbide (B4C) based ceramics possess a unique set of physical and mechanical proper-
ties, such as low density, high melting point, high elastic modulus, high neutron absorption
cross-section, and chemical durability. However, due to the strong direct covalent bonds
between the boron and carbon atoms, it is difficult to consolidate the B4C ceramics, which
limits applications.
Since direct reaction between boron and carbon is exothermic one may use combustion
synthesis (CS) method for fabrication of B4C compound.1 Spark plasma sintering (SPS) is an
advanced consolidation process by combination of uniaxial pressure and powerful DC pulsed
current to fabricate bulk materials.2 SPS is widely used to produce boron carbide ceramics.
However, the majority of these works were dedicated to SPS of B4C powders.3,4 In this work,
we developed a method for one-step fabrication of pure boron carbide bulk ceramics from
the elements, i.e. boron and carbon. This, so-called, reactive spark plasma sintering (RSPS)
method consists of CS of B4C from elemental precursors combined with simultaneous spark
plasma sintering.5–7
It was also demonstrated that preliminary high-energy ball milling (HEBM)8 of the B+C
powder mixture leads to the formation of B/C composite particles with enhanced reactivity.
Using these reactive composites in RSPS permits tuning of synthesized B4C ceramic micro-
structure. Optimization of HEBM + RSPS conditions allows rapid (less than 30 min of SPS)
fabrication of B4C ceramics with porosity less than 2%, hardness of ~35 GPa and fracture
toughness of ~ 4.5 MPa· m 1/2.

References
1. I.D. Kovalev, V.I. Ponomarev, V.I. Vershinnikov, S.V Konovalikhin, SHS-produced boron carbide:
Some special features of crystal structure, Int. J. Self-Propagating High-Temperature Synth. 21
(2012) 134–138.
2. Z. Munir, D.V.Quach, M.Ohyanagi, Electric current activation of sintering: a review of the pulsed
electric current sintering process, Journal of the American Ceramic Society 94 (2011) 1–19.

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3. S. Hayun, S. Kalabukhov, V. Ezersky, M.P. Dariel, N. Frage, Microstructural characterization of

spark plasma sintered boron carbide ceramics, Ceramics International. 36 (2) (2010) 451–457.
4. K. Sairam, J.K. Sonber, T.S.R.Ch. Murthy, C. Subramanian, R.K. Fotedar, P. Nanekar, R.C. Hubli,
Influence of spark plasma sintering parameters on densification and mechanical properties of boron
carbide, Int. Journal of Refractory Metals and Hard Materials, 42 (2014) 185–192.
5. D.V. Dudina, A.K. Mukherjee, Reactive spark plasma sintering: Successes and challenges of nano-
material synthesis, J. Nanomater. 2013 (2013) art. no. 6252182013.
6. R. Orrù, R. Licheri, A.M. Locci, A. Cincotti, G. Cao, Consolidation/synthesis of materials by elec-
tric current activated/assisted sintering, Mater. Sci. Eng. R Reports. 63 (2009) 127–287.
7. D.O. Moskovskikh, Y. Song, S. Rouvimov, A.S. Rogachev, A.S. Mukasyan, Silicon carbide ceram-
ics: Mechanical activation, combustion and spark plasma sintering, Ceram. Int. (2016) 1–8.
8. A.S. Rogachev, D.O. Moskovskikh, A.A. Nepapushev, T.A. Sviridova, S.G. Vadchenko, S.A. Ro-
gachev, et al., Experimental investigation of milling regimes in planetary ball mill and their in-
fluence on structure and reactivity of gasless powder exothermic mixtures, Powder Technol. 274
(2015) 44–52.

006
Oxidation behavior of iron boride coatings
M. Palcut*, J. Ptačinová, M. Drienovský, R. Čička, M. Kusý, M. Hudáková
Slovak University of Technology in Bratislava, Faculty of Materials Science and Technology
in Trnava, Institute of Materials Science, Paulínska 16, 91724 Trnava, Slovak Republic;
*
e-mail: [email protected]

In the present work, microstructure, phase constitution and high temperature oxidation kinet-
ics of iron boride coatings prepared by diffusion boronizing have been studied. Low carbon
steel S235JRG1 was powder-boronized by B4C at 1273 K for 45–150 min. Iron boride layers
with a distinct tooth-like microstructure were produced. The layers were found to be com-
posed of Fe2B and FeB in unequal amounts. The oxidation behavior of the layers was studied
by simultaneous thermal analysis in a flowing synthetic air for 21–24 h at 873–1173 K. Para-
bolic oxidation kinetics has been found. At 1173 K, two successive parabolic periods were
observed, followed by a breakaway oxidation behavior. The experimental rate constants were
found between 1.04×10−9 and 3.78×10−6 kg2 m−4 s−1, depending on temperature and oxidation
time. The activation energy for oxidation is 93 kJ mol−1. The oxide scales of the iron boride
coatings are characterized. Possible oxidation mechanisms are discussed and implications
towards high temperature stability of iron boride coatings are presented.

Acknowledgement
This work was supported by the Grant Agency VEGA of the Slovak Ministry of Education, Science,
Research and Sport project No. 1/0068/14 and by the European Regional Development Fund project
no. ITMS:26220120048.

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072
Contribution to the thermodynamic study and oxidation behavior
of HfB2-SiC ultra-high temperature ceramics
Cassandre Piriou1*, Sylvie Foucaud1, Olivier Rapaud1, Ludovic Charpentier2,
Marianne Balat-Pichelin2
1
SPCTS-CNRS, UMR 7315, Centre Européen de la Céramique (CEC), 12 rue Atlantis,
F-87068 Limoges Cedex, France; *e-mail: [email protected]
2
PROMES-CNRS, UPR 8521, 7 rue du four solaire, F-66120 Font-Romeu Odeillo, France
Keywords: UHTC, HfB2-SiC, Spark Plasma Sintering, oxidation

Ultra-High Temperature Ceramics (UHTCs), more specifically diborides of the IVb group,
are potential candidates for a large variety of applications, in particular as structural materials
for thermal protection of hypersonic vehicles exposed to high temperatures (> 1800 °C) and
to oxidation1.
The aim of this work consists in elaborating ultra-high temperature HfB2-SiC ceramic
composites used as structural materials for several applications, such as aeronautic and aero-
space areas and to understand oxidation mechanisms involved during their entry into the
atmosphere. The sintering of these materials at different compositions has been carried out
by Spark Plasma Sintering (SPS). This process is used to obtain fully dense materials (> 98%
relative density) with fine grains, at lower temperatures and shorter dwell times than con-
ventional techniques (natural sintering, hot pressing)2. In order to favor densification and to
obtain a homogeneous distribution of both phases in the final material, a study on the raw
powders granulometry has been necessary. An optimization of sintering conditions (applied
load, temperature and its hold time, heating rate) has been subsequently carried out in order
to elaborate fully dense samples by using parameters adapted to their environment. Obtained
bulk bodies have been oxidized at several temperatures with a solar furnace to approach
conditions to which hypersonic vehicles are subjected. Oxidation mechanisms have been
highlighted through the study of the oxidized layers by combining X-ray diffraction analysis
(XRD), Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectrometry (XPS)
and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). This work was helped
by the obtaining of kinetic data during oxidation tests. In order to supplement this study, a
first thermodynamic approach of the Hf-B-Si-C system has been made through the model-
ing of ternary diagrams, the aim being to constitute a coherent data base of this quaternary
system.

References
1. F. Monteverde and A. Belosi, “The resistance to oxidation of an HfB2-SiC composite”, J. Eur.
Ceram. Soc., 25, pp. 1025–1031, 2005.
2. D. Sciti, and al. “Spark Plasma Sintering of HfB2 with low additions of silicides of molybdenum
and tantalum”, J. Eur. Ceram. Soc., 30, pp. 3253–3258, 2010.

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894
Influence of the chemical composition on the mechanical properties
of spark plasma sintered boron carbide ceramics
Florian Réjasse*, Guy Antou, Nicolas Pradeilles, Alexandre Maître
SPCTS-CNRS, UMR 7315, Centre Européen de la Céramique (CEC), 12 Rue Atlantis,
F-87068 Limoges Cedex, France; *e-mail: [email protected]
Keywords: boron carbide, Spark Plasma Sintering, microstructure-property relationship, stoichiom-
etry

Due to its excellent mechanical properties (i.e. high hardness and high Young’s modulus) and
its low density, boron carbide is a promising ceramic phase which can be used as shielding
materials. These physical properties result from unusual characters of B-B and B-C bonds.
Boron carbide phase exists over a wide range of stoichiometry, i.e. from 8 to 20 at.% of car-
bon.1,2 Niihara et al.3 have shown that this variation of stoichiometry modifies the mechanical
properties (hardness and Young’s modulus). Indeed, these authors observed an increase of
the Vickers hardness with the rise of carbon content in the crystalline structure of boron car-
bide. Enhanced mechanical properties were obtained for C/B ratio of 20 at.%. However, the
measured hardness depends on the stoichiometry of the boron carbide phase, but can also be
altered by the existence of secondary phases located at the grain boundaries. Since Niihara
et al.3 have clearly demonstrated it, the excess of carbon in boron carbide samples leads to a
decrease of the hardness and the Young’s modulus. Indeed, boron carbide powder is usually
synthesized via the carbothermal route of boron oxide, which can lead to the presence of
residual reactants in the powders (e.g. free carbon, boron acid, boron oxide).
Consequently, this work firstly aims at characterizing the chemical composition of differ-
ent powders batches by using coupled analytical methods (i.e. XRD analysis and Rietveld
refinement to give lattice parameters, standard addition methods to quantify the amount of
free carbon, XPS). Then, dense monoliths with fine microstructure were elaborated using
the Spark Plasma Sintering process. The manufacture of dense specimens enabled to study
the relationships between the chemical composition (i.e. stoichiometry, influence of second-
ary phases) and the mechanical properties, without being altered by the presence of residual
porosity. The mechanical response was characterized at two different scales by nano- and
micro-indentation measurements in order to elucidate the influence of the stoichiometry of
boron carbide phase from the one of secondary phases on the mechanical properties.

References
1. Bouchacourt M, Thevenot F, J. Common Met. (1981);82:219–226.
2. Gosset D, Colin M., J. Nucl. Mater. (1991);183:161–173.
3. Niihara K, Nakahira A, Hirai T., J Am Ceram Soc. (1984);67(1):C-13.
4. B. Champagne, R. Angers, J. Am. Ceram. Soc. 62 (1979) 149–153.

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470
Microstructural design of melt infiltrated boron carbide
– aluminum ceramic – metal composites via spark plasma sintering
Irem Nur Gamze Şimşek1,2*, Gürsoy Arslan1
Department of Materials Science and Engineering, Anadolu University, Iki Eylul Campus, Eskisehir,
1

Turkey; *e-mail: [email protected]

Department of Metallurgical and Materials Engineering, Bulent Ecevit University, Farabi Campus,
2

Zonguldak, Turkey
Keywords: boron carbide, spark plasma sintering, ceramic–metal composite

Like other composites, ceramic–metal composites enable tailoring their properties with spe-
cial techniques and/or optimization of production parameters. B4C–Al ceramic–metal com-
posites are attractive materials due to their good mechanical properties and lightweight. One
of the simplest and effective methods to produce high ceramic volume fraction B4C–Al com-
posites is metal melt infiltration method. On the other hand, this method requires strict con-
trol of each production step to prevent the formation of deleterious reaction products which
may seriously degrade mechanical properties. Enhancement of material properties could be
achieved by controlling the microstructural progress. Studies suggest that a co–continuous
microstructure may improve mechanical properties of composite.1 This study focuses on how
to enhance the properties of such composites by controlling the progress of microstructure.
Spark Plasma Sintering (SPS) provides effective sintering at lower temperatures and short-
er times than conventional sintering methods. Besides, it is reported that partial SPS of B4C
may provide a continuous ceramic network.2 Same starting powders were also preformed by
cold isostatic pressing and used as reference samples. The partially sintered co-continuous
preforms as well as the reference specimens were-after having adjusted processing parame-
ters so as to yield the least amount of reaction products-melt infiltrated with an Al-Si alloy via
the pressureless melt infiltration method. Microstructure of the composites was investigated
by SEM and phase analysis was performed with XRD. Physical and mechanical properties
of composites were characterized by water immersion method, hardness and compression
tests, respectively. Findings were evaluated in terms of preforming method, starting powder
and infiltration conditions. The results obtained indicate that a proper microstructural design
enabled the achievement of a co–continuous ceramic–metal network, which in turn enhanced
both hardness and compressive strength of the produced composites.

References
1. H. Chang, J. Binner, and R. Higginson, “Dry sliding wear behaviour of Al(Mg)/Al2O3 interpenetrat-
ing composites produced by a pressureless infiltration technique”, Wear, 268, pp.166–171, 2010.
2. K. Sairam, J. K. Sonber, T. S. R. C. Murthy, C. Subramanian, et al., “Influence of spark plasma
sintering parameters on densification and mechanical properties of boron carbide”, International
Journal of Refractory Metals and Hard Materials, 42, pp. 185–192, 2014.

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067
Ultrahigh pressure deformation and Raman spectra of boron carbide
and its polymorphs
Ghatu Subhash
University of Florida, Gainesville, FL 32611-6250, USA; e-mail: [email protected]

The ceramic boron carbide (B4C) is known for its exceptional refractory properties, hard-
ness, strength, and impact resistance. Interesting properties of boron carbide include its poly-
morphism and susceptibility to amorphization, a solid-state phase transformation induced
by high pressures. The present study is a coordinated experimental and modeling effort on
the behavior of this unique material with the goal of optimizing its crystal structures for
enhanced performance. First, the rate-dependent response of the amorphized zone and the
evolution of its structure beneath indented surfaces in micro-grained and nano-grained boron
carbide were investigated. Using Raman spectroscopy, the consequences of amorphization
are addressed with regard to volumetric changes in the amorphized material and the stress
state in surrounding regions. To determine the origin of the amorphization process, numerous
density functional theory (DFT) simulations were performed to comprehensively identify
and quantify the structures formed in boron carbide specimens fabricated by hot pressing and
spark-plasma sintering. To offer insight on the kinetics of amorphization, simulated deforma-
tions were performed on representative polymorphs using DFT. Analysis of their response
to high hydrostatic compression and homogeneous shear has provided new insight into their
bonding behavior and Raman spectral shifts at the atomic level. These studies have enabled
excellent comparisons with experimental data from high-pressure environments up to 50
GPa, especially those of Hugoniot response. We have demonstrated that increases in hydro-
static pressure cause high-wavenumber Raman peaks to shift higher while low-wave num-
ber peaks shift lower, as observed in prior experimental investigations reported in literature.
Finally, this study reveals that introducing dopants into the large volume of “cage space” in
the virgin B4C structure may improve the stability, amorphization resistance, and therefore
mechanical performance of boron carbide. Overall, these results provide new insight into the
links between polymorph crystal structure, deformation response, and Raman spectra while
simultaneously laying the foundation for polymorph-level design of boron carbide.

645 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T09: Boron-based ceramics – Oral presentations

336
The importance of using borosilicate in geopolymer incorporating waste
Gianmarco Taveri1*, Enrico Bernardo2, Aldo R. Boccaccini3, Ivo Dlouhy1
1
Institute of Physics of Materials ASCR, Zizkova 22, Brno, Czech Republic; *e-mail: [email protected]
2
Department of Industrial Engineering, University of Padova, Italy
3
Institute of Biomaterials, University of Erlangen-Nuremberg, Cauerstrasse 6, Erlangen, Germany
Keywords: boro-aluminosilicates, Inorganic polymers, spectroscopy

Geopolymers, as cement-like materials, gained a lot of attention in the last decades as natural
replacement of Portland cement.1,2 In fact, the production process of this material is free of
CO2 emission, the major cause of the climate change. In this issue, Portland cement covers
the 8% of the annual emission of carbon dioxide in the atmosphere.1 The production of geo-
polymers incorporating wastes seems competitive to reduce the cost of production, and help
to empty the landfills.2
In this research work, fly-ash, a by-product from a bohemian power plant, and recycled
borosilicate glass (BSG) from pharmaceutical purposes were employed as primary alumi-
nosilicate sources for geopolymerization. The innovation in using BSG is the dissolution of
borates prior polycondensation, which was expected to take part in the final network as the
alumina does. By this way, a boro-alumino-silicate polymer is finally formed. Fourier Trans-
form Infrared (FTIR), among all, confirmed the presence of a resonance at about 830 mm–1,
associated to the vibration of tetrahedral borate (BO4), being this configuration the only ad-
missible to arrange in the product of the polycondensation. 11B NMR conducted on both BSG
and geopolymer confirmed the quasi-total depletion of trigonal borate (BO3) inside the BSG
in favour of a tetragonal one in the geopolymer.3 This proved that not only the borosilicate
successfully dissolved in the basic solution of sodium hydroxide, but also borate species
rearranged in a more appropriate configuration and linked to the aluminosilicate network.
29
Si NMR analysis carried out on geopolymer sample revealed a large presence of Q4(nAl)
environments, associated to a highly structured networking (3D cross-linked), which in turn
involve better mechanical properties.2 This means that the insertion of borates in geopoly-
mers is helpful for a better polymerization of the microstructure.

Acknowledgements
Project leading to this presentation has received funding from the European Union’s Horizon 2020
research and innovation programme under the Marie Sklodowska-Curie grant agreement no 642557

References
1. E. Arioz, Ö. Arioz, Ö.M. Koç, “The Effect of Curing Conditions on the Properties of Geopolymer
Samples”, Int. J. Chem. Eng. Appl. 4 (2013) 4–7.
2. M. Torres-Carrasco, F. Puertas, “Waste glass in the geopolymer preparation. Mechanical and micro-
structural characterisation”, J. Clean. Prod. 90 (2015) 397–408.
3. G. Taveri et al.: Journal paper manuscript under preparation.

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 646

 T09: Boron-based ceramics – Oral presentations

195
Preparation of B4C-HfB2-SiC eutectic composite by arc melting
Rong Tu*, Nian Li, Qizhong Li, Song Zhang, Lianmeng Zhang
State Key Lab of Advanced Technology for Materials Synthesis and Processing,
Wuhan University of Technology, 122 Luoshi Road, Wuhan, China; *e-mail: [email protected]
Keywords: arc-melting, eutectic boride and carbide, Vickers hardness, fracture toughness, electrical
conductivity, thermal conductivity, thermal expansion coefficient

B4C-HfB2-SiC based composites may possess the excellent combination properties of B4C,
HfB2 and SiC, such as extraordinary mechanical, electrical and thermal properties, and may
be applied as a new generation of ultra-high temperature structural materials, e.g., cutting
tools, plasma-arc electrodes, furnace elements, rocket nozzles and sharp leading edges of
propulsion system. In the present study, B4C, HfB2 and SiC based composites were prepared
by arc melting. The effects of the composition and microstructure on microstructure, me-
chanical, electrical and thermal properties were investigated.
B4C-HfB2 binary composites were prepared by arc melting using B4C and HfB2 as raw
materials. At the composition of 70B4C-30HfB2 (mol%), the uniform and fine eutectic micro-
structure in large area was obtained. The lamellar and regular eutectic microstructure was com-
posed of B4C matrix with HfB2 phase about 1 µm in thickness. The Vickers micro-hardness
of B4C-HfB2 composites significantly increased with increasing B4C content and showed the
maximum value of 31.2 GPa at the eutectic composition. The fracture toughness of B4C-HfB2
composites had the maximum value of 5.9 MPa m1/2 around the eutectic composition. Both
the electrical conductivity and thermal conductivity of B4C-HfB2 composite increased with the
increase of HfB2 content and decreased nearly concomitantly with increasing the temperature.
The electrical conductivity and thermal conductivity of B4C-HfB2 eutectic composite were
7.43×104 to 8.94×104 Sm–1 in the range of 298-800 K and 16 to 18 WK–1m–1 in the range of
298-973 K, respectively. The thermal expansion coefficient of B4C-HfB2 composites showed
the highest value of 7.18×10–6 K–1 in the range of 293–1273 K at the eutectic composition.
B4C-HfB2-SiC ternary eutectic composite was also obtained by arc melting. The ternary
eutectic composition of 45B4C–15HfB2–40SiC (mol%) was first identified with a lamel-
lar eutectic texture. HfB2 about 500 nm in thickness and SiC about 700 nm in thickness
were uniformly dispersed in B4C matrix of the eutectic composite. B4C-HfB2-SiC compos-
ites showed the highest Vickers micro-hardness of 35.7 GPa and highest fracture toughness
of 6.5 MPa m1/2 at the eutectic composition, which were both higher than that of B4C-HfB2
eutectic composites. The electrical conductivity of B4C-HfB2-SiC composites increased with
the increase of HfB2 content and nearly keep constant (0.937×104-1.09×104 Sm–1) from 298
to 800 K at the eutectic composition. The thermal conductivity of B4C-HfB2-SiC composites
increased with the increase of HfB2 content and the decrease of B4C content and decreased
with increasing the temperature. B4C-HfB2-SiC eutectic composite had the minimum thermal
conductivity, which decreased from 32 to 23 WK–1m–1 with increasing the temperature from
373 to 973 K. The thermal expansion coefficient of B4C-HfB2-SiC composite increased with
the increase of HfB2 content and the decrease of SiC content and showed the maximum value
of 6.42×10–6 K–1 in the range of 293–1272 K.
647 ECerS2017 / July 9–13, 2017 / Budapest, Hungary
T09: Boron-based ceramics – Oral presentations

222
Effect of functional additive on the SHS of TiB2
Ahmet Turan2, Mehmet Buğdaycı1,2, Kağan Benzeşik1, Onuralp Yücel1
İstanbul Technical University, Metallurgy and Materials Engineering, Maslak, Istanbul, 34469,
1

Turkey
Yalova University, Chemical and Process Engineering Department, Yalova, 77100, Turkey;
2

e-mails: [email protected], [email protected], [email protected], [email protected]

Optimum production condition of TiB2 via SHS was discussed on “Self-propagating High
Temperature Synthesis of TiB2” article.1 In order to enhance these results, the experiments
were carried out with the addition of NaCl and MgSO4·7H2O as catalysts.
In the present study, SHS of TiB2 ceramic powders was investigated. TiO2 and B2O3
powders were mixed with 90%, 100% and 110% of stoichiometrically required amount of
Mg powders. SHS experiments were conducted under both air and argon atmospheres to
determine the optimum process atmosphere. The effects of functional additive (NaCl and
MgSO4∙7H2O) were also carried out with the various addition rates of catalysts. SHS products
were leached in HCl media to purify their TiB2 contents. Fig. 1 (A) presents, XRD Patterns of
Unleached and Leached SHS Products Synthesized under Argon Atmosphere and Stoichio-
metrically 100% Mg Additon with Increasing NaCl Addition Rate, (B) shows MgSO4·7H2O.

Fig. 1. XRD Pattern of SHS Products

References
1. A. Turan, M. Bugdayci and O. Yucel, High Temp. Mater. Proc., 34(2) (2015) 185–193.
2. A.G. Merzhanov, “Self-propagating High-temperature Synthesis (SHS),” (ISMAN, Russia, 2002).

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 648

 T09: Boron-based ceramics

Poster presentations

900
HfB2, ZrB2 and Hf0.5Zr0.5B2 solid solution UTHC ceramics:
processing by SPS and mechanical properties
Alejandro Carrasco-Pena1*, Ryan Underwood1, Nina Orlovskaya1, Miladin Radovic2,
Demetrius Vasquez-Molina3, Fernando Uribe-Romo3, Salvatore Grasso4, Mike Reece4
Department of Mechanical and Aerospace Engineering, University of Central Florida,
1

4000 Central Florida Blvd, Orlando, FL 32816, USA; *e-mail: [email protected]

Department of Materials Science and Engineering, Texas A&M University, 400 Bizzell St,
2

College Station, TX 77843, USA

Department of Chemistry, University of Central Florida, 4000 Central Florida Blvd, Orlando,
3

FL 32816, USA
School of Material Science and Engineering, Queen Mary University of London, Mile End Road,
4

London E1 4NS, UK
Keywords: ultra high temperature ceramics, SPS, HfB2, ZrB2, Hf0.5Zr0.5B2, ring-on-ring

Mechanical properties of Spark Plasma Sintered (SPS) HfB2, ZrB2 and their Hf0.5Zr0.5B2 solid
solution were studied both at room and high temperatures. For SPS, 300g of pure HfB2 and
300g of pure ZrB2 powders (starck grade B) were ball milled in a planetary ball mill for 6
hours. To make 50/50 Hf-Zr-B solid solution, 150g of pure HfB2 and 150g of pure ZrB2 were
also ball milled together for 6 hours. WC 250 ml lined vial and 5–10 mm in diameter SiC
balls were used for milling in the ethanol as a liquid media. After the batch preparation, pure
HfB2 and ZrB2 samples were sintered at 2100 °C, while Hf0.5Zr0.5B2 solid solution was densi-
fied at 5 different temperatures between 1900 °C to 2300 °C in order to determine the optimal
temperature for its densification. After sintering of 21 mm in diameter and 6mm in thickness
pellets, the samples were machined into 20 mm in in diameter and 2 mm in thickness disks,
which were further used for the study at room and high temperatures of the properties by Res-
onant Ultrasound Spectroscopy. The Young’s, shear and bulk moduli, along with Poisson’s
ratio were measured up to 1000 °C. At the same time, an attempt is being made to measure
the biaxial strength of these ceramics using ring-on-ring biaxial strength testing technique. In
order to accomplish the measurement, the ring-on-ring testing jig is currently being designed
and manufactured, and after it is produced, the biaxial strength of HfB2, ZrB2 and their 50/50
solid solution will be measured.

649 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T09: Boron-based ceramics – Poster presentations

883
Study of structure and mechanical characteristics of hot pressed α-AlB12
with C and TiC additions
Artem Kozyrev, Pavlo Barvitskiy, Anton Shaternik, Viktor Moshil, Tatiana Prikhna
Institute for Superhard Materials, Natl. Acad. of Sci. of Ukraine. Avtozavodska str.2, 46, Kiev 04074,
Ukraine
Keywords: AlB12, mechanical characteristics, hot pressing

The samples of α-AlB12-based materials were prepared from α-AlB12 submicron powders
synthesized from hexagonal boron nitride. Blocks of 40 mm in diameter and 15 mm in height
were manufactured under hot pressing conditions (pressure 30 МPа, temperature up to 2200
°C) using inductive heating in the graphite dies covered inside by hexagonal boron nitride (in
order to isolate manufactured materials from graphite). The samples 9–30 mm in diameter
and 5–10 mm in height were manufactured under high (2 GPa) pressure at 1200–1400 °C
temperatures. The sintered materials were isolated from the graphite heater using containers
from hexagonal boron nitride.
The additions of carbon (17 mass/%) to the α-AlB12 lead to the formation of AlB12C2 and
fracture toughness increase, the material density increased just slightly. The additions of TiC
to α-AlB12 and sintering at 1950 °C under 30 MPa lead to the formation of AlB12C2 as well
and, in parallel, to the formation of TiB2. The mechanical characteristics (hardness, fracture
toughness, bending and compressing strength) of the sample 6 were rather high, but, besides,
the density increased up to 3.2 g/cm3. After sintering of the same α-AlB12 and TiC mixture
under high pressure (2 GPa) at comparatively low temperature 1200 °C the AlB12C2 was not
formed and the sample consisted from α-AlB12, TiC and some AlN. The higher sintering
temperature (1400 °C) under high pressure (2 GPa) did not lead to the formation of AlB12C2,
as well, but the formation of TiB2 and disappearing of TiC has been observed. Unfortunately,
mechanical characteristics of both samples were low. It should be mention that parameters
1400 °C and 1h at 2 GPa were the limit of our equipment.
The structure of material synthesized from α-AlB12 and 20% TiC according X-ray phase
analysis contained 74 wt. % of AlB12C2, 22 wt. % of TiB2, and 4 wt. % of Al2O3, while
SEM microprobe study revealed three main phases with the approximate stoichiometers
Al0.17B4.55C2O0.04N0.21, TiB2.58C0.8Al0.02 and Al2O3.79 B2.04C0.8.

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 650

 T09: Boron-based ceramics – Poster presentations

647
Infiltrated TiB2-steel composites
Or Rahamim, Shmuel Hayun, Helen Dilman, Nahum Frage
Department of Materials Engineering, Ben-Gurion University of the Negev, Beer-Sheva, Israel;
e-mail: [email protected]
Keywords: TiB2, infiltration, composites

Melt infiltration is one of the attractive techniques to fabricate ceramic–metal composites

with a wide range of mechanical properties. If molten metal wets ceramic particles free in-
filtration approach may be applied. It was established experimentally that the wetting angle
in the TiB2-carbon steel (0.7wt.%C) system of about 20° at 1450 °C is adequate for free
infiltration. Thermodynamic analysis of the interaction between TiB2 and molten steel was
performed and its results were taken into account to determine parameters of the infiltration
process. SPS-processed TiB2 preforms with 30vol% porosity were successfully infiltrated
with molten 1070 steel at 1450 °C under 10-4 torr vacuum. The infiltrated composites were
heat treated at 900 °C and quenched in oil. The Young modulus (of about 500 GPa) did not
change as after quenching, while hardness value increased form 1500 HV to 1900 HV for
infiltrated and thermal treated composites, respectively. The effect of thermal treatment on
the hardness value was attributed to the microstructural changes in steel matrix (form pearlite
to martensite).

651 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T10: Cultural heritage
Invited lectures

028
Non-invasive on-site analysis of enamelled pottery, glass and metal.
State of the art
Philippe Colomban1,2
1
Sorbonne Universités, UPMC Univ Paris 06, UMR 8233, MONARIS, 75005, Paris, France
2
CNRS, UMR 8233, MONARIS, F-75005, Paris, France; e-mail: [email protected]

For more than a decade, the strong miniaturisation of electromagnetic sources and detectors
led to the availability of different portable instruments, namely Raman microspectrometer,1–3
X-ray Fluorescence handheld analyzer4 and UV-visible spectrometer5. These instruments in-
form on the phase/structure, elemental composition and chromophores, respectively.6,7 At
the time of their production enamelled wares were advanced materials and their micro- and
nano-structure carries a lot of information about their making process, important information
to distinguish genuine from copy, or to trace technological exchanges.3–8 We present a review
of the state of the art of the non-invasive study of coloured artefacts and discuss representa-
tive examples of innovation or of technological transfer.

References
1. Ph. Colomban, V. Milande, L. Le Bihan, On-site Raman Analysis of Iznik pottery glazes and pig-
ments, J. Raman Spectrosc. 35 (2004) 527–535.
2. Ph. Colomban, The on-site/remote Raman analysis with portable instruments – A review of draw-
backs and success in Cultural Heritage studies and other associated fields, J. Raman Spectrosc. 43
[11] (2012) 1529–1535.
3. D. Mancini, C. Dupont-Logié, Ph. Colomban, On-site identification of Sceaux porcelain and
faience using a portable Raman instrument, Ceramics International 42[13] (2016) 14918–14927.
4. G. Simsek, Ph. Colomban, F. Casadio,, L. Bellot-Gurlet, K. Faber, G. Zelleke, V. Milande, L.
Tilliard, On-site identification of earliy Böttger red stonewares using portable XRF/Raman instru-
ments: 2, glaze and guilding analysis, J. Am. Ceramic Society 98[10] (2015) 3006–3013.
5. C. Fornacelli, Ph. Colomban, I. Turbanti Memmi, Toward a Raman/FORS discrimination between
Art Nouveau and contemporary stained glasses from CdSxSe1-x nanoparticles signatures, J. Ra-
man Spectrosc. 46[11] 2015 1129–1139.
6. Ph. Colomban, The destructive/non-destructive identification of enamelled pottery and glass arti-
facts and associated pigments – A brief overview, Arts 2013, 2(3), 77–110 doi:10.3390/arts2030077
7. G. Simsek, Ph. Colomban, S. Wong, B. Zhao, A. Rougeulle, N.Q. Liem, Toward a fast non-destruc-
tive identification of pottery: the sourcing of 14th-16th century Vietnamese and Chinese ceramic
shards, J. Cultural Heritage 16[2] (2015) 159–172.
8. Ph. Colomban, Y. Zhang, B. Zhao, Non-invasive Raman analyses of Falangcai and related Qing
porcelain. Searching evidence of the use of European pigment technology, Ceramics International,
submitted.

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 652

 T10: Cultural heritage – Invited lectures

215
Characterization of the Medieval pottery from the Studenica
Monastery, Serbia, a UNESCO World Heritage Site
Ljiljana Damjanović1*, Srna Stojanović1, Vesna Bikić2, Ivana Radosavljević Evans3,
Suzana Erić4, Kristina Šarić4
1
Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade, Serbia;
*
e-mail: [email protected]
2
Institute of Archaeology, Kneza Mihaila 35 / IV, 11000 Belgrade, Serbia
3
Department of Chemistry, Durham University, Durham DH1 3LE, UK
4
Faculty of Mining and Geology, University of Belgrade, Đušina 7, 11000 Belgrade, Serbia
Keywords: Medieval pottery, petrography, SEM-EDS, FTIR spectroscopy, high resolution XRPD,
multivariate statistical analysis

Medieval ceramics found in fortified towns and sacred places in Serbia are well-described
by archaeologists. However, systematic archaeometric studies of ceramic production have
recently started.1,2 This work focuses on the characterization of pottery excavated at the
Studenica Monastery, in central Serbia. Founded in the late 12th century, Studenica was the
cultural and spiritual center of medieval Serbia, but also a spiritual and architectural model
through centuries. Archaeological investigations identified two clearly distinct cultural ho-
rizons: the first (from the late 12th until the late 13th century) and the second (the 14th and
the first half of 15th century). Investigated pottery from the first cultural horizon consisted
of undecorated and unglazed cooking pottery while tableware was rare, and from the second
cultural horizon subject of investigation were unglazed and glazed vessels, both cookware
and tableware, including vessels decorated with sgraffito and painted motives. Mineralogical
and chemical composition and production methods of investigated pottery were determined
combining petrography, scanning electron microscopy with energy dispersive spectrometry,
Fourier transform infrared spectroscopy, high resolution X-ray powder diffraction, multivari-
ate statistical analysis. The studied pottery is composed of fragments of quartz, feldspars,
micas, pyroxenes and rock fragments (quartzites, schists, granitoids, volcanics, peridotites,
serpentinites, etc.) and matrix which shows different degree of crystallinity – from crystal-
line to amorphous. The firing temperature was estimated to be about 600 oC for the most of
cookware and in the range of 850–1000 oC for tableware. Multivariate statistical analysis of
FTIR and high resolution XRPD data, together with mineralogical and petrographical analy-
ses did not show significant differences among samples from two cultural horizons indicating
continuous pottery production process from XII until XV century.

References
1. Lj. Damjanović, I. Holclajtner-Antunović, U.B. Mioč, V. Bikić, D. Milovanović, I. Radosavljević
Evans, “Archaeometric study of medeival pottery at Stari (Old) Ras, Serbia”, J. Arch. Sci., 38, pp.
818–828, 2011.
2. Lj. Damjanović, U. Mioč, D. Bajuk-Bogdanović, N. Cerović, M. Marić-Stojanović, V. Andrić,
I. Holclajtner-Antunović, “Archaeometric investigation of medieval pottery from excavations at
Novo Brdo, Serbia”, Archaeometry, 58, pp. 380–400, 2016

653 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T10: Cultural heritage – Invited lectures

081
Transmission electron microscopy:
emerging investigations for cultural heritage materials
Philippe Sciau
CEMES, CNRS, Toulouse University, Toulouse, France; e-mail: [email protected]
Keywords: cultural heritage, imaging, ancient material, TEM

Transmission electron microscopy with its various imaging modes and its analytical abilities
is now an indispensable tool for chemical and structural characterization at the nanoscale of
all types of materials. One of the main advantages of this technique is that it generates an
image that enables us to determine atomic structure and perform highly localized chemical
analysis, make individual measurements on nano-objects and undertake the chemical and
structural study of interfaces and extended defects. This is certainly one of the best tech-
niques for characterization at this scale currently available. Cultural heritage materials do
not differ fundamentally from other materials except that they are more heterogeneous with
a more complex and imperfect structure1. In addition, many of them contain nanoparticles
or have a nanoscale structuration, which play a significant role in their physical properties or
are rich in information concerning their manufacture. TEM techniques are thus well suited
to investigate them especially because the developments of these last decades afford both
a more efficient sample preparation and faster data recording2. Without TEM techniques,
it would be impossible to reveal the true nature of lusterware of ruby glass. They have also
played a major role in the determination of optical and mechanical properties as well as the
manufacture of the Terra Sigillata slips. Their contributions were also essential in the study
of prehistoric pigments or to understand the chemical transformation of some painting pig-
ments. These successes should encourage more and more people to used TEM techniques for
characterizing divers cultural heritage materials. The use of advanced techniques, currently
largely employed in physical sciences, such as ASTAR technique, structural determination
from electron diffraction or electron tomography should likewise grow and open new per-
spectives.

References
1. Ph. Sciau and Ph. Goudeau, Eur. Phys. J. B 88, 132, 2015 (DOI: 10.1140/epjb/e2015-60253-8).
2. Ph. Sciau, Advances in Imaging and Electron Physics 198, 43, 2016 (DOI: 10.1016/
bs.aiep.2016.09.002).

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 T10: Cultural heritage

Oral presentations

256
Preliminary results on polished surface of Phoenician red slip ware
Lucilla Fabrizi1, Laura Medeghini1, Silvano Mignardi1, Lorenzo Nigro2, Federica Spagnoli2,
Federico Cappella2, Caterina De Vito1
1
Department of Earth Sciences, Sapienza University of Rome, P.le Aldo Moro 5, 00185 Rome, Italy
2
Department of Oriental Studies, Sapienza University of Rome, P.le Aldo Moro 5, 00185 Rome, Italy
Keywords: Red Slip Ware, Phoenician pottery, optical microscopy, X-ray diffraction, scanning elec-
tron microscopy

Red Slip Ware is a typical Phoenician production characterized by a shiny deep red slip which
is considered an important cultural marker that followed the spread of Phoenicia across their
Mediterranean colonies. Despite its archaeological relevance, this ceramic has not yet been
widely studied. Therefore, a selected number of samples unearthed in the Phoenician-Punic
site of Motya (Sicily, Italy), dating back from the 8th to 5th century BC, have been analyzed.
The archaeometric characterization of the slipped surface has been performed using opti-
cal microscopy, X-ray powder diffraction and scanning electron microscopy. The aim is to
explore the procedure used in the preparation, application and firing of the superficial layer
and to characterize the internal body. Petrographic analysis shows a predominance of sub
angular-rounded fragments of quartz along with minor amount of K-feldspar and nodules
of iron oxides as inclusions in the ceramic bulk; whereas the slip is characterized by a fine
grained structure with few and fine sized inclusions of quartz and K-feldspar. EDAX spectra
highlight that the red slip and the internal body of the vessels have similar elemental compo-
sitions, but with the coating Fe-enriched. Mineral assemblage and in particular the presence
of neoformed phases, i.e., K-feldspar, hematite and gehelenite, allows estimating the maxi-
mum temperature of firing of these artefacts in the thermal range 850–950 °C in oxidizing
conditions. In addition, the accessory minerals, i.e, rutile and zircon, can be considered im-
portant markers to identify the provenance of raw materials. The comparison with data from
a previous study on Motyan ceramics allows hypothesizing a local supply of raw materials
involved in ceramic productions.

References
1. L. Nigro, Vicino Oriente, “Before the Greeks: The earliest Phoenician settlement in Motya - Recent
discoveries by Rome «La Sapienza» expedition”, Vicino Oriente, XVII, pp. 39–74, 2013.
2. C. De Vito, L. Medeghini, S. Mignardi, D. Orlandi, L. Nigro, F. Spagnoli; P.P. Lottici, D. Bersani,
“Technological fingerprints of Black-Gloss Ware from Motya (Western Sicily, Italy)”, Appl Clay
Sci, 88–89, pp. 202–213, 2014.

655 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T10: Cultural heritage – Oral presentations

016
Geochemical characterization of Medieval pottery from
the Auvergne region of France by portable X-ray fluorescence analysis
Jay Franklin, Frederic Surmely1*, Sierra Bow
1
CNRS / DRAC, Clermont-Ferrand, France; *e-mail: [email protected]

Since 2000, several excavations and testing projects have been conducted on medieval sites
in the highlands of the Auvergne (France). The sites are interpreted as farms, isolated or
grouped in hamlets, occupied beetween the end of the 10th century and the end of the 12th
century.
Ceramics were recovered at all sites. A major question we have is whether the ceramics
were made locally on the sites themselves or if some or all were imported. Further, we hope
to address areal and regional interactions. While architecture across the sites is variable, and
we are currently developing a typology to address this, the ceramic forms are quite uniform,
at least macroscopically. To test our questions, we conducted portable x-ray fluorescence
(pxrf) analysis on pottery recovered from each site to characterize the chemical composition
of the paste. Preliminary analysis suggests significant inter-site variability, and we suggest
that ceramic manufacture and use during the Medieval here was very localized at the house-
hold and hamlet level.

079
Jun ware colours: chemistry and nanostructure
Hou Jiayu1, Trinitat Pradell2, Miao Jianmin1
1
Key Research Laboratory, The Palace Museum
2
Physics Department and Centrefor Research in Nano-Technology, Universitat Politècnica de
Catalunya, BarcelonaTech, Campus Baix Llobregat, c) Esteve Terrades 8, 08860 Castelldefels,
Barcelona, Spain

A selection of Jun wares found at Juntai and Zhiyaochang and Liujiamen kilns, official kilns
from the court, at Yuzhou City, Henan Province in China, showing various colours and ap-
pearances are analysed. The main novelty of this study is that the nanostructure is revealed
from polished areas of the glazes by a Focus Ion Beam (FIB) attached to a Scanning Electron
Microscope (SEM). The main advantage of this procedure is that the size and volume frac-
tion of the liquid-liquid nanostructures may be quantified at different areas of the glaze show-
ing different colours and optical effects. Differences between the different kiln productions
are highlighted and the origin of the colours and appearances discussed in terms of chemistry
and nanostructure.

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 656

 T10: Cultural heritage – Oral presentations

063
18th and 19th century garden ceramics:
investigation of manufacturers’ stamps in relation to compositional
change
Laura Karran, Belinda Colston1*
1
School of Chemistry, University of Lincoln, Lincoln, UK; *e-mail: [email protected]

In England, in the eighteenth Century, the fashion for a neo-classical style in architecture cre-
ated a growing demand for a range of classically-inspired products. Because the production
of stone items was both time-consuming and expensive, the necessity of finding a cheaper al-
ternative to stone resulted in the exploration of clay-based substitutes. Using a ball clay from
Dorset, UK, an artificial stone called Coade stone was introduced by Mrs Coade in 1769.
It is actually a stoneware ceramic and was used to create both architectural decoration and
garden ornaments. The Coade factory in Lambeth was in existence until 1840 but, following
its closure, other manufacturers emerged – such as Blashfield, Pulham and Doulton – who
produced similar materials during the 19th century.
The artefacts produced by these manufacturers are now considered of great historic value
so their correct identification is important, not only for the historic record, but also for the
provision of the necessary evidence to carry out informed conservation. Although many of
the products are stamped with a manufacturer’s mark, some have no indentation. As the sale
and copy of moulds was common practice at the time, stylistic considerations do not provide
reliable identification of unsigned artefacts, making scientific identification necessary.
Research by the authors has shown that by using X-ray fluorescence (XRF) analysis to
produce trace and bulk element profiles, it is possible to identify, and differentiate between,
the signed products of Coade, Blashfield and Doulton. Further research has shown that Pul-
ham products can also be identified by this method. However, these long-lived businesses
have had various phases of manufacture as indicated by changes in their stamp design. In or-
der to have confidence in our differentiation methodology, it is important to ascertain whether
a change in stamp reflects a compositional change in the product.
From elemental profiles, and subsequent multivariate statistical techniques, it is shown
that for Coade and Pulham products, a change in stamp does not reflect the use of a differ-
ent source material, and is likely therefore to indicate a change in management. In contrast,
for Blashfield and Doulton products, a change in stamp reflects a significant compositional
change, which is indicative of geographical or technological variation.

657 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T10: Cultural heritage – Oral presentations

806
A multi-analytical investigation of the Cucuteni pottery technology
from Eastern Romania
Florica Matau1, Lavinia Curecheriu2, Valentin Nica3, Alexandru Stancu4
Department of Interdisciplinary Research – Field Science, Alexandru Ioan Cuza University of Iasi,
1

Lascar Catargi Street, No. 54, 700107, Iasi, Romania; e-mail: [email protected]
Faculty of Physics, Alexandru Ioan Cuza University of Iasi, Carol I Boulevard, No. 11, 700506, Iasi,
2

Romania; e-mail: [email protected]

Faculty of Physics, Alexandru Ioan Cuza University of Iasi, Carol I Boulevard, No. 11, 700506, Iasi,
3

Romania; e-mail: [email protected]

Faculty of Physics, Alexandru Ioan Cuza University of Iasi, Carol I Boulevard, No. 11, 700506, Iasi,
4

Romania; e-mail: [email protected]

Keywords: pottery technology, Cucuteni-Trypillia civilization, SEM-EDX analysis, XRD analysis,
magnetic and dielectric measurements

The aim of this paper is to investigate the relationship between the emergent complexity of
the Cucuteni-Trypillia civilization (V–IVth millennia BC) and the specialization of their ce-
ramic craft production as it is reflected by increasingly homogeneous products. Traditionally,
this question has been addressed by traditional archaeological methods (typology, style and
context analysis) and only a few interdisciplinary studies have been published.1,2
In order to evaluate the technological parameters of the ceramic production we engage
a robust methodological approach to the analysis of ceramic sherd assemblages, including
painted and unpainted pottery, consisting in a combination of analytical techniques. We have
used Energy Dispersive X-ray spectroscopy (EDX) for spot analysis of the matrix and tem-
per of pottery samples from sites across the eastern region of present-day Romania. X-ray
diffraction (XRD) and magnetic and dielectric measurements were used to explore the firing
temperature and the effects of distinctive tempering agents on the mineralogical transforma-
tions due to different firing parameters. The microscopical investigation for detailed study of
groundmass microstructure (low magnification) and the degree of vitrification (high magnifi-
cation) was determined by Scanning Electron Microscopy (SEM) analysis.
By determining the chemical and mineralogical composition and the magnetic and di-
electric characteristics of the potshards it was possible to determine the similarities and dif-
ferences between different groups of pottery determined macroscopically. In addition, the
investigation of pottery production process clearly indicated the technological choices made
by the potters regarding raw material selection, paste recipes and firing process.

References
1. F. Matau, V. Nica, P. Postolache, I. Ursachi, A. Stancu “Physical study of the Cucuteni pottery
technology”. J. Arch. Science 40 (2), pp. 914–925, 2013.
2. N. Buzgar, A.I. Apopei, A. Buzatu “Characterization and source of Cucuteni black pigment (Ro-
mania): vibrational spectrometry and XRD study”. J. Arch. Science 40 (4), pp. 2128–2135, 2013.

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196
Chromatic characteristics of traditional Korean copper glaze
with the addition of copper oxide and sintering atmosphere
Hyunggoo No*, Ungsoo Kim, Wooseok Cho
Korea Institute of Ceramic Engineering & Technology, Icheon 17303, Korea;
*
e-mail: [email protected]
Keywords: material, glaze, copper oxide, color

The copper-red pottery was the first traditional Korean technique which colorized the red
by the reduction atmosphere sintering at high temperatures i.e. more than 1200 °C in the
12th century of Goryeo Dynasty. This study aimed at analyzing the factors which affect the
copper-red glaze coloration and understanding the influence of the copper oxide addition and
sintering condition on the glaze coloration. As the addition of copper oxide increased under
the oxidation condition of 0, 0.3l/min of the LPG supply, the color was created to Green and
Green-Yellow, respectively, with CIEa* value of '-' and CIEb* value of '+'. The CIEa*b*
distribution was developed in proportion to '+' value in 0.5 and 0.7l/min, the reducing atmo-
sphere and showed the Red group. The copper oxide was reacted with the CO gas and re-
duced to Cu2O or Cu with the increase in the LPG supply and it was judged that the specimen
was under the composite influence of Cu nuclei aggregation, metal Cu Globule and Cu2O.
This study purposed to establish the technical basis to restore the traditional copper-red glaze
by understanding materials and process technology of Korean copper-red glaze.

References
1. H.S. Hwang, A Scientific Study of Korean Copper-Red Ceramics, Unpublished Doctoral Disserta-
tion, Chung-Ang University, Seoul, 2008.
2. H.G. No, U.S. Kim and W.S. Cho, “A Study on Utilisation of Copper-Red Pigment Technology”,
Journal of Korea Society of Color Studies, 30(1), 107–116, 2014.
3. P.A. Cuvelier, C. Andraud, D. Chaudanson, J. Lafait and S. Nitsche, “Copper Red Glazes: A coating
with Two families of Particles”, Appl. Phys., 106(4), 915–929, 2012.
4. M. Wakamatsu, N. Takeuchi, H. Nagai and S. Ishida, “Chemical States of Copper and Tin in Copper
Glazes Fired under Various Atmosphere”, J. Am. Ceram. Soc. 72(1), 16–19, 1989,

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622
Combined spectroscopic analysis to study ceramics
Jolien Van Pevenage1, Luc Moens1, Peter Vandenabeele2
Department of Analytical Chemistry, Ghent University, Krijgslaan 281-S12, B-9000 Ghent, Belgium;
1

e-mail: [email protected]
Department of Archaeology, Ghent University, Sint-Pietersnieuwstraat 35 UFO, B-9000 Ghent,
2

Belgium; e-mail: [email protected]

Keywords: Raman spectroscopy, XRF spectrometry, ceramics, archaeometry

The study of ceramics in the field of cultural heritage is not only done by archaeologists and
conservators. Nowadays, also natural scientists such as physicists, chemists and geologists
are involved in their investigation, using different analytical techniques. Information about
the structure and composition helps towards identification and classification of the material
in terms of provenance determination1 and production processes2.
Next to Inductively-Coupled-Plasma mass-spectrometry (ICP-MS), X-ray diffraction
(XRD), and infrared (IR) spectroscopy3 also Raman spectroscopy4 and X-Ray Fluorescence
(XRF) spectrometry5 are widely applied to investigate the composition of ceramic materi-
als. These two analytical methods are considered as complementary as Raman spectroscopy
provides molecular information while XRF spectrometry gives elemental information about
the composition of the investigated material. Both techniques are non-invasive and allow
analysis of the material on micro-meter scale.
For the application of both techniques, both laboratory and mobile instrumentation is de-
veloped. Whether measurements are done in laboratory environment or in situ analysis is
performed depends on the material (shape, size, location, value) and the research question.
The combined application of both spectroscopic techniques is discussed through several case
studies.

References
1. M.J. Ayora-Cañada, A. Domínguez-Arranz, “Raman Microspectroscopic study of Iberian pottery
from the La Vispesa archaeological site, Spain.”, J. Raman Spectrosc., 43, pp. 317–322, 2012.
2. P. Colomban, R. de Laveaucoupet and V. Milande, “On-site Raman spectroscopic analy-
sis of Kütahya fritwares.”, J. Raman Spectrosc., 36, pp. 857–863, 2005.
3. R.A. Goodall, J. Hall, R. Viel and P.M. Fredericks, “A Spectroscopic Investigation of Pigment and
Ceramic Samples from Copan, Honduras.”, Archaeometry 51, pp. 95–109, 2009.
4. J. Van Pevenage, D. Lauwers, D. Herremans, E. Verhaeven, B. Vekemans, W. De Clercq, L. Vincze,
L. Moens and P. Vandenabeele, “A combined spectroscopic study on Chinese porcelain containing
ruan-cai colours.”, Analytical Methods 6(2), pp 387, 2014.
5. L. Van de Voorde, M. Vandevijvere, B. Vekemans, J. Van Pevenage, J. Caen, P. Vandenabeele, P.
Van Espen and L. Vincze, “Study of a unique 16th century Antwerp majolica floor in the Ramey-
enhof castle’s chapel by means of X-ray fluorescence and portable Raman analytical instrumenta-
tion”, Spec. Chim. Acta B, 102, pp. 28–35, 2014.

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Poster presentations

317
Data-driven ancient ceramics studying – case of Fanchang Kiln
Chenhao Qian1, Ziyang He2*
1
Department of Mechanical Engineering, Jiangnan University, Wuxi, Jiangsu, 214122, China
2
Department of Industrial and Manufacturing System Engineering, Iowa State University,
Ames, Iowa, 50010, USA; *e-mail: [email protected]
Keywords: EDXRF, chemical feature, Fanchang, Jingdezhen, random forests

The energy dispersive X-ray fluorescence (EDXRF) is used to determine the chemical com-
position of celadon body and glaze in Fanchang kiln and Jingdezhen kiln. Forty typical
shards in four cultural eras were selected to investigate the raw materials and firing tech-
nology. Random forests, a relatively new statistical technique, has been adopted to identify
chemical elements that are strongest explanatory variables to classify samples into different
cultural eras and kilns. The results indicated that the contents of Na2O, TiO2, and SiO2 vary
in celadon bodies from Fanchang and Jingdezhen, which implies that local clay was used to
manufacture celadon bodies in Jingdezhen kiln as a new type of celadon. By comparing the
chemical composition in glaze, we find that the chemical elements and firing technology of
Jingdezhen kiln are very similar to those in Fanchang kiln, especially for late Tang dynasty.
This study reveals the inheritance between Jingdezhen kiln and Fanchang kiln, and explains
the differences between two kilns.

References
1. J.M. Wu, M.L. Zhang, Q.J. Li, Chemical composition and chromaticity characteristic of Jilan Glaze
of Ming and Qing official kilns, Spectrosc. Spectr. Anal. 32 (8) (2012) 2254.
2. F.K. Zhang, Scientific and Technical Research Achievements in Ancient Chinese Pottery and Por-
celain, Science and Technology Press, Shanghai, 1985, p. 161.
3. L. Li, S.L. Feng, X.Q. Feng, Q. Xu, L.T. Yan, B. Ma, L. Liu, Study on chemical features of Long-
quan celadon at Fengdongyan kiln site in Yuan and Ming Dynasties by EDXRF, Nucl. Instrum.
Methods Phys. Res. B 292 (2012) 25–29.

661 ECerS2017 / July 9–13, 2017 / Budapest, Hungary

T11: Refractories
Invited lectures

715
The main role of silica gel technology on alumina castables
Olga Burgos-Montes1, Margarita Álvarez1, Antonio H. de Aza2, Pilar Pena2,
Carmen Baudín2
1
Refractarios ALFRAN, Sevilla, Spain; e-mail: [email protected]
2
Instituto de cerámica y Vidrio, CSIC, Madrid, Spain; e-mail: [email protected]
Keywords: castable, installation, sol-gel bonding, microstructure, hot mechanical properties

The use of unshaped refractory products is continuously increasing due to their well know
advantages: Time saving during shutdowns, less storage area needed, quick response from
manufacturing plants to customers, better performance together with lower prices and less
CO2 emissions during production.
The fundamental issue to ensure the optimum performance of castables is the installation
method. In this sense, the rheological behavior of castables has to be adjusted depending
on the specific installation method. This goal is achieved by the careful selection of addi-
tives and their amount. As examples, additives have to assure the adequate flowability of the
castable during the pumping step in shotcreting, the appropriate setting time of the gunning
systems, or the tixotropy showed by the LCC products.
Due to their critical role to make the installation step robust and safe, a number of different
additives are nowadays present in the market.
In addition to rheology optimization, a main point to consider is that most of these addi-
tives would also have an influence on the development of the microstructure of the castables
at high temperature, especially on phase development.
In this work, after a short overview of the role of additives on installation methods a com-
parison between two different model systems based on “no cement bonding” using silica to
obtain sol-gel bonding in cold conditions is done. One of them contains a colloidal stabilized
suspension and the other one, based on the “all-in-bag” idea, uses functionalized microsilica
particles. The rheological behavior together with the high temperature microstructural evolu-
tion and mechanical behavior are discussed.

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091
Reflections on refractory materials and their evaluation
Victor C. Pandolfelli
Federal University of São Carlos, Brazil

Survival of the refractory area is based on new products with engineered microstructures.
Nature presents examples of designs and evolution proof structures that should catch our
attention and interest. Nevertheless, mimicking nature also poses new challenges on how to
adapt and analyze these novel materials. Would, for example, the usual refractory mechanical
tests be sufficient to evaluate a lamellar structure with kinked and stable crack propagation?
If most of our community is not yet familiar with the importance of R curve profile, are we
prepared to measure the effects of KI, KII and T factor with the temperature? Sometimes, we
see the challenges only for the advanced refractory microstructure designs, but are we aware
that even our traditional currently used tests are far behind what represents the actual condi-
tions faced in the working environment? In order to take us out of our comfort zone, do we
really know how to measure the maximum working temperature of refractory materials? This
talk will present some of the challenges ahead for producing and characterizing the refracto-
ries to come and those that we are used to, but we still do not understand why they perform
well, based on our characterization processes. Along this continuous journey of looking at the
future and the past, we know, rephrasing T.S. Elliot, that “the end of our exploring, will be to
arrive where we started and know the place for the first time”.

868
Applied research on and application of refractory materials
in an industrial environment
Sido Sinnema*, Rinus Siebring, Paul van Beurden, Pieter Put, Paul Tamis
Ceramics Research Centre, Tata Steel Europe, PO box 10.000, 1970 CA Ijmuiden, the Netherlands;
*
e-mail: [email protected]
Keywords: refractories, value in use, fem modelling

Refractories are of critical importance for an energy-intensive industries such as iron and
steel making, the production of refractories constitutes the demand for novel materials with
improved characteristics and superior technological and economic performance. The refrac-
tory research is a truly interdisciplinary endeavor requiring knowledge and expertise from
diverse academic disciplines as well as contributions from the steel industry itself.1
The aim of the paper is to sketch a picture of different aspects in the refractory research
approach within an international steel company bridging the gap between the need from day
to day production and a the long term solutions academics can offer. In an industrial environ-
ment a refractory engineer should be able to deliver both direct support to the plant as well

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T11: Refractories – Invited lectures

develop experimental techniques and perform long term research bearing in mind the needs
of the company.
In this paper a few examples of recent research will be discussed, ranging from direct
support to middle and long term research supported by fundamental research programs of
academia.
From an end user point of view maintaining close relationship to refractories dedicated
universities and companies is of vital importance to operate production processes at a high
level. A network like FIRE (The Federation for International Refractory Research and Educa-
tion) is an excellent vehicle to achieve this goal in our experience.
FIRE with its unique multi-cultural and multi-disciplinary composition is able to exactly
draw on desired skills and provide a unique framework for furthering refractory education
within the context of multi partner research programs.2

References
1. A. Geigenmüller, H. Spindler, K.Lenk, Chr. G Aneziris, “Future Research in Refractorie; A Road-
map Approach”, Refractories Wordforum 6 (2014) [3], p. 68–74.
2. C. Parr, H. Harmuth, V. Pandolfelli, J. Poirier, M. Rigaud, S. Sinnema “Firing Research for Refrac-
tories in Steel Ladle Application”, UNITECR 2016, proceeding 239.

ECerS2017 / July 9–13, 2017 / Budapest, Hungary 664

 T11: Refractories

Oral presentations

464
Granulated RTP magnesia stabilised zirconia for refractories
Andreas Börger1*, Johan Loricourt2, Angelika Priese2
1
CARRD GmbH, Seebacher Allee 64, 9500 Villach, Austria; *e-mail: [email protected]
2
Imerys Fused Minerals Murg, Laufenburg, Germany
Keywords: zirconia, MgSZ, magnesia stabilised zirconia, refractories, granulation

Magnesia stabilised zirconia is a widely used material for refractory applications. Typically
either a pre-stabilised MgSZ (e.g. fused and crushed) or a mixture of monoclinic zirconia
and magnesium oxide is used as raw materials. These raw materials are mixed with bind-
ers, granulated and shaped to refractory parts. In this study different granulation methods
are compared to produce a ready-to-press MgSZ using MgO and monoclinic ZrO2 as raw
materials. During sintering (at 1650 °C) the MgO reacts with the zirconia to form a magnesia
stabilised zirconia (in-situ stabilisation). In this paper a comparison between spray dried and
mechanically granulated material is presented and discussed. For the mechanically granulat-
ed material a design of experiments was done in order to optimise the granulation parameters
and type and amount of organic additives. Also different particle size distributions of the raw
materials (especially of the used monoclinic zirconia) were used and several binder systems
were studied and their effect on the properties was evaluated.
The produced granulated material was uniaxially pressed to cylindrical parts. Special fo-
cus was taken on the analysis of pressing curves as well as the green and sintered properties.
The sintered specimens were analysed in terms of density, microstructure and porosity. Fi-
nally a comparison with parts produced from spray dried MgO-ZrO2 granulates is presented.

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073
An improved corrosion and thermal shock resistant sintered
mullite-zirconia refractory
M.L. Bouchetou1, A. Villalba Weinberg1,2,5, M. Weissenbacher3, O. Joubert4, C. Varona5,
D. Goeuriot2, J. Poirier1
1
CNRS, CEMHTI UPR 3079, Univ. Orléans, France
2
LGF CNRS UMR 5307, Mines Saint-Etienne, France
3
CARRD, Imerys, Villach, Austria
4
Imerys Refractory Minerals Clerac
5
Bony SA – Saint Etienne, France
Keywords: refractories, mullite-zirconia composite, andalusite, zircon, thermal shock, corrosion,
incineration

Mullite-zirconia composites are commonly used as refractories due to their excellent proper-
ties such as high strength and fracture toughness as well as good thermal shock and corrosion
resistances. The aim of the present research is to propose an improved corrosion resistant and
thermal shock resistant mullite-zirconia refractory. Generally, mullite-zirconia refractory raw
material is industrially produced through a fusion process by melting a mixture of zircon and
alumina in an electric arc furnace. Zirconia crystal grains are dispersed in a mullite matrix.
A glassy phase is additionally present.
In the present work, a new sintered mullite-zirconia raw material has been developed on
basis of andalusite, alumina and zircon. During sintering, the formation of mullite takes place
in different ways. The primary mullite formation results from decomposition of andalusite
(SiO2.Al2O3) into mullite (2SiO2.3Al2O3) and silica (SiO2). The secondary mullite formation
is effected by the reaction of alumina (Al2O3) and the silica (SiO2) from the decomposition
of zircon (ZrSiO4) and the excessive silica from the decomposition of andalusite. The mull-
ite-zirconia refractory composite has a mineralogical composition comprising 69% to 72%
(percent by weight) mullite and about 19% (percent by weight) zirconia. The microstructural
build-up consists essentially of fine zirconia particles homogeneously distributed in a mullite
matrix, wherein the average particle diameter of the zirconia particles is preferably less than
5 µm. The thermal shock resistance of the composite was tested by heating the samples up to
1200 °C and subsequently cooling to room temperature. The effect of the thermal shock was
proved by means of ultrasonic transmission technique. The thermal shock resistance of the
composite increases with the first and second thermal cycling and stays constant afterward,
whereas the thermal shock resistance of other materials like cordierite or alumina begin to de-
crease from the first thermal shock. Different industrial refractories based on mullite-zirconia
raw materials have been elaborated and characterized. The corrosion resistance against mol-
ten slags was tested in comparison to the commercially refractory bricks. It was found that
the molten slag penetrated the commercially refractory bricks deeply, whereas for mullite-
zirconia bricks very low penetration-depth was measured. In summary, this new family of
mullite-zirconia refractories presents high thermal shock and corrosion resistance against
molten slag and is well suitable for different applications such as the incineration of wastes.

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References
1. A. Bradecki and S. Jonas, Ceram. Int, vol. 36, 2010, pp. 211–214.
2. F. Cambier, C. Baudin De La Lastra, P. Pilate, and A. Leriche, Br. Ceram. Trans. J., vol. 83, 1984,
pp. 196–200.

665
Hercynite as active spinel
Jastrzębska, I.*, Szczerba, J.
AGH University of Science and Technology, al. A. Mickiewicza 30, 30-059 Kraków, Poland,
Faculty of Materials Science and Ceramics, Department of Ceramics and Refractories;
*
e-mail: [email protected]

Hercynite is a representative of sensu lato oxide spinel compound with a semi-structural for-
mula [Fe2+]Td[Al2]Oh, where Td and Oh indices designate tetrahedral and octahedral positions
in the spinel structure, respectively. FeAl2O4 melts at 1780 °C and possesses a low thermal
expansion coefficient, which make it applicable as modifying component in basic refracto-
ries for cement rotary kilns. What distinguishes hercynite from other alumina spinels is its
distinctive behaviour at elevated temperature, sometimes called “activity of hercynite”. This
work aims to show activity of single phase hercynite and hercynite substituted by low Mg2+
and Mn2+ ions content.
In this work hercynite and its solid solutions were prepared by a technique utilizing arc
plasma (Arc Plasma Synthesis, APS) in arc plasma facility SpekoArc300. This method was
found to be an effective route in obtaining hercynite spinels of relatively low inversion pa-
rameters.
Thermal activity of pure hercynite was investigated on both bulk and powdered sample in
order to reflect its behaviour during the operation and to get the near-equilibria conditions,
respectively. The bulk samples were kept at temperatures 600 and 1000 °C, for various peri-
ods of time, and then subjected to examinations by X-Ray Diffractometry (XRD) for phase
identification, Scanning Electron Microscopy with Energy-Dispersive Spectroscopy (SEM/
EDS), Electron Probe Micro-Analysis with Wavelength-Dispersive Spectroscopy (EPMA/
WDS) for microstructure analysis. Additionally, Mössbauer Spectroscopy was used for de-
termination of iron ions oxidation state and their local chemical symmetry as well as for
confirmation of ferrous/ferric ions-containing phases in a decomposed material.
The powdered samples of pure and substituted hercynite were examined by High Tem-
perature X-Ray Diffractometry (HTXRD) up to 1200 °C. HTXRD results showed a gradual
decomposition of hercynite proceeding in situ during measurements. This was manifested
by the change in phase composition, which finally led to obtain the most thermodynamically
stable αAl2O3 and αFe2O3 phases. In general, these final phases were being formed through
the stage transformations of less stable transitions phases accordingly: γ→δ→θ→α for Al2O3
and γ→α for Fe2O3. The detailed and complete hercynite decomposition mechanism was

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T11: Refractories – Oral presentations

demonstrated in this work. SEM observations showed a final hematite of an unusual scaleno-
hedral morphology. The significant difference in the influence of Mg2+ and Mn2+ on hercynite
decomposition were found and presented.

Acknowledgement
This work was partly financially supported by the statutory funds of the Faculty of Materials Science
and Ceramics AGH in Kraków.

962
Degradation of silicon carbide based refractories in CFB plants under
co-combustion conditions
Patrizia Miceli1, Daniela Olevano1, Umberto Martini1, Antonello Di Donato1,
Stefano Martelli2
Centro Sviluppo Materiali S.p.A. – Via di Castel Romano, 100 - 00128 Rome, Italy;
1

e-mail: [email protected]
Vesuvius PI – 4604 Campbells Run Road – Pittsburgh, PA 15205 USA;
2

e-mail: [email protected]
Keywords: silicon carbide, corrosion, co-combustion, refractory, CFB, thermodynamics

Producing energy in efficient and environmentally clean way is certainly one of the biggest
challenge for humankind towards a sustainable development. The energy mix composed by
fossil fuel, is still the major contributor. Biomass combustion or co-combustion is surely one
of the most promising energy source, together with hydro, solar, wind, to mitigate green-
house emission.1
The request of flexibility concerns not only the tendency to partially substitute coal with
biomass with the subsequent need to optimize this multi-fuel combustion but also to have
flexible power plant performance so to facilitate the use in conjunction with power genera-
tion from renewables.
However, biomass has significant different compositions2,3 and its combustion releases
ashes slag4 which can be aggressive for the power generation plants in particular for the re-
fractories lining their combustion chamber.
Silicon carbide, as brick or castable system, is generally used when a high resistance
to thermal cycling is required for its low thermal expansion and high thermal conductivity
hence good thermal shock resistance.
In the present case the analysis of SiC based refractories, after testing in Circulating Fluid-
ized Bed (CFB) pilot plant under co-combustion conditions, showed a curious degradation
behaviour, apparently inexplicable, but undoubtedly obeying to the thermodynamics of the
system. To validate this system, laboratory tests were conducted under controlled condi-
tions which reproduced the same degradation behaviour of SiC based refractories already
observed in pilot campaigns.

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Acknowledgement
This research activity is part of the European funded 7th Framework project MacPlus.

References
1. S.G. Sahu, N.Chakraborty, P.Sarkar, Ren. Sust. Energy Rev. 39 (2014) 575–586.
2. S.V. Vassilev, D. Baxter, L.K. Andersen, C.G. Vassileva, Fuel 105 (2013) 40–76.
3. S.V. Vassilev, D. Baxter, L.K. Andersen, C.G. Vassileva, Fuel 117 (2014) 152–183.
4. A.A. Khana, W. de Jonga, P.J. Jansensb, H. Spliethoff, Fuel Proc. Techn., 90 (2009) 21–50.

033
High temperature mechanical characterisation of in situ forming
spinel-alumina castables, using magnesia or magnesite as raw materials
P. Pilate1, N. Preux1, V. Lardot1, F. Cambier1, F. Holleyn2, O. Krause2, E. Brochen3,
C. Dannert3
BCRC, Belgian Ceramic Research Centre (member of EMRA) – Avenue Gouverneur Cornez, 4,
1

7000 Mons, Belgium; e-mail: [email protected]

Hochschule Koblenz, Rheinstrasse, 56, 56203, Höhr- Grenzhausen, Germany;
2

e-mail: [email protected]
FGF, Forschungs Gemeinschaft Feuerfest – Rheinstrasse, 58, 56203, Höhr- Grenzhausen, Germany;
3

e-mail: [email protected]
Keywords: thermomechanical, spinel, alumina, magnesia, magnesite

Alumina-spinel castables are used as steel ladle lining because of their superior slag and
thermal shock resistance compared to alumina materials. In high alumina castables, spinel
can be introduced as preformed spinel grains or by in situ reaction between alumina and mag-
nesia or a precursor, at service temperature, from 1100 °C. In situ formed spinel materials
exhibit a microstructure which is favorable to very good corrosion resistance. The reaction
also leads to a thermal expansion due to density difference between the product and reagents
with as result a good thermal shock resistance. However it always exists a need to master the
composition and to understand the thermomechanical behavior at service temperature and
mainly the relation with composition. In this work, four alumina-magnesia, cement bonded
castables were tested at high temperature with two different methods: strength and Young’s
modulus. As a reference, a high alumina castable was also investigated. The effect of sev-
eral parameters: composition, addition of magnesia or magnesite (carbonate), impurities and
microsilica addition were investigated. Strength was determined by bending strength at tem-
perature ranging from room temperature to 1550 °C. Strength resistance and the stress-strain
curves were recorded. Young modulus was measured with the resonant frequency technique
from room temperature to 1500 °C. Microscopic observation and XR diffraction were also
introduced to support the discussion and conclusions of the work. Results demonstrate the
real effect of parameters on high temperature mechanical behaviour, mainly sintering, phase
transformations and liquid phase appearance versus temperature. The alumina castable ex-
hibits a linear behaviour at room temperature and a limited nonlinear behavior at high tem-

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perature (1000–1500 °C). With magnesia addition, and depending on composition (magnesia
or magnesite addition, magnesia content, presence or not of microsilica), at high temperature,
the elastic modulus decreases and the non linear behaviour extends. Depending on the tem-
perature, materials exhibit a high ductility which is favorable to a good thermal shock resis-
tance. Results also allows relating a refractoriness limit (drastic fall of mechanical resistance)
versus composition.

Acknowledgement
This work was realized in the framework of a CORNET (network of ministries and funding agencies
in Europe) project: HISHOCK (2015-2017) and was funded by SPW (Belgium-Wallonie) and AIF
(Germany).

854
Microsilica as anti-hydration agent for basic refractory castables
Hong Peng, Bjørn Myhre
Elkem Silicon Materials, Kristiansand, Norway
Keywords: MgO castables, microsilica, hydration, brucite

Magnesia castables have been drawn a great attention in refractory industries, however they
have not widely been used. The major challenge is volume expansion and cracking due to
brucite (Mg(OH)2) formation during MgO hydration - a phenomenon commonly called “slak-
ing”. In this paper, the focus is on understanding the effect of microsilica on the hydration
behaviour of MgO that allow us to develop crack-free MgO castables. The flow-, set- and
hydration-behaviour during dry-out and curing have been studied. SEM and XRD techniques
were used to characterize the phase composition and microstructure after the dry-out pro-
cess and the results demonstrate that microsilica suppresses the hydration process of MgO.
A minimum of 3wt% microsilica is necessary to inhibit the hydration of MgO in lab-scale
specimens, while more microsilica is needed for industrial-scale samples. By controlling
the MgO hydration and dry-out behaviour, magnesia castables based on the MgO-SiO2-H2O
bond system have been developed; a perfect 600kgs block was produced with no problems.

References
1. Y. Watanabe, T. Ono, T. Yukinawa and S. Sakamoto, “Development and Application of Monolithic
Refractory Containing Magnesia Clinker”, Proc. 2nd. Int. Conf. Refr. Tokyo, Japan. p. 494–506,
1987.
2. Sandberg, B., Mosberg, T., “Use of microsilica in binder systems for ultra-low cement castables and
basic, “cement-free” castables”. Advances in Refractories Technology. Vol. 4. p. 245–258, 1989.
3. Wagner M. Silva, Christos G. Aneziris, and Modestino A.M. Brito, “Effect of Alumina and Silica
on the Hydration Behavior of Magnesia-Based Refractory Castables”. J. Am. Ceram. Soc., 94 [12],
p. 4218–4225, 2011.
4. Rafael Salomão and Victor C. Pandolfelli, “Microsilica Addition as an Antihydration Technique for
Magnesia-Containing Refractory Castables”. American Ceramic Society Bulletin, Vol. 86, No. 6,
p. 9301–9306, 2007.

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5. Rafael Salomão, L.R.M. Bittencourt, V.C. Pandolfelli, “A novel approach for magnesia hydration
assessment in refractory castables”. Ceram. Inter., 33(5), p. 803–810, 2007.
6. B. Myhre, H. Peng, and M. Luo, “Cement free MgO castables Part I, flow, setting and slaking”.
Proc. UNITCER’13, Canada, p. 881–886, 2013.
7. H. Peng, B. Myhre and M. Luo, “New additive packages for self-flowing high-alumina and MgO
based refractory castables”. Proc ALAFAR 2012, Cancun, Mexico, Nov. 5–8, 2012.
8. H. Peng and B. Myhre, “The road map of hydration behaviour off MgO based refractory castables”.
Proc ALAFAR 2014, Santiago, Chile. Oct. 28–31, 2014.

614
Development of aluminium titanate/porcelain ceramic matrix
composites having high thermal shock resistance
F. Prete1, G. Bonvicini1, E. Rambaldi1, G. Ridolfi1, M.C. Bignozzi1
1
CENTRO CERAMICO BOLOGNA, via Martelli 26, 40138, Bologna, Italy
2
DICAM, Department of Civil, Chemical, Environmental and Materials Engineering,
University of Bologna, via Terracini 28, 40131, Bologna, Italy

Porcelain represents one of the most known and common ceramic material, formulated from
a mix of clay, feldspar and quartz, sintered at temperatures between 1200 °C and 1400 °C,
to form a glass-ceramic composite. Aluminium titanate (Al2TiO5) is known for its excellent
thermal shock resi stance, resulting from the low thermal expansion coefficient, low ther-
mal conductivity, low Young’s modulus and for its good chemical resistance. In the pres-
ent work, aluminium titanate/porcelain ceramics composites with different percentages of
Al2TiO5 (up to 50 wt%)were prepared by uniaxial pressing and then fired at temperature
between 1200 °C and 1300 °C. The microstructural, mechanical and thermal properties were
characterized. Thermal shock resistance behaviour under water quenching of the as-prepared
ceramics was also evaluated. The results revealed that the addition of aluminium titanate to
porcelain matrix improves the properties of the aluminium titanate/porcelain ceramics and
that the thermal shock resistance tended to increase with increasing aluminum titanate con-
tent . This composite represent an optimum candidate to be used as refractory in the process
of metal casting.

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732
Impact of surface functionalization of carbon-bonded filters on steel
cleanliness
Enrico Storti*, Anne Schmidt, Steffen Dudczig, Christos G. Aneziris
Institute of Ceramic, Glass and Construction Materials, TU Bergakademie Freiberg,
Agricolastraße 17, 09599 Freiberg, Germany; *e-mail: [email protected]
Keywords: ceramic foam filters, carbon nanotubes, alumina, non-metallic inclusions

Non-metallic inclusions in cast metal parts often have a negative impact on properties such
as fracture toughness, tensile strength and fatigue resistance. Foundries require high purity
metal melts in order to limit the casting repairs and possibly avoid rejected castings. This
can be achieved by applying a filtration process after the ladle treatment. In the case of steel,
ceramic foam filters (CFFs), especially those based on zirconia and carbon-bonded alumina,
have been successfully employed for years.
Understanding the interactions between filter material and molten steel is essential to im-
prove the purity of cast products by filtration. Using a special steel casting simulator, carbon-
bonded alumina filters were immersed in a steel melt which contained artificially-generated
endogenous alumina particles. Uncoated and MWCNTs-coated ceramic filters were dipped
and rotated for 10 and 300 seconds in the melt at 1650 °C. For alumina-coated filters, chemi-
cal reactions at the filter/steel interface under quasi-static conditions were investigated using
spark plasma sintering (SPS) equipment. In addition, samples of the solidified steel were
taken after the immersion tests and analyzed by electron microscopy. The population of de-
tected inclusions was classified in terms of size and chemistry in order to compare the filtra-
tion efficiency of the different carbon-bonded filters.
Microstructure and phase analyses revealed that interfacial reactions between filter and
molten steel result in an a few hundred nanometers thin layer on the filter surface. During a
“reactive” stage, large plate-like alumina structures are formed on top of this layer. Thereby,
material is transported from the carbon-bonded material underneath (i.e. gaseous reaction
products) as well as from the molten steel (i.e. precipitating particles and endogenous inclu-
sions) to the filter/steel interface. The growth of these alumina particles stops as soon as the
carbon supply, which triggers the dissolution and precipitation processes at the interface, is
cut off. From that point on, endogenous inclusions are collected (“active” stage). In general,
it seems that the filters are most efficient during the reactive stage, i.e. as long as the interfa-
cial reactions take place.
Investigations of the steel samples after the test suggest various filtration effects, regard-
ing size as well as chemical composition of the remaining inclusions. Considering the total
number of inclusions, our alumina-coated and MWCNTs-coated filters deliver filtration ef-
ficiencies from about 70% up to over 90%. These values are significantly higher than those
achieved with state-of-the-art filters.

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756
Investigation of the mechanical and thermomechanical properties
of carbon-bonded alumina refractories with reduced carbon content
due to nano- and microscale additives
Dániel Veres1*, Nora Brachhold1, Jens Fruhstorfer1, Annika Mertke2, Christos G. Aneziris1
1
Institute of Ceramic, Glass and Construction Materials, TU Bergakademie Freiberg, Agricolastr. 17,
D-09599 Freiberg, Germany; *e-mail: [email protected]
2
Salzgitter Mannesmann Forschung GmbH, Eisenhüttenstrasse 99, D-38239 Salzgitter, Germany
Keywords: nanoscaled additives, silicon, carbon-bonded alumina, semi-conductive material, reduced
graphite

This study investigated the combined effect of nanoscaled additives (carbon nanotubes and
nanoscaled alumina) and semi-conductive silicon on carbon-bonded alumina with a reduced
primary carbon content of 20 wt%. It focused on the initial cold modulus of rupture and its
evolution on exposure to thermal shock. The use of the single additive groups or their com-
bination yielded an increased initial strength compared to the reference without additives. It
was shown that the combination of the additives resulted in a material that exhibited no statis-
tically significant decrease of the cold modulus of rupture in up to five thermal shock cycles.
To understand these effects, physical properties (total porosity, open porosity, true density)
were observed. The data showed that the microstructural reactions were complex. The com-
bination of all additives caused a decrease in the open porosity. The available data of the true
density analysis matched partly with the possible reactions. Especially the formation of SiC
whiskers was considered to be important during the coking process and the thermal shocks.
Furthermore, it was proposed that a deposition of carbon because of oxidation processes
followed by reactions with the additives, especially the semi-conductive silicon, occurred,
which might have a self-healing effect on the refractory matrix.

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251
Investigation of the influence of metallic additives on the
thermomechanical properties of carbon-bonded refractory composites
Andrzej Warchał1,2*, Damien André1, Duane DeBastiani2, Philippe Gullio2, Marc Huger1,
Stefano Martelli2, Stéphane Mazerat2, Séverine Romero-Baivier2
1
Université de Limoges, CNRS, ENSCI, SPCTS, UMR 7315, 12 rue Atlantis, 87068 Limoges Cedex,
France; *e-mails: [email protected], [email protected]
2
Vesuvius, 68 rue Paul Deudon, 59750 Feignies, France
Keywords: refractories, thermomechanical properties, carbon, antioxidants

Alumina-carbon refractories are widely used in the continuous casting of steel, e.g. for ladle
shrouds, monoblock stoppers and submerged entry nozzles. They are responsible for the steel
flow control and its protection against oxidation. To improve their own oxidation resistance,
several metallic additives such as Al, Al-Si and Al-Mg are added as antioxidants. In this
study, the influence of those antioxidants on the thermomechanical behaviour of carbon-
bonded refractories was studied. Model materials having simplified composition compared
to the real industrial ones were investigated so as to facilitate comprehension of mechanisms
responsible for the modification of mechanical properties. Behaviour of both cured (before
pyrolysis) and fired (after pyrolysis) materials was studied. The evolution of Young’s modu-
lus during firing was followed thanks to an ultrasonic pulse echography device. Damage
occurrence within the material was investigated by the acoustic emission technique. X-ray
diffraction measurements with Rietveld refinement enabled identification and quantification
of phases after firing. Stress-strain curves were obtained by tensile testing at room tempera-
ture. Obtained results show that the carbonaceous binder undergo transformation into pyro-
lytic carbon and that micro-cracks in material’s matrix are created during firing. It results in
a non-linear stress-strain behaviour. What is more, metallic additives react with carbon and
gases emitted from the binder to form new ceramic phases which rigidify the refractory. An-
tioxidants are added to carbon-bonded refractories so as to protect all forms of carbon from
oxidation. Nevertheless, this study showed that even a small quantity of metallic additives
may significantly modify their mechanical properties and thus have an influence on their reli-
ability and performance.

References
1. J. Werner, C.G. Aneziris, S. Dudczig. Young’s Modulus of Elasticity of Carbon-Bonded Alumina
Materials up to 1450ºC. J. Am. Ceram. Soc. 1–8, 2013.
2. B. Zhu, Y. Zhu, X. Li, F. Zhao. Effect of ceramic bonding phases on the thermo-mechanical proper-
ties of Al2O3-C refractories, Ceramics International, 6069–6076, 2013.
3. C. Atzenhofer, S. Gschiel, S. Harmuth. Phase formation in Al2O3-C refractories with Al addition, J.
Eur. Ceram. Soc., 2016.
4. D.G. Apostolopoulos, M. Frith, I. Strawbridge. Al/Mg alloy as an antioxidant in Magnesia-Graphite
Refractories. Steel Times, 11–12, 18, 1994.

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Poster presentations

870
Geopolymer matrix composites as innovative sustainable refractories
Lorenza Carabba1, Elisa Rambaldi2, Giovanni Ridolfi2, Maria Chiara Bignozzi1,2
1
Department of Civil, Chemical, Environmental and Materials Engineering, University of Bologna,
via Terracini 28, Bologna, Italy; e-mail: [email protected]
2
Centro Ceramico, via Martelli 26, Bologna, Italy
Keywords: geopolymer, ceramic refractory, sustainability, thermal shock resistance

Geopolymers are nowadays considered as one of the most attractive materials from the sus-
tainability point of view as they can be made by using secondary raw materials and cured at
room temperature.1 Besides this, geopolymers may be characterised by high technical per-
formances that can be tailored and improved, for instance by designing geopolimer matrix
composite materials.
The present work aims to develop innovative and sustainable refractory geopolymers for
industrial applications. Different carbon fly ash based geopolymer mixes were optimized
to withstand high temperature by adding milled refractory scraps coming from industrial
production of alumina-based refractory rollers. Geopolymerization was carried out at low
temperature (20 < T < 80 °C) followed by a room temperature curing.
The processing, microstructure and properties of geopolymer composites have been inves-
tigated. The thermal stability was assessed by heating microscope analysis, dilatometry and
thermal exposure in muffle furnace. In addition, electron microscopy studies (SEM/EDS)
and mineralogical quantitative analyses (XRD Rietveld-RIR method) were performed. Re-
sults showed that the microstructure of fully reacted geopolymers consists of an amorphous
and porous matrix with embedded alumina-based particles.
The investigated materials are able to resist to thermal shock above 800 °C, remaining mi-
crostructurally stable.

Reference
1. Davidovits J. Geopolymer Chemistry and Applications. Saint-Quentin: Institut Géopolymère;
2008, p. 3–18.

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302
The influence of silica colloidal on properties of castables bonded
with calcium aluminate cement
Pingan Chen1, Feng Wang1, Boquan Zhu1, Xiangcheng Li1,2
1
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and
Technology, Wuhan 430081, P.R.China; e-mail: [email protected], [email protected]
2
School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, UK
Keywords: calcium aluminate cement, silica colloidal, workability, green mechanical strength

Calcium aluminate cement (CAC) has been used as one of the most common binders in the
field of refractory castables. However, there are some drawbacks for refractory castables
bonded with CAC, in which the low mechanical strength during curing process is a big
problem. The use of silica colloidal as a binder for refractory castables has attracted great
interest due to its gelling properties in recent years, but the bad workability and low green
mechanical strength during demoulding process have greatly constrained the silica colloidal
application in refractory castables. In this work, the combined binder of CAC and silica col-
loidal has been made to overcome the above disadvantages. The workability, apparent poros-
ity and bulk density, cold modulus of rupture (CMOR) and cold compressive strength (CCS)
of castables were measured. Phase and microstructure evolution were characterized by the
techniques of XRD and SEM. The results showed that with a fixed ratio of water/cement, the
flow values decreased with the content of silica colloidal addition increasing. The apparent
porosity change of castables was very limited at the temperature range of 110 and 1100 °C;
however, it was decreased drastically when the heating temperature rose to 1600 °C, and
both the CMOR and CCS were increased by more than triple. When 5.0wt.% silica colloidal
was added and after heating treatment at 1100 °C, the CMOR and CCS of castable samples
were increased from 5.8 MPa and 56.75 MPa to 20.9 MPa and 152.42 MPa, respectively. The
XRD study indicated that the addition of silica colloidal didn’t change the mineral phases of
castable samples after heating treatment. The investigation of microstructural characteristics
by SEM revealed that a network structure was formed in the castables with the addition of
silica colloidal at 1100 °C, whereas it was a loose structure in the castables without addition
of silica colloidal. It was found that the nanosized SiO2 particles of silica colloidal were not
only filled into the pores in the castables to obtain high packing density, but also promoted
the hydrate formation in the pores due to its nucleation effect. The gelling effect of silica col-
loidal and hydration process of CAC together improved the mechanical strength of castable
samples at the temperature range of 110 and 1100 °C. Therefore, the combined binder of
silica colloidal and CAC can be considered as a promising alternative binder for refractory
castables.

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127
Effect of testing conditions on the thermal diffusivity measurements
of nuclear fuels via the flash method
Christelle Duguay*, Mathias Soulon
CEA, DEN, DEC, Cadarache F-13108 Saint-Paul-lez-Durance, France;
*
e-mail: [email protected]
Keywords: thermal diffusivity, flash method, nuclear fuel, uranium, ceramic

The nuclear fuel is a ceramic produced by powder metallurgy route. The knowledge of its
thermal conductivity is a fundamental data for a better prediction of the fuel performance in
reactor. The thermal conductivity is derived from a thermal diffusivity measurement, whose
value may be affected by parameters such as the origin of the powders, the fabrication pro-
cess used, the fraction of porosity of the sintered fuel....and must be measured accurately.
Within the Fuel Studies Department, the Uranium Fuels Laboratory has acquired a thermal
diffusivity Light Flash Apparatus (LFA HyperFlash 467, manufactured by the Netzsch com-
pany) to complete its range of characterization capabilities devoted to nuclear fuels.
The device implements the flash method, which is a standard method for measuring the
thermal diffusivity. The test consists of subjecting the lower surface of a small and thin sam-
ple, with plane and parallel faces, to an energy pulse of very short duration (provided here by
a xenon flash lamp). The resulting temperature rise (thermogram) is recorded on the opposite
upper face of the sample (using here an InSb infrared detector cooled with liquid nitrogen).
The thermal diffusivity value is inferred from the interpretation of the thermal curve. The
analysis software provides different theoretical models (such as those of Cowan and Cape-
Lehman) for the interpretation of the experimental thermograms.
Measurements can be performed up to 500 °C under controlled atmosphere. Several sam-
ples (up to 16, depending on their geometry) can be characterized in a single test.
In the present work, aiming at a better understanding of the factors that affect thermal dif-
fusivity measurements using the flash method, the effect of parameters related either to the
specimen (coating, thickness, porosity,…) or to the operational conditions were investigated
on uranium-based ceramics.

References
1. Standard test method for thermal diffusivity by the flash method, ASTM standard E1461-13, Oc-
tober 2013, 11p.
2. Standard practice for thermal diffusivity by the flash method, ASTM standard E2585-09, July 2009,
10p.

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536
Effect of heating conditions on the properties of bauxite refractory
castable: a design of experiments study
Ilona Kieliba1*, Jacek Podwórny2, Jacek Szczerba1
1
AGH University of Science and Technology, Faculty of Materials Science and Ceramics,
Department of Ceramics and Refractories al. A. Mickiewicza 30, 30-059 Cracow, Poland;
*
e-mail: [email protected]
2
Institute of Ceramics and Building Materials, Refractory Materials Division in Gliwice, Poland
Keywords: low cement refractory castable, bauxite, design of experiment

The consumption of monolithic refractory materials is steadily increasing which is connected

with the constantly expanding range of applications of refractory castables and the rapid de-
velopment of new technologies ensuring their high quality.
Physic-mechanical properties of monolithic refractory materials are dependent on many
key factors and one of them are no doubt the heating conditions.
The aim of the present study was to determine, using the 2n Factorial Design, the relation-
ship between the heating conditions of low-cement bauxite castable and their properties i.e.
the apparent density, open porosity, permanent linear changes, as well as Young’s modulus,
compressive strength and bending strength at ambient temperature. The investigations were
based on experimental design methods which allowed to minimalize the number of experi-
ments and samples needed to identify the investigated relationships. To analyze the obtained
results the advanced analytics software STATISTICA was applied. It have been proved that
the investigated three factors i.e. heating ratio to 450 °C, dwell time at 450 °C, heating ratio
to 800 °C and their interactions significantly influence the properties of bauxite refractory
castable.

Acknowledgements
The study was partially supported by the Institute of Ceramics and Building Materials, the Refractory
Materials Division in Gliwice and statutory refunds no. 11.11.160.617-AGH University of Science and
Technology, Faculty of Material Science and Ceramics.

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141
The influence of MgAl2O4 spinels occurrence status on thermal
properties of refractory alumina-spinel castables
Xiangcheng Li1,2*, Yulong Wang1, Boquan Zhu1*, Pingan Chen1
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and
1

Technology, Wuhan 430081, P. R.China

School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, UK;
2

*
e-mails: [email protected], [email protected]

MgAl2O4 spinels-contained refractory castables possess good resistance to both thermal

shock and molten slag. In this paper, MgAl2O4 spinels were introduced into the alumina-
based refractory castables through spinel-contained in aluminate cement (CMA), pre-synthe-
sis and in-situ formation respectively. The results showed the existence status of the spinels
could have a great influence on the generation of CA6 and the thermo-mechanical properties
of the refractory castables. The spinels in CMA give rise to the higher residual cold modulus
of rupture of the castable after thermal shock and better resistance to molten slag due to the
particle reinforcement and excellent ions-absorbing capacity respectively. The introduction
of pre-synthesis spinels powders in the castables mean the large size in the particles or crys-
talline and lead to the poor slag corrosion resistance. The in-situ formation of MgAl2O4 with
large surface area could improve the slag penetration of the castables, while that also may
cause the microcracks and deteriorate the corrosion resistance of the refractory castables.

485
Influence of ZrSiO4/SiC modifiers on “alkali bursting” effect of
aluminosilicate refractories studied by heating microscopy thermal
analysis and other methods
Dominika Madej, Jacek Szczerba
AGH University of Science and Technology, Faculty of Materials Science and Ceramics,
Department of Ceramics and Refractories, al. A. Mickiewicza 30, 30-059 Krakow, Poland

The corrosion chemistry of SiC/ZrSiO4-modified bauxite, andalusite and mullite refracto-

ries has been studied using a post-mortem approach that considers both K+ and Ca2+ ions
as the main corrosive agents existing in the cyclone preheater applied in the cement pro-
duction line.1,2 An industrial scale corrosion test at 4.stage cyclone preheater in Polish ce-
ment plant where the temperature reaches 1100 ºC was performed. Final results from X-ray
fluorescence (XRF), X-ray Diffraction (XRD) and Scanning Electron Microscopy/Energy
Dispersive Spectroscopy (SEM/EDS) analysis revealed significant changes in both chemical
composition and phase-mineral composition of refractory material. The transient progress
of corrosion reactions was investigated as the function of distance from the face exposed to
the corrosive media (hot face) to the relatively little altered middle zone of aluminosilicate

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refractory bricks. Chemical alterations of refractory aggregates and SiC/ZrSiO4 grains were
examined and discussed on the basis of phase equilibria in binary (CaO-SiO2, K2O-SiO2) and
ternary (K2O-Al2O3-SiO2, CaO-Al2O3-SiO2) systems. Ca and K-Si-oxide phases along with
Ca-aluminosilicate and K-aluminosilicates were found in the corroded refractory samples.
Thus, the wear phenomenon called as “alkali bursting” of aluminosilicate refractories con-
taining ZrSiO4 or SiC compounds was also studied in situ by the heating microscopy thermal
analysis.

Acknowledgement
The research was performed at Faculty of Materials Science and Ceramics of AGH within the confines
of the project no 11.11.160.617.

References
1. D. Madej, J. Szczerba, Fundamental investigations on the high temperature corrosion of ZrSiO4-
containing andalusite refractories in cement kiln preheater, Journal of the European Ceramic Soci-
ety 36(3) (2016) 875–883.
2. D. Madej, J. Szczerba, Detailed studies on microstructural evolution during the high temperature
corrosion of SiC-containing andalusite refractories in the cement kiln preheate, Ceramics Interna-
tional, 47(2) (2017) 1988–1996.

919
Fabrication of perlite insulation bricks: effect of firing temperature
and perlire content
Seyyed Hossein Mirhosseini*, Leila Sharifi, Farnaz Assa, Hossein Ajamein,
Alireza Salman Mohajer
Academic Center for Education, Culture and Research, Yazd branch, Iran;
*
e-mail: [email protected]
Keywords: perlite, furnace, insulation brick, porous structure

Various insulating materials such as bricks (perlite, diatomite, mullite, vermiculite, chamotte,
etc.), blocks, insulating castable masses and fibers are commonly used in order to save the
energy consumption in industrial furnaces.1,2 The purpose of this study was to determine the
technical characteristics of perlite insulation bricks production in accordance with interna-
tional standards (ASTM 134-84, C 182-83, C 210-85, C 93-84). In this study, 10-30% of
perlite (P10, P20, P30), 70–90% of ball clay and water as the ingredients of insulation bricks
were mixed. To improve the properties and reduce the firing temperature and waste trans-
portation, 3–7% of phosphoric acid 85% w/w solution was used. The samples were shaped
as rectangular cubes with dimensions of 228×114×64 mm by an extruder, and subsequently
were dried and fired at 900–1100 °C. Finally, the variations in samples’ properties were ana-
lyzed at different temperatures.3 The results showed that the samples with 30 wt% perlite and
7 wt% phosphoric acid in firing temperature of 900–1000 °C reached to desirable properties
including compressive strength of about 30–35 kgf/cm2, bulk density of 0.42–0.45 g/cm3 and
applied temperature of around 1100 °C.

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Fig. 1. Variations of physical and mechanical properties of fabricated samples with different perlite contents

References
1. L. Aditya, T.M.I Mahlia, B. Rismanchi, H.M. Ng, M.H. Hasan, H.S.C. Metselaar, O. Muraza and
H.B. Aditiya, “A review on insulation materials for energy conservation in buildings”, Renew.
­Sustainable Energy Rev., 73, pp. 1352–1365, 2017.
2. S. Celik, R. Family and M.P. Menguc, “Analysis of perlite and pumice based building insulation
materials”, J. Build. Eng., 6, pp. 105–111, 2016.
3. O. Gencel, “Characteristtics of fired clay bricks with pumice additive”, Energy Build., 102, pp.
217–224, 2015.

562
Study on magnesium silicate hydrates (M-S-H phase)
Ryszard Prorok, Edyta Śnieżek, Jacek Szczerba
AGH University of Science and Technology, Faculty of Material Science and Ceramics,
Department of Ceramics and Refractories, al. A. Mickiewicza 30, 30-059 Krakow, Poland
Keywords: refractories, MSH phase, unshaped refractory materials

The magnesium silicate hydrates (M-S-H phase) has a potential wide application in refrac-
tory basic castables, as cement free bonding system. This is connected with its high bonding
strength, ability to control hydration process of magnesium oxide and advantageous phase
composition after heat treatment. The aim of this study was to investigate evolution of the
M-S-H phase and its structure with the time.

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The study pastes were composed of two kinds of raw materials: industrial oxides (sintered
magnesia and microsilica) and chemically pure oxides (magnesium oxide and nanosilica)
with water, in water to solid ratio equal 0.5. The obtained mixtures after preparation, has been
ageing at 20 ˚C.
The samples of pastes were studied and analyzed by DTA-TGA-EGA, XRD, FTIR and
NMR analysis. Performed analysis revealed that result of reaction in mixture of MgO, SiO2
and water was a poorly crystalline product nearing to layer magnesium silicates embedded
in more amorphous matrix.

Acknowledgement
This work was partially supported by the statutory funds of the Faculty of Material Science and Ceram-
ics no. 11.11.160.617.

561
Influence of secondary components with perovskites and spinel type
structure on corrosion resistance of magnesia based materials
Edyta Śnieżek*, Ryszard Prorok, Jacek Szczerba
AGH University of Science and Technology, Faculty of Materials Science and Ceramics,
Department of Ceramics and Refractories, al. A. Mickiewicza 30, 30-059 Krakow, Poland;
*
e-mail: [email protected]
Keywords: refractories, corrosion, magnesia, spinel, calcium zirconate

The highest thermal expansion coefficient of MgO among all the refractory materials, low
resistance to sudden temperature variations and high elasticity modulus are the main disad-
vantages of MgO. Therefore, it is necessary to introduction the second or more components
in order to overcome these disadvantages. However, the number of components is limited
because it is often connected with a low melting eutectics. For magnesia and other basic
refractory materials, very interesting is the CaO-MgO-Al2O3-ZrO2 tetrahedron system. It is
composed of four high refractory simple oxides, which are characterized by high melting
points exceeding 2000 °C. The potential phase compositions can be refractories from the
MgO-CaZrO3/MgO-MgAl2O4/MgO-CaZrO3-MgAl2O4 systems.
The work presents the recognizing of the new phases formation as a result of the chemical
corrosion between phases from this kind of the basic refractories and calcium silicates, cal-
cium aluminates and ferrites. The XRD analysis was used to determine the phase composi-
tion. On the basis of SEM observations accompanied by the EDS chemical analysis in micro
areas, changes in the microstructure was discussed. The results were discussed taking into
account phase diagrams and the activity of corrosion agents. The activity of the corrosion
agent – “liquidus curve slop coefficient” can be calculated as the ratio between the difference
between the melting temperature of the basic oxide and the eutectic temperature and percent-
age share of corrosion agents in the eutectic melt.

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The invariation points in the subsystem MgO-CaZrO3-C2S-C3S reaching temperatures of

1750 and 1760 °C. The presence of Al2O3 and Fe2O3 causes a considerable decrease of the
temperature of liquid phase formation. The deep of liquid phase penetration into materials
can be controlled by MgAl2O4:CaZrO3:MgO ratio. Replacing part of MgAl2O4 by CaZrO3
improves significant corrosion resistance.

Acknowledgement
The work was partially supported by the statutory funds no 11.11.160.617 of the Faculty of Materials
Science and Ceramics — AGH University of Science and Technology in Cracow, Poland.

494
Structure and microstructure evolution of hercynite (FeAl2O4)
substituted by Ni2+ ions
Jacek Szczerba, Ilona Jastrzębska
AGH University of Science and Technology Faculty of Materials Science and Ceramics Department
of Ceramics and Refractories al. A. Mickiewicza 30 30-059 Krakow, Poland

Hercynite represents 2-3 type spinel group with a normal cation arrangement of general
chemical formula (A)[B]2O4, where () and [] indicate tetrahedral and octahedral coordination
of appropriate atoms, respectively.
In this work a series of spinel compounds from hercynite FeAl2O4to nickel aluminate were
obtained by the Arc Plasma Synthesis (APS). Spinel materials were synthesized in an arc plas-
ma furnace SpekoArc300 in an inert Ar atmosphere from analytically pure oxide powders.
The following stoichiometric compositions were prepared: Fe1-xNixAl2O4(x=0;0.3;0.5;0.7
and 0.9) by a tetrahedral substitution of Fe by Ni.
The obtained spinel materials were characterized in view of their phase identification by
the powder X-Ray diffraction method (pXRD). pXRD patterns were numerically analyzed
in order to determine structural parameters of spinel compounds: lattice parameter and oxy-
gen positional parameter. Mössbauer effect in the spinel materials was measured at room
temperature to determine a local coordination of Fe, oxidation state of ferrous/ferric ions
and a relative Fe content in the materials. Finally, microstructure changes of hercynite were
observed with the increased content of Ni2+ ions by the SEM-EDS technique.
Nickel ions were found to positively influence hercynite synthesis by creation of solid
solution with FeAl2O4, causing a gradual decrease in Fe3+ content with the increased Ni2+
amount.

Acknowledgement
The research was performed at Faculty of Materials Science and Ceramics of AGH within the confines
of the project no 11.11.160.617.

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717
Setting behavior of unshaped refractory materials
Jan Urbánek
Department of Glass and Ceramics, University of Chemistry and Technology, Prague,
Czech Republic; e-mail: [email protected]

Refractory unshaped materials represent a mixture of aggregate and bonding agent (or agents).
They are used to produce monolithic refractory linings, preformed shapes, repair mixes,
mortars and mastics.1 Bonding agents are usually formed by hydraulic or chemical bond.
­Hydraulic binders solidify and harden at normal condition during about 24 hours. Setting
time can be shortened or extended by using set accelerators or set retarders. Water elimina-
tion at relatively small temperature interval during its heating to working temperature is big
disadvantage of hydraulic binders. The mentioned deficit might be critical for application
of repair mixes, which are required to have a short setting time and short time to heating on
working temperature. On the other hand, chemical binders eliminate water at larger tempera-
ture interval during heating material. So, heating can be performed with higher speed. It is
necessary to optimize a composition of a refractory mixture to assure required setting time,
which is determined by an application.
The aim of this work was to determine an influence of composition of two refractory
mixtures with chemical bond on their workability, fluidity and primarily on setting time.
Refractory castable with chemical phosphoric bond was chosen to study setting rate. Alumi-
nosilicate, mullitic materials were chosen as an aggregate. Mixture of reactive γ-Al2O3 with
phosphoric acid, which was hardened by magnesium oxide, was chosen as a bonding agent.
A rotational rheometer was adjusted (including measurement methodology) for measurement
of setting time and rheological properties of mixtures. Measurements were made using the
arrangement of vane rotor-infinite medium at rotational and oscillatory regime. Influence of
a hardener and other factors, as for example amount and concentration of phosphoric acid,
particle size, amount of binder and aggregates, addition of flow agents and temperature on
rheological properties of mixture, setting rate and properties after hardening were studied.
Second studied, unshaped material consisted of aggregates from aluminosilicate, mullitic
materials again and mixture of aluminate cement with phosphoric acid was used as a binder
component. Because of application of mentioned material was for purpose of repair mixes,
the sticky compact consistency of the material (binder, cement, putty) had to be assured.
Influence of amount and concentration of phosphoric acid, particle size, amount of binder
and aggregates, addition of flow agents, temperature on rheological properties of refractory
mixture, setting time and properties after hardening was studied. A certain part of calcium
ions was changed by ions of calcium salts, due to requirement of adhesiveness of mixture.
Strength of joint was determined by a three-point bending test after solidification and harden-
ing.

Reference
1. František Tomšů, Štefan Palčo, Žárovzdorné materiály Díl IV., Praha, 2009.

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322
Perspectives of topaz rocks in the technology of aluminosilicate
ceramics and refractories
Tatiana Vakalova*, Valery Pogrebenkov, Ksenia Kamyshnaya
Department of technology silicates and nanomaterials, Tomsk Polytechnic University, Tomsk,
30 Lenina st, Russia; e-mail: [email protected]
Keywords: topaz, mullite, fluoride, mineralizer, synthesis, crystallization

The total content of mullite and its structural and morphological condition (prismatic or nee-
dle-shaped particles) are important for the regulation of technical and operational properties
of aluminosilica refractory ceramic. At present there are a variety of techniques to increase
the yield of mullite and methods for controlling the habitus and crystal state of its particles.
One of them is the use of activating addition. The perspectives of topaz application for this
purpose are determined by the nature of its thermal decomposition products: acicular mullite
formation and release of volatile fluoride compounds known as active mineralizers in silicate
system.1 Needle and a fibrous habit of mullite from topaz determine its relevance to the com-
posite ceramic materials due to reinforcing role of crystalline intergrowth.
Applied to the high-alumina refractories it was established that character of topaz addition
action is determined by their quantity in the composition of aluminosilicate refractory mass.
Topaz in small quantities (up to 0.5–1.0%) acts as a mineralizing additive which intensi-
fies the process of formation of mullite prismatic habit. With the increase in the content of
more than 2% topaz along with the mineralizing action serves as a crystal-forming additives.
In this case it provides the nucleation of prismatic mullite (at 2–14% topaz) or synthesis of
acicular and fiber mullite (if ceramic mass contain more than 14% of topaz).
Mineralizing effect of topaz additives in the clay is reduced to a complex promotional
effect of gaseous fluoride released during dissociation topaz. They activate the process of
mullite formation both by increasing the defectiveness of intermediate products and by acting
on the rheological and reaction properties of silicate melt.
In the mixtures of mullite composition from a pure oxides mineralizing effect of small ad-
ditions topaz is reduced to activate the synthesis the mullite of elongated prismatic forms due
to the complex influence of products thermal decomposition of topaz - mullite and gaseous
fluoride. The chemically active fluorides increase the defectiveness of the crystal lattice of re-
acting substances and create favorable conditions for their high temperature interaction. The
action mullite from topaz is reduced to function of center crystallization during solid-phase
synthesis a mullite from oxides. The introduction of topaz additives in quantities of 1–3% in
a stoichiometric mixture for the synthesis of mullite reduces firing temperature (at 50–100
°C), improved mechanical strength (at 30–50%), electrical properties (enhancing dielectric
strength 1.3–2 times, reduced dielectric losses at 15–30%) and other ceramic materials.

Reference
1. T.V. Vakalova, V.M. Pogrebenkov, O.A. Chernousova. “Structure-phase transitions upon firing of
new ceramic feedstock, topaz-containing rocks”, Steklo i Keramika, 6, pp. 24–27, 2002.

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467
Sialon-based refractory materials prepared from the aluminium
oxynitride SHS-derived powders
Alan Wilmański, Mirosław M. Bućko*
AGH University of Science and Technology, Faculty of the Materials Science and Ceramics, al.
Mickiewicza 30, 30-059 Krakow, Poland; *e-mail: [email protected]

Sialons which are a specific solid solutions in the Al2O3-Si3N4 system are widely applied as
refractory materials due to their good mechanical properties, high thermal shock resistance,
and corrosion resistance, especially against molten metals. Dense sialon materials are ob-
tained by pressureless sintering or by HP, HIP and SPS techniques. The starting materials for
sintering are previously synthesized monophased powders or mixtures of respective oxides
and nitrides usually silicon nitride and corundum. Reaction sintering can be performed also
using aluminium nitride, silicon oxide and metallic aluminium and silicon powders. Such
process is performed in nitrogen atmosphere. In the present work SHS-derived aluminium
oxynitride with spinel structure, γ-alon, powder was used as a precursor of sialon-based ma-
terials. The γ-alon powder was mixed with different amount of silicon nitride powder and 1
mas% of yttrium oxide then compacted samples were pressureless sintered at 1750 °C for
2 h in argon. It was stated that the samples with small amount of silicon nitride in the start-
ing powder mixture were composed of corundum and Si2Al4O4N4 β-sialon. An increase of
silicon nitride content led to materials composed of the same sialon as a major phase with
small amount of Si3Al6O12N2 X-sialon. Another β-sialon, Si4Al2O2N6, was the main phase in
the samples with the highest amount of silicon nitride and the same X-sialon was the comple-
mentary phase. Mechanical properties of the sintered materials as well as resistance to liquid
aluminum based alloys reveal strong correlations with their phase compositions. The com-
posites containing corundum show highest hardness, strength and fracture toughness while
the best performance in the liquid metals the sialon-sialon composites.

Acknowledgements
The present work was supported by the AGH University of Science and Technology, Faculty of Ma-
terials Science and Ceramics under the grant no. 11.11.160.617. Support was also given by the Polish
Ceramic Society.

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293
A study on the microstructural analysis of slag corroded MgO based
self-flowing castable refractories
Azade Yelten1, Ferhat Tocan2, Suat Yilmaz1
Department of Metallurgical and Materials Engineering, Istanbul University, 34320 Avcilar, Istanbul,
1

Turkey; e-mail: [email protected]

PiroMET Refractory Plant, Çerkeşli OSB Mah. İMES 2.Cad. No.3 41455 Dilovasi, Kocaeli, Turkey;
2

e-mail: [email protected]
Keywords: MgO based castable refractories, Slag-refractory corrosion, microstructural analysis

MgO brick refractories are extensively used in basic steel production processes. However,
hydration of MgO when mixed with water constitutes a problem. This study focuses on the
composition of an MgO-based castable refractory composed of 94% wt. of MgO, 2% wt. of
SiC and 6% wt. binder and dispersant. Self-flow test was applied to the prepared MgO based
castable mass according to ASTM C 860 standard. After sufficient spread was achieved, the
mass was shaped by casting into suitable moulds with 50×50×50 dimensions. Castable re-
fractory samples were sintered by firing for 2 h at 1600 °C. Cold crushing strength test was
performed on the sintered samples in accordance with the DIN 51067 (ISO ENV 1402-6)
standard. Also, water absorption, apparent porosity and bulk density tests were carried out
depending on the DIN 51056 and DIN 51065 (ISO EN 993-1) norms. Before starting the
slag-refractory corrosion test which was done with respect to the DIN 51069 (pot method)
standard, ground slag powder (<100 µm) was charged to the bottom of the pots. Slag-refrac-
tory corrosion test was conducted by heating the pots to 1600 °C with 10 °C/min heating
rate and keeping at this temperature for 2 h. Castable refractory samples interacting with the
slag were axially cut by using the diamond cutting tool and hence the slag penetration area
was calculated. X-Ray Diffraction (XRD) and Scanning Electron Microscope-Energy Dis-
persive Spectroscopy (SEM-EDS) studies were realized on the samples taken from the not-
interacting and slag-interacting regions. In this way, the microstructure of the corrosion that
occurred starting from the refractory contacting slag surfaces to the points where penetration
proceeded is investigated.

References
1. W. Lee, E. Moore, E. Robert, “Evolution of In Situ Refractories in the 20th Century”, J. Am. Ceram.
Soc., 81(6), pp. 1385–1410, 1998.
2. E.Y. Sako, M.A.L. Braulio, V.C. Pandolfelli, “Microstructural Evolution of Magnesia-Based Casta-
bles Containing Microsilica”, Ceram. Int., 38(7), pp. 6027–6033, 2012.
3. R. Salomão and V.C. Pandolfelli, “The Role of Hydraulic Binders on Magnesia Containing Re-
fractory Castables: Calcium Aluminate Cement and Hydratable Alumina”, Ceram. Int., 35(8), pp.
3117–3124, 2009.
4. S. Yilmaz, “Corrosion of High Alumina Spinel Castables by Steel Ladle Slag”, Ironmak. Steelmak.,
33(2), pp. 151–156, 2006.

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364
Investigation of pyroplastic behaviour of porcelain bodies with different
mineralogical contents
Yıldız Yıldırım*, Cigdem Yigit Pala
Kaleseramik R&D Center, Canakkale, Turkey; *e-mail: [email protected]
Keywords: porcelain body, pyroplastic deformation

Since the 1980s, the neogene basin of Şile has become a very important region to meet the
clay reserve of Turkey as the demand for raw materials especially in the ceramic ware indus-
try. The total reserve for ceramic clays in the region is more than 200 million tons and, it is
considered to be the heart of Turkey in respect of the quality and reserves. In the district Şile,
approximately 2.5 million of clays are provided to the industry per year. Ukrainian clay was
used as a reference clay. Firstly, Istanbul region clays and Ukrainian Clay were characterized
chemically and physically by X-ray diffraction, X-Ray Fluorescence, Fourier IR Spectros-
copy and SEM. Istanbul region clays contain kaolinite, illite, chlorite and montmorillonite
and accessory phases (anatase, goethite, siderite). Technogical properties and pyroplastic
deformation of Ukrainian Clay and Istanbul Region Clays was investigated by using 50%
clay, 40% feldspar and 10% quartz glaze porcelain body. Than effect of mineralogical con-
tent of clays to pyroplastic deformation and technological properties of bodies were investi-
gated. It was concluded high amount of illite and montmorillonite content reduced the water
absorption because of the lowering of the melting point. However, pyroplastic deformation
of the bodies was reduced by adding clay which include high amount illite where increasing
amount of montmorillonite affected adversely.

References
1. S. Ferrari, A.F. Gualtieri. Applied Clay Science 32 (2006) 73–81.
2. Michele Dondi, Mariarosa Raimondo, Chiara Zanelli. Applied Clay Science 96 (2014) 91–109.
3. Lisandra R. dos Santos Conserva, Fábio G. Melchiades, Suelen Nastria, Anselmo O. Boschi,
Michele Dondi, Guia Guarini, Mariarosa Raimondo, Chiara Zanelli. Journal of the European Ce-
ramic Society (2016), Article in Press.

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T12: Art and ceramics
Invited lectures

929
Self-portrait of a ceramic artist who combines Asia’s East and West
Mutlu Başkaya
Turkish Ceramic Society, Istanbul, Turkey; e-mail: [email protected]

As a Turkish ceramics artist, I will describe the contemporary artistic viewpoint by exempli-
fying works I produce in this context. I will also talk about the curatorial duty I have under-
taken in the establishment of the Turkish Museum within the Fule International Ceramic Art
Museum (FLICAM) in the Shannxi Fupping Ceramic Art Village in China. This work united
the most eastern and western part of Asia. Besides, I also took the curatorship of Ukrainian
and Croatian museums.

840
Social criticism in Turkish contemporary ceramic art
Fatma Batukan Belge
Turkish Ceramic Society, Fatih Sultan Mehmet Vakif University Faculty of Fine Arts, Istanbul,
Turkey; e-mail: [email protected]
Keywords: criticism, conceptual art, contemporary art, Turkish ceramic art

As in all works of art, the content of the work is important also in ceramics. The motivation
of each artist is different. Some act with internal motivations, others are sensitive to social
events. Today’s ceramic artists produce very strong works and make social criticism in the
name of contemporary art. In addition to global issues such as identity, subculture, gender,
human rights, ecology they address topics that reflect the political atmosphere of the country,
such as Gezi Resistance, cultural corruption, the values of the Republic, freedom of expres-
sion. The artist turns to witness of time and installs the events in social memory.

References
1. Aydınlık newspapers, Fatma Batukan Belge.
2. BERİL ANILANMERT / Daha Çok ATEŞ / More Fire, Çanakkale Seramik Publication.
3. The Blue Art / Zehra Çobanlı Ceramics, 2005.
4. Çağdaş Türk Seramiği’nde Güngör Güner’in Yeri, 2008, Fatma Batukan Belge.
5. http://www.yadawei.net/single-post/2016/09/27/Conceptual-Ceramics-or-Functional-Pottery
6. http://ceramicartsdaily.org, September 12, 2011.

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093
Franz Collection
Franz Chen
Franz Collection, Inc., Taipei, Taiwan; e-mail: [email protected]

Franz Chen started his porcelain art brand, Franz Collection, in 2001. Chen’s mission is
to revive the heritage of Chinese porcelain and create eternal value for civilizations. Franz
Collection has made breakthroughs in terms of porcelain form, color, and texture. These
achievements are a result of combining 3D sculpting technology with traditional handicraft
methods, as well as the brand’s own unique glaze formula and patented “undercut demold-
ing technique”. The combination of technology, culture, and art enables Franz Collection to
create artworks that deliver the values of truth, goodness, and beauty and touch the hearts of
consumers worldwide.
Since its inception, Franz Porcelain has been honored with many international awards
such as “The Best in Show Gift Award” and “Fashion Accessory Line of the Year” in the
USA and “Best Ceramic Gift” in England. Additionally, FRANZ was awarded the “Seal of
Excellence for Handicrafts” from the United Nations Educational, Scientific and Cultural
Organization seven years in a row.
Franz Chen was personally awarded:
Presidential Innovation Award in Taiwan, 2014
25 Influential Chinese in Global Fashion – Forbes China, 2012
Entrepreneur of the Year 2012 Taiwan – Ernst & Young, 2012
Outstanding Porcelain Entrepreneur Award – Chinese Association of Ceramics, 2007
Creative Culture Best Contribution Award in China, 2007

237
Contemporary ceramic art and traditional pottery techniques –
where is the point?
Biljana Djordjević
National Museum in Belgrade, Trg Republike 1A, Belgrade, Serbia;
e-mail: [email protected]
Keywords: ceramics, ceramic art, traditional pottery techniques, cultural heritage

In recent years, ceramics has regained its importance. This fact is obvious in everyday life.
The ecological component of ceramics makes it a desirable material in the struggle against
global pollution. This fact is obvious in the worlds of science and art as well. As a phenom-
enon, ceramics provides artists with multiple opportunities, relying on experimentation and
new technologies. Successful results can be seen in the context of the two modules of the
project entitled Ceramics and its Dimensions – “Shaping the Future” and “Future Lights in

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 T12: Art and ceramics – Invited lectures

Ceramics”. Nevertheless, the traditional techniques and technological approaches are still at-
tractive for contemporary artists. How does traditional pottery making enrich contemporary
art ceramics? What are the achievements of the synergy of the traditional ceramic technology
and artistic aspirations? What is the role of contemporary ceramics in cultural heritage pro-
tection? These are the questions that this paper will attempt to give answers to.

401
Future lights – addressing the upcoming generation of ceramics
and design
Rhiannon Ewing-James1, Maria Joanna Juchnowska2, Monika Müller3
1
Artist/Designer, Creative Producer, The British Ceramics Biennial,
e-mail: [email protected]
2
Artist/Designer, Mari JJ Design by Maria Joanna Juchnowska, e-mail: [email protected]
3
Artist/Designer, e-mail: [email protected]
Keywords: future lights, future ceramics, new designs, ceramics and its dimensions, emerging de-
signers

The Future Lights competition has been designed for young and emerging talents in ceramics
who need an appropriate platform to further their career. This competition has the intention of
helping to shape and encourage the upcoming generation of ceramics and design by instilling
the responsibility of progress and growth in those emerging professionals.
The Future Lights 2017 award winners will be used as a case study to illustrate the signifi-
cant effects of the Future Lights competition. Further exploring how the platform opportunity
is necessary in building a strong, collaborative and dynamic future which furthers the appre-
ciation of innovation with the ceramic material in European contemporary life.

933
Craftsmanship alone is not enough
Antony Quinn
Dept of Ceramic Design, Central Saint Martins, London, UK; e-mail: [email protected]

A diverse and profoundly transformable material, clay offers new designers and artists the
possibility to push beyond the accepted ceramic applications into conceptually challenging
contexts and outcomes.
This paper seeks to explore how contemporary artists, designers and crafts people exploit
the materials traditional archetypes and production processes to comment, challenge or trans-
form our understanding of what clay can do.

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T12: Art and ceramics – Invited lectures

Drawing comparisons across a range of practices the paper will address the following
questions; How does technological formation of clay explore craftsmanship and production
values? When placed in a public context does clay allow for transformative engagement? Can
we examine production values and systems through production? Does the handing down of
skill from maker to maker offer opportunity for innovation? Does clays ubiquity offer trans-
gressive, provocative opportunities?
These questions act as thresholds to a discussion about the modern context for Ceramics
from education to practice and present us with the opportunity to interrogate a range of de-
signers and makers, their work and attitudes through this lense.

707
A portrait of the ceramicist as a young man:
a reconsideration of a new way of promoting ceramics education,
with a roadmap for developing a centre of excellence in ceramics
John T. Tynan
Design & Crafts Council of Ireland, Crusheen, Ireland; e-mail: [email protected]

A reconsideration of a new way of promoting ceramics education, with a roadmap for devel-
oping a Centre of Excellence in Ceramics.
This presentation explores the differing and often conflicting needs between young future
makers, ceramic craft and design educationalists, bureaucratic government agencies and the
specific needs of those economically active in the craft and design industry.
As the spirit of the young artist is enthused with an enthusiastic ‘fire in the belly’ to learn
flourish and stamp their own identity upon a brave new world of adulthood, the ceramic
educationalist is charged with the tricky dual role of inspiring this love of the art whilst at the
same time being mindful of what might be usefully needed to survive and thrive in the future
craft and design industry into 2020 and beyond.
The presentation will include a case study of how a new emerging ‘Centre of Excellence
(C of E) in Ceramics’ is being developed at Thomastown in Ireland and about how in creating
this new C of E the journey to re-package tried and tested traditional ways of pottery teaching
can help influence the future making of a vibrant thriving ceramics industry.

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Oral presentations

089
Influence of chamotte addition on the physical and mechanical
properties of red mud bodies
Nermin Demirkol1, Ebru Tir2, Emine Keskin1
Ceramic,Glass&Tile Prog., Vocational School of Degirmendere Ali Ozbay, Kocaeli University,
1

Kocaeli, Turkey
Ceramic&Glass Dept., Fine Art Faculty, Marmara University, Istanbul, Turkey;
2

e-mails: [email protected], [email protected], [email protected]

Keywords: chamotte, red mud, mechanical properties, physical properties, slip casting

Red mud is a highly alkaline waste product composed mainly of iron oxide that is generated
in the industrial production of aluminum. Used red mud contains 30–35 weight % iron oxide
(Fe2O3). Mechanical properties and density of red mud bodies are lower than chamotte bod-
ies. For increasing these properties 5, 10, 15 and 20 wt% chamottes were added to red mud
bodies produced by 40 wt% solid content slip seperately. Slip casted samples were sintered
at 900 and 950 °C.
Physical and mechanical properties were determined by measuring density, firing shrink-
age, water absorption, bending strength and Vicker microhardness (HV). Structural char-
acterization was done X-Ray diffraction method (XRD). The best physical and mechanical
properties were obtained with the red mud samples containing 15 wt% chamottes and sin-
tered at 950 °C. On the other hands, slip casted red mud samples containing 20 wt% cham-
ottes didn’t depart from the plaster mold.

134
Archaeometry studies of Portuguese ceramics (pottery and tiles)
produced in the region of Lisbon – 16th to 17th c.
I. Ferreira Machado1,2*, L.F. Vieira Ferreira1
1
CQFM- Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology,
Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal;
*
e-mail: [email protected]
2
Polytechnic Institute of Portalegre, P-7300-110 Portalegre, Portugal
Keywords: ceramic pastes, Lisbon ceramic productions, XRF

Portuguese tin-glazed earthenware production is usually associated to 16th c. contexts, al-

though findings of tin glaze ware exist from Mata da Machada kiln (1489 to 1530) and for
tin glaze tiles from Santo António da Charneca (SAC) kiln, both located in the south shore of
Tagus river, about 20 km away from Lisbon1. Moreover, cobalt blue sherds from 12th–13th c.

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T12: Art and ceramics – Oral presentations

recovered at Silves Castle (South of Portugal) archaeological excavations2, revealed a paste

with a composition typical of clays of Miocene origin, like the ones used in Lisbon pottery
productions, suggesting that Lisbon workshops were already producing tin-glazed pottery, at
that time. This is an example, among many others, of the importance of ceramic pastes char-
acterization on attempt to establish the provenance of the ancient pottery.

Fig. 1. Scatterplot of K/Si versus Ca/Si count ratios for the ceramic pastes
of 16th-17th c. Lisbon pottery and tiles

Scatterplots of K/Si versus Ca/Si count ratios allow us to identify quite distinct groups
when characterizing composition of pottery pastes, with almost no calcium in the ceramics of
Mata da Machada and SAC kilns, while the production of Lisbon workshops exhibit a large
range of calcium content. As far as our studies revealed, this pattern is typical of Lisbon pro-
ductions. However, when we introduce the tiles (Fig. 1) it is clear that the amount of calcium
presents a huge increase, indicating the use of distinct clays, with higher calcium content, and
lower temperatures of firing the pastes, or an intentional addition of calcium compounds in
these productions.
In this work, we present a study of representative sherds of tin-glazed productions of the
Lisbon region, dated from the 16th–17th centuries, using X-ray fluorescence emission (XRF),
micro-Raman and X-ray diffraction (XRD). Special focus is done on pastes composition of
pottery and tiles, as well as possible clays used by potters working in this region.

References
1. L.F. Vieira Ferreira, D.S. Conceição, D.P. Ferreira L.F. Santos, T.M. Casimiro, I. Ferreira Machado,
“Portuguese 16th century tiles from Santo António da Charneca’s kiln: a spectroscopic characteriza-
tion of pigments, glazes and pastes”, J Raman Spectroscopy 45, 838–847, 2014.
2. L.F. Vieira Ferreira, R. Varela Gomes, M.F.C. Pereira, L.F. Santos, I. Ferreira Machado, “Islamic
ceramics in Portugal found at Silves Castle (8th to 13th c.): An archaeometric characterization”,
Journal of Archaeological Science: Reports 8, 434–443, 2016.

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100
Usage of sugar beet pulp ash in stoneware body as a raw material in
ceramic art
Pınar Güzelgün
Sakarya University, Sakarya, Turkey; e-mail: [email protected]

Existing for ages as a utility or an artistic object, use of ceramic materials have expanded to
vast number of areas varying from domestic use to medicine and to space technology.
Besides studies for diversification of raw materials used in ceramic body, research and
development studies in ceramics also includes exploration of new inorganic and organic
materials to be used as aggregates.
Providing a chance of reuse to industrial waste materials, quantities of which are increas-
ing in a tremendous speed, have an importance not only for being an success indicator of
the energy saving policy of a country, also for offering a higher utilization of resources and
lastly, for economic reasons. In this study; potential of using sugar beet pulp as an ingredient
in ceramic body is investigated and chemical analysis of sugar beet pulp, which is a waste
product of “Konya Refinery of Sugar” manufacturing
In 21st century, where urge of consumption in modern societies surpasses the power of
production, it is aimed to provide economic and ecologic outcomes with revaluation of sugar
beet pulp as a raw material for ceramics in ceramic industry and ceramic art. Such reuse, as
a result, saves an amount of natural resources which we are running out steadily, provides
a protection for suffering environment and also becomes a new kind of raw material for ce-
ramic artists for searching new possibilities in ceramic body.

246
The color effect of magnetite and chromite in ceramic stoneware glazes
Selvin Yeşilay1*, Fikret Aydoğdu2, Münevver Çakı3
1
Anadolu University, Faculty of Fine Arts, Department of Glass, Eskişehir, Turkey;
*
e-mail: [email protected]
2
Dumlupınar University, Kütahya Vocational School of Technical Sciences, Kütahya, Turkey
3
Anadolu University, Faculty of Fine Arts, Department of Ceramic Arts, Eskişehir, Turkey
Keywords: ceramic pigments, hematite, chromite, stoneware glaze, colorants

Ceramic colorants are added to a glaze or a clay to create colour. In ceramic glazes the
colour is obtained by the dispersion of pigments and opacifiers. These colorants can create
a multitude of colours depending on other materials they interact with. On several factors,
the colouring effects of the pigments and stains depend. These factors are: nature of the raw
materials, the firing temperature, time and kiln atmosphere.

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The colouring metal oxides need to be subjected to various processes in order to meet
stable and standard characteristics and to be ready for industrial use. And this is the ce-
ramic stain manufacturing industry. Many different techniques and technology can be used
in industrial dye production. The current market price of black paint, which is an industrial
ceramic colorant, is relatively expensive.
In this study, magnetite and chromite ores were used to reduce the cost of black pigment
production. These two ores, which have very low loss on ignition, have produced very effec-
tive results in the production of black pigment. Produced pigments are used in the coloring of
stoneware ceramic glazes after calcination, recipe preparation and micronization. The colour
and texture effect of the black dye on the ceramic glazes were investigated. The cost of dye
produced from magnetite and chromite is considerably reduced compared to other pigments
in the market.

References
1. M. Schabbacha et.al., “Colour in ceramic glazes: Efficiency of the Kubelka–Munk model in glazes
with a black pigment and opacifier”, Journal of the European Ceramic Society, Volume 29, Issue
13, pp. 2685–2690, 2009.
2. C. Barry Carter, M. Grant Norton, “Ceramic Materials: Science and Engineering”, Springer Sci-
ence & Business Media, 716, 2007.
3. David Harris Cohen, Catherine Hess, Looking at European Ceramics: A Guide to Technical Terms,
Getty Publications, 91, 1993.
4. B. Eftekhari Yektaa, et. al., “ Synthesis of glass-ceramic glazes in the ZnO–Al2O3–SiO2–ZrO2
system, Journal of the European Ceramic Society, Volume 27, Issue 5, 2007, Pages 2311–2315.

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Poster presentations

404
Museums as centers of diffusion of creativity, design and technique
Jaume Coll Conesa
Museo Nacional de Cerámica “González Martí”, Valencia, Spain

As institutions related to Heritage and creativity, museums can play an important role both
in preserving the legacy of the past and in projecting it to the future, as well as showing new
proposals and technological developments to society. The museum enjoys a privileged posi-
tion to serve as a platform for dissemination in initiatives such as “Future Lights”, promoted
by the European project “Ceramics and its dimensions”. The National Ceramic Museum
“González Martí” in Valencia (Spain), has gained a long experience in this field through the
connection between artists, entrepreneurs, training centers and specialists. The objective of
our communication will be to present these experiences drawing general conclusions that
can be useful for the development of the project while exposing the current situation in our
social environment.

245
The composition design of artistic aventurine glazes containing
hematite ore
Keriman Pekkan1, Eda Taşçı2, Münevver Çakı3
Dumlupınar University, Faculty of Fine Arts, Department of Ceramic and Glass, Kütahya Turkey;
1

e-mail: [email protected]
Dumlupınar University, Department of Material Sciences and Engineering, Kütahya Turkey;
2

e-mail: [email protected]
Anadolu University, Faculty of Fine Arts, Department of Ceramic Arts, Eskişehir, Turkey;
3

e-mail: [email protected]
Keywords: aveturine effect, hematite, artistic glaze

Aventurine glaze is a special type of an artistic glaze in which the separation of isolated indi-
vidual crystals shimmering on the glaze surface. Crystals has the characteristic appearance of
flitters, sheets or spangles suspended in a glassy phase. These types of glazes possess a high
decorative and artistic value. Therefore, evaluating them on the ceramic bodies enhances
the esthetical appearance and makes the final product unique. Generally aventurine effect is
obtained by using high amounts of Fe2O3 in the chemical glaze composition. In this study,
aventurine glazes are developed by contributing hematite ore raw material into the glaze for-
mulation instead of directly using Fe2O3. Newly studied glazes are wet milled in a porcelain
jar for 20 min and then glaze slips were applied onto both pre-fired ceramic substrates and
wall tile bodies. Firings were conducted firstly at laboratory conditions at 900-1000-1050-

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1150 οC in an oxidizing atmosphere and after that industrial fast firings were conducted at a
peak temperature of 1150 οC at Altın Çini and Seramik Co. Inc. A possible aventurine effect
was proposed to show the variation of glaze colour patterns with the increasing of firing tem-
perature. All of the glaze surfaces were smooth and glossy after laboratory firings. Moreover,
dark brown colour with yellowish transition effect on the glaze surface was obtained under
industrial fast firings. L*a*b values were measured by a spectrophotometer. Final surfaces
of the aventurine glazes were characterized by a X-ray difractometer (XRD). Glaze samples
were visualized by scanning electron microscopy (SEM) and energy dispersive x-ray (EDX)
techniques.

References
1. Pekkan K., Taşçı E. ve Gün, Y. “Development of Low Temperature Temmoku Glazes and Their
Industrial Applications” 5th Mediterranean Clay Meeting, p. 91, 25–29 September, Çeşme, İzmir,
Turkey, 2016.
2. Jianfeng Zhu, Pei Shi, Fen Wang, Ting Zhao, Hao Jiang, “ Preparation of separative-phase fancy
glaze derived from iron ore slag” Ceramic International, Vol. 42, Issue 4, March 2016, P. 5250–
5257.

591
Transform from industrial ceramic product to artistic form
İstem Şencan Tosun
Qua Granıte Organize sanayi Bölgesi AYDIN/ Söke/ Turkey; e-mail: [email protected]
Keywords: industrial ceramic, raw waste, ceramic art, sculpture, imitation granite

Natural granites can be quite estethic materials for making sculptor. Not only natural granite
materials but also imitation granite tiles can be quite estethic materials. From this viewpoint,
in this study’s aimed to create art objects using wastes of raw ceramic tiles which are imi-
tated from natural granites. Industrial raw ceramic tile wastes are provided by Oua Granite
Ceramic Factory. Raw wastes collect from dimentions is 60 × 60 × 2 cm which bodies co-
lourized with different colours. Forementioned raw tiles are formed as sculptures by hand.
Formed some of the sculpture pieces fired in Qua Granite manufacturing roller kiln and other
the sculpture pieces fired in laboratory chamber kiln. Forms finished by, combined with fired
sculptor pieces and using different sort of material (like glass, metal and wood, etc.)

References
1. Tosun, Ozgur. İlkel benliğin Yakın Dönem Sanatında Bıraktığı İzlere Bir Örnek: Basquiat İdil e-
dergi volume 4, issue 17 (2015) from http://www.idildergisi.com/makale/pdf/1422869249.pdf
2. Sürmeli, Kader. Dada Hareketinden Kavramsal Sanata İnönü Ünivesity Journal of Art and Des-
ing ISSN: 1309-9876 Vol:2 / No:6 (2012) from http://dergipark.ulakbim.gov.tr/inustd/article/view-
File/1027000060/1027000059
3. Şahin, Hikmet. Posmodern Sanat İdil e-dergi, volume 1, issue 5 (2012) from http://www.idildergisi.
com/makale/pdf/1354789942.pdf
4. Encyclopedia Britannica Inc. (5-12-2016 ) Ready Made https://global.britannica.com/art/ready-
made 17.02.2017

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133
Portuguese blue-on-blue 16th–17th c. pottery
L.F. Vieira Ferreira1*, I. Ferreira Machado1,2
1
CQFM- Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology,
Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal;
*
e-mail: [email protected]
2
Polytechnic Institute of Portalegre, P-7300-110 Portalegre, Portugal
Keywords: Portuguese ancient ceramics, Lisbon blue on blue pottery, XRD, XRF, micro-Raman

Blue on blue (berettino) sherds appeared in numerous production and consumption archaeo-
logical excavations in Lisbon and other archaeological sites in Portugal (mid 16th–beg 17th
c.). The abundance of this interesting faience lead us to compare it with similar pottery from
other well-known production centres in Italy, namely Liguria (Savona and Albisola), Spain
(Triana kilns) and Low Countries.
Differences in the diffraction patterns of the sherds’ pastes from the four countries were
observed. In most samples cobalt blue silicate was identified in the dark blue or light blue
glazes by the use of micro-Raman spectroscopy and diffuse reflectance spectra.
A comparison was also made for all blue on blue sherds studied here with many others
16th–17th c. sherds from Lisbon using bivariate plots of K/Si vs. Ca/Si. Lisbon and Seville
pottery behave very differently, whereas Italian and Low Countries sherds occupy intermedi-
ate positions.
By combining the use of the mineralogical composition for the pastes obtained with the
use of XRD diffractograms – and also of the spectroscopic characterization (XRF, Raman
and GSDR spectroscopies) for pastes and glazes – we conclude that the blue on blue pottery
found at the Lisbon dated from the 16th/17th c. was produced in Lisbon workshops, using Mio-
cene raw materials collected locally1. The Pliocene kaolinites’ sands, common in the south
shore of the Tagus River in the production of pottery and tiles, were not used for the blue on
blue pottery productions in Lisbon.
All this information points to a conclusion that archaeologists believed for quite some
time, that blue on blue berettino found in Portugal and its colonies was not exclusively made
in Italy and Seville. The large amount of plates and bowls using such decorative technique
suggested that production was in fact internal and made in the same workshops where Por-
tuguese faience was manufactured. One has to reinforce the importance of this discovery for
Post-Medieval Portuguese archaeological studies. This paper demonstrates that Lisbon was
not only producing a different type of pottery but supplying the internal market and possibly
sending large amounts of this ware to Portuguese overseas colonies and even to North Euro-
pean countries and their colonies.

Reference
1. L.F. Vieira Ferreira, A. Gonzalez, M.F.C. Pereira, L.F. Santos, T.M. Casimiro, D.F. Ferreira, D.S.
Conceição, I. Ferreira Machado, “Spectroscopy of 16th century Portuguese tin-glazed earthenware
produced in the region of Lisbon”, Ceram. Int., 41, pp. 13433–13446, 2015.

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Austria

Mechanical characterization of LiTaO3 and LiNbO3 single crystals for

smartphone applications
Manuel Gruber1*, Daniel Kiener2, Peter Supancic1,3, Robert Danzer1, Raul Bermejo1
1
Institute of Structural and Functional Ceramics, Montanuniversität Leoben, 8700 Leoben, Austria;
*
e-mail: [email protected]
2
Erich Schmid Institute of Materials Science, Montanuniversität Leoben, 8700 Leoben, Austria
3
Materials Center Leoben Forschung GmbH, Leoben, Austria
Keywords: lithium tantalate, lithium niobate, biaxial strength, toughness, fractography

Lithium tantalate (LiTaO3) and lithium niobate (LiNbO3) single crystals possess various at-
tractive properties such as piezo-electricity, pyro-electricity, non-linear optical behaviour,
making them interesting for many electronic devices (e.g. modulators, transducers or detec-
tors). In the smartphone market, for instance, these ceramic materials have found important
application as surface acoustic wave (SAW) filter substrates for high frequency data transfer.
For this application, the single crystals are grown under specific “cuts” and the surfaces
are conditioned (polished and metallized) to tailor the material’s anisotropy and meet the
required functionality. Finally, components are solder joined to a functional ceramic (or poly-
mer) substrate. Due to the different thermal expansion coefficients and Young’s moduli be-
tween the combined materials (e.g. ceramics, metals, polymers), significant internal (residu-
al) stresses can be generated during the fabrication process. If the tensile stresses overcome
the strength of the brittle single crystals, cracks initiate and propagate, leading to reduction
of the functionality or complete failure of the microelectronic module. Although appropriate
functional characterization of these materials can be found in literature, a lack of knowledge
exists regarding their mechanical properties.
In this work, a throughout understanding of LiTaO3 and LiNbO3 single crystals was as-
sessed in terms of strength and fracture resistance with respect to the cutting direction and
surface quality of the wafer. The biaxial strength was evaluated on plate-like specimens, us-
ing the ball-on-three-balls test, and results were interpreted using Weibull statistics. Addition-
ally, in-situ tests of FIB-notched micro cantilevers were conducted to quantify the fracture
toughness of the most critical cleavage planes. The materials response to contact damage was
also analysed using nanoindentation. Experimental findings showed a significant difference
in strength between LiTaO3 and LiNbO3 for the same surface finishing. In addition, deviation
from Weibull statistics was observed in LiNbO3. Fractography of the tested samples helped
identifying cleavage planes, showing differences in the fracture patterns for both materials.
This may be explained by the different fracture toughness and cutting orientation with respect
to the loading plane.

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 Student speech contest

The results of this work provide fundamental knowledge on the mechanical performance
limits of functional ceramic single crystal materials with regard to the crystal orientation and
surface conditioning.

Belgium

Sol-gel synthesis and low-temperature deposition of thin SiO2 layers

as scratch resistant coatings for functional films
Matthias van Zele*, Isabel van Driessche, Klaartje de Buysser
Department of Inorganic and Physical Chemistry, Ghent University, Ghent, Belgium;
*
e-mail: [email protected]
Keywords: roll-to-roll coating, scratch resistance, low temperature, low emissivity, SIMS

In recent years, functional window films have gained much interest. These windows films
can be used for a wide variety of applications. Some common examples of these applications
are UV-blocking, window tinting, insulation and shatter resistance. Most of the window films
are functionalized by thin layers on a flexible substrate. It is also known that these thin layers
are not stable in air and prone to deterioration caused by moisture and abrasion. This draw-
back can be overcome by the deposition of an additional scratch resistant coating.
A thin silica coating was deposited on a polyethylene terephthalate (PET) film with a
thickness of 60 µm, functionalized with a thin metal oxide layer. This oxide layer was de-
posited by sputtering and is often used for functional window films. It is shown by contact
angle measurements that the silica precursor and the metal oxide have a good chemical com-
patibility. The precursor composition was modified to be applicable in industrial settings by
keeping chlorides out of the reaction mixture. The effect of organic acids compared to the
effect of hydrochloric acid on the sol-gel chemistry1,2 was inquired by studying the kinetics
of the condensation reactions.
Secondly, the drying behavior of the precursor solution was optimized for coating. This
was done by introduction of a precondensation step and a final quenching step. These ad-
ditional steps were monitored by 29Si-NMR3,4. It is shown that these steps lead to a better
condensation of the precursor after deposition and a decrease in drying time. Subsequently,
the shelf life of the precursor was looked into. It was shown that the precursor solution was
sufficiently stable to assure continuous deposition during at least one working shift of eight
hours.
The precursor solution was deposited onto the substrate by reverse gravure roll-coating5.
The ratio between web speed and application speed was optimized to obtain sufficient wet-
ting of the film. A temperature program for in-line drying of the coating is set up. The tem-
perature program is important to transfer the results to industrial setups where the time avail-
able for drying is limited. One must keep in mind that the temperature should be high enough
to obtain complete drying of the precursor solution while it should be low enough to avoid
melting or breakdown of the organic substrate.

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The deposited coatings were subject to application tests, which consisted of cross hatch
(ASTM D3359), Pencil hardness (ASTM D3363) and visual light transmittance tests. The
results showed that the deposited coatings had a good adhesion to the substrate. The pencil
hardness turned out to be 3H and a drop in visual light transmittance of maximal 3% was
recorded.
The determination of the thickness of a transparent coating on a transparent substrate is
very difficult. Secondary ion mass spectrometry (SIMS) combined with optical profilometry
has shown to be an ideal approach to tackle this problem. These methods have been used to
correlate coating thickness with pencil hardness and adhesion onto the substrate.
Patent pending.

References
1. J. Zarzycki, Journal of Sol-Gel Science and Technology, 8, 17–22.
2. C. Brinker and G. Scherer, Journal of Non-Crystalline Solids, 1985, 70, 301–322.
3. T. Iwamoto, K. Morita and J.D. Mackenzie, Journal of Non-Crystalline Solids, 1993, 159, 65–72.
4. A. Depla, D. Lesthaeghe, T.S. van Erp, A. Aerts, K. Houthoofd, F. Fan, C. Li, V.V. Speybroeck, M.
Waroquier, C.E.A. Kirschhock and J.A. Martens, The Journal of Physical Chemistry C, 2011, 115,
3562–3571.
5. F.C. Krebs, Solar Energy Materials and Solar Cells, 2009, 93, 394–412.

Czech Republic

Mechanical properties of hybrid ceramic composites prepared

by ice-templating
Jakub Roleček1*, David Salamon2, Zdeněk Chlup2
Central Europe Institute of Technology, Brno University of Technology, Brno, Czech Republic;
1

*
e-mail: [email protected]
Central European Institute of Technology – Institute of Physics of Materials, Academy of Sciences of
2

the Czech Republic, Brno, Czech Republic

Keywords: ice-templating, alumina, epoxide, hybrid composites, strength

Ice-templating, also known as freeze-casting, is a relatively simple, inexpensive, and very

versatile technique to fabricate bulk porous scaffolds with controlled microstructure. The
basic idea of ice-templating is to obtain porosity that is replica of ice crystals, by freezing
suspension and subsequently removing the ice crystals by sublimation of the solvent. Typical
processing steps of the ice-templating process are shown in the Fig. 1.
Promising application of ice templating is preparation of hybrid ceramic materials. Effort
in designing and manufacturing hybrid ceramic composites is to emulate nature’s toughening
mechanisms by infiltration of polymers into ceramic structures. Such biomimetic materials
have significantly better mechanical properties (tensile strength, fracture toughness) than the
individual compounds that they are made of. However, for future applications is necessary to
scale up ice-templating process. The main challenge linked with large scaffolds prepared by

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ice-templating method is achieving of controlled ice crystals growth throughout the whole
sample volume. This phenomenon is caused by loss of sufficient temperature gradient in the
ceramic suspension as the solidification front moves away from the cooling plate. Thus it is
necessary to precisely control the ice-templating process.
Ceramic suspension containing alumina (Al2O3) in water was used in this work. An influ-
ence of suspensions solid loading and additives on formation of lamellar roughness and inter-
lamellar bridges was investigated during ice-templating of large ceramics scaffolds. Effects
of these microstructural ceramic parts of hybrid composites on mechanical properties were
studied and discussed.

Fig. 1. Typical processing steps of the ice-templating process

Acknowledgment
This work is supported by The Technology Agency of the Czech Republic via project TE02000162
“Centre of advanced materials and technologies for protection and safety enhancement”.

Finland

Pulsed laser ablation in supercritical carbon dioxide to synthesize

photocatalytically active nanoparticles
Amandeep Singh1*, Jorma Vihinen2, Mari Honkanen1, Leo Hyvärinen1,
Juha-Pekka Nikkanen1, Turrka Salminen3, Erkki Levänen1
1
Laboratory of Materials Science, Tampere University of Technology, Tampere, Finland;
*
e-mail: [email protected]
2
Laboratory of Mechanical Engineering and Industrial Systems, Tampere University of Technology,
Tampere, Finland
3
Laboratory of Photonics, Tampere University of Technology, Tampere, Finland
Keywords: nanoparticles, pulsed laser ablation in pressurized fluids, supercritical carbon dioxide,
Raman, ablation in controlled atmosphere

In the past decade, nanotechnology and nanoscience have expanded rapidly in almost all ad-
vanced fields in the industry1. More specifically, the ubiquitous influence of nanomaterials in
almost every field of industry has led to a sudden and urgent global demand of nanoparticles.
In this regard, pulsed laser ablation in liquids (PLAL) technique has sought to revolutionize

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Student speech contest

the production of nanoparticles since the list of potential materials for PLAL is immense,
which means nanoparticles can be synthesized from this limitless list of potential materials
by using PLAL2,3. The productivity of PLAL technique has been questioned in the past and
concluded as a shortcoming of the method, but with latest demonstrations of productivities
higher than 4 g/h, PLAL easily competes against other colloidal synthesis techniques. The
next revolutionary step in the domain of PLAL synthesis is pulsed laser ablation in pressur-
ized fluids. Kuwahara et al., reported that the ablation efficiency of copper in CO2 was several
tens of times more at higher pressure compared to lower pressure4. In the field of pressurized
fluids, a fluid is said to be in its supercritical state when its temperature and pressure exceed
its respective critical point values. When combined with PLAL, supercritical fluids, such as,
supercritical carbon dioxide (ScCO2), have been reported to support formation of interesting
reaction fields for plasma technology and nanotechnology5. In this study, we demonstrate
pulsed laser ablation (PLA) in ScCO2 to synthesize photocatalytically active nanoparticles by
ablation of a titanium target. ScCO2 is an interesting fluid, which allows high reaction rates
compared to liquids due to higher diffusivity in supercritical fluids. Moreover, it is possible
to change the solvent power just by changing the temperature and pressure, which will cause
change in the solubility5.
In our study, a titanium target in ScCO2 was ablated at 20 MPa and 40 °C using a 1062 nm
fiber laser. The ablated target and the synthesized nanoparticles were studied by TEM, XRD,
Raman spectroscopy, and methylene blue (MB) discoloration tests. TEM showed presence
of networks of almost perfectly round nanoparticles with diameters varying from 5 nm to 36
nm. The network structure was comprised of chains of nanospheres with a mean diameter
around 13 nm. The electron diffraction pattern showed the particles were highly crystalline
which was substantiated with the high peaks in XRD pattern. The MB discoloration tests
indicated the photocatalytic activity of the synthesized nanoparticles. By discussing the key
results from XRD and Raman for the phases formed from titanium, this study demonstrates
the potential of PLA in ScCO2 to create novel nanomaterials.

References
1. Zhang, D., Gökce, B. & Barcikowski, S. Laser Synthesis and Processing of Colloids: Fundamentals
and Applications. Chem. Rev. 117, 3990–4103 (2017).
2. Barcikowski, S. Amendola, V. Marzun, G. Rehbock, C. Reichenberger, S. Zhang, D. Goekce, B.
Handbook of Laser Synthesis of Colloids. 154 (2016). doi:http://dx.doi.org/10.17185/duepub-
lico/41087
3. Gökce, B., Amendola, V. & Barcikowski, S. Opportunities and Challenges for Laser Synthesis of
Colloids. ChemPhysChem 18, 983–985 (2017).
4. Kuwahara, Y. et al. Nanosecond Pulsed Laser Ablation of Copper in Supercritical Carbon Dioxide.
Jpn. J. Appl. Phys. 48, 40207 (2009).
5. Machmudah, S., Kuwahara, Y., Sasaki, M. & Goto, M. Nano-structured particles production using
laser ablation of gold plate in supercritical CO2. J. Supercrit. Fluids 60, 63–68 (2011).

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France

In situ HT-ESEM study of MO2 (M = Ce, Th) first stage of sintering:

from neck elaboration to microstructure design
G.I. Nkou Bouala1*, N. Clavier1, J. Léchelle2, N. Dacheux1, R. Podor1
1
ICSM, UMR 5257 CEA/CNRS/ENSCM/Université Montpellier, Site de Marcoule, BP 17171, 30207
Bagnols/Cèze, France; *e-mail: [email protected]
2
CEA/DEN/DEC/SESC/LLCC, Site de Cadarache – Bât. 352, 13108 St-Paul lez Durance, France
Keywords: sintering, ceramics materials, in situ microscopy

As a key-step in the elaboration of ceramics materials, such as nuclear fuels (UO2), the sinter-
ing has been studied for years. If grain growth processes were investigated thanks to experi-
mental works and calculations, the elaboration of necks during the first step of sintering was
generally assessed only through numerical models, frequently based on simple configura-
tions (two spherical single crystals in contact).
In order to complement such numerical approaches, the elaboration of necks during the
sintering of CeO2 and ThO2 microspheres, herein used as model compounds, was experimen-
tally observed by HT-ESEM1. The study of the morphological modifications in a single grain
first led to determine the variation of the number of crystallites included in the sphere and the
attached mechanisms, i.e. oriented attachment then diffusion. Also, the time required to reach
a spherical single crystal grain was evaluated for each temperature2.
The kinetics associated to the evolution of neck, contact angles and centers displacement
during the sintering of two microspheres were then evaluated. In this case, the evolution of
polycrystalline assemblies and of single crystals was studied in parallel (Fig. 1). The com-
parison of these results with that supplied by the SALAMMBO model then allowed us to
estimate the bias associated to the polycristallinity of the powders3,4.

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Fig. 1. In situ HT-ESEM observation of CeO2 microspheres sintering at 1050°C: (a) poly- and (b) single-
crystal particles

References
1. R. Podor, N. Clavier, J. Ravaux, L. Claparède, N. Dacheux and D. Bernache-Assollant, Dynamic
aspects of cerium dioxide sintering: HT-ESEM study of grain growth and pore elimination, J. Eur.
Ceram. Soc., 32, 353–362, 2012.
2. G.I. Nkou Bouala, R. Podor, J. Léchelle, A. Mesbah, N. Dacheux and N. Clavier, In situ HT-ESEM
study of crystallites growth within CeO2 microspheres, Ceram. Intern., 41, 14703–14711, 2015.
3. G.I. Nkou Bouala, N. Clavier, J. Léchelle, S. Martin, N. Dacheux and R. Podor, From in situ HT-
ESEM observations to simulation: how does polycristallinity affects the sintering of CeO2 micro-
spheres, J. Phys. Chem. C, 120, 386–395, 2016.
4. G.I. Nkou Bouala, N. Clavier, J. Léchelle, J. Monnier, C. Ricolleau, N. Dacheux, and R. Podor,
High-temperature electron microscopy study of ThO2 microspheres sintering, J. Eur. Ceram. Soc.,
37, 727–738, 2017.

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Germany

Fabrication of crack healing ZrO2 composites containing Nb2AlC repair

fillers
Jonas Biggemann1, Martin Stumpf1, Tobias Fey1, Ken-ichi Kakimoto2, Peter Greil1
Department of Materials Science and Engineering, Institute of Glass and Ceramics,
1

Friedrich-Alexander-Universität Erlangen-Nürnberg, Martensstr. 5, D-91058 Erlangen, Germany

Department of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso-cho,
2

Showa-ku Nagoya 466-8555, Japan

Keywords: MAX phase, repair filler, crack healing

The lifetime of ZrO2 advanced engineering ceramics is limited due to flaws like microcracks
and micropores formed during manufacturing process or service, leading to catastrophic fail-
ures of ceramic devices under high load. Ternary carbides with nanolaminar crystal structure,
also called Mn+1AXn phases, gained recent interest for their unique combination of metallic
and ceramic properties. Further studies explored the oxidation abilities of Mn+1AXn, demon-
strating multiple crack healing capability at high temperatures1–3. In this work, the possibility
of utilizing Mn+1AXn phases as repair fillers in a ZrO2 matrix is presented, whereby fracture
toughness can be enhanced and high temperature crack healing behavior of the composites
enables an improved reliability of these engineering ceramics.
Single-phase Nb2AlC powder was synthesized by pressureless annealing of NbC/Nb/Al
raw powder mixtures. The successful synthesis and phase purity was verified by XRD mea-
surements. ZrO2-Nb2AlC composites loaded with 0–20 Vol% Nb2AlC repair filler were fab-
ricated by pressureless sintering and Spark Plasma Sintering (SPS) methods, examining the
influence of applying extremely high heating rates during sintering on the composite stability
and density. With XRD measurements it was shown that only with SPS completely dense and
phase pure samples could be manufactured, due to the thermal controlled decomposition of
Nb2AlC in ZrO2.
Mechanical properties (hardness, Young’s Modulus) and porosities of the resulting ZrO2-
Nb2AlC composites were determined, revealing an independence of the examined Nb2AlC
content, which is required for structural applications of these composites as for example ther-
mal barrier coatings. To investigate the high temperature behavior and possible crack healing
abilites, oxidation kinetics of the composites were studied up to 1400 °C by the determination
of the oxide layer thickness and morphology. Artificial cracks were introduced in the ZrO2-
Nb2AlC composites by Vickers indentation and the effect on bending strength and fracture
toughness was measured. In 3-point-bending tests the composites with 20 Vol% repair filler
showed full strength recovery after annealing in air at 1200 °C.

Acknowledgment
Financial support from the DFG project GR961/33 – 2 is gratefully acknowledged.

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References
1. G. Song et. al., “Oxidation-induced crack healing in Ti3AlC2 ceramics”, Scr. Mat., 58, pp. 13–16,
2008.
2. S. Li et. al., “Multiple crack healing of a Ti2AlC ceramic”, J. Eu. Ceram. Soc., 32, pp. 1813–1820,
2012.
3. G. Bei et. al, “Crack Healing in Ti2Al0.5Sn0.5C-Al2O3 Composites”, J. Am. Ceram. Soc., 98 [5], pp.
1604–1610, 2015.

Hungary

Silicon nitride-based composites reinforced with zirconia nanofibres

Eszter Bódis*, Zoltán Károly, János Szépvölgyi
Plasma Chemistry Research Group, Institute of Materials and Environmental Chemistry,
Research Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest, Hungary;
*
e-mail: [email protected]
Keywords: spark plasma sintering, Si3N4, ZrO2 nanofibre, electrospinning, mechanical properties

Silicon nitride (Si3N4) ceramics exhibit remarkable combinations of mechanical, chemical

and thermal properties; however, the main concern for its widespread application is their low
fracture toughness. In order to enhance the fracture behaviour we present an alternative route
to improve the fracture toughness of Si3N4 and we prepared ZrO2 nanofibres to combine two
types of toughening effects such as fibre–toughening and phase transformation toughening.
For comparison, besides the ZrO2 nanofibres reinforced composites (ZrO2f/Si3N4) we also
studied the reinforcing effect of ZrO2 particles (ZrO2p/Si3N4). Si3N4-based ceramics mixed
with various fractions of ZrO2 additions are fabricated by liquid phase spark plasma sintering
(SPS) at 1600 °C. We studied the microstructure and mechanical properties of ZrO2f/Si3N4
and ZrO2p/Si3N4 composites. It was found that fracture toughness and flexural strengths show
significant improvements in the case of ZrO2 fibre reinforced Si3N4 composites. The sample
loaded by 15 wt% ZrO2 fibres had 10.05±0.7 MPa·m1/2 fracture toughness and 543±19 MPa
flexural strength, which means 105% and 115% improvements respectively, regarding to the
reference sample. The incorporation of fibre into the Si3N4 composite can be an effective way
to increase the fracture resistance and avoided the catastrophic fracture behaviour since ZrO2
fibre is able to improve mechanical properties of the composites in a complex way, such as
phase transformation toughening and fibre-toughening mechanisms.

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Iran

Processing of Si3N4 for EDM-able bodies

Selin Gharibian*, Farhad Golestanifard, Seyyed Mohmmad Mirkazemi, Mahdiar Taheri
School of Metallurgy and Materials Engineering, Iran University of Science and Technology,
Tehran, Iran; *e-mail: [email protected]
Keywords: silicon nitride, titanium nitride, electrical discharge machining, electrical conductivity

Silicon nitride (Si3N4) as a structural ceramic has been studied intensively, thanks to its ex-
ceptional profile of properties such as high strength and hardness, chemical stability, and
good wear as well as remarkable corrosive resistance at high temperatures. In spite of its
impressive properties, owing to its high hardness and difficult machining, the wide usage of
the silicon nitride has been limited, especially in applications that require reproducible 3D
bodies with precise dimensions. A successful approach is to incorporate electrically conduc-
tive reinforcements into silicon nitride matrix. This incorporation makes the composite elec-
trically conductive, so that electrical discharge machining (EDM) can be employed. EDM is
an attractive machining method, which is only applied to the electrically conductive bodies.
Moreover, it is a precision machining method, using that the shaping process is possible in
relatively concise period of time.
In the present research, titanium nitride (TiN), as an electrically conductive phase, ranging
from 20 to 40 vol. % was added to silicon nitride. Sintering of the composite bodies was done
with pressureless sintering (PS) and direct hot pressing (HP). In order to reach the maximum
relative density, pressureless sintering of the composites was carried on by two-step sintering
cycle at maximum temperature of 1650, 1700, and 1750 °C. Relative density of 97.9% was
achieved for the sample with 40 vol. % TiN sintered at 1750 °C. This sample has the highest
fracture toughness (7.1±0.3 MPa.m1/2) and the lowest electrical resistivity (2.16×10–6Ωm)
among the other samples.
Due to the decrease in thermal gradient between coil and graphite die, direct hot pressing
was used. To do so, the graphite die was connected to electrical power directly. The relative
density of 99.8% was achieved for the sample with 40 vol. % TiN, sintered at 1700 °C. This
composite also showed remarkable mechanical properties such as bending strength and frac-
ture toughness. Bending strength (904±81 MPa) and fracture toughness (7.3±0.7 MPa.m1/2)
increased by increasing the amount of TiN. The electrical resistivity of the sample with 40
vol. % TiN was measured 1.9×10–5Ωm. Machining of the composites, sintered by both pres-
sureless sintering and hot pressing was successfully done by electrical discharge machining,
as well. Investigation of the surface roughness of the samples, EDM-ed under two different
electrical currents was done by a profilometer.

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Italy

Fabrication and properties of hybrid, liquid-repellent coatings

Federico Veronesi*, Mariarosa Raimondo, Magda Blosi, Giulio Boveri, Guia Guarini
Institute of Science and Technology for Ceramics, National Research Council (CNR-ISTEC), Faenza,
Italy; *e-mail: [email protected]
Keywords: nanostructured coatings, superhydrophobic surfaces, sol-gel

The control of the wetting properties of solid surfaces is extremely relevant for a wide spec-
trum of industrial applications, i.e. building industry, electronics and renewable energies.
Thus, huge efforts have been devoted to the fabrication of surfaces with tailored wetting
properties. More specifically, many scientists focused on the mimicry of the so-called Lotus
Effect, which can be observed on the surface of lotus leaves: water drops do not stick, rather
they remain spherical and roll off very easily. Such behavior is due to the combination of a
dual-scale, hierarchical surface structure (i.e. on the micro- and the nano-scale) with a chemi-
cal composition that leads to low surface energy. A surface with such characteristics will be
able to trap air within its features and will not let water drops penetrate, thus hindering stick-
ing and allowing removal. Therefore, in our studies we followed a biomimetic approach for
the design of liquid-repellent surfaces.
First, we developed a hybrid coating mimicking the Lotus Effect. The inorganic compo-
nent of the coating was obtained via dip-coating the surface with a suspension of alumina
nanoparticles; the resultant gel film was first heat-treated, then transformed into a boehmite
AlOOH layer with a peculiar flower-like nanostructure by immersion in boiling water. We
investigated the formation of a properly structured coating on different materials, adjust-
ing process parameters (e.g. dispersant, treatment temperature) to achieve the best results
in terms of wetting properties. In fact, after chemical modification with a fluoroalkylsilane
(FAS) to decrease surface energy, the coating was superhydrophobic (SH), with a water con-
tact angle (WCA) well above 150° and contact angle hysteresis (CAH) lower than 10°. XPS
analyses confirmed the grafting of FAS chains to the surface, while DFT calculations provid-
ed a deeper insight into the formation of the FAS monolayer. We also extended the repellence
to other liquids, causing great increase in contact angles with low surface tension liquids
(e.g. alkanes and oils), thus the coating could also be defined as oleophobic. Furthermore,
this coating showed excellent resistance to chemically aggressive environments, maintaining
superhydrophobicity even after prolonged testing.
We also pursued an alternative approach to liquid repellence. Once again we followed a
biomimetic approach, taking the slippery surface of pitcher plant as a model. We started from
the aforementioned hybrid coatings and added a fluorinated lubricant to fill the pores in the
coating and to create a continuous liquid film. In such situation, a liquid drop is in contact
with the liquid phase rather than with the solid surface. These innovative materials are called
Slippery Liquid-Infused Porous Surfaces (SLIPSs). Even though they displayed much lower
WCA than regular SH surfaces, they still had exceptionally low CAH (about 2°) and water
drops showed no sign of adhesion. These surfaces have potential self-healing properties,

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 Student speech contest

as the infused oil should be able to repair damaged areas where the liquid film is depleted.
Moreover, SLIPSs might show liquid repellence even in adverse conditions, e.g. under high
pressures at which SH surfaces usually fail. The properties of these surfaces still have to be
fully explored, but the first observations are extremely appealing.
In summary, we fabricated and optimized two biomimetic coatings with notable liquid
repellence. Their application in many industrial fields is yet to be achieved, but the huge
potential advantages foster further research and investigations to improve their performance
and properties.

References
1. M. Raimondo, M. Blosi, A. Caldarelli, G. Guarini and F. Veronesi, “Wetting behavior and remark-
able durability of amphiphobic aluminum alloys surfaces in a wide range of environmental condi-
tions”, Chemical Engineering Journal, 258, 101–109, 2014.
2. T.-S. Wong, S.H. Kang, S.K.Y. Tang, E.J. Smythe, B.D. Hatton, A. Grinthal and J. Aizenberg,
“Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity”, Nature, 477,
443–447, 2011.

Latvia

Phase transition of Ba4Gd3F17 nanocrystals in Er3+ doped transparent

glass ceramics
Guna Krieke*, Anatolijs Sarakovskis
Institute of Solid State Physics, University of Latvia, Riga, Latvia; *e-mail: [email protected]
Keywords: glass ceramics, upconversion luminescence, oxyfluoride, site-selective spectroscopy

Transparent oxyfluoride glass ceramics are suitable hosts for rare earth ions. The low phonon
energy of the crystalline phase combined with transparency, good chemical and mechanical
properties of oxide glass matrix are desirable for optical applications.1 Among other rare
earth ions, erbium is a widely investigated candidate for infrared to visible upconversion
luminescence (UCL) processes, however the efficiency of UCL depends on the properties of
the host material. Previously highly efficient UCL has been detected in Ba2+ containing glass
ceramics with fluorite and distorted fluorite type nanocrystals,2 nevertheless there is limited
information about UCL in fluorite derived phases.
In this research we report novel transparent Er3+ doped oxyfluoride glass-ceramics con-
taining Ba4Gd3F17 nanocrystals, prepared from melt quenched glasses with general composi-
tion of 17Na2O-9BaF2-(8-x)GdF3-xErF3-6Al2O3-60SiO2 (x = 0.1–4) in mol%. Intense UCL
resulting from energy transfer between Er3+ ions was detected under near-infrared excitation
in these glass ceramics (see Fig. 1). Longer characteristic decay times, higher UCL inten-
sity and splitting of the luminescence bands compared to the precursor glass indicated the
incorporation of erbium ions in the crystalline phase. The thermal treatment of the precursor
glasses promoted the growth of nanocrystals. The formation of fluorite type nanocrystals was

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Student speech contest

detected using X-ray diffraction, however changes in the morphology and deviations in the
luminescence and luminescence excitation spectra suggested ordering of the fluorite phase.
For comparison, single-phase Er3+ doped cubic and rhombohedral Ba4Gd3F17 were prepared
and the local environment of Er3+ in both polycrystalline ceramics and glass ceramics was
analysed using site-selective spectroscopy. A phase transition in glass ceramics in the tem-
perature range 650–700 °C was detected and associated with the ordering of cubic phase
resulting in the formation of rhombohedrally distorted fluorite type Ba4Gd3F17.

Fig. 1. Photograph of the glass and glass ceramics doped with 1 mol% ErF3 obtained by the heat treatment
at different temperatures, excited with 975 nm

Acknowledgments
This work was supported by National Research Program IMIS2 and Arnis Riekstins “MikroTik” dona-
tion. Donations are administered by the University of Latvia Foundation. The authors express gratitude
to Reinis Ignatans and Jevgenijs Gabrusenoks for Rietveld analysis and Raman spectra measurements.

References
1. P.P. Fedorov. A.A. Luginina, and A.I. Popov, “Transparent oxyfluoride glass ceramics,” J. Fluor.
Chem., vol. 172, pp. 22–50, 2015.
2. G. Krieke and A. Sarakovskis, “Crystallization and upconversion luminescence of distorted fluorite
nanocrystals in Ba2+ containing oxyfluoride glass ceramics,” J. Eur. Ceram. Soc., vol. 36, no. 7, pp.
1715–1722, 2016.

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 Student speech contest

The Netherlands

Transport through grafted ceramic membranes

Renaud Merlet
Inorganic Membranes, MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217,
7500 AE Enschede, The Netherlands; e-mail: [email protected]
Keywords: organic solvent nanofiltation, grafting, gamma aluminum oxide, PDMS, Spiegler Kedem
model

Unlike their polymeric counterparts, ceramic membranes benefit from a rigid architecture
which does not swell in the presence of organic solvents. However, their hydrophilic surfaces
makes them ill-suited to organic solvent nanofiltration. Grafting short chains of PDMS not
only shrinks the pore to the desired size but also renders them suitable for organic solvent
nanofiltration (OSN). These membranes exhibit particular transport phenomena due to the
localized swelling of the PDMS. The degree of swelling is solvent-dependent, which impacts
both the permeability and retention of the membrane.1
We have examined how solvent mixtures permeate and solutes are retained across PDMS-
grafted gamma-alumina selective layers supported on alpha-alumina. Four types of mem-
branes were fabricated: two initial pore sizes of alumina, 5 nm and 9 nm, each grafted with
two sizes of PDMS, either a degree of polymerization n = 10 or n = 20. A range of solvents
and their mixtures were tested, from ethanol to toluene, in a cross-flow setup from pressures
10 to 40 bar. Characterization by permporometry and contact angle, as well as retention and
permeability measurements indicated a membrane well suited to OSN applications. Param-
eters such as the size of the initial pore, swollen pore and solute are inputs to a version of the
Spiegler Kedem, modified to predict the performance of these grafted ceramic membranes.
By allowing the diffusion (but not convection) of solutes through the swollen graft, we find
that predictions obtained through this Spiegler Kedem model agree with the experimental
data.1

Acknowledgments
Both the Netherlands Organisation for Scientific Research (NWO) and the Institute for Sustainable
Process Technology (ISPT) are thanked for their financial support.

Reference
1. R.B. Merlet, C.R. Tanardi, I.F.J. Vankelecom, A. Nijmeijer, L. Winnubst, Interpreting rejection
in SRNF across grafted ceramic membranes through the Spiegler-Kedem model, J. Memb. Sci.
(2016). doi:10.1016/j.memsci.2016.12.013.

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Student speech contest

Norway

Development of all-oxide thermoelectric stacking device

Nikola Kanas1,2*, Michael Bittner2, Kjell Wiik1, Tor Grande1, Armin Feldhoff2, Truls Norby3,
Mari-Ann Einarsrud1
1
Department of Material Science and Engineering, NTNU, Trondheim, Norway;
*
e-mail: [email protected]
2
Institute of Physical Chemistry and Electrochemistry, Leibniz University, Hannover, Germany
3
Department of Chemistry, University of Oslo, Norway
Keywords: processing, oxides, thermoelectric device

Due to high stability, environmental friendly impact and reasonable cost, oxides are interest-
ing for thermoelectric devices for energy conversion at high temperature. Besides the advan-
tages, oxides have challenges due to efficiency and processing. The efficiency of a single
TE material is described by the ZT or figure of merit, which includes Seebeck coefficient,
electrical and thermal conductivity. An all-oxide thermoelectric device (Fig. 1) contains an
n- and a p-type conductor separated by an insu-
lator. The direct p-n junction is the crucial part
of the device having the same function as the
metal current-collector being the limitation for
high temperature applications for conventional
devices.
Development of this new device design re-
quires improved efficiency of the oxide materi-
als through designed microstructure followed
by an advanced ceramics processing approach.
For our all-oxide device, we have selected
Ca0.932MnO3 (CMO), Ca3Co4O9 (CCO) and
LaAlO3 (LAO) as n-type, p-type and insulator
materials respectively, based on coefficients of
thermal expansions. Each of these three oxides
were synthetized and sintered using spray py-
rolysis and spark plasma sintering (SPS). The
all-oxide thermoelectric device was developed
using aqueous tape casting followed by co-sin-
tering using SPS. Power output and efficiency
of the device were recorded from 700 to 800
°C in air. We observed reaction layer at the p-n
junction. Chemical stability and compatibility
of the three materials are discussed. The work
will report on the fabrication of the TE materi-
als and device with their TE properties. Fig. 1. A single pair of thermoelectric device

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 Student speech contest

Acknowledgement
Financial support from The Research Council of Norway (RNC) - Nano2021, THELMA-project
(Proj. no. 228854) is gratefully acknowledged.

References
1. S. Walia et al. “Transition metal oxides Thermoelectric properties”, progress in Materials Science,
58 (2013) 1443–1489.
2. M. Bittner et al. “Oxide-Based Thermoelectric Generator For High-Temperature Application Using
p-Type Ca3Co4O9 and n-type In1.95Sn0.05O3 Legs”, Energy Harvesting and Systems. DOI: 10.1515/
ehs-2016-0002.

Poland

Strontium oxynitride phosphor doped with Eu2+ ions:

phase purity/optical properties relationship
Barbara Adamczyk1*, Dirk Poelman2, Małgorzata Sopicka-Lizer1, Katleen Korthout2,
Daniel Michalik1
Department of Materials Science and Metallurgy, Silesian University of Technology, Krasinskiego 8,
1

40-019, Katowice, Poland; *e-mail: [email protected]

Lumilab, Department of Solid State Sciences, Ghent University, Krijgslaan 281, S1, B-9000 Gent,
2

Belgium
Keywords: oxonitridosilicate, flux, phosphor, photoluminescence characterization, solid state synthe-
sis, gas pressure synthesis

Eu2+-doped SrSi2O2N2 was prepared via a gas pressure method or a solid state reaction meth-
od with various amount of Na2CO3 fluxing agent. The phase composition of obtained materi-
als was studied using X-ray diffraction. The local environment of the activator ions in the
structure was examined using X-ray absorption near-edge spectroscopy (XANES). The pho-
toluminescent properties were investigated by emission, excitation and quantum efficiency
measurements. Decay times and thermal stability of the powders were determined as well.
Obtained results show that nitrogen and CO partial pressure during the process of syn-
thesis influence the phosphor crystallization. It has been found that usage of Na2CO3 flux
improves crystallization of the desired phase, enhancement of optical properties was also
visible. An optimum concentration of the flux was 5 wt% since exceeding this value resulted
in formation of an excessive amount of glassy phase, as well as some evidence of the second-
ary phase formation.

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Student speech contest

Romania

Multiferroic properties of Eu-substituted BiFeO3 ceramics

Vasile-Adrian Surdu1*, Adelina Ianculescu1, Victor Kuncser2, Paul Ganea2,
Ecaterina Andronescu1
1
Department of Science and Engineering of Oxide Materials and Nanomaterials,
Faculty of Applied Chemistry and Materials Science, University Politehnica of Bucharest, Romania;
*
e-mail: [email protected]
2
National Institute of Materials Physics, Bucharest Magurele, Romania
Keywords: bismuth ferrite, multiferroics, spark plasma sintering

BiFeO3 ceramics exhibit a number of interesting functional properties, however, it presents

difficulties when it comes to processing in terms of thermodynamic instability during heat-
treatments and reaction kinetics.
The focus of the study was to investigate the influence of Eu substitution in BiFeO3 ceram-
ics upon structural modification and its implications on functional properties. In this work,
Bi1-xEuxFeO3 (x = 0; 0.05; 0.10; 0.15; 0.20) powders were prepared by sol-gel method. Pow-
der densification was obtained through spark plasma sintering method at 650 °C at an applied
pressure of 50 MPa.
The powders and ceramics were characterised in by means of X-ray diffraction, scanning
electron microscopy coupled with energy-dispersive X-ray spectrometry. Electrical and mag-
netic properties were investigated by impedance spectroscopy and, respectively, vibrating
sample magnetometry.

Acknowledgments
The SEM images obtained on the samples were possible due to EU-funding project POSCCE-A2-
O2.2.1-2013-1/Prioritary Axe 2, Project No. 638/12.03.2014, ID 1970, SMIS-CSNR code 48652.

Serbia

Spider silk-ceramics composites

Svetlana Dmitrović*, Branko Matović
“Vinča” Institute of Nuclear Sciences, CenterExtrim-Lab, University of Belgrade, Belgrade, Serbia;
*
e-mail: [email protected]
Keywords: spider silk, composite, calcite, ceria, europium, maghemite

Spider silk (SS) has been well known by its extraordinary mechanical properties paired with
biocompatibility and possibility of transformation into a various material forms. In this work
SS was used as a template for synthesis of three novel biomaterials: SS-calcite composite,
SS coated with europium doped ceria nanoparticles, and SS coated with superparamagnetic

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γ-Fe2O3 nanoparticles. SS-calcite composite was synthesized by simple method using biomin-
eralization approach. The biomineralization process was observed during five days and it
was found that two days of treatment were sufficient to obtain pure rhombic-shaped calcite
crystals homogeneously dispersed trough 3D spider mesh. With increasing the incubation
time, the number and size of crystals increased. SS coated with Eu doped nanoceria was eas-
ily obtained by time and cost effective precipitation synthesis procedure. The SS fibers were
homogeneously coated with Eu doped CeO2 nanoparticles with average nanoparticle size of
3 nm due to a great affinity of ceria to oxygen rich functional groups of SS proteins. Eu3+
was introduced as an activator ion in ceria crystal lattice and luminescent properties of the
obtained composite were investigated by excitation spectra. SS coated with superparamag-
netic γ-Fe2O3 nanoparticles was obtained with similar precipitation technique. Maghemite
nanoparticles were uniformly distributed on the surface of SS fibers and magnetic properties
of obtained composite were described. These three novel composites open new possibilities
for spider silk based materials in various fields, especially for biomedical application.

Fig. 1. (a) SEM micrograph of SS-calcite composite; (b) NLM image of SS coated with Eu-doped ceria
nanoparticles; (c) SEM image of SS coated with maghemite nanoparticles

Acknowledgment
This project was supported by the Ministry of Education and Science of Serbia (Project number 45012).

References
1. S. Dmitrović, B. Jokić, M. Prekajski, J. Pantić, D. Zmejkoski, A. Zarubica, B. Matović, “Synthesis
and characterization of spider silk calcite composite”, Processing and Application of Ceramics, 10
(1), pp. 37–40, 2016.
2. S. Dmitrović, M.G. Nikolić, B. Jelenković, M. Prekajski, M. Rabasović, A. Zarubica, G. Branković,
B. Matović, “Photoluminescent properties of spider silk coated with Eu-doped nanoceria”, J Nano-
part Res 19:47, 2017.

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Slovakia

The effects of tip sharpness and coating thickness on nanoindentation

measurements in hard ceramic coatings on softer substrates by FEM
Dušan Németh*, František Lofaj, Tamáš Csanádi
Institute of materials research, SAS, Košice, Slovakia; *e-mail: [email protected]
Keywords: nanoindentation, tip radius, W-C coating, hardness

The FEM modeling combined with the experimental nanoindentation hardness and indenta-
tion modulus depth profiles with the indenter tips with different radii on hard W-C coating/
softer steel substrate with different coating thicknesses revealed strong influence of the tip
radius and coating thickness on the shape of hardness and indentation modulus depth pro-
files and subsequent underestimation of coating property values extracted from the profiles.
The effects of tip radius and coating thickness on hardness profiles have the same physical
reason - faster penetration of the zone of plasticity into substrate at the same relative indenta-
tion depths when indenter tip radius increases and/or coating thickness is reduced. Thus, the
validity of the “10% rule” is limited also by the indenter radius. The main parameters critical
for proper nanoindentation measurements in the studied W-C coating/steel substrate system
include indenter tip radius ≤500 nm, coating thickness ≥0.5 μm and the ratio of the tip radius
to coating thickness ≤0.1.

Acknowledgments
The financial support provided by the projects APVV-15-0168, VEGA 2/0187/15 and MERA RUS+
LightMat4Space is acknowledged. The equipment used in the work was acquired from the project
“Research Centre of Advanced Materials and Technologies for Recent and Future Applications” PRO-
MATECH, ITMS project code: 26220220186.

Slovenia

Formation mechanism of PLD-derived Pb(Mg1/3Nb2/3)O3-PbTiO3

thin films
Urška Gabor*, Matjaž Spreitzer, Danilo Suvorov
Advanced Materials Department, Jožef Stefan Institute, Ljubljana, Slovenia;
*
e-mail: [email protected]
Keywords: pulsed-laser deposition, PMN-PT epitaxial thin films, Pb-excess, cation stoichiometry

Pb-based materials with PbZr1-xTixO3 (PZT) at the forefront remain to dominate the field
of piezoelectrics, as lead-free alternatives are still facing some fundamental and process-
ing issues.1 Epitaxial thin films of Pb[Mg1/3Nb2/3]O3-PbTiO3 (PMN-PT) exhibit piezoelec-

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tric properties superior to PZT.3 Notably, the preparation of lead-based materials is also not
obstacle-free, the main one being the volatility of Pb. In order to realize the full potential of
the materials, formation of Pb-deficient pyrochlore inclusions needs to be circumvented. We
have shown that, in addition to meticulous control of the growth parameters and compensat-
ing for the lead-loss by using targets with an optimal amount of Pb-excess, it is also very
important to select the right underlying material, not only in terms of lattice matching, but
also to consider the sticking coefficients for the deposited materials. Despite a smaller lattice
mismatch with SrTiO3, LaNiO3 was more successful in stabilizing the perovskite phase.
In PMN-PT with three diverse B-site cations it is also imperative to control the ratio of
the cations, which is largely affected by the dynamics of the laser plasma plume. In order
to understand the material transfer, we examined the composition of the films by means of
EDXS analysis using a single-crystal standard. As the process pressure plays a key role in
the transfer, films prepared at different pressures were further analyzed with transmission
electron microscopy (TEM). We found that increasing the pressure resulted in a substantial
improvement of the electrical properties, beyond of what can be achieved by simply avoiding
pyrochlore formation. Experiments with oxygen/argon mixtures showed that this effect is not
related to oxygen vacancies in the films prepared at lower pressures.
While the formation of ferroelectric PZT has been thoroughly studied and exploited for
domain engineering, few studies on relaxor-PT systems can be found in the literature. Under-
standing the mechanism of the PMN-PT growth process is a powerful tool for improving the
quality of the layers, and could furthermore be used to construct guidelines for other multi-
component systems with volatile constituents, including lead-free materials.

Fig. 1. TEM images (left), revealing the domain structure, and measured permittivity (right) of samples
prepared at 0.13 mbar (A) and 0.27 mbar (B). The last column (*) implies the potential for shifting the
boarder even further

Acknowledgment
This research is financed by Slovenian Research Agency grant number PR-06231 and M-Era.Net proj-
ect number J2-6759.

References
1. P.K. Panda and B. Sahoo, “PZT to Lead Free Piezo Ceramics: A Review”, Ferroelectrics, 474, pp.
128–143, 2015.
2. S.H. Baek et al, “Giant Piezoelectricity on Si for Hyperactive MEMS“, Science, 334, pp. 958–961,
2011.

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Spain

Nd3+ doped transparent oxyfluoride glass-ceramics

Giulio Gorni1*, Jose Joaquin Velázquez1, Laura Pascual2, Glenn Christopher Mather1,
Alicia Durán1, Gang Chen3, Mayur Sundararajan3, Rolindes Balda4,5, Joaquin Fernández4,5,
María Jesús Pascual1
1
Ceramics and Glass Institute, CSIC, Madrid, Spain; *e-mail: [email protected]
2
Catalysis and Petrochemistry Institute, CSIC, Madrid, Spain
3
Department of Physics and Astronomy, Ohio University, Athens, USA
4
Applied Physic Department I, Superior School of Engineering, País Vasco University, Bilbao, Spain
5
Materials Physics Centre, CSIC-UPV/EHU, San Sebastian, Spain
Keywords: glass-ceramics, crystallisation, laser, optical fibres, neodymium

The growing field of photonics demands the design of new rare-earth (RE)-based optical ma-
terials for their use in optical telecommunications, solid-state lasers and other applications.
Oxyfluoride glass-ceramics (GCs) are promising RE-hosting candidates due to their good
processing and optical properties. They combine the good chemical and mechanical stability
of oxide glass matrices with the excellent optical properties of low phonon energy fluoride
nano-crystals (NCs).1
Among the rare-earth ions, Nd3+ has been recognized as one of the most efficient for solid-
state lasers in crystals and glasses due to its intense 4F3/2-4I11/2 emission at around 1.06 µm.
In literature only few works about optical GCs fibres are encountered, making this field of
research really attractive.
In this work transparent glass-ceramics bulk and fibres containing LaF3 NCs and doped
with Nd3+ ions with concentrations of 0.1–2 mol% have been prepared by melt-quenching
followed by a controlled crystallization process.2 The crystallization mechanism of fluoride
NCs has been studied by DTA and HR-TEM showing that the crystal growth is a diffusion-
controlled process and the NCs size is limited to 9–12 nm. Further structural characterization
was obtained by means of XRD, SAXS and XANES (ESRF facility). A detailed optical char-
acterisation, also supported by EDXS, shows that Nd3+ ions in the GCs are incorporated both
in the crystalline and amorphous phases. By a selective excitation it was possible to isolate
the emission of Nd3+ ions in the NCs obtaining a considerable increase in the luminescence
efficiency and to reproduce the spectroscopic properties of pure Nd3+ doped LaF3 crystals
prepared with complex crystals grow techniques.
Optical fibres with Nd3+ doped glass-ceramics core and SiO2 cladding have been also pre-
pared and studied in detail. The same structural and optical behaviour as for GCs bulk sam-
ples has been obtained. It offers the possibility to reproduce in the optical fibres the properties
encountered for bulk samples. The first studies show the light propagation into the Nd3+ GC
core with attenuation of 16 dB/m, similar to other non-silica fibres.

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Fig. 1. (a) Selective excitation of GC bulk sample. (b) EDXS analysis in STEM mode and (c) HR-TEM of
crystals in a GC fibre

References
1. P.P. Fedorov et al., “Transparent oxyfluoride glass ceramics”, J. Fluorine Chem., 172, pp. 22–50,
2015.
2. G. Gorni et al., “Selective excitation in transparent oxyfluoride glass-ceramics doped with Nd3+”, J.
Eur. Ceram. Soc., 37, pp. 1695–1706, 2017.

Turkey

Production of IV-B group boride composite ceramics via SHS

Mehmet Buğdaycı1,2, Ahmet Turan2, Kağan Benzeşik1, Onuralp Yücel1
1
Istanbul Technical University, Metallurgy and Materials Engineering, Maslak, Istanbul, 34469,
Turkey; *e-mail: [email protected]
2
Yalova University, Chemical and Process Engineering Department, Yalova, 77100, Turkey
Keywords: SHS, composite ceramics, borides, ZrB2, TiB2

TiB2 and ZrB2 are important metal borides. They are being used in various industrial areas
such as space technology, nuclear industry owing to their unique physical properties such
as high thermal/electrical conductivity, high melting point and low density. In the SHS ex-
periments, a mixture of ZrO2, TiO2, B2O3 and Mg powders were used in order to produce
advanced ZrB2-TiB2 composite ceramic powders. The metal oxide powders have over 97%
purity and 150 µm average grain sizes. In the experimental set, TiB2-ZrB2 composite powders
were produced by SHS and leaching processes. In this experiment set TiB2 and ZrB2 ratios
were changed and optimum conditions were determined, initial conditions and results of
these series are presented in Table 1.
After the SHS experiments leaching process was carried out, Fig. 1 indicates leached and
unleached products of ZrB2-TiB2 composite powders.

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A%40 ZrB2 %60 TiB2 – B%50 ZrB2 %50 TiB2 – C%60 ZrB2 %40 TiB2

Fig. 1. XRD Graphs of Unleached and leached ZrB2-TiB2

Table 1. Initial conditions of ZrB2- TiB2 SHS experiments

No Zr/Ti ZrO2 (g) TiO2 (g) B2O3 (g) Mg (g) SHS Product(g)
1 90/10 23.20 2.96 41.90 31.92 90.00
2 80/20 20.64 5.92 40.12 33.33 90.30
3 70/30 18.04 8.89 38.32 34.31 71.90
4 60/40 15.46 11.85 36.53 36.14 71.80
5 50/50 12.89 14.82 34.74 37.54 91.20
6 40/60 10.31 17.78 32.94 38.95 94.90
7 30/70 7.73 20.74 31.20 40.40 57.00
8 20/80 5.15 23.71 29.30 41.72 97.50
9 10/90 2.57 26.67 27.57 43.16 60.30

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United Kingdom

A phase diagram study of (Ba,Ca)(Zr,Ti)O3 piezoceramics from

combining structural and functional measurements
Chang Shu1*, Daniel Reed1, Yang Bai2, Hana Hughes2, Tim Button1
1
School of Metallurgy and Materials, University of Birmingham, Birmingham, UK;
*
e-mail: [email protected]
2
CEITEC, Brno University of Technology, Brno, CZ
Keywords: lead-free piezoceramics, phase transitions, crystal symmetry, functional properties

Piezoelectric ceramics have been widely used in sensors, actuators and ultrasonic trans-
ducers due to their ability to achieve efficient conversion between electric and mechanical
vibrations. There is an urgent desire to move to lead-free materials achieving comparable
piezoelectric performance to lead-based materials. One of the most promising alternatives is
the pseudobinary system zBa0.70Ca0.30TiO3-(1-z)BaZr0.20Ti0.80O3 ((Ba,Ca)(Zr,Ti)O3) due to the
presence of a morphotropic phase boundary (MPB) in the phase diagram, and reports of large
piezoelectric coefficients comparable to lead-based systems1.
However, with the development of the structural study in this lead-free system, there was
a debate on the crystal structure of the MPB region: (1) MPB was a single boundary separat-
ing the rhombohedral and tetragonal phases1; (2) the MPB region was actually a separate
orthorhombic (Amm2) phase region, bridging the polymorphic transitions between the rhom-
bohedral and tetragonal phases.2
In this study, all zBa0.70Ca0.30TiO3-(1-z)BaZr0.20Ti0.80O3 ceramics (z = 0-1, with z = 0.1
step) were fabricated systematically by conventional solid state method, using pre-calcined
Ba0.70Ca0.30TiO3 and BaZr0.20Ti0.80O3 powders as reagents. The phase purity and compositions
of sintered ceramics were determined by XRD. The determination of phase transitions was
achieved by measuring the temperature dependence of both structural and functional proper-
ties on the same batch of ceramics. The temperature dependent dielectric properties and fer-
roelectric hysteresis loops revealed phase transition points, while the corresponding changes
in crystal symmetry were observed by Raman spectroscopy and synchrotron radiation pow-
der X-ray diffraction. A conclusive phase diagram based on in situ structural and functional
properties measurements is therefore constructed and shown as figure below.

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Fig. 1. Combined phase diagram of zBa0.70Ca0.30TiO3-(1-z)BaZr0.20Ti0.80O3 (z = 0-1)

Acknowledgments
The authors gratefully acknowledge support from: Diamond I11 beamline, the AWM Birming-
ham Science City Hydrogen Energy project; the project CEITEC-Brno University of Technology –
CZ.1.05/1.1.00/02.0068 from ERDF.

References
1. W. Liu and X. Ren, “Large Piezoelectric Effect in Pb-Free Ceramics”, Phys. Rev. Lett., 103, pp.
257602, 2009.
2. D.S Keeble, et al., “Revised structural phase diagram of (Ba0.7Ca0.3TiO3)-(BaZr0.2Ti0.8O3)”, Appl.
Phys. Lett., 102, pp. 092903, 2013.

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