Structural Nanocomposites - Perspectives For Future Applications-Springer Berlin Heidelberg (2013)

Engineering Materials
James Njuguna Editor
Structural
Nanocomposites
Perspectives for Future Applications
Engineering Materials
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James Njuguna
Editor
Structural Nanocomposites
Perspectives for Future Applications
123
Editor
James Njuguna
School of Engineering
Institute for Innovation, Design & Sustainability
Robert Gordon University
Aberdeen
UK
ISSN 1612-1317 ISSN 1868-1212 (electronic)

ISBN 978-3-642-40321-7 ISBN 978-3-642-40322-4 (eBook)
DOI 10.1007/978-3-642-40322-4
Springer Heidelberg New York Dordrecht London
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Springer-Verlag Berlin Heidelberg 2013

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Preface
This book acknowledges that the key to success of modern structural components
is tailored behaviour of materials. A relatively inexpensive way of obtaining
macroscopically desired responses is to enhance base material properties by
addition of micro or nanoscopic matter, i.e. to manipulate the macrostructures.
Accordingly, in many modern engineering designs, materials with high complex
microstructures are now in use.
The macroscopic characteristics of modified base materials are the aggressive
change of an assemblage of different ‘pure’ components especially at nanoscale. A
key challenge to nano-enhancement is dispersion methods for the development of
polymeric nanocomposites, which is covered in ‘‘Dispersion Methods of Carbon
Nanotubes for the Development of Polymeric Nanocomposites: Characterization
and Application’’. Nanostructured materials have great potential as reinforcement
materials in polymers (polymer matrix) when used to modify and improve their
physical and mechanical properties. Examples of unique properties achievable
today are covered on nanotubes/thermoplastic nanocomposites on nanotubes/
thermoplastic nanocomposites (Thermoplastic Nanocomposites with Carbon
Nanotubes) and thermal and mechanical properties of graphite-based nanocom-
posites (Graphite-based Nanocomposites to Enhance Mechanical Properties). With
ease to manufacture in bulk, nanomaterials are finding increasingly more practical
applications (e.g. in the manufacture of plastic auto-aero parts, structures, implants
and ceramics to microelectronics). ‘‘Optimization and Scaling up of the
Fabrication Process of Polymer Nanocomposites: Polyamide-6/Montmorillonite
Case Study’’ therefore focuses on optimization and scaling up of the fabrication
process of polymer nanocomposites.
Due to the molecular size of their reinforcement, polymer nanocomposites offer
the possibility to develop new materials with unusual properties. These include
photoactivity (Influences of Morphology and Doping on the Photoactivity of
TiO2 Nanostructures), foam-glass-crystal materials presented in ‘‘Foam-Glass-
Crystal Materials’’ and high temperature polymer nanocomposites covered in
‘‘High Temperature Polymer Nanocomposites’’ is focused both on physical mod-
ification of traditional polymers as well as synthesis of new monomers from which
new polymers are obtained with interesting new properties that can provide
opportunities for novel applications. Impact and energy absorption performance
(experiments, modelling and simulations) are presented in both ‘‘Energy
v
vi Preface
Absorption and Low-Velocity Impact Performance of Nanocomposites: Cones and

Sandwich Structures’’ and ‘‘Predictions of Energy Absorption of Aligned Carbon
Nanotube/Epoxy Composites’’. It is shown that nanotechnolgy and nanoscience
indeed offers promising results and a unique level of mechanical properties
enhancement and/or control by involving the use of nano-sized organic and inor-
ganic particles. An important area of research on antibacterial applications is the
central focus of ‘‘Silver Nanocluster/Silica Composite Coatings Obtained by
Sputtering for Antibacterial Applications’’, Materials with antibacterial properties
are more and more requested in several fields where the risk of microbial
contamination is considered a relevant issue.
Foams play a key role in many technological applications. A huge amount of
research was done in the last two decades to develop low-toxicity fire retardants on
foams. The use of flame retardants to reduce the flammability of polymers and
production of smoke or toxic products during their combustion is nowadays an
important aspect of the research, development and application of new materials.
As an example, ‘‘Recent Advances on the Utilization of Nanoclays and
Organophosphorus Compounds in Polyurethane Foams for Increasing Flame
Retardancy’’ looks into recent advances on the utilization of nanoclays and
organophosphorus compounds in polyurethane foams for increasing flame retar-
dancy. Finally, ‘‘Ecological Assessment of Nano Materials for the Production
of Electrostatic/Electrochemical Energy Storage Systems’’ covers the ecological
assessment of nanomaterials for the production of electrostatic/electrochemical
energy storage systems. The ecological implications (regarding known environ-
mental effects) of carbon-based nanomaterials are analysed using Life Cycle
Assessment (LCA) approach.
This book covers important issues and topics that are attractive to the scientific
community. It is a useful tool for scientists, academicians, research scholars,
polymer engineers and industries as it is a unique set of valuable contributions
from renowned experts. This book is also supportive for undergraduate and
postgraduate students and hope fully an inspiration to many young scientists to
devote their efforts in nanomaterials research.
The editor acknowledges the great effort put into this book by the contributing
authors. He is very thankful to all the contributors and also to a great team at
Springer for brilliant editorial support.
James Njuguna
Contents
Dispersion Methods of Carbon Nanotubes for the Development

of Polymeric Nanocomposites: Characterization and Application . . . . 1
C. Manteca Martínez, A. Yedra Martínez and I. Gorrochategui Sánchez
Thermoplastic Nanocomposites with Carbon Nanotubes . . . . . . . . . . . 19

Shyam Sathyanarayana and Christof Hübner
Graphite-Based Nanocomposites to Enhance

Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Shanta Desai and James Njuguna
Optimization and Scaling up of the Fabrication Process of Polymer

Nanocomposites: Polyamide-6/Montmorillonite Case Study . . . . . . . . . 75
K. Pielichowski, T. M. Majka, A. Leszczyńska and M. Giacomelli
Influences of Morphology and Doping on the Photoactivity

of TiO2 Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Nasser A. M. Barakat and Muzafar A. Kanjwal
Foam-Glass-Crystal Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143

O. V. Kazmina and B. S. Semukhin
High Temperature Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . 165

K. Balasubramanian and Manoj Tirumalai
Energy Absorption and Low-Velocity Impact Performance

of Nanocomposites: Cones and Sandwich Structures . . . . . . . . . . . . . . 187
James Njuguna, Sophia Sachse and Francesco Silva
Predictions of Energy Absorption of Aligned Carbon

Nanotube/Epoxy Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
D. Weidt and Ł. Figiel
vii
viii Contents
Silver Nanocluster/Silica Composite Coatings Obtained

by Sputtering for Antibacterial Applications . . . . . . . . . . . . . . . . . . . 225
Cristina Balagna, Sara Ferraris, Sergio Perero, Marta Miola,
Francesco Baino, Andrea Coggiola, Daniela Dolcino, Alfio Battiato,
Chiara Manfredotti, Ettore Vittone,
Enrica Vernè and Monica Ferraris
Recent Advances on the Utilization of Nanoclays

and Organophosphorus Compounds in Polyurethane
Foams for Increasing Flame Retardancy . . . . . . . . . . . . . . . . . . . . . . 249
Javier C. Quagliano, Victor M. Wittemberg and Irma C. Gavilán García
Ecological Assessment of Nano Materials for the Production

of Electrostatic/Electrochemical Energy Storage Systems . . . . . . . . . . 259
M. Weil, H. Dura, B. Simon, M. Baumann, B. Zimmermann, S. Ziemann,
C. Lei, F. Markoulidis, T. Lekakou and M. Decker
Dispersion Methods of Carbon Nanotubes
for the Development of Polymeric
Nanocomposites: Characterization
and Application
C. Manteca Martínez, A. Yedra Martínez and I. Gorrochategui

Sánchez
Abstract Composites use is increased worldwide quickly because they present

significant advantages over traditional materials, as metals. It is able to get
improved and tailored properties to each application by means the formulation.
Initially, composites were used in advanced technologically sectors as aeronauti-
cal, although the technological advance and manufacturing cost reduction have
promoted their use in different industrial sectors as building, renewable energies,
automotive, sports, nautic, etc. In all cases there are needs to reduce weight, to
improve the resistance in aggressive environments and to keep high performances
during the life-span in more demanding applications. In this chapter is shown the
development of thermoset multiscale composites with improved properties,
making special emphasis in the dispersion method of the nanoreinforcements.
Thermoset multiscale composites consist of glass fibers as reinforcement and
multiwall carbon nanotubes (MWCNTs) as nanoreinforcement. MWCNTs have a
huge potential as nanoreinforcements polymeric matrices because they present
unique and excellent mechanical, thermal and electrical properties with a com-
petitive cost. Moreover, currently in the market there is enough availability of
these nanomaterials for using in industrial scale. As polymeric matrix has been
used polyester resin. These new low cost polymer composite/nanocomposite
materials improved with nanoreinforcements opens new market opportunities in
large-volume applications as structural composites: civil engineering works,
transport sector, etc. The main challenge is to transfer the MWCNTs excellent
properties to the polymeric matrix. It requires dispersing the nanoreinforcements
as individual particles in the polymeric matrix, to avoid agglomerates. For this
reason, it has studied and implemented an advanced dispersion techniques of high
shear forces called Three Roll Mills. Following, it has been performed a novel and
detailed quality and quantity characterisation of the dispersion rate combining
different techniques: viscosity measurements and confocal Raman spectroscopy.
C. Manteca Martínez A. Yedra Martínez (&) I. Gorrochategui Sánchez

Fundación Centro Tecnológico de Componentes (CTC), Santander, Spain
e-mail: [email protected]
J. Njuguna (ed.), Structural Nanocomposites, Engineering Materials, 1

DOI: 10.1007/978-3-642-40322-4_1, Springer-Verlag Berlin Heidelberg 2013
2 C. Manteca Martínez et al.
Later the samples was characterised from mechanical point of view. It has been
obtained a high MWCNTs/CNFs dispersion rate within the matrix by using 3-roll-
milling process. It has permitted to work with nanoreinforcements low content:
from 0.1 wt % to 1 wt %, obtaining good results with 0.1 wt %. Moreover, it is a
process easy to industrial scale up. MWCNT’s distribution map based on intensity
RAMAN spectra (at G band) has been obtained. All samples present a high dis-
persion rate of the nanoreinforcements. Furthermore, correlation between viscosity
increasing and nanoreinforcements content and dispersion rate has been observed.
From mechanical point of view, the samples present better behavior than original
sample (without nanoreinforcements). Depending of nanoreinforcements content
and parameters during the dispersion process, the mechanical improvements can
be (in the tensile test) up to 13 % in tensile strength and 15 % in Young module,
and (in flexural test) up to 26 % and 84 %. Finally is shown an example of
structural application of these materials: panel sandwich.
1 Introduction
The use of advanced composite materials is becoming increasingly popular in the

manufacturing of structural elements in recent years [1–3]. Thus, traditional
materials such as steel, wood or aluminum are being replaced in some applications
by advanced composite materials, with better specific properties [4].
Within the large variety of composite materials in the market, those formed by
organic matrices (epoxy, vinylester, polyester, …) and high strength fibres (glass,
carbon, aramid, …) are the most developed and used in an industrial level [5, 6].
These new materials have been applied almost exclusively in technologically
leading industries such as aeronautics or aerospace, although at present, other
industries as the civil works sector is starting to use them [2]. In particular,
composite materials of glass fibre polyester resin are used in the transportation
industry, chemistry, civil works and sports, due to its low density, good
mechanical performance (its excellent relations stiffness/weight and resistance/
weight), chemical stability, aggressive environment resistance, long life, low cost
of manufacture, installation and maintenance [5, 6].
In recent years, the trend in the development of advanced reinforced composites
with additives is the reduction of their size, from macro and micro scale to
nanoscale [7]. The introduction of new nanoadditives can develop nanocomposites
with properties tailored to the requirements of the end user application. Examples
of such nanoadditives are: nanoclays, nanoparticles of aluminium oxide, titanium
oxide, carbon nanotubes and nanofibres, etc. The use of these nanoadditives can
improve mechanical, electrical, fire resistance composite properties [8, 9].
Nanostructured materials have great potential as reinforcement materials in
polymers (polymer matrix), used to modify and improve their physical and
mechanical properties. It is a consequence of the nanoscale dimensions of the
Dispersion Methods of Carbon Nanotubes 3
fillers: increases the surface/volume ratio, reduces the distance between particles
and increases the ratio form (s = l/d, where l:length and d:diameter). These new
properties and/or improvements achieved will be influenced by the shape, size and
volume fraction of the fillers, dispersion and interfacial bonding of nanoparticles in
the polymer matrix [7, 10].
In particular, carbon nanotubes (CNTs) have one of the highest specific surface
areas in nanostructured materials. This feature allows that a small quantity of
nanostructured material is able to influence a large volume of the polymer matrix,
because they can provide a contact area much higher than traditional particles
[7, 10, 11]. This is a great advantage in comparison to traditional fillers used in
composites, where it is necessary to introduce a higher quantity to get significant
benefits that can worsen other aspects and features of the material [12]. To obtain
an effective reinforcement of the polymeric matrix with CNTs, it is necessary to
take into account the following requirements [7, 13, 14]:
• CNTs quality: length/diameter ratio, degree of purity and integrity.
• Dispersion: CNTs must be dispersed as individual particles into the polymer
matrix.
• Functionalization of the nanomaterials: high interfacial bonding of the indi-
vidual CNTs with the polymer matrix in order to achieve transfer of stresses
from the matrix to the CNTs.
2 Materials
The most used fibre reinforced polymer (FRP) are thermoset resin reinforced with
high strength fibres, because they present characteristics like low cost, easy fab-
rication, simplified installation, low weight and high variety of shape and size, that
make them desirable for design in industrial applications [15].
The fibres are responsible to provide structural properties in composites like
strength and stiffness. They also provide thermal stability and electrical conduc-
tivity or insulation (depending on the type of fibre). Reinforcing fibres show dif-
ferent forms: short chopped fibres, long continuous fibres, woven fabric or mat.
The final properties of composites depend on the configuration and combination of
the fibres [16].
The thermoset resin is the matrix material that joins the fibres, distributes and
transfers the external loads to the fibres. The resin separates the fibres individually
and prevents the propagation of cracks. It provides protection to fibres against
external damage which may result from mechanical abrasion or chemical reactions
with the environment. Finally the resin provides flexibility on the shape during the
manufacturing and good surface finish quality [16, 17].
Glass fibres are the most widely reinforcement in FRP because of its avail-
ability, low cost (cheaper than other type of fibres like carbon, boron or aramid)
and good mechanical properties. The typical diameter of glass fibres range from 5
to 25 lm, being flexible and easily conform to different kind of shapes [16].
Unsaturated polyesters (UP) form an important group of thermoset resins
employed to manufacture polymer composites. This resin is used in different
sectors and applications: roofing and building insulation, sport cars bodies,
translucent roofing panel in lorries, public transport vehicles, aircraft radomes,
ducting, spinners, chemical storage vessels, chemical plant components, swim-
ming pools, stacking chairs and sports equipment [6].
Carbon nanotubes are an allotropic form of carbon. It consists of a number of
graphene layers rolled to form a cylindrical tube. Its diameter ranges from one to
ten nanometers and its length reaches several hundreds nanometers, even
micrometers [18]. There are several types of carbon nanostructures: single-walled
nanotubes (SWCNTs), multi-walled nanotubes (MWCNTs) and carbon nanofibres
(CNFs) [10]. MWCNTs were observed in 1991 when Ijima imaged a product of an
arc discharge experiment. CNTs show unique mechanical and electrical properties.
They present high mechanical properties strength and stiffness) and high electrical
and thermal conductivity, providing potential applications for a variety of areas
such as reinforcements in composites, nanoprobes, displays, sensors, energy
storage and electronic devices [10, 18, 19].
3 Nanomaterials Dispersion Within Thermosetting Resin
One of the most important aspects to transfer the excellent properties of the
nanomaterials to the polymeric matrix is the dispersion rate. The main challenge is
to disperse the nanoparticle as individual particles in the polymer matrix.
When the fillers size is reduced, the distance among particles in the matrix is
reduced too. Some authors [8] have established a relationship between the distance
between nanoparticles and their volume fraction (%) for single-wall nanotubes. It
has been obtained based on the theoretical model of hexagonal dense packed [14].
For instance [8], at a volume fraction of 4 % the distance between two nanotubes
is around 2.8 nm. If the polystyrene is assumed as polymeric matrix with a chain
diameter of 0.8 nm, there is only a small gap for the polymer to penetrate between
the nanotubes. So, in this example, the maximum volume fraction of SWCNT that
could be used is 10 %. In general, it is very difficult to introduce high volume
contents of nanoparticles in a polymeric matrix. When the nanoparticles volume
content is high, they could be agglomerated.
On the other hand, nanomaterials present a high specific surface area because of
its nanometric scale. In consequence they tend to aggregate due to adhesive forces
(electrostatic and Van der Waals forces). For this reason, it is necessary to use
effective dispersion techniques. These techniques have to be able to break up the
agglomerates and distribute the individual nanoparticles in the polymer without
producing damage in their nanostructure.
Fig. 1 Sonication equipment

to disperse nanomaterials
Currently, different methods are being used to disperse nanomaterials into

polymeric matrices. The main methods are:
• Sonication
Sonication technique applies ultrasound energy to disperse particles in liquid
media. It involves introducing an ultrasound probe into the mix of resin and
nanofillers. It generates high local vibrational energy, separating the agglom-
erated nanoparticles. This method is suitable for small volumes and low viscous
materials. However, this high local energy leads to breakage and damage of
nanoparticles reducing the aspect ratio [14, 20] (Fig. 1).
• Stirring
This method is suitable to disperse nanoparticles in medium liquid viscosity
systems. This method applies high shear forces to disrupt the agglomerates. The
high shear forces can be obtained by different principles: rotating dics, rotor–
stator systems or ball mill [8, 14].
Design of the impeller, mixing speed, size of balls, process time, among other
parameters, control the dispersion result [14] (Fig. 2).
• Calendering (Three roll milling)
This method is a suitable technique to disperse microparticles in different media.
This technique breaks the agglomerates by the crushing forces of the rollers and
the high shear forces resulting from the rollers. This method can be used to
process from low viscosity products to thick materials and from small to large
volumes [20, 21].
Following this method is explained in more detail because is the one applicable
for CNTs in polymer matrices.
Fig. 2 Rotating disc to disperse particles in different matrices
4 Three-Roll Milling Process
4.1 Principles
One of the promising methods to disperse CNTs in thermoset resins is the three-
roll milling technique. This technique is a standard method to disperse micro-
particles in industry (e.g. colors, electronics, cosmetics, food, adhesives, etc.), but
is becoming a promising technique to achieve good dispersion rate with nano-
particles [14, 20]. The main advantages of this method include high particle dis-
tribution, temperature control, preventing contamination, small and large batches,
easy process control, low material loss, etc. [21].
In this technique, mixing and dispersion of MWCNTs take place in the vortices
which are located between the rollers by combining the crushing force of the
rollers and the high shear forces resulting from rollers speeds and the distance
between the rollers [21], as shown in Fig. 3.
The process to disperse the nanoparticles using this technique is described next.
First, CNTs are manually mixed into the neat resin, and then the mix is fed into the
feed roller and center roller by the hopper. In this gap occurs a first dispersion of
the aggregates and the final dispersion is performed in the gap between the center
roll and apron roller.
With this technique are achieved high shear forces able to obtain good results in
dispersion of nanostructures within polymer matrices, besides being easily scalable
to industrial level.
CNT/UP
resin
Dispersed
product
GAP 1 GAP 2
Fig. 3 Carbon nanotubes resin dispersion on the rollers and diagram of three-roll milling method
Other techniques that apply shear forces to distribute the CNTs into thermoset
resins like rotating discs don’t reach a degree of dispersion as high as three roll
milling.
In both techniques, the dispersion of the nano-particles is due to the shear forces
generated, responsible for breaking the aggregates of CNTs. In the case of rotating
disc (mechanical stirring), these shear forces are created between the container
wall and the stirring metal disc, however, in the three-roll milling the dispersion of
the mixture takes place in the vortices which are between the rollers.
The strain rate and shear stress are calculated according to the following
equations:
Dv
c¼ ð1Þ
Gap
Dv
s¼g ¼g c ð2Þ
Gap
where Dv is the speed difference between metal disc and container wall for
rotation disc technique and speed difference between rollers for the three-roll
milling technique, Gap is the distance between the container wall and the metal
disc or the distance between the rollers, and g is the viscosity of the sample.
According to this, assuming the parameters shown in the Table 1, for rotation
disc technique the shear stress is constant because the distance between the con-
tainer wall and the metal disc is fixed during the dispersion process, whereas for
three-roll milling technique, decreasing the distance between the rollers increases
the shear stress.
Table 1 Example of dispersion parameters

Dispersion process Speed (rpm) Gap
Rotation disc 2,000 &20 mm
Three-roll mill 230 40, 25, 15, 10, 5 lm
Fig. 4 Optical images of sample (resin ? 0.1 wt%) produced by rotation disc technique (left)
and three-roll milling technique (right)
The shear stresses generated are three orders of magnitude higher in the three-
roll milling technique. These forces are able to break up the nanotubes aggregates
and disperse them into the polyester resin, as shown in the pictures (see Fig. 4),
without breaking or damaging the nanotubes, because the nanotubes have a much
higher tensile strength that three-roll milling process generates.
4.2 Preparation of Samples
There are several processes to fabricate fibre reinforced thermoset polymers. For
selecting a process, different factors influences the decision such as production
rate, product shape and size, the type of thermoset polymer to be used, cost,
properties required, quality, etc. [15, 16].
In general, the manufacturing process of fibre reinforced thermoset polymers
consists of four steps [15, 16]:
• Impregnation: The target of this step is to achieve that the resin flows into the
fibres to form a plate called laminate.
• Lay-up: Consists of placement the laminates at the desired form as dictated by
the design.
• Consolidation: In this step the layers are in close contact and the air is removed.
• Solidification: This is the final step that achieves the final shape of the product.
This stage depends on the type of polymer used. Usually, pressure or vacuum is
needed during the step. The solidification rate depends on the type of thermoset
polymer and the polymerization kinetics.
Manufacturing
Pre-dispersion multiscale
Mixed CNTs Dispersion by Curing and
by mechanical composite:
and resin by three roll mold
hand stirring milling Hand lay-up release
VARIM
Fig. 5 Scheme of manufacturing nanocomposite
The introduction of nano-particles into thermoset polymer as additives involves

changes in impregnation step. A suitable processing technique is necessary to
disperse the nano-particles agglomerates into the thermoset polymer.
The manufacturing of fibre reinforced polyester resin nanocomposite will be
carried out in three steps: (1) addition of the nanoreinforcement into the polyester
resin and dispersion; (2) addition of the hardener and impregnation by hand lay-up
or vacuum assisted infusion molding (VARIM); and (3) the curing and mold
release stage. An example of a schematic illustration of the process is shown in
Fig. 5.
Dispersion by three roll milling consist of several sequential stages, where in
each one of them the distance between rollers (gap) was reduced up to 5 lm and
rollers speed was kept constant (feed roller: 25 r.p.m., center roller: 76 r.p.m. and
apron roller: 230 r.p.m.).
5 Samples Characterization and Potential Applications
5.1 Dispersion Characterization
There are several characterization techniques to determinate the structure and

properties of the nanocomposite: x-ray diffraction, transmission electron micros-
copy, scanning electron microscopy, dynamic mechanical thermal analyses,
mechanical properties, flammability, etc. [9].
These techniques could be combined with other methods as rheology, Raman
spectroscopy and atomic force microscopy to provide a better knowledge of the
dispersion of a polymer nanocomposite [9, 22]. An example of the use of these
techniques is presented here.
The study of the degree of dispersion carried out by the measure of the viscosity
in each stage of three-roll milling process and the determination of the stresses and
shear strain rates that are generated during the dispersion process. Strain rates and
shear stresses are calculated from expressions (1) and (2), discussed above.
Fig. 6 Shear stress and viscosity of an UP suspension with 0.1 %wt MWCNTs as a function of
strain rate
Figure 6 shows the shear stress and viscosity respect strain rate of each stage of
three-roll milling dispersion process of an unsaturated resin containing MWCNTs
(0.1 wt%).
Taking into account that a high dispersion rate of carbon nanotubes is related
with high strain rate values during the dispersion process, it is observed that an
improvement of the dispersion of carbon nanotubes involve an increasing of
viscosity. Decreasing the distance between rollers, the shear stresses rise followed
by an increase in viscosity of the sample. These shear forces are capable of
disrupting the carbon nanotubes aggregates in the polymer matrix causing an
increase of the sample viscosity two orders of magnitude higher respect the neat
polymer matrix.
Viscosity measurements were performed in order to analyze the effect of
increasing the carbon nanotubes content on the viscosity. Figure 7 shows the
results of viscosity respect carbon nanotubes content of the samples after a three-
roll milling dispersion.
Clearly, it is observed that as the MWCNT content increase, the viscosity of the
sample rise too. Samples containing 1 wt% MWCNT (or more content) showed a
high degree of viscosity. These high viscosity values become the mix in an
unwieldy paste.
Raman spectroscopy is commonly used to characterize and identify materials,
providing chemical and structural information of materials. It is a high resolution
non destructive technique with an easy sample preparation and operated at room
temperature [18]. It is a commonly technique for characterize carbon nanotubes. A
general Raman spectrum of MWCNT is shown in Fig. 8. The Raman features of
Fig. 7 Viscosity at various carbon nanotubes content for three-roll milling dispersion process
Fig. 8 Raman spectrum 4000

from MWCNTs bundles
3500 D
Raman Intensity (U.A)
3000 G D'
647 nm
2500
2000
D G
1500
D'
1000
500
514 nm
0
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900
-1
Frequency (cm )
MWCNT are the tangential (G band) mode at higher frequencies and the disorder-
induced D band. The G band (at 1,582 cm-1) has two peaks (G+ and G-) related to
the circumferential (TO) and axial (LO) atomic vibrations. The D band appears at
1,350 cm-1 and its related to the presence of defects in the nanotubes walls
[18, 23].
To know the carbon nanotubes dispersion within the resin were performed
Raman tests in samples containing MWCNT in different percentages.
Fig. 9 Distribution map of UP/0.1 % MWCNT
From the intensities of the spectra (Band D) collected from the scans were
obtained distribution maps of MWCNT within the matrix, as shown in Fig. 9.
The black areas of the image correspond to areas in the sample where there are
not carbon nanotubes, corresponding to low intensities of the spectra. Gray and
white areas are associated with the presence of carbon nanotubes, which results in
higher intensities in the spectra obtained. The highest intensities correspond to
high concentrations of nanotubes that suggest there are aggregates in the sample
(white colour areas). Therefore, a correct dispersion will have greater percentage
of gray colour areas and a lesser percentage of black and white colour areas.
The distribution maps of MWCNT’s in the matrix were analyzed using a
specific image analysis software. With this software it can be quantified the
nanotubes content within the matrix in the scanned area. The results were shown in
Table 2 and Fig. 10 shows some pictures of the samples analyzed.
According to the results, in general, a high degree of dispersion was achieved
for all samples developed, as shown by the low percentage of black areas
(% MWCNT absence) and high percentage of gray areas.
5.2 Mechanical Characterization
Carbon nanotubes present high strength and stiffness as well as high aspect ratio
which make them candidate to improve the mechanical properties of polymers
Table 2 Results obtained after treatment of the images produced from the Raman spectra
Sample % MWCNT filling % MWCNT absence Scan size
(% black area) (lm)
% white area % gray area
UP/0.1 %MWCNT 27.44 72.22 0.29 72 9 72
UP/0.5 %MWCNT 8.79 90.26 0.95 30 9 30
UP/0.7 %MWCNT 3.77 95.61 0.62 30 9 30
UP/1 %MWCNT 3.01 95.44 1.55 30 9 30
Fig. 10 Distribution maps of MWCNT/polyester composites: a MWCNT 0.5 wt%. b MWCNT

0.7 wt%
[14]. Figure 11 depicts the tensile behavior of nanocomposites under ambient

conditions. Tensile characteristics were determined following UNE-EN ISO 52724
with 250 9 25 9 4 mm specimens [24]. It is observed that the addition of
nanofillers improves the tensile properties. Depending of nanoreinforcements
content the mechanical improvements can be up to 13 % in tensile strength and
15 % in tensile modulus [25]. The tensile strength decreases with rising nanotubes
content but remains above that of the unfilled nanocomposite.
All the samples show a similar behavior. The failure mode was delamination
(separate layers involving crack opening, sliding shear and scissoring shear) as a
result of a reinforcement-matrix interaction weak [8, 14, 26, 27] (see Fig. 12).
Figure 13 shows the flexural behavior of nanocomposites. For bending prop-
erties UNE-EN ISO 14125 was the used standard with 800 9 15 9 4 mm spec-
imens [28]. It is observed that the flexural strength and modulus improved with the
(a) (b)
Tensile Strength (MPa)
Tensile Modulus (GPa)

600 50
500 445 434 431 425 424
410 40
30 30 30 31
400 27 28
30
300
20
200
100 10
0 0
0 0,1 0,3 0,5 0,7 1 0 0,1 0,3 0,5 0,7 1
MWCNT Loading (wt%) MWCNT Loading (wt%)
Fig. 11 Tensile strength (a) and tensile modulus (b) versus carbon nanotubes content for UP/
Glass fibre/MWCNT nanocomposites
Fig. 12 Delamination failure mode of a tensile test specimen
(a) (b)
Flexural modulus (GPa)
Flexural strength (MPa)
427 444 424 426 30

500 408
363
400 18 18 17 17
20 16
300
10
200 10
100
0
0 0 0,1 0,3 0,5 0,7 1 0 0,1 0,3 0,5 0,7 1
MWCNT Loading (wt.%) MWCNT Loading (wt.%)
Fig. 13 Flexural strength (a) and flexural modulus (b) versus carbon nanotubes content for UP/
Glass fibre/MWCNT nanocomposites
addition of carbon nanotubes. Depending of nanoreinforcements content the

mechanical improvements can be up to 26 % in flexural strength and 84 % in
flexural modulus [25].
Due to the material anisotropy two failure mechanisms were found: fibre tensile
fracture and interphase shear failure [26, 27] (see Fig. 14).
B
B
A
Fig. 14 Bending specimen. a Fibre fracture. b Interphase shear failure
5.3 Structural Application: Panel Sandwich
Structural sandwich panels are products used primarily in order to perform

enclosures in building, refrigeration sector and transport sector (railway carriage).
This widespread use is due to its physical and thermal properties, such as design,
economic and safety [17].
Manufactured panels are formed by a skin made of a metallic material or
reinforced polymeric matrix, and a core consisting of modified polyurethane rigid
foam [17, 29].
Functions associated with structural sandwich panels are [17, 29, 30]:
• High bearing capacity with low weight.
• Fire protection in case of fire.
• High thermal-acoustic insulation.
• Good barrier to water and steam.
• Excellent air tightness.
• High resistance to weathering and harsh environments.
Fig. 15 Sandwich panel

prototype
• Easy to install.
• Can be easily fixed or replaced in case of damage.
• Long life with low maintenance costs.
Sandwich panels have been developed with improved mechanical performance

by incorporating MWCNT’s in very low proportions (up to 1 wt%). Moreover, the
raw materials used present high performances/cost rate, involving a low cost final
product (see Fig. 15).
References
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nano-reinforced composites. Compos. Sci. Technol. 66, 3115–3125 (2006)
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Engineering. CRC Press, US (2002)
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Structure, Properties and Applications. Springer Science, Berlin (2008)
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based nanocomposites: a review. Composites: Part A 41, 1345–1367 (2010)
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nanotubes. Phys. Rep. 409, 47–99 (2005)
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paneles sándwich fabricados por Pultrusión, XXVI Encuentro del Grupo Español de Fractura
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30. Web www.sandwichpanels.org
Thermoplastic Nanocomposites
with Carbon Nanotubes
Shyam Sathyanarayana and Christof Hübner
Abstract The potential impact of light-weight structures with multifunctional

properties for engineering applications drives significant research and develop-
ment activities on nanocomposites. Polymer nanocomposites especially those with
carbon nanotubes (CNTs) are very attractive for conductive composites with good
structural characteristics. The biggest challenge facing the commercial success of
CNT based composites is the intrinsic strength of their agglomerates which pre-
vents good filler dispersion in the matrix, a key attribute for any reinforcement.
This chapter is a review of the CNT incorporated thermoplastic composites pro-
cessed mainly containing economic multi-walled carbon nanotubes (MWCNTs).
We present an overview of CNTs (their structure, production process, properties,
surface modification, applications etc.) and the mechanism of their dispersion in
thermoplastic matrices. The processing of thermoplastic matrices via the con-
ventional twin-screw compounding approach is discussed along with the influence
of process parameters on MWCNT dispersion. The role of secondary processing
operation on composite properties is also highlighted. The mechanical, electrical
and thermal properties of the thermoplastic-CNT composites are reviewed high-
lighting the key findings and shortcomings. We conclude throwing some light on
the developments on multi-scale reinforcements in polymeric matrices.
S. Sathyanarayana (&)
Polymer Engineering, Fraunhofer Institute für Chemische Technologie ICT,
Joseph von Fraunhofer Strasse 7, 76327 Pfinztal, Germany
C. Hübner
Advanced Materials & Systems Research, BASF SE, B001, Carl-Bosch-Strsse 38,
67056 Ludwigshafen, Germany

20 S. Sathyanarayana and C. Hübner
1 Introduction
The ever increasing demand for improved properties of polymer matrices espe-
cially for light-weight structures and multifunctional characteristics has strongly
shifted the focus of researchers on nanomaterials as reinforcements. The devel-
opment of polymer nanocomposites has been a significant area of research and has
evolved significantly over the last two decades owing to the ability of nanoscale
reinforcements to create remarkable property enhancements at relatively low filler
concentrations, compared to conventional composites. Nanocomposites based on
polymeric matrices gained significant interest after the report of nanoclays filled
nylon-6 by Toyota in 1993 [1], but the actual mention of the term was first found in
the work on Lan and Pinnavaia [2]. Surprisingly automobile tires in which carbon
black acts as a reinforcement is also an example of a nanocomposite. However, the
term ‘‘nanocomposite’’ is not generally used to describe such composites. A
nanocomposite is considered to be a multiphase solid material where one of the
phases has one, two or three dimensions of less than 100 nm according to Ajayan
et al. [3]. According to the ISO/TS27687 standards the nanofillers are classified
based on their dimensions as 1-D (e.g. platelet, lamella; thickness \100 nm), 2-D
(e.g. tube, fiber; diameter \100 nm) and 3-D (e.g. bead, sphere; all dimensions
\100 nm) nano-objects [4].
The growth of different types of nanomaterials starting from nanoclays, cel-
lulose nanowhiskers, carbon nanofibers, carbon nanotubes (CNTs), graphenes,
nano-oxides like nanosilica, nanoalumina, titanium dioxide etc. has led to the
development of composites with extremely attractive macroscopic properties–
multifunctional in most circumstances depending on their inherent characteristics.
Excellent electrical, thermal, mechanical, optical, fire-retardant, barrier, anti-bac-
terial and scratch resistant properties of these composites have been reported and
the results are only getting better with time. The high surface to volume ratio of
these fillers facilitates the attainment of desired macroscopic functionality at
substantially lower filler loading fractions. The biggest challenge with these
nanofillers however has been with dispersing them in the host matrix to take
advantage of their theoretical potential. Table 1 gives an overview of the areas of
application for the well known and widely employed nanofillers.
Table 1 Areas of possible applications for different nanofillers

Area of application Type of nanofillers
Tribology Fullerene like tungsten sulphide, zeolith, nanoclay, nanosilica
Antibacterial properties Titanium dioxide, zinc oxide, copper oxide, silver
Electrical properties Carbon nanotube, carbon nanofiber, graphene
Mechanical properties Cellulose nanowhisker, nanoclay, carbon nanotube, graphene
Flame retardency Nanoclay, carbon nanotube
Barrier properties Nanoclay
Self cleaning surfaces Titanium dioxide, nanosilica
Surface modification Nanosilica (AEROSIL)
Coatings Nanosilica, nanoalumina, zinc oxide
Thermoplastic Nanocomposites with Carbon Nanotubes 21
Carbon based nanomaterials are highly attractive due to their ability to tran-
sition an insulating polymer matrix to a conductive composite, in addition to the
proven advantage in achieving excellent structural properties. CNTs stand out
among the other carbon based fillers like carbon fibers or carbon nanofibers which
require higher filler loading fractions to exhibit similar levels of electrical con-
ductivity. Graphene tipped to be a strong competitor for the CNTs on the other
hand is still in its infancy, and large production volumes of these materials is still
challenging. CNT based polymer composites have been a significant area of
research in the last couple of decades owing to CNTs high aspect ratios with
nanometric dimensions, low mass density and intrinsically superior electrical [5–
8], mechanical [8–11], and thermal properties [8, 12, 13].
Continuously lowering costs of CNTs, especially multiwalled carbon nanotubes
(MWCNTs) with increase in demand and production capabilities augments
favorably for a huge polymer-CNT nanocomposite market. Interesting observa-
tions on MWCNT based composites have been plenty starting from different ways
of MWCNT synthesis to its application in electromagnetic shielding (EMI) [14–
17], sensors [18–20], electrostatic charge dissipation (ESD) [21], flame retardancy
[22], wind turbine blades [23], photovoltaic packaging [24], electrically con-
ducting cables [25] etc.
The potential of CNTs as fillers for multifaceted product development in
polymer matrices certainly tilts the tide in its favour compared to its competitors.
Due to the renown challenge involved with dispersing the CNTs in thermoplastic
matrices for good macroscopic properties of the composites, thermoplastic com-
posites with CNTs (primarily MWCNTs) is the main focus of attention in this
chapter.
2 Carbon Nanotubes: An Overview
The interest in the special allotrope of carbon called CNTs was greatly stimulated
by the observations of tubular forms of carbon with nanometric dimensions by
Iljima [26], and succeeding reports on the capabilities to synthesize these nano-
particles in large quantities [27, 28]. CNTs belonging to the fullerene family are
geometrically idealized to be a cylinder formed by concentrically rolled graphene
sheets. They are typically of a few nanometers in diameter and microns in length.
2.1 Structure of CNT
Similar to the structure of graphite, the sp2 hybridized CNT has each of its atoms
bonded to three neighboring atoms in an hexagonal array. As the cylindrical
structure of the CNT is brought about by the rolling up of the graphene sheets, the
type of CNT would depend upon the number of concentric cylinders. CNTs
Fig. 1 Different types of

CNTs—based on the number
of tube walls. Reprinted from
[141], Copyright (2003) with
permission from Elsevier
principally exist as SWCNTs, double-walled carbon nanotubes (DWCNTs) or as

MWCNTs (Fig. 1).
The intrinsic properties of the CNTs would stem from their atomic arrangement
(or in other terms the way their graphene sheets are rolled), the type of CNT and
their individual geometric dimensions. The rolling up of the graphene sheets and
hence the atomic structure of the CNTs is well defined by tube chirality. The
chirality is given by the chiral vector Ch ¼ n~ a1 þ n~ a2 where ð~ a2 Þ are the unit
a1 ; ~
vectors and (n,m) are the number of steps along the unit vector of the hexagonal
lattice [29]. This gives rise to three possible orientation forms for the carbon atoms
of the CNTs. If n = m, it leads to the ‘‘armchair’’ structure while the ‘‘zigzag’’
structure results when m = 0. Any other orientation is referred to as the ‘‘chiral’’
structure. The electronic conduction of the CNTs is dependent on its chirality.
CNTs possessing an ‘‘armchair’’ chirality are metallic, semi-metallic when (n–m)/
3 = i and n = m, where i is an integer and semi-conducting otherwise [30]. The
chirality of a MWCNT is extremely complex as each of the concentric nanotube
walls could carry different chiralities. Figure 2 shows the nomenclature system of
CNTs and the different chiral forms of SWCNTs [(a) arm chair, (b) zigzag, (c)
chiral].
Fig. 2 System of CNT nomenclature [142] (Left); Chiral forms of SWCNTs (Right). Reprinted
from [143], Copyright (1995) with permission from Elsevier
2.2 Synthesis of CNTs
Arc discharge, laser ablation and chemical vapor deposition (CVD) are three
principal techniques by which CNTs are synthesized. They are briefly described
below. The schematic of the different techniques are shown in Fig. 3.
The arc discharge approach is probably the easiest to synthesize MWCNTs,
however the quality of the resulting CNTs and the pattern of growth is not the best
while comparing to the production by other techniques [31]. In the arc-discharge
approach, two graphite electrodes are placed 1 mm apart in an inert atmosphere
and a direct current of about 50–100 A at a voltage of 20 V is applied across them.
The vaporization of carbon at these conditions result in a high temperature dis-
charge (also termed as plasma) resulting in the consumption of the anode and the
formation of deposits on the surface of the cathode from where the CNT grows.
The typical yield of this process ranges from 30 to 90 % and the principal
advantage of this process is the economic production of MWCNTs without a
catalyst. The doping of the anode with a metal catalyst would result in the for-
mation of SWCNTs [30]. The principal drawback of the arc-discharge approach is
the production of shorter and impure CNTs which mandates a purification step to
generate high quality CNTs.
The laser ablation technique uses a high power laser to form the discharge
product unlike the direct current (DC) generated electricity in the arc-discharge
approach. Laser is shot on a graphite source that is placed in an oven under inert
atmosphere at temperatures of around 1,100–1,200 C. The carbon vapors formed
under these conditions expands and cools resulting in the formation of CNTs and
other members of the fullerene family depending upon the set process conditions.
MWCNTs are the principal product and are shorter in length compared to arc-
Fig. 3 Techniques for CNT synthesis [144]. a Arc discharge, b Laser ablation, c CVD
discharge process [30, 32], but the addition of a metal catalyst to graphite would
result in SWCNTs. The typical yield of this process is around 70–80 % and the
purity of the produced nanotubes is significantly higher. Good product control is
possible; however this comes with the trade-off of high production cost due to
higher power requirements for operating the laser.
CVD is the widely adopted industrial approach for producing CNTs owing to
its scalability. When a carbon containing gaseous source like acetylene, methane
etc. is passed over a metal catalyst at temperatures ranging from 550 to 1,200 C it
results in the freeing up of carbon atoms on the decomposition of the gas, which
recombines in the form of CNTs on the metallic substrate. This method is widely
adopted for flexibility in controlling the quality and exercising good control over
the dimensions of the formed product. The yield varies from 20 to 100 % with
minimal need for purification of the synthesized CNTs due to the negligible traces
of amorphous carbon. Very long CNTs can be produced by this approach. The
production of extremely pure SWCNTs is possible with controllable diameters, but
the MWCNTs that are formed with the CVD process has more structural defects
[33], and are highly entangled compared to the arc discharge and laser ablation
approach.
2.3 Properties of CNT
CNTs are known for their intrinsically high mechanical, thermal and electrical
properties. The sigma bonds which make up the C–C bonding in CNTs attributes
to their excellent mechanical characteristics. Elastic modulus of 1.2 TPa and
tensile strength of about 50–200 GPa have been reported for CNTs [34]. However,
there does not seem to be a consensus on the reported mechanical behaviour
among published literatures. Their high axial and low lateral thermal conductivity
also add to their significance. Although theory predicts a room temperature ther-
mal conductivity of 6,000 W/mK [35], Kim et al. estimate the thermal conduc-
tivity of MWCNTs to be 3,000 W/mK [36], and Pop et al. report 3,500 W/mK for
SWCNTs [37]. This is significantly higher than the thermal conductivity of dia-
mond (1,000–2,200 W/mK) which is reported to be one of the best known thermal
conductors [38].The oxidative thermal stability for both MWCNTs and SWCNTs
are greater than 600 C which compares strongly with that of 450–650 C for
graphite. Their co-efficient of thermal expansion is very minimal which supports
the excellent thermal conductivity of these materials. SWCNTs show electrical
conductivities of the order of 102–106 S/cm, while it ranges between 103 and 105
for MWCNTs. The lower scales are very similar to the reported in-plane electrical
conductivity of graphite of about 200–2,500 S/cm [39], indicating the dominative
electrical properties of CNTs compared to one of the best reported electrical
conductors in graphite. They also boast of extremely high intrinsic electron
mobility of greater than 105 cm2/Vs [40], which is very similar or even higher than
graphite.
The extraordinary multi-faceted properties of CNT confer to these materials a

significant potential to be used in a wide-variety of applications. The intrinsic
tendencies of the CNTs to exist as agglomerates due to their van der Waals (vdW)
forces of attraction (0.5 eV/nm) [41], by large limits the realization of the com-
plete potential of these materials as nanoscale reinforcements in different host
matrices.
2.4 Commercially Available CNTs
Commercially available CNTs that primarily results out of the CVD process are
highly disorganized and have a highly agglomerated morphology with a significant
agglomerate strength. This inability to produce individualized and aligned mor-
phologies severely inhibits the theoretical potential of CNTs as to what could be
expected out of CNT yarns or forests. Although it is highly complicated to achieve
aligned CNT morphology in a commercially viable process, the cohesive or the
vdW forces of attraction that results in the agglomerated morphology of CNTs
could at least be minimized in order to gain a competitive advantage with CNTs as
polymeric fillers. The initial or the primary CNT agglomerates have to be broken
down theoretically into individual CNTs or in other terms dispersed well into the
polymer host to translate the intrinsic characteristics of the CNTs to their com-
posites. This has remained a significant challenge over the years and any effort to
maximize the quality of dispersion on industrial scale could result in taking these
nanocomposites close to application.
Due to its availability in bulk and lower costs, MWCNTs would be the ideal
choice for high volume industrial applications; hence attention would be focused
on MWCNT dispersion in thermoplastics in this Chapter. Scanning electron
micrographs (SEM) images of two of the most widely reported type of MWCNTs
in literature namely Baytubes C150P (Bayer Material Science, Germany) and
NanocylTM NC7000 (Nanocyl S.A., Belgium) are shown in Fig. 4.
These pictures indicate a highly entangled network of MWCNTs with sizes
ranging up to a few hundred microns, unusual for a material described as nano-
filler. Alig et al. describe the structure of loosely packed larger agglomerated
NC7000 as a ‘‘combed yarn’’ structure while that of C150P as a ‘‘birds nest’’ with
smaller tightly held primary agglomerates [42]. Although the geometries of these
MWCNTs do not differ significantly, the average deformation stress (at 25 %
strain) of C150P with a bulk density of 120–170 kg/m3 [43], is 0.64 MPa [44],
while that of NC7000 with a bulk density of 60 kg/m3 [45], is 0.39 MPa [44]. This
difference in the deformation stresses of the MWCNTs will be a critical factor in
determining the magnitude of processing parameters and consequently the extent
of processing shear required to create equivalent dispersion qualities with these
two different CNT types.
Fig. 4 Low and high magnification images of NC7000 (Top), C150P (Bottom)
2.5 Modification of CNT Surface
Modification of the CNT surface is an approach widely adopted to render the

surface of the inert CNTs compatible to interact efficiently with the polymer and
also weaken their intrinsic vdW forces of attraction. This is also termed as CNT
functionalization. Functionalization both by chemical and physical means has been
largely reported.
Chemical functionalization is done either on the side walls of the nanotubes or
by creating defects on CNT surfaces by acid treatments. This is expected to result
in a very strong matrix-CNT interaction with a trade off on the structural char-
acteristics of CNTs. The sp2 hybridization of carbon is transformed to sp3 to create
active sites for effective interaction with polymer accompanied with the loss of p
conjugation bonds on the outer walls. Covalent functionalization of CNTs could
modify CNT stacking morphologies by altering hydrogen bonds resulting in
improved CNT solubility in solvents [46]. But, covalent functionalization tends to
negatively affect the physical and chemical integrity of CNTs. Strong acid treat-
ments affects the geometry of the CNTs resulting in increased filler percolation
thresholds [47]. Covalent treatments could also negatively affect the intrinsic
electrical properties of the CNTs and have a profounding effect on the metallic
characteristics of metallic CNTs [48]. Enhanced reactivity between CNT and the
polymer would result in wrapping or encapsulation of CNT surfaces by the
polymer due to coupling or grafting lowering the bulk conductivity of the com-
posite [49]. The phonon scattering length is also expected to be lowered leading to
lower thermal conductivities [50]. Covalent treatments are mainly aimed at
improving polymer-CNT compatibility and CNT dispersion. Effective achieve-
ment of this could lead to improved structural characteristics accompanied with
losses in electrical and thermal conductivity of the composite.
Physical functionalization is done by polymer wrapping (vdW forces and p-p
stacking), surfactant adsorption on CNT surface (physical adsorption) and endo-
hedral techniques (capillary principle). Although this technique would not damage
CNTs a weak CNT-polymer interaction could be expected out of these approaches.
Non-covalent or physical treatment of CNTs result in the outer tube walls sub-
jected to more treatment than the inner tubes [51]. This could result in the CNTs
being bundled even after treatment. Hence mechanical treatments like milling,
ultrasonication etc. should precede this treatment. Since physical methods don’t
result in significant CNT structural damage, their composites could be expected to
show enhanced electrical conductivity as the p-conjugation of the CNTs and their
electron transfer paths could maintain their identities. Polymer wrapping of CNT
surfaces cannot be completely ruled out resulting in lower electrical conduction.
Mechanical property enhancements cannot be expected to be on a larger scale
because the chance for the interfacial strength to improve is minimal because of
lack of chemistry.
The techniques of chemical and physical modifications are however, relatively
expensive which limits modification of the CNT for large scale applications. A
review by Bose et al. [52], discusses the positives and the drawbacks of both
physical and chemical functionalization in detail on the properties of CNT based
polymer composites.
2.6 Applications of CNTs
The intriguing properties of CNTs have led to many research efforts leading to
uncovering the potential prospects of employing CNTs in practical applications.
Although it has been very complex to translate the theoretical potential of CNTs
till date into potential applications, efforts are still ongoing towards understanding
the intrinsic properties of CNT and ways to implement them in real life. The
benefits of CNTs are expected to be significantly realized from an economical
perspective when they are used as functional fillers for materials like plastics,
ceramics etc., however their potential to be used as such (especially SWCNTs in
flexible electronics applications) is also being widely worked on. This is supported
from the finding that 69 % of the global CNT market share of $472.9 million in
2010 was the contribution of the plastics and composites industry [53].
Although a wide variety of applications could result owing to superior CNT

properties, they can principally be classified into three main categories of
mechanical (structural composites for aerospace and automotive industries, tex-
tiles, sport goods, etc.), thermal (flame retardant additives, coatings, electronic
circuitry etc.) and electrical & electronics (semi-conducting materials, electronic
circuitry, fuel supply systems of automobiles, navigation systems etc.). The multi-
functional derivates that stems out by a combination of these properties on the final
part application adds significant value to the applications of CNTs.
The European Chemical Industrial Council (CEFIC) classifies the potential
applications of CNT on the basis of time into short term—those products based on
CNT already available or will shortly be available (e.g. conductive composites,
sensors, electromagnetic shielding, sport goods), mid-term (e.g. coatings, lithium-
ion battery, fuel cells, semiconducting materials, petrochemical catalysts etc.) and
long term—those currently under the scope of research & development (e.g. drug
delivery, microwave antennas, medical implants etc.) [54].
Some of the existing commercial applications of the CNTs include the long
range vessel LRV-17 from Zyvex Marine made of a carbon fiber-nanocomposite
system consisting of carbon fiber reinforced plastic (CFRP) and CNTs which
enables reduction in structural weight, efficient fuel usage and increased range
[55], and a 25 times stronger tennis racket by Völkl made of CNT compared to
carbon fibers (at same weight) which would eventually result in more kinetic
energy returned to the ball [56]. Aldila have also reported to have used CNT based
epoxy composites for golf shafts for vibration damping [57].
2.7 CNTs: A Market Outlook
The production capacity of CNTs is expected to grow globally from 3,141 to

12,806 metric tons in 2016 at a Compound Annual Growth Rate (CAGR) of
10.5 % according to Centre for Knowledge Management of Nanoscience and
Technology (CKMNT), India [53]. As per their 2011 forecast the total CNT
market is to yield around $1.1 billion by 2016 at a CAGR of 10.5 %.
A Frost and Sullivan report published in 2011 forecasts a $35.52 million market
for CNT in the automotive composites by 2015, indicative of a market share of
3.6 % at 1 % CNT loading [58]. The report also predicts a 10 % penetration of
CNT in the construction industry, 15 % in the fibers and textile domain, and about
25 % in the intumescent coating market. From an electronics industries’ stand-
point, the largest share for CNT is expected for the displays (1 - [5 %) and
flexible displays (1–10 %), whereas only 1 % penetration in the sensor market is
foreseen. Significantly, CNTs are also expected to gain a 1–5 % share in the total
authentication market. With recent developments in research, it is expected that
these numbers will continue to rise in spite of a foreseen potential threat by
graphene which is expected to gain a significant market share especially in the
electronics industry.
3 Processing of CNT Incorporated Thermoplastic

Nanocomposites
The level of CNT dispersion visible on the composite morphology is a direct

function of the type of polymer and CNT employed, the processing approach and
the process factors. The morphology and therein the macroscopic properties of the
composite are dictated by the thermo-mechanical history during processing.
Several processing methodologies such as solution casting [59–61], melt mixing
[62–67], solution mixing [59, 60, 68], different methods of in situ polymerization
of the monomer in the presence of CNTs [69, 70], coagulation spinning [71],
mechano-chemical pulverization [72], solid-state shear pulverization [73], electro
spinning [74] etc. have been adopted for the synthesis of polymer-MWCNT
composites. In this section only the predominantly preferred approaches namely
solution processing, in situ polymerization and melt mixing would be discussed in
brief.
Solution processing is one of the widely utilized approaches owing to its
simplicity. It involves dispersion of the CNT in a suitable solvent by sonication
and/or stirring followed by mixing with a solution of the polymer host, evaporation
of the solvent and drying with or without vacuum. Ultrasonication is widely
employed to break the CNT agglomerates as the shear in the solution mixing
process is significantly low. The type of ultrasonication (ultrasonic bath or horn),
bath temperature, rate of sonication (frequency and time) and the nature of the
solvent could have a strong influence on the properties of the product. This method
can be successful with the right choice of solvent and complete removal of the
solvent during the drying stage, however it is not easily scalable. It is widely
adopted for preparing composites based on thermosetting matrices where a sig-
nificant magnitude of shear is not required as the low viscosity of the host would
result in good infiltration of the CNT agglomerates facilitating dispersion.
In situ polymerization of monomers in the presence of CNTs is another widely
used technique for composite preparation. This technique is proposed to form a
very good chemical affinity between the polymer chains and the CNTs in most
cases, but depending on the nature of the reactants a non covalent interaction is a
definite probability. The polymerization of the monomer in the presence of an
initiator is carried out with CNTs in the vicinity enabling the production of
composites with high CNT loadings. A mix of polymer grafted CNTs and free
polymer chains are obtained which creates a favorable environment for the
development of a highly compatible polymer-CNT interface. The low viscosity of
the starting monomer facilitates better infiltration into the CNTs and consequently
their dispersion. CNT based composites of polystyrene (PS), poly (methyl meth-
acrylate) (PMMA), and vinyl monomers are commonly produced using this
approach. Yuan et al. show significant enhancement in the mechanical properties
of PS-MWCNT composites prepared by a combination of in situ polymerization
followed by melt mixing owing to strong interfacial adhesion between the CNT
grafted PS and the PS matrix [75].
Owing to its simplicity and adaptability for a commercial scale up melt mixing/
compounding seems to be the most commonly employed approach for thermo-
plastic polymer/MWCNT nanocomposites. This method is most suitable for
polymers that cannot be processed with the solution processing approach owing to
its inability to dissolve in commonly employed solvents. The higher magnitude of
shear during the melt mixing process facilitates the breakup of the CNT
agglomerates followed by simultaneous dispersion and distribution in the polymer
melt. For a melt mixing process to give optimum dispersion quality optimization
of all the process parameters like the screw configuration, screw speed, through-
put/residence time, barrel temperatures, filler feeding position etc. is imperative.
3.1 Mechanism of CNT Dispersion in Thermoplastics
Dispersion of CNT in thermoplastics is a simultaneous sequential process starting

with the wetting of the CNT agglomerates by the polymer melt, infiltration of the
polymer melt into the CNT agglomerates, disintegration of agglomerate fractions
weakened by the infiltration process and shear forces into small fractals by
mechanisms of erosion and/or rupture followed by their distribution in the polymer
host (Fig. 5). This mechanism of filler dispersion is strongly influenced by the
processing approach, associated process parameters and the nature of the polymer
and the CNTs.
For effective wetting of the primary CNT agglomerates by the polymer melt,
the interfacial energy difference between the polymer and the CNT should be at its
minimum. As the interfacial energy difference between polar thermoplastics like
polycarbonate (PC), polyvinyl chloride (PVC) etc. with the hydrophilic CNTs is
significantly low, excellent CNT dispersion is achievable with these matrices
resulting in extremely low filler percolation thresholds for the final macroscopic
properties [67, 76–78]. On the other hand polyolefins exhibit a very high inter-
facial energy difference with the CNT limiting the level of CNT dispersion in the
composite [62, 79]. Incorporation of surface functionalities to the CNT is a
solution to render compatibility with the polymer; however this is an expensive
approach as detailed earlier.
Fig. 5 Mechanism of CNT dispersion

Infiltration of the polymer melt is principally governed by the mobility of the

polymer chains (dependent on viscosity), the available pore radius or in other
terms the agglomerate density of the CNTs, the strength and size of the CNT
agglomerates and surface tension variations between the polymer and the CNT.
Lower polymer viscosity or high melt temperatures and low agglomerate density
would aid faster infiltration, while minimal interfacial energy difference between
the polymer and the CNT would enhance the efficiency of infiltration. The infil-
tration process can be manipulated by the choice of the raw-materials and the
process parameters which will be discussed in detail later in Sects. 3.2 and 3.3.
The magnitude of applied shear stresses arising due to the viscous flow on the
CNT agglomerates during processing must be above the inherent strength of the
agglomerates (ra) for dispersion to occur. The dispersion of the weakened primary
agglomerates by preceeding wetting and infiltration would take place by mecha-
nisms of rupture/and or erosion governed by a dimensionless fragmentation
number (F) which is directly proportional to the product of the melt viscosity (g)
and the shear rate (cr) and inversely proportional to the inherent maximum
agglomerate strength (ram). The magnitude of contribution of the infiltration step
towards the reduction in ra could play a role in regulating the maximum shear
stress that has to be exerted on the agglomerates. It is to be remembered that
enhanced shear stress could result in tube breakage and also could lead to possible
polymer degradation. Though rupture and erosion would co-occur, a significantly
larger magnitude of F (F 1) would result in a situation where rupture would
dominate while lower F (F 1) would result in dispersion dominated by erosion
[80]. The mechanism of rupture is comparatively faster than erosion owing to the
instantaneous breakage of primary agglomerates into smaller fractals in the for-
mer, while a slowly peeling of individualized CNTs occurs from the outer surface
of the primary agglomerate fraction in the latter. Distribution of the dispersed
agglomerate fractals takes place simultaneously with the disintegration or the
rupture of remaining agglomerates over the course of the process. Idealizing this in
the context of twin-screw extrusion, the residence time in the extruder would
determine the extent of filler dispersion for a given set of process parameters and
material combination.
3.2 Influence of Raw Materials
The selection of a suitable polymer host and the intrinsic characteristics of that
polymer host is one of the critical factors affecting the quality of filler dispersion in
the final composite. An increased affinity between the polymer and the CNT would
result in better wetting of the CNT agglomerates which is the preliminary step in
the mechanism of dispersion. Polymers like PC and PA which has lower interfacial
energy difference could result in better wetting of the CNT agglomerates and
hence better dispersion while the quality of dispersion in polyolefins is poor owing
to its hydrophobic nature and higher interfacial energy difference with CNT.
Exceptionally polystyrene (PS) presenting a polar characteristic shows poor CNT

dispersion morphology owing to the high chain stiffness due to its phenyl groups.
The viscosity of the polymer melt governs the extent of melt infiltration into
the agglomerates and the dominating mechanism of filler dispersion via rupture or
erosion. Lower polymer viscosity would result in better melt infiltration, but could
result in lower magnitude of viscous flow shear stresses during processing. Higher
polymer viscosity would hinder easier and faster melt infiltration but can result in
increased shear stresses for agglomerate breakage. Magnitude of the shear stresses
required for dispersion of CNT is also dictated by the intrinsic characteristics of
the CNT. Kasaliwal et al. discuss the influence of PC melt viscosity and molecular
weight on the level of MWCNT dispersion and conclude that lower matrix vis-
cosity resulted in better melt infiltration leading to better MWCNT dispersion and
hence lower electrical resistivities in the composite [81].
The type of CNT especially its number of walls, length, aspect ratio,
agglomerate strength and morphology, and the nature of surface functionalization
are factors to be considered while designing the process and the associate
parameters for its dispersion in a polymer matrix. A CNT with higher agglomerate
strength would present increased difficulties to melt infiltration compared to a CNT
type with more loosely packed agglomerates even if larger agglomerate size
fractions are present in the latter. High aspect ratios of CNT are beneficial for
efficient load transfer and hence improved mechanical properties at low percola-
tion thresholds. However, it could complicate dispersion owing to the enhanced
available surface area for intra-CNT interactions compared to employing CNTs
with low aspect ratios. A balance between the level of dispersion and the aspect
ratios of the CNT are quite critical for the end properties as elucidated by Castillo
et al. on their work on PC incorporated with different types of CNTs [78]. The
enhancement in the compatibility of the CNT with the polymer by functionali-
zation techniques also plays a role in dictating the level of MWCNT dispersion in
the polymer host. Menzer et al. found that the altering of the CNT lengths by ball
milling resulted in compact agglomerate morphologies and reduction in CNT
lengths contributing to higher electrical and rheological percolation thresholds in
the composite [62]. Idealizing this to the reduction in the length of CNTs as a
function of processing, it would be wise to prefer CNTs with longer average
lengths.
3.3 Influence of Process Parameters
The typical melt mixing or compounding parameters namely screw speed, barrel
temperature, material throughput, screw configuration and residence time would
have to be tailored to specific thermoplastic polymer-CNT system in order to
achieve the desired CNT dispersion quality for maximum composite performance
[65, 67, 82]. As dispersion is a continuous mechanism influenced by the shear
stresses generated by the viscous flow governed by these parameters, addressing
the individual contribution of these factors is complicated. This section briefly

outlines the individual effects and complementary influences these factors would
have on the level of CNT dispersion from a processing perspective.
A higher screw speed would result in an increased specific mechanical energy
input (SME) of the process resulting in enhanced shear stresses and thereby
dominant dispersion mechanism by rupture. A higher screw speed also would
result in a decreased level of screw fill and a lower residence time for the melt in
the extruder at a condition where the other parameters are kept constant. Higher
screw speeds could also result lower polymer viscosity aiding faster melt infil-
tration, but at the same time can result in polymer degradation and also negatively
affect the aspect ratio of the CNTs [82]. Lower speeds on the other hand would act
opposite to what has been detailed with significant limitation on the level of
generated shear stresses. A higher screw speed was found to be helpful in
achieving good filler dispersion when employing matrices that are not known to be
compatible with the CNTs like PS, PP and when using CNTs with a high
agglomerate strength [65, 83].
Melt or barrel temperatures influence the melt viscosity of the polymer and
thereby the level of infiltration and the magnitude of generated shear stresses for
agglomerate dispersion. Lower melt viscosities are highly recommended for faster
and better infiltration of the CNT agglomerates while higher melt viscosities are
important for enhanced shear stresses. The desired level of dispersion would
determine the domination of the melt infiltration step or the creation of enhanced
shear stresses for higher fragmentation numbers.
Low material throughputs would result in higher SMEs, lower degree of
screw fill, and higher local melt residence time leading to improved CNT dis-
persion quality with trade-off on production volume. Throughput levels are also
regulated by the feeding capacity of the nanomaterial feeder owing to very low
bulk density of the CNT along with a very low volume fraction of filler feed.
An optimum screw design must be able to provide the desired level of SME
for the pre-set extrusion parameters and is generally a combination of mixing,
kneading and transportation elements. The magnitude of SME, the nature of the
CNT agglomerates and the desired residence time of the melt in the extruder
would dictate the screw configuration. The screw configuration should be designed
keeping in mind of the other process factors. When a high speed is required for
processing composites containing high agglomerate strength CNT, the screw
design must be able to accommodate this process with a sufficient residence time
to allow for other dispersion steps like wetting and infiltration. An enhanced
residence time is bound to result in polymer degradation while shorter residence
times may not provide the desired level of dispersion.
The position of filler feeding becomes important when dealing with CNTs.
CNTs with enhanced intrinsic agglomerate strength like the Baytubes C150P are
recommended to be fed along with the polymer in the principle feeding port in
order to allow for increased residence time for agglomerate dispersion. Side
feeding of the filler NanocylTM NC7000 which has a lower agglomerate strength is
recommended owing to its loosely packed agglomerate structure with better dis-
persion envisioned by a dominant melt infiltration [84].
We have carried out comprehensive investigations on the influence of the twin-
screw process parameters on MWCNT dispersion in PP, PS, PPE/PS and PC and
have understood that the ideal processing parameters is strongly dependant on the
nature of the matrix and its compatibility with the CNTs [65–67, 83].
3.4 Strategies for Improving CNT Dispersion During

Processing
Functionalization of CNTs by physical or chemical means as discussed earlier has

been reported to result in improved CNT dispersion in polymer matrices. This
approach is however not commercially viable owing to the high costs, scale up
limitations and environmental issues. Hence, it becomes important to focus on
alternative strategies via which CNT dispersion in a polymer matrix can be
improved.
‘‘Nanodirekt’’ is an approach involving the dispersion of nanomaterials in water
or solvents followed by a direct addition of this homogeneous dispersion into the
polymer melt [85]. The dispersing medium will evaporate immediately and the
nanoparticles will stay finely dispersed in the polymer matrix. This method ensures
that the dry nanofiller is not fed directly into the extruder eliminating potential
health hazards associated with handling of nanofillers.
Subjecting the polymer-CNT melt to ultrasonic waves in the extruder has
resulted in improved CNT dispersion in PEEK (polyether ether ketone) in the work
of Lewis and Isayev [86]. Isayev et al. have demonstrated this approach also on
polyetherimide (PEI)/MWCNT composites [87]. Weiss et al. on their work on PP-
CNT composites with two different types of CNT however state that the efficiency
of employing an ultrasound during the extrusion process is strongly dependant on
the type of the CNT employed [88].
Enhanced nanofiller dispersion in a polymer matrix is aided by supercritical
carbon dioxide (sc-CO2) assisted processing. Different variants of this method
have been adopted by research groups. Nguyen and Baird propose an approach in
which a pressurized CO2 chamber is employed to assist in the exfoliation and
delivery of the clay into a stream of polymer melt in the extruder [89]. A modified
hopper in the feed section of the extruder to allow polymer and clay to interact
with sc-CO2 before processing was proposed in the work of Zerda et al. [90]. Clay
particles were pre-treated with sc-CO2 in a pressurized vessel and then rapidly
depressurized into another vessel at atmospheric pressure to force the clay platelets
apart in the work of Manke et al. [91]. Though this approach has been widely
reported for nanoclays, there exists a possibility for extending it to the CNTs. Chen
et al. demonstrated an identical process employed by Nguyen and Baird for the
processing of CNT/poly(phenylsulfone) (PPSF) composites [92].
Incorporation of processing additives is a simple and economical strategy for

enhancing CNT dispersion in thermoplastics. The addition of peroxide during
twin-screw compounding led to a substantial improvement in the quality of
MWCNT dispersion in PP owing to the reduction in PP melt viscosity (facilitating
better melt infiltration into the agglomerates), reduction in ther interfacial tension
between PP and CNTs (leading to better melt wetting of the agglomerates), and
surface functionalization of carbon nanotubes (resulting in weakening the intra-
filler attractive forces) [64]. Better wetting and infiltration of the MWCNTs by
polyethylene glycol resulted in a significant improvement in MWCNT dispersion
in PE [93].
3.5 Influence of Secondary Processing on Composite

Properties
Though good primary filler dispersion is a pre-requisite for good macroscopic

characteristics of the composite, widely employed secondary processing or fin-
ishing operations for nanocomposites like injection or compression molding also
have a major role in regulating final composite properties. The thermo-mechanical
history generated on the composites due to these operations has an effect on the
level of primary CNT dispersion (created with the extrusion process). Compres-
sion molding results in the re-agglomeration of the previously dispersed CNTs
facilitated by the reduction in the viscosity of the matrix at a specific process
temperature, pressure and holding time. A network of re-agglomerated CNTs
forms multiple conductive pathways in the polymer leading to good composite
electrical properties, though theoretically one such pathway is sufficient for
achieving conductive properties. Higher melt temperatures and longer holding
times have been reported to result in lower electrical percolation threshold and
better composite conductivity [76]. It must however be remembered that the re-
agglomeration of the dispersed CNTs could negatively affect the mechanical
characteristics. Injection molding on the other hand is associated with a significant
magnitude of secondary shear compared to the compression molding process
resulting in filler orientation. The temperature gradient existing between the low
temperature mold wall and the high temperature melt results in the freezing of the
outer core, lowering the bulk conductivity of the composite. Injection molding is
widely preferred from an industrial perspective being a high volume manufac-
turing process and hence the tailoring of the process parameters to achieve good
macroscopic characteristics of the composite becomes important. Villmow et al.
recommend lower injection velocities to limit orientation effects and higher melt
temperatures for good electrical conductivity [94]. Mold temperature and holding
pressure had a minimal influence in their work. Elevated mold temperatures could
minimize the effect of temperature gradient. Some of the important factors to be
considered during the production of a CNT incorporated thermoplastic composite
are summarized in Fig. 6.
Fig. 6 Tailoring a CNT incorporated thermoplastic composite
4 Effect of CNT Dispersion and Functionalization

on Composite Properties
The properties of CNT incorporated thermoplastic composites are mainly depen-

dent on the level of CNT dispersion in the host matrix and the nature of polymer-
CNT interaction. These two factors in turn is a complicated function of the type of
host matrix and its inherent characteristics, the type and surface functionality of
the CNTs, processing methodology and associated parameters as detailed in the
previous section. Hence, the important macroscopic properties of the CNT filled
nanocomposites namely mechanical, electrical, and thermal properties would be
elucidated upon in this section.
4.1 Mechanical Properties
Carbon nanotubes are envisaged to be ideal reinforcements for polymeric matrices

owing to their exceptional mechanical properties. However, this does not alone
ensure composites with excellent structural characteristics. The extent of disper-
sion and distribution of CNTs in the polymer host, alignment/orientation of CNTs
in the matrix, the aspect ratio of the CNTs in the final composite, and the nature of
the interface between the polymer and CNTs are considered to be crucial factors
having an effect on the mechanical properties of the polymer-CNT composite.
In the case of reinforcements with nanofillers, the quality of filler dispersion is

extremely important as the presence of large scale agglomerates would substan-
tially lower the efficiency of load transfer. The level of CNT dispersion is pri-
marily determined by the compatibility between the polymer and the CNTs, in
addition to the methodology of composite processing. Achieving a good dispersion
of CNTs in a thermoplastic matrix has been a perennial problem, but matrices like
PC, PVA, PA etc. [67, 95, 96], show very good CNT dispersion morphologies.
This is probably due to their polar nature and lower interfacial energy difference
with the CNTs. On the other hand, the polyolefins have been so far considered the
hardest of the thermoplastic matrices to achieve a good CNT dispersion. But recent
results on PP and PE [64, 93], show that this challenge could be overcome by the
employment of functional additives. Controlling or characterizing distribution of
nanofillers in the matrix has so far been almost impossible, but is very critical to
tune composite functionality. Prashantha et al. report an increase of the modulus
and tensile strength of PP containing 1 wt% MWCNT (due to significantly
enhanced MWCNT dispersion in PP processed by masterbatch containing 20 wt%
MWCNT) by 1.27 and 1.18 times respectively [97], further additions of MWCNT
did not improve the structural characteristics significantly. Castillo et al. [78], and
Sathyanarayana et al. [98], report minimal/no increase in the tensile properties of
PC-CNT composites, inspite of achieving excellent CNT dispersion in PC.
The interfacial shear strength (IFSS) which governs the maximum stress
transfer from the polymer to the CNTs is strongly dependant on the nature of the
polymer-CNT interface. If the interface is strong (due to good polymer-CNT
adhesion), the external load applied on the composite is efficiently transferred
across the interface to be borne by the CNTs. Coleman et al. report an increase in
the Young’s modulus, tensile strength and toughness of PP by 3.1, 3.9 and 4.4
times respectively on the addition of 1 wt% thin-walled MWCNTs. The CNTs
were chemically grafted with chlorinated PP chains [95], which could have pos-
sibly contributed to enhanced load transfer via a strong interface. In another
example of a development of a strong interface, the CNTs modified by grafting
with PS via in situ polymerization and melt mixed with PS resulted in an increase
of impact strength by 250 % at 0.32 wt% MWCNT loading compared to pristine
PS while the un-modified CNTs resulted in 150 % increase of impact properties at
an identical CNT loading [75]. However, there are many instances in which
functionalization have resulted in the deterioration of composite properties [52].
As the load transfer efficiency is also determined by the length of the CNTs, it is
important to maintain the aspect ratio of CNTs as high as possible after composite
processing. Krause et al. [99], and Castillo et al. [78], have demonstrated the
reduction in the length (and subsequently the aspect ratio of the CNTs) on melt
processing. Figure 7 shows the comparison of length distribution of as-received
MWCNTs and that of the PC-MWCNT composite processed by melt mixing
containing 2 wt% of identical MWCNTs. Reduction in aspect ratio would lead to a
case where long fibers would have to be treated as short fiber reinforcements and
hence substantial increase in the composite modulus cannot be expected [100].
Incorporation of CNTs with high aspect ratios in PLA resulted in improved
Fig. 7 Length distribution

comparsion of NanocylTM
NC7000: before (pristine
MWCNTs) and after
processing (as recovered
from a melt processed PC
composite with 2 wt%
MWCNTs. x10, x50 and x90
were calculated indicating
that 10, 50, and 90 % of the
nanotubes lengths are smaller
than the given value.
Reprinted from [99],
Copyright (2011) with
structural characteristics of the melt processed PLA-CNT composites than those

observed on the composites containing low aspect ratio CNTs [101]. This holds
true over the whole range of investigated CNT concentrations from 0.5 to 3 wt%.
The authors claim that the higher hydrodynamic radii of the high aspect ratio
CNTs present as randomly bent fibers (to an extent) and as self-entangled flocs is
responsible for higher effective filler volume fraction and hence improved
mechanical properties.
Idealizing reinforcements with endless glass/carbon fibers, it is known that long
aligned fibers are important for high structural characteristics. Hence, it becomes
important to create and/preserve the alignment of the CNTs in the composite. It is
important to mention here that aligned CNTs are seldom available commercially
due to the complexities and costs involved with their production. Orientation of
CNTs during composite processing on the other hand has also been reported to
negatively affect the electrical properties of the composites [94]. The importance
of straightening and aligning the CNTs on the mechanical properties of the PA66-
CNT composites produced by rotational winding is illustrated in the work of Wang
et al. [102] (Fig. 8). The reduction in CNT waviness and their presence as indi-
vidual filaments on stretching the composite by 7 % resulted in a substantial
improvement in the elastic modulus of the un-stretched composite (E = 14 GPa)
by 290 %. The corresponding tensile strength increased from 225 to 630 MPa, a
190 % improvement on stretching. CNT alignment, long CNTs and decreased
waviness all simultaneously result in significant improvements in mechanical
behavior. These results significantly outnumber the properties achieved on other
CNT incorporated PA composites processed by conventional composite process-
ing techniques [103, 104]. However, the production of composites by this
approach is not conventional.
Reports on substantial improvements on mechanical properties of the com-
posites do exist, but are very rare. In most cases it is not close to anywhere as to
what theories predict. There is no doubt that the researchers working in this area
Fig. 8 Top: SEM images of a as-drawn CNT dry ribbon showing wavy nanotubes, b stretched
CNT dry ribbon representing reduced CNT waviness, c non-stretched CNT/nylon 6,6 composites
showing wavy nanotubes, and CNT/nylon 6,6 composite after stretching with different ratios:
d stretched for 2 %, e stretched for 4 % and f stretched for 7 %. Bottom: Enhancement in the
mechanical properties of the composites as a function of stretching. Reprinted from [102],
Copyright (2011) with permission from Elsevier
would unanimously agree that most literatures on thermoplastic CNT nanocom-

posites do not tend to report on the mechanical properties of the composites.
Results on melt processing of composites especially with those considering
MWCNTs however are not very encouraging. Analyzing the reviews on
mechanical properties and other related literature on thermoplastic-CNT com-
posites reports it is very evident that the theoretical potential of CNTs has so far
not been transferred to substantially enhance structural characteristics of its
composite. This could be attributed to the following reasons:
• Irrespective of how well the composites have been processed, achieving indi-
vidually dispersed CNTs is not realistic.
• Aggregated morphologies of the CNTs in the polymer host are ubiquitous. Due
to the cohesive strength of the agglomerates, there exists a small agglomerate
fraction irrespective of the extent of shear stresses exerted on the composite melt
during processing.
• Increasing magnitude of shear stresses applied to break up the CNT agglom-
erates could result in a trade-off of the aspect ratio of the CNTs. Reduction in the
CNT length would have a significant effect on the surface area and the effective
load bearing length (or the critical length) of the CNTs.
• Functionalization of CNTs carried out to weaken their intrinsic vdW forces
could lead to increasing defect density on the CNTs (or disturbing the perfect C–
C bond of graphene responsible for high mechanical characteristics), thereby
reducing the efficiency of reinforcement.
• The polymer-CNT interface is weak/not significantly developed to efficiently
transfer the external load from the polymer to the reinforcing filler.
• Small, wavy and randomly oriented CNTs do not carry the same inherent
mechanical characteristics as long, straight and unidirectional CNTs, thereby
idealizing CNT reinforcement in a thermoplastic as reinforcement with short
fibers instead endless fibers.
It is also very important to point out that the mechanical properties reported
here are just to illustrate the potential of CNTs as reinforcements. While inter-
preting the results from mechanical testing, it is important to consider all the
accompanying factors like the type of processing, raw materials, type of testing
etc. Bryne and Gun’ko in their review have summarized the huge variations in the
mechanical property observations on a similar matrix material that can be brought
about by employing different processing routes [105]. Castillo et al. report the
influence of five different types of commercially available MWCNTs on the
mechanical properties of PC-MWCNT composites at different filler loadings [78].
For a comprehensive reading on the mechanical properties of polymer-CNT
composites, and positive and negative influences of functionalization on composite
properties we would like to divert the attention of the readers to some interesting
reviews [52, 105–108].
4.2 Electrical Properties
The extremely attractive electrical characteristics of CNTs have lived up to their

potential as excellent conductive fillers for the insulating polymer matrices.
Substantially high electrical properties have been widely reported on polymer-
CNT composites. CNTs claim their advantage over conventional carbon black as
conductive fillers for polymer matrices due to their high aspect ratio and conse-
quently electrical properties at much lower filler percolation thresholds without
compromising on the density, mechanical properties, thermal properties etc. of
their host matrices.
The electrical percolation threshold is the critical filler concentration at which
the insulator to conductor transition occurs. At this juncture, the electrical
conductivity of the composite jumps significantly due to the formation of a con-

ductive pathway. The electrical percolation can be at its theoretical lowest with
only one such conductive pathway when well dispersed CNTs are present with a
shorter tunneling distance of less than 1.8 nm [109], in a specified matrix free
volume. Figure 9 shows the evolution of the conductive characteristics in CNT
filled polymer composites. While the electrical properties of the composites is a
result of dominative behaviour of the insulating polymer below the percolation
threshold, the formation of multiple conductive pathways by individual CNTs and
conglomeration of agglomerates beyond percolation saturates the conductive
characteristic of the composites.
The percolation threshold is estimated using the scaling law which describes the
statistical percolation behavior in the vicinity of percolation. It is given by
r / ðw wc Þt ð1Þ
where: r—experimental volume conductivity for w C wc, w—MWCNT concen-
tration (wt%), wc—critical/percolation MWCNT concentration (wt%), t—critical
exponent governing the dimensionality of the system.
Munson-McGee predict that the critical volume fraction for the formation of the
percolation network will vary from less than 1 % to more than 20 % depending on
filler orientation and aspect ratio from a formulation based on statistical arguments
[110]. Celzard et al. also emphasize the fact that the theoretical percolation
equation must be modified for fillers having higher aspect ratios based on their
interpretations of the excluded volume concept [111]. Although the usage of the
equation for statistical percolation is common, possibilities of kinetic percolation
(filler mobility due to mechanisms like diffusion, convection etc.) should not be
Fig. 9 Evolution of
electrical conductivity as a
function of CNT content in a
composite
Fig. 10 Electrical
percolation threshold of
MWCNTs in commonly
employed thermoplastic
polymer matrices
independent of the composite
processing approach and
MWCNT surface
functionality. Data on epoxies
(a thermoset) is also reported
for comparison. Data
compiled from [117, 145]
excluded which was the main reason for contradicting results reported in the work
on Bai and Allaoui [112], and Martin et al. [113]. Electrical percolation of CNTs in
polymer matrices vary from as little as 0.0025 wt% to as high as 15 wt% as could
be seen from Fig. 10. This huge variation is due to the fact that electrical perco-
lation is dependent on the nature of matrix [63–67] and the type of CNT [78, 84],
aspect ratio of the CNTs [47, 114], extent of CNT dispersion [64, 65], CNT
functionalization [49, 115], processing approach and parameters [65, 84], and
alignment and orientation of the fillers [94, 102].
Higher filler percolation thresholds in the range of 1–3 wt% CNT content are
common in melt mixed thermoplastic-CNT composites processed with commer-
cially available CNTs [65, 93, 97, 98]. It is generally lower for matrices presenting
a favorable environment for a good CNT dispersion. The variation in the electrical
resistivity in different thermoplastic matrices (with varying viscosities) containing
an identical CNT type is illustrated in Fig. 11. The significant reduction in the
aspect ratio of the composites due to their exposure to higher magnitudes of shear
stress whilst melt processing as compared to other production approaches is also
attributed to be another major reason for higher filler percolation thresholds. This
shear stress is however important for achieving good filler dispersion, also an
important criterion for good electrical properties of the composites at lower filler
loadings.
Although, the dispersion morphology of the CNTs is primarily affected by
extrusion, the widely employed secondary processing or the final shaping step for
thermoplastic matrices namely compression molding or injection molding have
been reported to have a substantial influence on the electrical properties of the
composites. The reasons for difference in the electrical properties of the com-
posites resulting out of these production techniques had been discussed earlier.
The influence of process parameters of the compression molding [64, 76] and the
injection molding [94, 116] have been studied in detail, and has been reported to
have an overwhelming influence on the electrical properties of the composites.

Fig. 11 Electrical volume resistivity of different thermoplastic matrices containing Baytubes
C150P. Reprinted from [63], Copyright (2012) with permission from Elsevier
Figure 12 shows the influence of CNT dispersion (as a function of extruder process
conditions) and the nature of the secondary shaping operation on the electrical
properties of the composites
Although a wide variety of factors have been listed for its influence on the
electrical properties of the composites, consensus cannot be arrived on which has
the pivotal role. Lot of contradicting reports does exist in literature. Bauhofer and
Kovacs in their review find that the nature and type of the polymer host along with
the technique of composite production are much more significant for good
Fig. 12 Influence of CNT dispersion in PP from the compounding process on volume resistivity
(=1/conductivity) of the compression molded composites—composites were processed at
500 rpm with and without peroxides ‘‘Px’’ as additives and 1,100 rpm (Left). Difference in the
electrical properties between injection molded and compression molded composites—C1 and C2
represent 1 and 2 wt% CNT content in PP (Right). Adapted from [64], Copyright (2013) with
electrical properties compared to the influence that the type of CNTs and their
production process could have [117].
4.3 Thermal Properties
The extraordinarily high intrinsic thermal conductivity and excellent thermal

stability of the CNTs are of considerable interest for applications like nano-elec-
tronics and conductive polymer films. The high thermal conductivity of the CNTs
is owing to the atomic vibrations or phonons while the increase in the thermal
stability of the composites due to the incorporation of CNTs is a result of its high
electron affinity (of 2.65 eV [118]) enabling them to act as radical scavengers.
The expected improvements in the thermal properties of the polymers with
CNT addition, especially in the context of good thermal conductivity has however
not been achieved. The transportation of phonons is more likely to occur through
the insulating matrix rather than that of the ideally visualized case through CNTs
as the difference in the thermal conductivities between the CNT and polymer is
very small, i.e. of the order 104 W/(m.K) [119]. Compare this to the 15–19 orders
of magnitude difference in the electrical conductivity! The interfacial or the
boundary resistance between the CNTs and the matrix acts as a barrier to heat flow
decreasing the overall conductivity of the composite. CNT surface functionali-
zation [120], and aspect ratio [121], along with CNT dispersion in the polymer
host are considered to be important factors regulating the thermal conductivity of
the composites. Reports on thermal conductivities of epoxy-SWCNT composites
are handful [122–124], while on thermoplastic matrices with MWCNTs are sel-
dom to illustrate any conductivity increase/decrease.
The strong radical accepting capacities of the CNTs interrupt the released
radicals from oxidation of the polymer, delay the rate of radical propagation and
hence decrease the rate of degradation. This results in substantially enhanced
thermal stability of the composites containing CNTs. The onset of degradation and
temperature of maximum degradation of PS at 300 and 365 C respectively were
enhanced to 313 and 398 C and 337 and 407 C respectively on the addition of 1
and 2 wt% MWCNT [65]. Increasing additions of CNT did not further enhance the
thermal stability of the composites as enhanced intra-filler interactions due to CNT
agglomeration at higher filler loading reduces the effective CNT surface area
available for accepting free radicals. Similarly, the addition of 2 wt% MWCNT to
PP enhances the thermal stability of the composite with an increase in the onset
and maximum temperature of degradation by 40 and 85 C, the increase also
dictated by the enhanced quality of MWCNT dispersion in PP [64]. These results
also highlight the importance of having a good CNT dispersion in the matrix.
CNTs have been reported to act as nucleating agents in semi-crystalline
matrices [47, 82, 95]. The incorporation of CNTs to the polymers also affects the
glass transition temperature, as the part of the polymer in close proximity to the
CNTs will have properties much different than the bulk matrix owing to the
restrictions imposed on its mobility due to the alterations of the conformational
entropy and chain kinetics. An increase of glass transition temperature at lower
filler loadings and a decrease at higher loading fractions (due to predominant intra-
filler interactions contributing to the development of an interphase) has also been
reported [65].
Wu et al. demonstrate a significant improvement in the flame retardancy of melt
mixed PET (polyethylene terephthalate)-MWCNT composites with liquid bi-
sphenol A bis(diphenyl phosphate) (BDP) as a dispersing additive. The uniformly
dispersed CNTs in PET acted as a support for the char released by the oxidation of
PET and BDP. The network layer consisting of the CNTs and char acted as a heat
shield effectively reducing the exposure of PET to external atmosphere and the
heat feedback of the heat flux [125] (Fig. 13). Kashiwagi et al. have also dem-
onstrated similar effects with MWCNT incorporated PP composites [126]. A good
CNT dispersion and a better polymer-CNT interface along with increasing filler
content could augur well for excellent flame retardant characteristics [127].
In addition to the aforementioned commonly listed characteristics of CNTs in
composites, their functionalities also extend to tuning the non-linear property
[128] and improve the photoluminescence of polymer-CNT composites [129].
These areas are subjected to very less research inspite of their tremendous
potential for engineering applications.
Fig. 13 Schematic of the

network of CNT-char
network acting as a heat
shield for PET. Reprinted
from [125], Copyright (2013)
with permission from
Elsevier
From an outlook on the analysis of the mechanical, electrical and thermal

properties of CNT incorporated polymer matrices in this chapter and also by
analyzing reviews (recommended for further reading in this manuscript) it seems
that the potential of CNTs as fillers for polymer matrices is not fully realized. CNT
dispersion in thermoplastics and consequently improved polymer-filler interactions
seem to be key criterion influencing the macroscopic properties of the composites.
Employing as-received CNTs mandates high shear stresses on processing leading
to reduction in CNT aspect ratio. In order to compromise this, CNT functionali-
zation or the use of dispersing additives are widely recommended. The statistic
presented in Fig. 14 is from a review on the effect of functionalization on the
electrical and mechanical properties of polymer-CNT composites. It is seen that in
most cases the increase in electrical property comes with a trade-off of a potential
reduction in structural characteristics and vice versa. This complicates scenario for
advising a particular approach to tailor the desired composite functionality with
CNTs as fillers.
At this juncture, the reader ponders about the potential of CNTs as fillers for
thermoplastic matrices. Although excellent electrical properties and (to an extent)
thermal properties have been achieved on thermoplastic polymer-CNT composites,
substantial improvements in the mechanical properties of these composites are far
from being realized due to the various reasons detailed earlier. Long, aligned,
perfectly grown infinite CNTs would be ideal; current research has been led in this
Fig. 14 a Overall statistics of the journal papers reviewed in this article which addresses the
influence of various pre-treatment in polymer/CNT composites and compares with respect to
pristine CNT; b Statistics showing the strengths (+) and weaknesses (-) of covalent and non-
covalent types of pre-treatment on the composite properties (statistics also includes paper which
report simultaneous improvement in both structural and electrical properties). Reprinted from
[52], Copyright (2010) with permission from Elsevier
direction however the economics of scale up and production on a sustainable scale

have not been successfully realized thus far. Hence, there is now a desperate need
to look for alternate solutions to tap the multifaceted properties of CNTs into
commercial applications. The fact that enhancing the structural properties of the
composites is the challenge focuses our attention towards multi-scale reinforce-
ments. The established success of conventional glass or carbon fibers as fillers for
structural reinforcements positions them as strong contenders for incorporation as
secondary fillers in addition to CNTs for the development of a composite with
multi-functional properties. It is however important to ensure that the addition of
glass/carbon fibers do not significantly alter the electrical and thermal character-
istics of the composites brought in by the presence of CNT networks.
5 Multifunctional Composites with Multi-Scale

Reinforcements
Fiber reinforced composites (FRC) have revolutionized engineering structures

over the last three decades owing to high-strength to weight ratio, flexibility and
ease of processing with conventional techniques, and prospects of tuning their
functionality. Although the in-plane properties of the FRC’s are extremely high,
the contribution to its load bearing capacity along the z-direction primarily arises
from that of the matrix (which has much lower mechanical properties). Nano-
metric dimensions of the nanofillers could facilitate their easy infiltration between
the micron-sized fillers leading to better interlaminar properties. In addition to this,
the attractive nature of CNTs to impart good electrical and thermal properties
offers enormous scope for development of multi-functional light weight com-
posites structures to compete for engineering dominance with metallic and ceramic
Fig. 15 Multi-scale reinforcement concept—Individual addition of fillers (Left), Hybrid fillers

(Right)
reinforcements. Two possible forms of multi-scale reinforcements could be

thought of (Fig. 15):
• Individual addition of the fillers into the polymer host [98, 130].
• Employment of hybrid fillers wherein the nanostructures are grown insitu on the
surface of the carbon/glass fibers (parent structures) via the CVD process [131–
133], coated on woven parent surfaces [134], and deposited on fiber surfaces
using electrophoresis [135, 136].
Figures (16, 17, 18) illustrates micrographs of hybrid fillers processed via
different techniques.
The employment of hybrid filler structures in literature is widely discussed in
the context of composites based on thermoset matrices. Considering the scope of
production of multi-scale composites, the use of these hybrid fillers for thermoset
composites is justifiable as the integrity of the nanostructure on the parent could be
easily preserved during composite processing. On the contrary, with the processing
approach for thermoplastic composites (especially polyolefins) and the harsh
Fig. 16 MWCNTs grown on glass fiber surface through CVD—morphology of the hybrid fibers
is observed in different forms: through scanning electron microscopy (SEM) of the fibers (a and
b) and optical microscopy of the cured, polished composite (c). Reprinted from [132], Copyright
(2012) with permission from Elsevier
Fig. 17 Hybrid fillers prepared via coating of nanofillers on parent surfaces—fracture surface of
fiberglass/vinyl ester composites with silane-SWNTs: a 50 lm scale bar magnification and
b 5 lm scale bar magnification. Reprinted from [134], Copyright (2007) with permission from
Elsevier
Fig. 18 SEM images of carbon fibers with (a) SWNTs and (b, c) MWNTs deposited by
electrophoresis. Reprinted from [135], Copyright (2007) with permission from American
Chemical Society
conditions involved there is a strong possibility for the nanostructures to detach

from their parent surfaces consequently leading to reduction in the reinforcement
efficiency. The addition of glass fibers to the polymer-CNT masterbatch stands out
as the most feasible approach for the production of thermoplastic composites
taking advantage of the properties of both glass fibers and CNTs.
Sathyanarayana et al. demonstrated individual addition of the bi-filler system of
MWCNTs and short glass fibers (two variants: one with a compatible sizing to PC
and the other with an incompatible sizing) to PC via melt compounding and
injection molding [98]. Whilst 2 wt% MWCNT addition to PC resulted in a elastic
modulus and tensile strength increase of a meager 10 % and 5 % respectively,
addition of 20 wt% short glass fibers to this composite resulted in a substantial
187 % and 86 % increase of the corresponding properties. The increase in the
modulus was independent of the type of the glass used, but the tensile strength
improvement was significant only when the glass fiber with a compatible sizing
with PC was employed. Glass fiber addition however lowered the impact prop-
erties of PC, but the presence CNTs compensated for the decrease. The contri-
bution to enhancement in the thermal and electrical properties of the bi-filler
composite arose due to the presence of CNTs, with increasing glass fiber additions
slightly lowering the efficiency of reinforcement. The SEM micrographs of these
composites are presented in Fig. 19.
A short reference to some interesting results with thermoset based multi-scale
composites is being made here to illustrate the potential of these materials. Lv
et al. grafted MWCNTs of varying lengths on carbon fibers using the injection
CVD approach [137]. The MWCNT lengths and the orientation were controlled by
the nanostructure growth time and the adopted surface treatment on the carbon
fibers. Single fiber fragmentation tests showed an 175 % improvement in the
interfacial shear strength of the hybrid fiber (containing 47.2 lm of aligned
nanostructure on the parent) compare to the pristine carbon fiber. The SEM
morphologies from their work are presented in Fig. 20. Zhang et al. achieved
150 % improvement in the IFSS of CNT-CF reinforced epoxy composites [138].
Zhu et al. report an increase of 45 % in the shear strength in their effort to increase
the properties along the z-axis for carrying transverse loads on a glass fiber
reinforced vinyl ester composite with nanotube integration. The CNT loading was
Fig. 19 a Good CNT dispersion in PC, b PC with 20 wt% glass fibers with PC compatible
sizing, c Individual morphologies of the filler kept in the bi-filler composite, d Magnified view of
a single glass fiber with a polymer sheathing (some CNTs were also identified on the sheathing)
from the bi-filler composite [98]
0.015 wt% in the midplane ply [134]. Gojny et al. carried out resin transfer
molding for the production of glass-fibre-reinforced polymers (GFRP) with
nanotube/epoxy matrix. They report enhancements in the modulus, tensile
strength, fracture toughness and the anisotropic electrical properties of the com-
posites containing 0.3 wt% MWCNTs (modified by amine functionalization)
[139].
Irrespective of how good the hybrid-filler is, the macroscopic property
enhancements of the composites would strongly depend on the extent to which the
nanostructures are dispersed in the matrix. The strength of the nano-filler-parent
interface and the linkage between the nanostructure and the host matrix are con-
sidered to be crucial. The biggest challenge facing the multi-scale composites
especially on thermoset matrices is the fact that high volume fraction of nanofillers
would lead to processing difficulties due to its ability to enhance the viscosity of
the resin significantly. The need for environmentally benign applications for
example light weight structures with multifunctional characteristics will no doubt
drive the market towards the development of composites with multi-faceted
properties.
Fig. 20 SEM images of unsized CFs (a) before and (b) after the surface treatment, and CFs
grafted by (c) entangled MWCNTs and (d–f) aligned CNTs. Reprinted from [137], Copyright
(2011) with permission from Elsevier
6 Synopsis
The principal objective of this chapter was to give a comprehensive overview on

the potential of CNTs as fillers for thermoplastic polymer matrices processed by
techniques suitable for large scale production. Thermoplastic matrices present
significant challenges for achieving a good CNT dispersion primarily due to its
high melt viscosity and high interfacial tension between the polymer and the CNTs
as compared to thermosets. As a consequence the efficiency of CNTs as fillers for
thermoplastic matrices is far off from what theory would predict.
We have elucidated in short the world of CNTs starting from its production,
properties, surface modification, applications and a brief market outlook. Although
understanding of the complicated mechanism of CNT dispersion in thermoplastic
is crucial, equally important is to understand the influence of raw-materials and the
process parameters. The complex picture of achieving a good CNT dispersion that
was presented in terms of processing with the twin-screw extruder, and the
influence that the secondary shaping operation could have on the composite
properties present a strong case that mandates a careful selection of the raw-
materials and process conditions. Functionalization of CNTs as a technique to
improve CNT dispersion is widely discussed in literature, but is very expensive
and present problems of scale up for large scale production. Hence, we focused on
special techniques like the use of ultrasound, supercritical fluids, processing
additives etc. whilst processing in the extruder as non-conventional approaches to
enhance CNT dispersion in a thermoplastic matrix.
Although the potential of CNTs as fillers for mechanical reinforcements do not
look promising after analyzing many literature reports, Loos and Schulte claim
that CNTs are the most viable strengthening option for composites with strengths
up to 11.61 GPa on analysis of their cost versus property relation compared to
carbon fibers [140]. The latter could be beneficial for producing composites with
strengths up to 4.18 GPa, Young’s modulus up to 383 GPa with a possible com-
promise on toughness. However, according to them and most literatures, in order
for CNTs to be competitive enough they would have to be produced with high
purity as long aligned structures with high aspect ratio, in large volumes and at low
cost. Also, issues such as CNT dispersion, distribution and orientation in the
matrix and enhanced polymer-filler compatibility must be addressed quickly for
competitiveness and commercial success.
The addition of CNTs has contributed immensely for enhancing the electrical
conductivity of the composites at substantially low filler percolation thresholds.
The review of literature indicates that this is influenced by many factors. Thermal
properties of the composites have also been reported to be enhanced by the
addition of CNTs, but not many literature reports are available to claim this
strongly. It could thus be generalized that the presence of CNTs as fillers for
polymer matrices promises to have a substantial influence in enhancing the elec-
trical, and to an extent thermal properties of the composites, however the
improvement in mechanical properties is far from existing imagination.
Multi-scale reinforcements with CNTs, principally for electrical and thermal
properties, and traditional fillers like glass or carbon fibers, for structural prop-
erties, look to be a promising solution towards the development of multifunctional
composites. The individual addition of these fillers or the development of a hybrid
filler, wherein the carbon nanostructures are grown on the parent glass/carbon fiber
surface, to be incorporated into the polymer host are two possible approaches for
achieving the multi-scale reinforcements. These materials show some promise,
however they are predominantly reported on thermosetting matrices. Going for-
ward, there is a strong belief that the potential of these fillers would also translate
well into excellent macroscopic properties on a thermoplastic composite.
Acknowledgments Shyam Sathyanarayana thanks the European Community’s Seventh

Framework Programme (FP7-PEOPLE-ITN-2008) for his funding through the Marie Curie
Fellowship under grant agreement number 238363 during his stay at the Fraunhofer Institute für
Chemische Technologie ICT.
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Graphite-Based Nanocomposites
to Enhance Mechanical Properties
Shanta Desai and James Njuguna
Abstract Carbon based materials such as diamond and graphite are known to
mankind for ages. Graphite is highly anisotropic and the properties of single layer
of graphite were known for long. In recent years, nanoscale materials using carbon
nanotubes have provided opportunities for researchers to engineer new materials
with enhanced properties but graphite-based fillers in the polymer nanocomposites
has taken forefront in research of many area upon the discovery of graphene, a
single layer of graphite by Andre et al. in 2004 due to its extraordinary properties.
Due to high surface energy and low density, it is difficult to disperse graphene in
polymeric matrix and hence some of the methods identified to homogenously
disperse graphite-based fillers are described here such as solution mixing, melt
mixing, in situ polymerization and grafting. Nanocomposites prepared using
graphite-based reinforcements to enhance mechanical properties in different
polymeric matrix is discussed. Finally, applications and challenges of commer-
cialization of these nanocomposites are presented.
1 Background
Nanocomposites attracted researchers since 1987 after a research group in Toyota

demonstrated large mechanical property enhancement using reinforcements
(montmorillonite) of less than 100 nm in size in a Nylon-6 matrix [52]. Since then,
many polymer systems with different nano-reinforcements have been investigated
to achieve properties of interest.
S. Desai (&)
Composites Evolution Ltd, Chesterfield S41 9QG, England
J. Njuguna
Institute for Innovation, Design & Sustainability, Robert Gordon University,
Aberdeen AB10 7GJ, UK

62 S. Desai and J. Njuguna
In recent years, the development of synthesis for nanoscale materials such as

silica, clay, carbon nanotubes has provided opportunities for researchers to engi-
neer new materials with enhanced properties. Amongst these, polymer nano-
composites comprise an emerging class of materials where nanoscale fillers with at
least one characteristic length smaller than 100 nm are well-dispersed within a
polymer matrix have shown enhancement in properties compared to those with
micron-size fillers [6, 18, 24, 33, 38, 46, 55, 62] Exfoliated clay nanocomposites
have been studied intensely and some of the materials are now in commercial
applications such as automobile exteriors and food packaging [17].
Carbon based materials such as diamond and graphite has been known to
mankind for ages. Graphite has high strength and excellent transport (electrical
and thermal) properties. Natural graphite flakes based composites with reasonably
high thermal conductivity (750 W/m K) have been fabricated by Desai [11].
Graphite is the stiffest material found in nature with Young’s modulus 1,060 MPa
which is several times that of clay hence, graphite based nanocomposites can offer
superior properties compared to that with clay platelets/nanoclay [8]. Also,
graphite based nanocomposites have lower cost compared to some other carbon
based nanocomposites such as carbon nanotubes (CNT) reinforced
nanocomposites.
Since late 1990s research has reported nanocomposites fabricated using inter-
calated, expanded or exfoliated graphite nanoflakes in polymeric matrix for
enhancement of properties and its applications in different areas [5, 7, 12, 33, 40,
49, 61].
However, a new enthusiasm has been developed in the polymer nanocompos-
ites research area upon the discovery of graphene, a single layer of graphite [30].
The properties of single layer of graphite were known for long but It was only
recently that Andre K. Geim and Konstantin S. Novoselov showed a method to
produce a single layer of graphite/ graphene and were awarded the 2010 Nobel
prize in Physics.
Graphene is a monolayer of sp2-hybridized carbon atoms arranged in a two-
dimensional lattice. It has attracted research in many areas due it its extraordinary
properties [9, 15, 64]. It has been predicted that a single defect-free graphene
platelet could have an intrinsic tensile strength higher than that of any other
material [59]. James Hone’s group [23] measured mean breaking force of
1,770 nN for free standing monolayer of graphene membrane using nano-inden-
tation in atomic force microscopy. They reported the material to be able to
withstand ultra-high strains (*25 %) and had Young’s modulus of 1.0 TPa.
Graphene sheets that make graphite suffer in composites is due to its strong
surface attraction. Unless these sheets are separated and homogenously dispersed
within the polymer matrix, the full potential of graphene-based nanocomposites
cannot be realised. Hence, pristine graphene materials are unsuitable for interca-
lation by large species such as polymer chains (graphene has a tendency to
agglomerate in a polymeric matrix), the agglomeration can be prevented by dif-
ferent chemical modification methods [16]. First graphite oxide is prepared from
natural graphite. After oxidation, a number of methods have been identified to
Graphite-Based Nanocomposites to Enhance Mechanical Properties 63
obtain soluble graphene some of them include covalent modification by amidation

of the carboxylic groups [31, 54], non-covalent functionalisation of reduced
graphene oxide [2, 39, 44], nucleophilic substitution to epoxy groups [4], diazonium
salt coupling [27] and reduction of graphite oxide in a stabilisation medium [32].
In this chapter we have attempted to present in brief the preparation routes,
studies showing the use of graphite-based reinforcement in nanocomposites to
enhance mechanical properties and applications/future of the graphite-based
nanocomposites. It is rather impossible to present every area of composites with
graphite-based reinforcement as these fillers have been used to enhance different
properties based on application due to the multifunctional properties of pristine
graphite. Hence, this chapter is delimited to present the use of graphite-based
reinforcement in nanocomposites to enhance of mechanical properties.
2 Preparation Routes of Graphite-based Nanocomposites
Since expanded graphite, exfoliated graphite or graphite nanoplatelets found their

place in polymer matrix based composites, a number of methods have been
identified to prepare graphite reinforced composites. In recent years, polymer
based nanocomposites reinforced with expanded graphite (EG) have shown sub-
stantial improvements in mechanical, electrical, thermal and barrier properties
over the unmodified polymer. As graphite nanosheets could have enormous sur-
face area (up to 2,630 m2/g) considering both sides of the sheets are accessible, the
dispersion of these nanosheets in a matrix plays an important role in the
improvement of physical and mechanical properties of resultant composites [51].
This can be achieved by combination of both synthesis and processing techniques
that produce exfoliated graphite and good dispersion of the prepared particles in
the matrix. The production of exfoliated graphite is well documented in literature
and many dispersion routes of EG, graphite nanoplatelets (GNP) and graphite
oxide (GO) are reported.
There are different processing techniques that are described here are solution
mixing sonication, shear combined sonication and shear mixing, melt mixing,
in situ polymerization, grafting (from and to approaches).
2.1 Solution and Shear Mixing
Solution based methods involve mixing of colloidal suspensions of graphite based

filler/material with the selected polymer either in solution form or by dissolving the
polymer in the suspension by stirring or shear mixing. The composite is then
precipitated from the suspension and dried or further processed for testing and
application. Composite can also be obtained by casting the suspension into a mold
and extracting the solvent. However, in this method there is a danger of aggregation
of the filler content which can potentially lower the final properties of the resultant
composite [29]. This method is widely reported in the literature and solutions are
prepared in water or organic solvents. Using this method a wide range of com-
posites with GNPs/GO are prepared in different polymeric matrix e.g. GO-poly-
styrene [44], GO-polycarbonate [19] and GO-PMMA [10]. Sonication can be used
to mix water based polymers in solution e.g. GO-poly vinyl alcohol (PVA) [56].
2.2 Melt Mixing
In melt mixing method the graphite-based filler usually in a powder form is mixed
under high shear with the melted polymer. Although this method is economical, it is
difficult to get a homogenous dispersion of the filler using this method [34]. Hence,
to improve dispersion filler can be pre-treated with surfactants to improve misci-
bility with the polymer melt. Some studies have been reported where melt mixing
method is used to prepare composites without prior treatment but handling and
processing of such melt material was found to be difficult and challenging [22].
2.3 In-Situ Polymerisation
In this method of dispersion, the filler is mixed in a monomer or multiple

monomers followed by polymerization in the presence of the dispersed filler. The
composite is obtained using solution mixing method that is precipitation, extrac-
tion or casting. This method is highly effective in dispersing graphene based fillers
and is sometimes referred to as intercalation polymerization. Originally this
method was investigated for nanoclay/polymer composites and it is now extended
to graphite-based fillers [41, 42]. Recent studies have shown improved dispersion
of GO filler in PMMA/GO composites where a microintiator was used to inter-
calate GO prior to in situ polymerization of methyl methacrylate [21].
2.4 Grafting
Pure carbon materials have relatively lower surface functionality and hence it is
difficult to form covalent bonds between the polymer and such surface when used
as filler material in composites. However, GO has surface rich in functional groups
and these have been exploited to introduce covalent bonding between GO platelets
and polymer matrix. There are two ways of forming the bonds (a) grafting-from
approach and (b) grafting-to approach.
In grafting-from approach, the alcohol groups present in GO platelet surfaces
are covalently bonded to atom transfer radical polymerization (ATRP) initiators
via esterification to form chemically modified graphite (CMG). The polymer is

grown via ATRP from the surface of GO platelets i.e. CMG platelet is added to a
polymer matrix (compatible to ATRP) via solution mixing method and a polymer
is grown on GO via ATRP. A composite is then precipitated/extracted or casted.
The nanocomposites prepared using this technique is shown to have improved
mechanical and thermal properties as compared to neat matrix polymer [14].
A grafting-to approach is a converse of grafting-from approach where func-
tional groups of GO platelet are attached to a polymer via end groups of the
polymer e.g. grafting of PVA to GO platelets via carbodiimide-activated esteri-
fication [47]. In this technique, it is difficult to precisely determine the reactive site
on GO platelet as can be determined in grafting-from approach technique [35].
3 Enhancement of Mechanical Properties

Using Graphite-based Reinforcement
The in-plane elastic module of pristine defect free graphene is approximately 1.1
TPa and is the strongest material measured on a micron length scale [23]. How-
ever, due to its low wet-ability, it gives rise to poor dispersion in polymer matrix
and thereby decreases its mechanical properties of the resulting nanocomposites
[52]. The wet-ability can be increased by oxidation and or functionalisation
(introducing defects) of graphite/graphene sheets/GNPs that provide improved
dispersion in polymer matrix at the risk of lowering conductivity of the resulted
nanocomposites.
Miller et al. [28] mitigated the risk of lowering conductivity by using a covalent
bonding approach between graphene and epoxy matrix. This approach showed 5-
fold increase in electrical conductivity, 30 % improvement in strength and a 50 %
improvement in stiffness.
In a study by Ramanathan et al. [37], it was shown that functionalised graphite
sheets (FGS) had wrinkled morphology which attributed to superior mechanical
and thermal properties in FGS-PMMA nanocomposites. They studied the variation
of graphene loading on Young’s modulus of the composite and compared it to that
of neat PMMA and found that at 0.01 % by weight of graphene increased the
modulus of the nanocomposites by over 30 % as compared to neat PMMA. When
the graphene loading was increased to 1 % by weight the Young’s modulus of the
resultant composite increased by 80 % above that of neat PMMA however the
ultimate tensile strength of the composite increased only by 20 %.
Liang [25] prepare PVA/GO nanocomposites and these nanocomposites
showed enhanced mechanical performance which is attributed to the large aspect
ratio of the graphene sheets, the molecular-level dispersion of the graphene sheets
in the PVA matrix, and mainly due to strong interfacial adhesion due to hydrogen-
bonding between graphene and the PVA matrix. For example, with only 0.7 wt %
GO the tensile strength increased by 76 % from 49.9 to 87.6 MPa and the Young’s
modulus increased by 62 % from 2.13 to 3.45 GPa with respect to the parent
polymer.
Zhao et al. [60] used sodium dodecylbenzene sulphonate (SDBS) as a surfactant

and prepared nanocomposites with chemically reduced graphite oxide (CRGO) in
an aqueous solution containing PVA and the stabilizing SDBS. They studied the
effect of filler loading (0–3.0 % volume fraction) on tensile strength and elongation
at break (see Fig. 1). 150 % improvement of tensile strength and a nearly 10 times
increase of Young’s modulus were achieved at a graphene loading of only 1.8 %
volume fraction. The value of elongation at break decreased from 220 % for the
polymer to 98 % for the composite with the same loading. They found the tensile
strength to increase with an increase in volume fraction of the filler however,
elongation at break showed an inverse relation with filler volume fraction.
EG/epoxy nanocomposites were prepared using different process methods by
Yasmin et al. [58] (see Fig. 2) and mechanical behavior of the prepared nano-
composites were compared.
The nanocomposites prepared by different techniques using 1 % by weight EG/
Epoxy nanocomposites showed higher elastic modulus (see Fig. 3) but lower
tensile strength as compared to neat epoxy when tested under identical conditions.
The increase is modulus in generally is found to be due to better dispersion of
nanoparticles/fillers and good interfacial adhesion between the particles and the
epoxy matrix which restrict the mobility of polymer chains under loading [53].
The stiffening effect can also be attributed to the alignment of the graphite layers
and the polymer chains to the loading direction as seen in PP/clay composites
where the alignment of clay layers and PP chains with loading direction con-
tributed to the stiffening effect [26].
The modulus of the nanocomposite was found to increase with increase in
percentage weight of particle content for a given preparation method. Figure 4
shows comparison of the elastic modulus of EG/epoxy and clay/epoxy nano-
composites prepared by shear mixing method with 1 and 2 % by weight particle
content.
Rafiee et al. [35, 36] compared mechanical properties of graphene-based epoxy
nanocomposites with single-walled nanotubes (SWNT) and multi-walled carbon
nanotubes (MWNT) based epoxy nanocomposites with 0.1 ± 0.002 % nanofiller
and found that graphene-based epoxy nanocomposites showed superior mechani-
cal properties and fatigue resistance compared to SWNT and MWNT filler based
epoxy nanocomposites.
Zhen and Gao [63] prepare nylon-6 - (PA6-) graphene (NG) composites by
in situ polymerization of caprolactam in the presence of graphene oxide (GO).
Composites of varying weight fractions of graphene were prepared by varying the
ratio of caprolactum to GO. Homogenous grafting of up-to 78 % by weight of
nylon 6 was seen on graphene sheets. This uniform grafting favoured homogenous
dispersion of graphene sheets in PA6 matrix and suppressed the crystallization of
PA6 chains. They further prepared NG fibres by melt-spinning process and found
that the tensile strength and the Young’s modulus increased by 2.1 and 2.4 times
respectively with only 0.1 wt % of graphene loading thus showing graphene to be
a promising reinforcement in composites to enhance mechanical properties (see
Fig. 5).
Fig. 1 Tensile strength and elongation at break versus volume percentage of graphene filler
(taken from Zhao et al. [60])
Bortz et al. [3] prepared graphene based nanocomposites at concentrations of

0.1, 0.25, 0.5, and 1 wt % with a bisphenol A/F diglycidyl ether blend as the
polymer matrix. The resin was added to the graphene oxide/acetone suspension
and heated for slow solvent evaporation. It was further heated under vacuum to
ensure complete removal of acetone. The dispersion was passed through 3-roll
calendar mill with different rotations per minute and the obtained dispersion was
diluted with neat resin to obtain the different weight fractions. The test samples
were prepared by mixing a harder to the dispersion, degassing it in the mould and
casting individual test samples.
Fig. 2 Processing techniques used to prepare EG-Epoxy nanocomposites (taken from Yasim
et al. [58])
Fig. 3 Variation of elastic

modulus of 1 % by weight
EG/epoxy nanocomposites
for different processing
techniques (taken from
Yasmin et al. [58])
They found that the flexural strength and flexural modulus increased with
increase in GO content whereas Tensile modulus was enhanced by 12 % at
0.1 wt % GO but with further increase in GO content a decrease in tensile mod-
ulus was observed. At 1 % wt of GO, the tensile modulus was similar to that of
Fig. 4 Variation of elastic

modulus as a function of
particle content for
nanocomposites prepared
using shear mixing method
(taken from Yasmin et al.
[58])
Fig. 5 AFM image showing grafting of polymer on graphene sheet (brush like structure) and
graph showing stress versus strain curves for NG fibres and neat Nylon 6 (taken from Zhen and
Gao [63])
neat resin. A similar trend was seen in ultimate tensile strength but the maximum
enhancement was seen with 0.5 % weight of GO. Enhancement was also seen (see
Fig. 6) in critical stress intensity factor (KIC) and critical strain energy release rate
(GIC). It can be seen that this enhancement was significant as GO content increased
up-to 0.5 % weight however; with further increase in GO content a saturation of
toughening effect was observed.
Steurer et al. [45] studied thermally reduced GO (TrGO) or exfoliated GO
based polymers in different polymer matrices [poly(styrene-co-acrylonitrile)
(SAN) and polycarbonate (PC) shown below Fig. 7]. Since the density of TrGO is
very low, solution blending was carried out by pre-mixing TrGO with base
polymer in different loadings and then a melt-compound was formed of the
Fig. 6 Behaviour of mechanical properties of the nanocomposite with varying weight fraction of
graphene oxide (taken from Bortz et al. [3])
Fig. 7 comparison of Young’s modulus of nanocomposites with different reinforcements in

SAN and PC matrix (taken from Steurer et al. [45])
additive with the base polymer using a mini-twin screw extruder. The properties of
the formed nanocomposites were compared to composites with MWNT and
conducting carbon black based polymer nanocomposites.
Jiang and Drzal [22] also prepared nanocomposites with GNP-high density
polyethylene (HDPE) using melt-blending technique followed by injection
molding and compared with composites filled with carbon fibres (CF), carbon
black and glass fibres. They found that GNP-HDPE nanocomposites showed
equivalent flexural stiffness and strength compared to HDPE based composites
with carbon black and glass fibres but lower than the composites with carbon fibres
for a fixed volume fraction of reinforcement.
4 Application and Future
Polymer nanocomposites can have with additives of one-dimensional, such as

nanotubes and fibres, two-dimensional, which include layered clay minerals or
graphene sheets, or three-dimensional, including spherical particles in a polymer
matrix. Graphene has attracted considerable attention because of its unique and
outstanding mechanical, electrical and electronic properties, which result in it
being one of the most popular candidates for the development of functional and
structural graphene-reinforced composites.
The introduction of graphene sheets into polymeric matrices has been proposed
as an alternative (Stankovich et al. [44]) or supplementation [57] to more tradi-
tional carbon nanotube (CNT) reinforcement. Several studies have shown
improved mechanical, electrical and thermal properties for graphene-based poly-
mer composites.
Indeed, graphene-based polymer nanocomposites is a rapidly growing area of
nanoengineered materials, providing lighter weight alternatives to CNTs-based
nanocomposites with additional functionality at nano-scale [20]. Graphene appears
to bond better to the polymers in the epoxy, allowing a more effective coupling of
the graphene into the structure of the composite. This property could result in the
manufacture of components with high strength to weight ratio for such uses as
windmill blades or aircraft components.Conductive graphene/graphite-based
nanocomposites have applications in field effect transistors (FETs), Solar cells
(and other opto-electronic devices) and memory storage devices. All these
applications depend on high conductivity. Photo-voltaics and optoelectronics reply
on the fact that monolayers of graphene are about 98 % transparent but still have
high electrical conductivity. This makes graphene suitable for photoexcitation and
exiciton mobility/diffusion as transparent conducting electrodes [13, 43, 48].
Although we have seen here and in other published research findings that
graphene based polymer nanocomposites have tremendous potential for applica-
tion in automotive, electronics, aerospace and packaging due to its multifunctional
properties, however, the development and applicability of graphene-based polymer
nanocomposites will be limited by the lack of effective methods for scalable
graphene production, difficult manipulation of graphene sheets in processing due
to its extremely low bulk density, and the lack of local sites or tensioned bonds on
the graphene sheets to anchor functional moieties to make it process friendly and
compatible with other materials.
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Optimization and Scaling
up of the Fabrication Process of Polymer
Nanocomposites: Polyamide-6/
Montmorillonite Case Study
K. Pielichowski, T. M. Majka, A. Leszczyńska and M. Giacomelli
Abstract Although polyamide (PA) nanocomposites reinforced with montmoril-

lonite (MMT) are processed for more than two decades, the primary technological
problem related to optimization of processing conditions to fully exploit properties
of these nanomaterials has still to be addressed. The processing of polymer
nanocomposites by melt intercalation consists, in principle, of the following
stages: preparation and drying of raw materials, preparation of a premix master-
batch, dosing the premix masterbatch into a feeding zone, heating and melting the
polyamide-based matrix, an extrusion of a fluid composition followed by a set of
auxiliary operations. The process of obtaining polyamide nanocomposites with the
desired properties depends on numerous processing parameters that, when varied,
affect the quality of manufactured products. Therefore, in this chapter techniques
for obtaining polyamide-6/montmorillonite nanocomposites (PA6/MMT NCs), are
presented along with discussion of the optimization process for the preparation of
PA nanocomposites. Important technological problems arising during the
processing are discussed in this chapter, as well as present issues which need to be
addressed in scaling up the production from laboratory to industrial scale.
1 Introduction
Nanotechnology has been playing an increasingly important role in science and

technology for the last 20 years. Popularity of the nano- concept is reflected in
numerous academic and industrial research activities in this area and emergence
K. Pielichowski T. M. Majka (&) A. Leszczyńska

Department of Chemistry and Technology of Polymers, Cracow University of Technology,
ul. Warszawska 24, 31-155 Kraków, Poland
M. Giacomelli
Grado Zero Espace, via Nove, 2/A, Montelupo Fiorentino, Italy

76 K. Pielichowski et al.
need for opening new courses specializing in the field of nanotechnology [1–3].
The new polymer nanomaterials can be produced on the base of both thermoplastic
and thermoset polymers [3, 4]. Thermoset nanocomposites find their use mostly in
the shipbuilding and coating industry. The ability to easily and repeatedly form
thermoplastic nanomaterials is a big advantage, which makes these materials
useful in many industries, especially in the automotive or packaging sectors.
Thermoplastic polymer nanocomposites can be obtained in several ways described
in numerous scientific publications, however, the most common and efficient
method is melt intercalation [3–8]. Polymer melt intercalation involves annealing
(usually under shear) of a mixture of polymer and layered silicate above the
softening point of the polymer [5]. During annealing, polymer chains diffuse from
the bulk polymer melt into the galleries between the silicate layers. This method
enabled the production of nanocomposites of e.g. polyolefins, polyoxymethylene,
polyamide, polycarbonate, poly(ethylene terephthalate), and polystyrene [3–13].
Science is focused both on physical modification of traditional polymers as well as
synthesis of new monomers from which new polymers are obtained with inter-
esting new properties that can provide opportunities for novel applications. These
new materials may show better properties such as chemical, barrier, physical and
mechanical properties [2–5, 11, 13–15]. In melt mixing process crucial role plays
the use of different types of fillers which, thanks to their unique characteristics,
influence the properties of final products. Intercalation of nanofiller into the
polymer matrix, depending on its nature, changes mechanical, optical, biological,
surface or thermal properties of the composites. The achievement of significantly
better nanocomposites properties primarily depends on nanoadditive surface
energy and specific surface area developed in nanocomposite, the degree of
organization on the surface, the shape and size of the nanofiller particles and the
spatial arrangement of particles in polymer matrix [2–5, 11, 13, 16–20]. 3D
structured compounds which are widely used are, e.g. metals and non-metal
oxides, carbides, borides, nitrides or carbon black, talc and chalk; compounds
having the 2D structure, such as layered silicates or graphene and molybdenium
disulfide and compounds of 1D structure as carbon nanotubes and carbon nanof-
ibers [3, 5, 11, 13, 15, 18, 20–23]. Renewable additives are also used such as
natural fibers, microfibrillated cellulose [3, 5, 24]. Very often, the polymer matrix
is added with a certain percentage of recycled granulate or materials are produced
exploiting recycled or biodegradable matrix. Now, these nanobiocomposites are
produced also by using advanced methods and technologies [1–6, 19, 20, 25].
Novel nanomaterials are used e.g. in medicine as modern medical supplies, in
packaging industry as multi-layer food films (Bayer [26], Clariant [27],
Honeywell—Aegies [28], Nanocor Inc. [29]), in automotive industry as interior
decorating applications of cars, tanks and car bumpers (GE Plastics [30], UBE—
Ecobesta [31], Polykemi [32]), in aeroplane industry [33], in the electrical and
electronic industry as insulations for cables and electrical equipment (Hyperion-
Catalysis Int. [34], Kabelwerk Eupen [35]), or in coating materials, including
marine paints and varnishes (Polymeric Supply Company [36]).
Optimization and Scaling up of the Fabrication 77
2 Processing of Polymer Nanocomposites
Polymer nanocomposites are two- or multiphase materials containing continuous

and dispersed phase(s), usually obtained by modification of the traditional poly-
mers by introducing and dispersing the nano-sized additives in the polymer matrix
[3, 5, 9, 37–41]. The polymer matrix is a thermoplastic or thermoset polymer, and
the second component (the filler) may be selected on the basis of its physical
structure (including particles size and shape) and chemical nature [3, 5, 9, 41].
Until now, various polymer/ceramic, polymer/metal, and polymer/non-metal
composites were obtained and characterized. The well-known methods for prep-
aration of polymer nanocomposites include:
• Intercalation of polymer or prepolymer from solution,
• In situ intercalative polymerization,
• Sol–gel technology,
• Melt intercalation.
Intercalation of the polymer or prepolymer from solution is a technique
involving the preparation of polymer solution in the solvent, that is modified by
addition of cation exchanged layered silicate. The polymer become adsorbed onto
the nanoparticles. After removal of the solvent by e.g. evaporation under vacuum
nanofiller remains intercalated/exfoliated and the polymer nanocomposite is
obtained. The advantage of this method is that intercalated nanocomposites can be
synthesized based on polymers with low or even no polarity, but the major
technological drawback is the excessive use of the solvent [3, 5, 9, 41].
In the first step of intercalative in situ polymerization in the presence of layered
silicates, the filler should be swollen by liquid monomer or pre-polymer solution. The
monomer migrates into the galleries of layered silicate so that the polymerization
reaction can occur between the intercalated sheets. In the second step, the interca-
lated substrate is subjected to polymerization, which occurs between the layers of the
silicate. Depending on the type of monomer or prepolymer the polymerization can
take place under the influence of the added initiator such as azobisisobutyronitrile
(AIBN) or catalyst such as metallocene ([Zr(n-C2H5)2 Me(THF)]+) or Ziegler–
Natta catalyst, or it may be initiated by temperature or irradiation. In the in situ
intercalative polymerization, the crucial issue is the good choice of a suitable cata-
lyst, which affects homogeneity of the dispersion [3, 5, 9, 41].
The sol–gel method involves the synthesis of the silicate mineral in the polymer
matrix, using aqueous solutions or gels containing the polymer and the silicate
building blocks. As precursors for the clay silica sol, magnesium hydroxide sol and
lithium fluoride were used. During this process the polymer assists a nucleation
and growth of inorganic host crystals and gets trapped in layers when they are
increased. However, synthesis of minerals requires high temperatures which
degrade the polymer matrix. Another problem is the tendency of silicate layers to
aggregate [3, 5, 9, 41, 42].
Quite efficient way to obtain polymer nanocomposites with layered silicates is

melt intercalation. It involves dispersing of appropriately modified layered silicate
in the polymer melt. Shear forces cause delamination of nanosilicate layers.
Moreover, when the silicate is compatible with the polymer matrix, the polymer
can enter the space inside the layers and form either an intercalated or an exfo-
liated nanocomposite. This process requires the use of a single or, better, a twin-
screw extruder, having a suitable profile. Intercalation in melt allowed to obtain
nanocomposites based on PE, PP, PA, PS, PVA, PVC, PET and the liquid
crystalline polymers on lab and industrial scale [1–3, 5, 7–9, 41].
Not all of the presented methods applied for polymer nanocomposites prepa-
ration are used on an industrial scale due to technical and economical reasons. The
most common method in technological practice is the melt intercalation which
requires the use of processing machines that are usually already available in
polymer processing companies. Production losses during the use of this technique
are small and the technique is quite versatile, i.e. it allows the manufacture of
many nanocomposite products using a variety of thermoplastic polymer matrix
mixed with various types of additives. Other advantages include high production
speed, high quality of products while assuring their reproducibility. On the other
hand, there are some technological problems related to the processing of different
types of polymer matrices in the presence of a nanofiller, especially degradation of
low molecular weight compounds that are used as nanofiller’s modifiers (e.g. to
enhance organophilization) under processing temperature and shearing forces
action [2, 3, 6–9, 12, 13, 20, 25, 39, 41, 43].
3 Fabrication and Characterization of PA6/

Montmorillonite Nanocomposites
Polymer/ceramic nanocomposites are one of the most interesting classes of

materials that have been developed in recent years. Under the concept of layered
silicates the natural 2:1 clay minerals are enclosed. In this group montmorillonite,
which is the main component of bentonite rocks occurring mainly in Europe,
North America and Asia, was found very attractive for the preparation of poly-
meric nanocomposites and, without a doubt, the most commonly used for this type
of applications [3, 5, 17, 20, 41].
3.1 Characteristics of Montmorillonite
Montmorillonite (MMT) is a mineral mined from the ground and respectively

purified, processed and modified to be compatible with the polymer matrix.
Montmorillonite is used as nanoadditive, due to its specific structure. Silicates are
based on the structure of SiO4 whose corners are occupied by oxygen atoms and the
silicon atom is in the center of the tetrahedron [3, 5, 17, 20, 41]. Montmorillonite
(Fig. 1) is composed of 2:1 packages, containing one layer of octahedral with
aluminum—oxygen—hydroxyl sheet, which is closed between two layers of tet-
rahedral with silicon—oxygen sheets. MMT crystals posses permanent negative
layer charge because of the isomorphous substitution in either the octahedral sheet,
where species such as Mg2+, Fe2+, or Mn2+ replace Al3+, or in the tetrahedral sheet,
typically because of substitution of Al3+ or occasionally Fe3+ cations for Si4+. This
charge must be balanced by the alkaline cations such as H+, Li+, Na+, K+ or Ca2+.
Oxygens anions placed in tetrahedra vertices are directed to the center of
structure and with hydroxyl groups, they are surrounded by other cations of alu-
minum, iron or magnesium, thereby forming together octahedrons [3, 5, 17, 20, 41,
44–54]. The two tetrahedral layers are connected by strong atomic-ion bonds with
one octahedral layer, creating a package, which is a characteristic structural unit of
montmorillonites, joined in an infinite two-dimensional nets. Between these
packages are metal cations, especially sodium or calcium and water molecules,
connecting them together [3, 5, 15, 17, 20, 41, 44–54]. Polymer–clay interactions
have been actively studied in the sixties and seventies of the last century but since
1990s MMT is consciously applied as a nanofiller for polymer composite mate-
rials. It creates so called gallery or interlayer of cations balancing electric charge
[55–57]. The thickness of the layer packet is about 1 nm and lateral dimensions
range from about 300 Å to several microns, depending on the composition and
structure of silicate and method of preparation [55–60]. Due to the nature of the
galleries there are different types of montmorillonite, for instance sodium mont-
morillonite (Na+—MMT), calcium montmorillonite (Ca2+—MMT) or hydrogen
montmorillonite (H+—MMT).
Fig. 1 Basic structure of montmorillonite [5]

3.2 Interactions Between Polyamide-6 and Montmorillonite
Layered silicates are hydrophilic and incompatible with most polymers (due to
their hydrophobicity), and in particular with non-polar polymers, such as large-
scale produced polyolefins. They are miscible in their original form only with
hydrophilic polymers such as poly(ethylene oxide) or poly(vinyl alcohol).
Therefore, for the use of layered silicates as nanofillers it is necessary to modify
them to achieve better compatibility with polymer matrix, and, in consequence
better properties [61–68]. This process involves the exchange of the metal cations,
located in the interlayer space of MMT, with an organic cations, particularly a
quaternary ammonium cations. After such an exchange, the modified montmo-
rillonite, in which the interlayer distance is increased (hence facilitating the
penetration of the monomer or polymer molecules in the interlamellar spaces), has
been achieved. Besides, the mineral becomes more hydrophobic, thus increasing
its compatibility with most of polymers [69–75]. From the point of view of
processing of polymer nanocomposites, it is possible to obtain three different
structures of polymer/layered silicate composite:
• The microcomposite structure—where the polymer and organoclay are present
as two separated phases;
• The intercalation structure—regular introduction of polymer chains between the
layers of clay;
• The exfoliation structure—silicate layers with a thickness of 1 nm are randomly
dispersed in polymer matrix.
The components of the nanocomposite have different specific properties, which

cause that next to the nanoparticle surface an adsorption layer of polymer is
formed. This adsorbed polymer layer has different properties from that of pure
polymer in melt. The thickness of the boundary polymeric layer increases with
increasing interactions between the polymer matrix and the nanofiller and ranges
usually between 2 and 9 nm. Adsorption of macromolecules on the surface of solid
nanofiller reduces the possibility of their movement and conformational changes.
If adsorption is selective, then macromolecules of lower molecular weight are
much more easily adsorbed. The phenomenon of selective adsorption may include
an interaction of suitable functional groups with the surface of nanofiller. Content
of the nanofiller also affects rate of crystallization, degree of crystallinity and the
nature of the crystalline phase [57–59, 72, 73]. Small content causes that the phase
separation boundaries in nanocomposite are increased several times, compared to
the conventional composite. In nanocomposites there are strong interactions
between the polymer matrix and surface of nanoparticles, which, along with high
specific surface area of nanoparticles, bring more pronounced changes in polymer
properties, in comparison with conventional fillers. To improve the properties of
polyamide composites as structural materials two parameters have to be
considered: the size of the contact surface of the dispersed phase (filler) and the
interaction between the continuous phase and the dispersed one [55–60, 69–75].
If the polymer is not able to intercalate between silicate layers followed by

dispersing nanofiller therein, a conventional phase separated microcomposite is
obtained. Weak physical attractions between the organic and inorganic compo-
nents in the nanocomposite systems lead to relatively poor mechanical properties.
Furthermore, agglomeration of particles tends to reduce the strength of composite
materials. Therefore, the type of surfactant used for surface modification of MMT,
the length of hydrocarbon chain, and packing density of surfactant on the clay
layer play an important role in structure formation [55–60, 69–76]. The nano-
composites with uniformly distributed silicate plates having irregular spatial
arrangement in the polymer matrix, without preserving its original parallel pack-
ing, are referred as exfoliated nanocomposites and were reported as having the best
physical and mechanical properties [77, 78]. For instance, nanocomposites based
on organoclay having two alkyl chains were found to have better properties than
those based on organoclays with only one alkyl chain. This was attributed to better
affinity of polymer to alkyl chains than silicate surface. Therefore, in this case the
increased amount of the alkyl chains should lead to a better dispersion of
organoclay. The low packing density of the inner layer of organic modifier causes
clasp adsorbed monolayers. If the packing density is increased, the chains adopt a
more extended conformation. Exfoliated or delaminated structure increases
interaction between polymer matrix and clay, changing the properties of the final
nanocomposite radically. In technological practice it is not easy to achieve com-
plete exfoliation of clay—this is due to the fact that the silicate layers are highly
anisotropic and most of the polymer chains in systems are physically bound to the
surface of the layered silicate [55–60, 69–75].
4 Optimization
Preparation of polyamide nanocomposites reinforced by montmorillonite requires

an individual approach. Numerous factors influence the process of preparation of
nanocomposites with desired properties. Even a small change in one parameter of
processing significantly affects the quality of final materials. In the ‘Laboratory of
Processing of Polymer Nanocomposites’ in the Department of Chemistry and
Technology of Polymers at the Cracow University of Technology optimization
procedures and guidelines of fabrication conditions of polymer nanocomposites
have been intensively developed in recent years. The processing of polymer
nanocomposites by melt intercalation consists of the following steps: the selection
of the suitable raw materials, preparation of a premix masterbatch, dosing the
premix masterbatch into a filling zone, heating and melting the polymer matrix, an
extrusion of a fluid composition solidification of the nanocomposite in water bath,
and finally pelletizing and drying. The optimization process for the preparation of
polyamide-6/montmorillonite nanocomposites in the laboratory scale has been
performed based on a mini-technological line shown in Fig. 1.
This mini-technological line includes: a twin screw co-rotating extruder

Thermo Scientific Rheomex PTW 16/25 XL, cooling tank and granulator ZAMAK
G-16/325 and volumetric feeder produced by Brabender, which is compatible with
extruder. Based on the results obtained from studies using this mini-line, some
suggestions and recommendations related to optimized fabrication of polyamide-6/
montmorillonite nanocomposites were formulated.
4.1 Selection of Raw Materials
The proper selection of raw materials is a crucial step that governs the quality of
the final product. Manufacturers involved in the production of fillers offer a large
variety of modified nanoadditives. It is possible in most cases to choose the type of
filler dedicated to a given polymer matrix and specific recommendations for
processing of such system are given, too. Depending on the type of organic
modifier used, fillers are more or less compatible with a specific polymer matrix.
However, the thermal stability of modifier limits the temperature of processing of
polymer matrix. Usually, the lower the molecular weight of the modifier, the faster
the decomposition at high temperatures, deteriorating the compatibility and initi-
ating the decomposition reactions of the polymer matrix. An useful example could
be a layered silicate—montmorillonite, which is usually modified with quaternary
ammonium salts, mainly dialkyl-dihydrogenated tallow ammonium salt (DADHT)
(in our work denoted as 72T) or dialkyl-benzyl-hydrogenated tallow ammonium
salt (DABHT) (in our work denotated as 43B). The flashpoint of dimethyl-dihy-
drogenated tallow ammonium (DMDHT) salt is 25 C and boiling point is 135 C
while, on the other hand, the flashpoint of dimethyl-benzyl-hydrogenated tallow
ammonium salt (DMBHT) is 110 C. These temperatures are about 100 C lower
than e.g. polyamide-6 processing temperatures. Despite this fact, montmorillonite
modified by DMDHT salt and other alkyl derivatives is recommended as nano-
additive for polyamide matrices, but appropriate processing conditions (described
in the following sub-chapters) must be selected. The content of a modifier may
also influence the thermal stability and other properties of MMT-based systems—
investigations on polyamide-6/MMT nanocomposites, in which montmorillonite
was modified by different DMDHT salt content, revealed that the addition of MMT
with low content of DMDHT increased thermal stability of the nanocomposite,
and the addition of MMT with high content of DMDHT increased strength
properties of the nanomaterials [79–81] From technological point of view,
montmorillonites as minerals differ in elemental composition which is associated
with mining place. Differences are also due to performance of the crushing,
grinding and cleaning operations. As a consequence, the montmorillonites can
differ in the degree of purity and the number of exchangeable cations in their
galleries. Generally, similar types of the quaternary ammonium salts are used to
modify MMT, but they usually differ in the percentage share of long hydrocarbon
chains originating from natural allows. It can be understood that the modifier is in
fact a mixture of quaternary ammonium salts with a tallow chain composed of e.g.
20 % of C16, 50 % of C18 and 30 % of C20.
Selection of raw materials includes proper choice of polymer matrix. Each of
the polymer types has characteristic technological features and specifications that
must be considered during processing. The molecular weight of polymer deter-
mines its viscosity in the melted phase, and, in consequence the processing
conditions, e.g. rotational speed of screws. For instance, the use of polyamide-6
with low molecular weight (in the order of 40,000) allows its processing at
temperatures around 220–235 C, whereby the higher molecular weight polymer
has to be processed at temperatures higher by about 10–15 C, which in turn
significantly promotes degradation of low molecular weight organic modifiers.
Therefore, when using a polyamide matrix with high molecular weight it would be
logical to use the filler with lower content of modifier.
4.2 Drying of Raw Materials
A very important requirement related to the processing of some polymeric

materials, especially polyamides, is to provide a dry masterbatch into the feeder or
directly into filling zone. Polyamide must be stored in a dry place at temperature
close to this in the workplace. If the material is stored at a temperature lower than
the ambient temperature, before the opening of the container or big bag, the
polyamide must be brought to a room temperature of the processing machinery to
avoid condensation of water from the air on cold granules. Polyamide, delivered
by the manufacturer in the form of granules, should be dried under appropriate
conditions, even despite the assurances that it is ready for immediate use. The
moisture content in the polyamide is a particularly important factor that has a
direct influence on the melt viscosity, stability, mechanical properties, and, finally,
the appearance of the product. At processing conditions water or its vapour take
part in chemical reaction with the polyamide (hydrolysis) causing a reduction of
polymer molecular weight. It may also interact with volatile low molecular weight
degradation products of quaternary ammonium salts leading to different secondary
products. Therefore, manufacturers of polyamide suggest that the moisture content
in the material shall not exceed 0.2 wt%, and in some cases even 0.1 wt%. On the
other hand, drying is a highly energy-consuming process, and, therefore, a com-
promise between the speed of drying, the drying temperature and the moisture
content in the polymer matrix should be reached. Such measurements have been
conducted in our laboratory and the results indicate that the polyamide-6 should be
vacuum-dried in the temperature range 75–80 C for 3–24 h, with the recom-
mendation for 75 C/6 h [82]. Apart from polymer drying, the nanoadditive—
montmorillonite—should be dried as well, since it contains small amount of water
adsorbed on the crystal structures. Usually montmorillonite is dried using vacuum
ovens at a temperature of 80–100 for 3 h.
4.3 Preparation of a Masterbatch
Mass content of a nanofiller in the polymer matrix plays a fundamental role as it

directly influences the structure and morphology of resultant polymer/MMT
nanocomposite. The high degree of intercalation of montmorillonite between
polymer chains significantly improves the mechanical and barrier properties of the
nanocomposite, but may result in a reduction of thermal stability of nanomaterials
[83, 84]. Larger enhancement effects were reported when greater surface area of
filler contact with the matrix, and there are strong interactions between the two
phases. Therefore, nanocomposites should display a high surface of contact area
between clay layers and polymer, which considerably improves the properties of
the products even when the silicate content in the matrix is at low level [2–5, 11,
13]. For instance, concentrations of filler in the range of 2.5–5 wt% caused an
increase in the strength modulus. Moreover, complete exfoliation had a positive
influence on the stiffness of the nanocomposites [3–7]. This effect was explained
by the fact that the number of planes in a single MMT stack is equal to the number
of planes in exfoliated single plane system. In polymer nanocomposite when the
number of planes per one stack increases, the number of MMT planes being in
contact with polymer decreased, then the strengthening efficiency is reduced.
Nanocomposites containing more than 5 wt% of layered silicates are characterized
by higher brittleness, due to collapse of the bonds between the silicate and the
polymer matrix. It leads to spatial defects of nanocomposites, often in the form of
visible cracks on the surface [3–7, 85, 86]. When the planar bonds between matrix
and clay stack breaks, the microgaps are formed, usually around the large silicate
heterogeneities [6, 7, 85–88]. The morphology plays an important role in the
development of strengthening mechanism because the distribution of silicate
intercalated regions is equally important to improve the stiffness of the nanocom-
posites [5–7, 85, 86, 89]. It has been found that the presence of larger content of
layer silicate than 5 wt% reduces also the thermal stability of polymer nanocom-
posites. The nanofiller is able to accumulate heat that, when emitted later on, may
accelerate the polymer decomposition [90]. Moreover, organically modified clays
(e.g. by alkylammonium cations) can catalyze degradation of the polymer matrix
[3–7, 85–89]. The appropriate amount of silicate allows to obtain a suitable dis-
tribution of clay platelets in the polymer matrix which improves the barrier prop-
erties by creating a labyrinth path for the evaporating gases [3–7, 85–89].
Carefully selected raw materials should be mixed in a specially designed
tumble mixer, and the mixing time is 5–15 min. This period of time is sufficient to
allow the nanofiller to equally cover the polymer granules. The mixing time for a
given polymer/MMT system is dependent on the amount of raw material and the
mixer type. The raw materials should be mixed at not too high rotational speed to
avoid dust formation that could be dangerous to the workers exposed to its action
[91].
4.4 Dosing of a Masterbatch
Results of tests performed using the processing line presented in Fig. 2 show that
the dosing rate of the masterbatch into the feed zone has a significant influence on
the whole fabrication procedure. In the laboratory conditions, feeders are often
used to dose at an appropriate speed raw materials into the feed zone of the
extruder. The control is done using an integrated software applied to control the
extruder that is able to detect the feeder. The feeder (Fig. 3) is provided with two
spring screws for dispensing the masterbatch granules.
The rotational speed of the screws is adjusted to the corresponding rotational
speed of extruder and is given as a percentage of extruder screws speed. Before
performing any operation, the feeder should be calibrated. Such a calibration has
been successfully performed using the 0.2, 0.3, 0.5, and 1.0 % of extruder’s screws
speed which was set on 50, 100, 150, 200, 240 rpm. Information on the stable
work of the feeder at a speed of 0.3 % in relation to the rotational speed of the
extruder screws was used to optimize the extrusion process, and further tests were
performed in order to check the properties of the polyamide nanocomposite with
montmorillonite when using various screws speeds. Nanocomposites of PA6
containing 3 wt% of organically modified MMT were prepared at four different
rotational speeds 100, 150, 200 and 240 rpm and then tested in terms of
mechanical and thermal properties. The values of modulus of elasticity measured
for neat PA6 and PA6/MMT nanocomposites during static bending tests showed
clear dependence on the rotational speed of screw applied in the production step
and the behaviour of unmodified PA6 was different from that observed for
nanocomposites. The modulus of elasticity (E) of PA6 decreased with increasing
screw speed showing a minimum at speed of 200 rpm while the E values measured
for nanocomposites displayed a maximum for the same rotational speed (Fig. 4).
It is worth to notice that in industrial practice increasing the capacity of pro-
duction line by increasing the rotational speed of extruder could be done at the
expense of mechanical performance of pristine polymer. This unfavourable effect
Fig. 2 Mini-technological
line located in the
‘Laboratory of Processing of
Polymer Nanocomposites’ at
the Cracow University of
Technology
Fig. 3 Feeder for dosing a

masterbatch
is not expected to occur for PA6/MMT nanocomposites since those materials

exhibited maximum enhancement when produced at high rotational speed.
An important issue is the choice of the heating zone, to which the masterbatch
is dispensed. For instance, fibrous fillers are usually dosed into the successive
zones whereby the polymer is added to the first feed zone—this is due to the fact
that the fibers may be disintegrated by screws if they were supposed to follow the
whole extrusion route. Powder fillers are rather dosed together with the granulate
in the first zone to allow efficient compounding.
4.5 Extrusion of Polyamide-6/Montmorillonite

Nanocomposites in the Laboratory Scale
Optimization of the extrusion process is the most important part of the

optimization of whole technology for obtaining the polyamide-6/montmorillonite
nanocomposites, which includes selection of the type of extruder, configuration of
the extruder screws, selection of heating zones temperature, selection of the length
of screws, selection of the temperature zones of the die, selection of screws speed
Fig. 4 Modulus of elasticity for PA6 and its nanocomposites versus extruder screw speed
and residence time of the material in cylinder. Depending on the type of extruder
different melt homogenization can be achieved. Co-rotating twin screw extruders
are ensuring a high homogenization of the composition and these extruders are
usually used for the preparation of polymer nanocomposites.
In order to achieve the appropriate homogenization optimization of the extru-
sion process is necessary. Homogenization process can be divided into thermal and
mechanical one. Thermal homogenization occurs due to temperature fluctuations
along the extruder barrels, as well as in the cross-section. The so called ‘active’
part of the screw is responsible for the transfer of a particle (in relation to other
particles) along the axis of the screw, whereby the passive part is responsible for
the transport of melt from the feed zone to the die. In modern processing equip-
ment, different segments of the screws are responsible for different processes.
Some of them are responsible for melting of the pellets, some other for appropriate
dispersion of the filler in the matrix, and there are also parts designed for venting.
The way the individual segments are placed along the screw affects the mechanical
and thermal properties of the obtained products. Sometimes, wrong configuration
of screws does not allow to achieve the selected rotational speed, and therefore the
residence time of the material in the extruder gets changed. The residence time of
polyamide-6/montmorillonite nanocomposites in the extruder with different screws
speeds is shown in Fig. 5.
Using the rotational speed of 50 rpm, 1 g of sample remained inside the
extruder for 93.3 s; with 100 rpm—63.0 s; with 150 rpm—48.3 s; with
200 rpm—43.0 s; and when using 240 rpm it remained for only 37.3 s. Certainly,
an increase of the screws speed reduces the residence time of the composition
inside the cylinder, but, on the other hand, higher speed provides high shear forces
Fig. 5 The residence time of polyamide-6/montmorillonite nanocomposites in extruder with

different screws speeds
that facilitate the exfoliation of clay layers, though, excessive shearing may cause
decomposition of the material. Therefore, a compromise should be sought between
the (short) residence time of the material inside the extruder and the screws
rotation speed to achieve proper homogenization. Concerning the screws dimen-
sions, too long screws not only lengthen the residence time inside the machine but
also increase the consumption of raw materials. In the laboratory scale, an efficient
extruder {with a length of screws equal to 25 L/D [L—length, D—diameter of the
screw (16 mm)]; 6 heating zones} is able to produce (at a speed of 240 rpm and
the dosing speed of 0.3 %) 300 g of the composition during 30 min of processing,
provided an appropriate configuration of the screws is secured (Fig. 6).
Abrasive wear of screws occurs primarily at the edges of the thread and on the
surface contact of the cylinder when clay minerals are dosed with a polymer as a
premix masterbatch. Over the time, diameter of screw core gets slightly reduced
due to wear in the transition and feeding zone. The viscosity of the molten material
has a significant influence on the pressure inside the cylinder. If the polymer
contains an (nano)additive, its viscosity increases and liquidity decreases. This
means that the torque on screws is increased and in some cases the increase of
zones temperature was forced. The viscosity of the liquid material is primarily a
function of the molecular weight—the higher the molecular weight the highest the
viscosity and thus higher temperatures are required to reduce the processing torque
since too high torque can damage the laboratory equipment. On the other hand,
high temperatures have negative impact on polymer matrix and organic modifiers
of the filler. Therefore, it is necessary to identify the proper temperatures of the
heating zones and the die, as it was done for polyamide-6/montmorillonite system
(Table 1).
Fig. 6 Examples of different configurations of screws for polyamide-6 composites
Table 1 The selected processing conditions for polyamide-6/montmorillonite nanocomposites

using mini-technological line
Twin co-rotating screw extruder
Flow rate (%) Rotational speed (1/min) Heating zones
0.3 240 1 2 3 4 5 6 Die
Temperature (C) 245 245 245 250 255 250 260
Atmospheric venting – – – – Yes – –
Length of the zones (mm) 80 60 60 64 60 76 23
L/D 5.00 3.75 3.75 4.00 3.75 4.75 –
Cooling tank
Length of cooling surface (mm) 1,500
Tank volume (dm3) 27
Height of bath (mm) 1,081
Water temperature (C) 18
Granulators
Size of pellets (mm) 1
Rotational speed (1/s) 12
The melt viscosity decreases with an increase in shear rate; for this reason, by
increasing the speed of extrusion, one can also reduce the viscosity of the melt. It
is generally agreed that energy delivered by the screw should constitute about
80 % of the energy required to raise the temperature evenly. It follows that it is
necessary to take into account the construction and operating characteristics of the
screw. Attention should also be paid to the location of the heating elements in
small laboratory equipment. If the extruder heaters are located at the bottom of the
cylinder, substantial temperature gradient may occur even though the sensors will
show that the desired temperature has been reached. The upper part of the cylinder
will be under-heated for long time. For this purpose, first cylinder may be warmed
up about 20 C higher than the established processing temperature.
After reaching a given value, the temperature should be reduced to the
corresponding one. It is worth to mention that low temperature of the melt can
cause undesirable effects such as formation of heterogeneities in the melt that may
nucleate e.g. degradation reactions which lead to a decrease of polymer molecular
weight and worsening of the properties of the final product. There are generally
two degradation routes operating at processing conditions: (1) hydrolysis due to
presence of moisture in the material, and (2) thermal degradation. Therefore, it is
important to:
• Assure a moisture content in the material as low as possible;
• Select the proper content of raw materials;
• Set the appropriate dose rate of materials;
• Select proper length of screws, as well as their configuration and the rotational
speed;
• Set the proper temperature profile of particular heating zones and the die.
4.6 Cooling of Polyamide-6/Montmorillonite Nanocomposites
After extrusion process the nanocomposite strip should be cooled down. In

polymer compounding lines this process is done using a cooling bath. Polyamides
are semi-crystalline polymers and depending on cooling mode different values of
crystallinity degree can be achieved. The degree of crystallization has a significant
influence on the product properties, including mechanical properties, moisture
absorption and chemical resistance. The neat polyamide-6 displays a polymorphic
behavior showing the c- and a-crystalline phase. Under the processing conditions
where PA6 was subjected to high shearing and cooling rates as well as stretching
of the extruded polymer string while solidifying it showed mainly the c crystalline
phase that reflected a strong diffraction peak with a maximum at 21.5 covering the
small double-peak of the a-modification on WAXD diffractograms. Such crystal
morphology could origin from the processing condition which favored the for-
mation of c crystals. The main diffraction peak observed on WAXD diffractogram
of PA6/MMT nanocomposite occurred at the same value of 2h as that observed
for neat PA6. Therefore, no changes in the crystallographic structure of PA6 were
induced in this material by the presence of MMT layers and processing conditions
were principal factors controlling the crystalline morphology of PA6 in as obtained
nanocomposites.
It has been observed that the water temperature in cooling bath increased by
2–4 C due to collecting the heat if bath was not cooled. The increase was
moderate due to small mass of polymeric material extruded on laboratory scale,
but it is recommended to control the water temperature in cooling bath at industrial
scale and provide constant parameters of PA6 crystallization.
4.7 Pelletising of Polyamide-6/Montmorillonite

Nanocomposites
From the cooling bath, the nanocomposite strip is directly brought to the granulator,
where the successive step of cutting it into the granules takes place. It is important
that the pellets present dimensional consistency. In the processing line settings it is
possible to fix the drawing speed and rotation speed of a cutting edges to produce
pellets with a given size. In practice, to avoid decontaminations it is important to
clean regularly the pellets’ container in the granulator and the cutting knives.
4.8 Drying of Polyamide-6/Montmorillonite Nanocomposite

Pellets
Drying of pellets of polyamide-6/montmorillonite nanocomposite is necessary

because the material during cooling is in direct contact with water. The content of
moisture in polyamide nanocomposites has to be carefully controlled as it strongly
influences the material’s behaviour in next processing steps. The moisture content
changes rheological behavior of molten mass, and it can lead to formation of
inhomogeneities, such as interior bubbles, during injection molding. Besides, it
could disturb maintaining of the dimensional stability of the final product within
an assumed tolerance. Therefore, nanocomposite pellets should be dried following
the protocol established for pristine polyamide-6, i.e. for 6 h at 75 C using a
vacuum dryer.
4.9 Injection Molding of Polyamide-6/Montmorillonite

Nanocomposite Pellets
Optimization of injection molding process of PA6/MMT nanocomposites was

done using a laboratory scale injection molding machine presented in Fig. 7. This
machine is equipped with a cylinder and one-slot injection molds which are heated
electrically. Instead of screw plasticizing the polymer matrix (as usual in indus-
trial-size machines) here is a plunger, which has several important functions in the
process.
During operation, the cylinder, the form and the plunger are heated to an
appropriate processing temperature. The plunger is connected with a pneumatic
system of injection molding machine driven by compressed air coming from the
compressor. Nanocomposite pellets are fed into the cylinder and the tip of plunger
is placed in the cylinder. After plastification, the material is injected. When the
cylinder comes into contact with the mold, the plunger is pushed into the cylinder
transferring thus the melt to the mold. After the composition is injected, the
Fig. 7 Laboratory-scale
injection molding machine
pneumatic system moves the plunger and cylinder to its original position. During
this time, the injected bar is cooled in the mold. Then the sample is removed from
the mold, already ready for testing/further use.
Before proceeding to injection molding on laboratory scale, preliminary tests
should be performed to find out:
• The number of profiles that can be obtained with a single filling of cylinder;
• The optimum temperature of the cylinder;
• Residence time;
• The optimum temperature of the mold;
• The total duration of the process.
The temperature in the cylinder is the temperature at which the polymer (in this
case polyamide-6) undergoes melting. The melting point of the polymer matrix
can be determined using e.g. differential scanning calorimetry (DSC). Initially, in
our experiments the cylinder temperature was set at 232 C. Next, it was inves-
tigated how much time it takes to melt the polyamide at the given cylinder tem-
perature—if this time is longer than 3.5 min, it would require to increase the
cylinder’s temperature. A longer residence time of the heated material within the
cylinder may lead to oxidative degradation of the polymer. Since PA6/MMT
nanocomposites displayed rather narrow processing window the optimal cylinder
temperature can be defined as this one that allows the polyamide melting within
2–3.5 min without decomposition. The residence time of nanocomposite materials
in the cylinder shall be kept within this time limits to avoid decomposition of
organic modifier, too. The next parameter to be optimized is the temperature of the
mold. The mold temperature influences the mechanisms of crystallization of
polyamide-6/montmorillonite nanocomposites. In the process of crystallization
two basic processes occur: the formation of the nucleating sites and growth of the
crystals. It is possible to distinguish between homogeneous and heterogeneous
nucleation depending on the processing conditions. In the first case, in the molten
polymer material certain groups of atoms present close spatial arrangement; when
these clusters achieve the necessary critical size, they can act as (homogeneous)
nucleating agents; this requires the use of large undercooling, which can be
achieved by lowering the temperature of the mold. In the second case, the for-
mation of nucleating agents occurs on the surface of the solid phase in contact with
the molten polymer. The nucleation occurs on the fine particles of montmorillonite
dispersed in the polymer matrix. Under such conditions, the crystallization takes
place at a much lower supercooling than the pure polyamide-6 [92–94]. According
to this theory, during the injection molding of profiles it can also be expected that
the crystalline phase will quickly appear next to the walls of the mold. In this zone,
due to the large drop in temperature, and thus a considerable supercooling, a
number of nucleating agents may be formed. In the process of injection molding of
the tested materials the temperature of the mold was 80 C. On the other hand,
residence time of the material in the mold (Fig. 8) is in the range of 10 s when
using a single mould form of laboratory injection molding machine.
The sample after removal from the mold is subjected to further, slow cooling
under air. Different temperature of the mold causes different absorption of the heat,
lengthening or reducing the time of cooling to room temperature, and, hence,
influencing the mechanical properties of the obtained products. Both for pure
polyamide matrix and polyamide-based nanocomposites the larger undercooling
favors the crystallization, increasing thus the impact strength of materials.
Venting takes place on the mold surface and in this micro-scale there is no need
or possibility to construct the mold with heated ingots or with venting parts. It is
important to keep the injection pressure at constant level so the plunger is inserted
to the cylinder always with the same force. In our experiments the injection pressure
was 10 Bar; higher pressure may cause distortions, spoiling of the plunger and
cylinder, as well as may be dangerous for the operator. Operator plays an important
role in this technological process, performing the processing and controlling the
final product’s quality. The operator can visually detect defects such as scorch
marks due to local overheating, pollutions, voids, etc., and try to avoid them by
changing raw materials. Processing parameters or replacing the mold.
Fig. 8 A single mould form

5 Technological Problems Associated with the Fabrication

Process of Polymer Nanocomposites
Each technological process, including fabrication of polymer nanocomposites by

processing methods, reveals some problems which must be eliminated during the
development stages of this technology. It is not an easy task and usually requires
previous experience with the materials involved, as well as skills to predict (as
much as possible) the behavior of the composition during numerous operations
throughout the process. Sometimes, small oversights can cause large changes at
the technology output, leading to major worsening of the final product properties.
Some technological problems have already been presented in the previous sub-
chapters, but the full description should include also other issues. One of them is
proper storage of raw materials. For polyamides, even if the polymer granulate is
packed in laminated bags to protect it against absorption of moisture, after a long
storage time a certain amount of water is absorbed. The bags should be kept closed
at the ambient temperature with no sunlight access. The hopper or feeder should be
loaded with quantity of material which is sufficient for at least 1 h of work, and
closed by a tight cover. Unused pellets should not come into direct contact with
atmospheric air and sunlight, and later on brought back to the bag, which should be
then sealed. At the stage of preparation and dosing of the masterbatch for the feed
zone, there are sometimes problems with deposition of nanofiller powder on the
walls of the container and feeder. If containers, feeders or drum mixers have a
rough surface, the nanofiller may enter into micro-spatial surface defects. There-
fore, it is recommended to use devices with a smooth surface. Another techno-
logical problem—adhesion of the nanofiller to the granules—may be solved by
wetting the pellets with an easily volatile solvent and then mixing them with an
appropriate amount of additive. The solvent improves the adhesion of the nano-
filler to the surface of the granules and, after evaporation, it leaves nanofiller well-
dispersed on polymeric granules. However, it seems that losses during stirring and
dosing of the masterbatch to the extruder on laboratory scale are hard to avoid—in
our studies the total amount of losses (from weighing of the raw materials to
producing pellets) was ca. 19 % for composition mass of 350 g with 3 wt% of
MMT (Table 2).
Those losses are mainly caused by the adhering of nanofiller and pellets on the
walls of feeder, and in the areas which are not or hardly available for masterbatch
dosing screws. This is the case when the dosing screws are located in such a way
Table 2 Total amount of materials losses for PA6/MMT nanocomposites fabrication on lab
scale
Polymer MMT wt% of Masterbatch The losses Total amount Total amount
weight (g) weight filler (%) weight (g) during extrusion of losses (g) of losses (%)
(g) (g)
339,519 10,503 3.09 350,022 36,929 66,976 19.13
that the filler is not properly dosed since pellets settle on the bottom. It should be
noted that the remaining unused materials can be returned to the feeding zone, but
then the properties of products may change.
The losses during injection molding of nanocomposites pellets, using laboratory
injection molding machine, are estimated at 2–5 %. Breaks occurred during
extrusion are due to sudden machinery stops, when the torque increases rapidly.
Each modern extruder has safety lock that enables the work in some restricted
processing conditions when e.g. too high torque may damage the screws. There-
fore, for example, a quite widely used safety lock automatically stops the
machinery whenever the torque reaches a certain value (e.g. 100 nm). To reduce
the torque higher processing temperatures may be applied, but this may cause
decomposition of polymer matrix and/or organic modifier. For instance, during
extrusion of polyamide-6/montmorillonite nanocomposites under the conditions
presented in Table 3 a torque of 80–100 nm was achieved. The obtained
nanocomposites were partially degraded, showing a dark-yellow appearance.
This technological problem can be solved by applying an increased speed of the
screws. The residence time of material in the extruder is then short enough to
prevent an undesirable thermal degradation of material. The examples of torque
behavior during PA 6/MMT extrusion processes are shown in Fig. 9a and b.
The improper extrusion conditions were too low temperature and screws speed
(150 rpm) were applied resulted in continuous shutdown of the machine (Fig. 9a).
Nanocomposite material during the machine downtime was still present and heated
inside the cylinder, resulting in degradation of polymer matrix. After increasing
the temperature and rotational speed (to 240 rpm), the extrusion process stabilized,
as shown in Fig. 9b. Visible torque oscillations in the range of 20 nm result from
irregular dosing of raw materials to the feed zone. Introduction of each portion of
Table 3 Wrong conditions set during the extrusion of polyamide-6/montmorillonite

nanocomposites
Twin co-rotating screw extruder
Flow rate (%) Rotational speed (1/min) Heating zones
0.2–0.5 100–170 1 2 3 4 5 6 Die
Temperature (C) 250 250 260 260 270 270 275
Atmospheric venting – – – – Yes – –
Length of the zones (mm) 80 60 60 64 60 76 23
L/D 5.00 3.75 3.75 4.00 3.75 4.75 –
Cooling tank
Length of cooling surface (mm) 1,500
Tank volume (dm3) 27
Height of bath (mm) 1,081
Water temperature (C) 18
Granulator
Size of pellets (mm) 4-6
Rotational speed (1/s) 1-7
raw materials resulted in the torque increase. Other factors that affect the quality
and characteristics of the process are (1) venting and (2) cooling of the feeding
zone. Venting in one of the last heating zones of the extruder should be applied,
otherwise even for the materials properly dried, bubbles can appear in the melt.
They arise because the low molecular weight compounds present in the compo-
sition degrade during processing without the possibility to evaporate. The use of
Fig. 9 The examples of the behavior of the torque during extrusion process: a wrong extrusion
conditions, b proper extrusion conditions
venting not only decreases the pressure inside the cylinder but also efficiently
eliminates the bubbles present in melt state, making their evaporation easier.
Cooling of the feeding zone is necessary to compensate the large amounts of heat
coming from adjacent heating zones and caused by abrasion of granules by screws.
An overheating may cause degradation of polymer nanocomposite material and
eventually a breakdown of the machine. Therefore, efficient cooling of first feed
zone with compressed air (preferred) or water should be applied.
6 Scaling up of the Fabrication Process of Polymer

Nanocomposites
As polymer nanocomposites become more and more popular in many real-world

applications, development of effective and versatile industrial-scale nanocom-
posite processing methods is of great interest nowadays. For instance, the com-
mercial success of nano-enabled products for the automotive market is expected
for numerous applications such as external body parts, interior and under-bonnet
parts, coating and fuel system components, etc. Scaling up will primarily increase
capacity of production but this process requires several steps to be performed
properly:
• Design of micro-scale technologies,
• Implementation of lab-scale experiments,
• Design, implementation and optimalisation of macro-scale technologies,
• Technical verification of the technology,
• Troubleshooting.
Scaling up is a complex issue that needs to take into account various factors.
This can be confirmed by the results achieved within different EC funded projects
aimed at scaling up production of polymer nanocomposites based on thermoset
and thermoplastic matrices from laboratory scale to industrial scale [95]. As an
example one could name the ‘‘Polyfire’’ project, carried out at Sheffield Hallam
University [96] which deals with layered silicates-based fillers that have already
been proven to have flame-retarding properties when added to certain polymers
including polypropylene, polystyrene and polyamide, among others. The scaling
up production goes from tests performed in the laboratory scale to the macro scale
experiments [97].
However, there are still some limitations and challenges for scaling up nano-
composites production, such as:
• Processing limitations—extruders and injection molding machines have usually
a different configuration in the micro (lab) and macro (industry) versions.
Processing on a large scale requires a new configuration of the screws, cylinders,
dies and molds scaled to larger dimensions. This requires changes in the con-
ditions of nanocomposite processing, e.g. the length and configuration of the
screws, rotational speed of the screws, temperatures of the heating zones, the
number of heating zones, the cooling mode of zones, type and size of molds
used for injection, etc.
• Processing costs—the production of nanocomposites on a commercial scale at
viable prices requires proper optimization of the technology in terms of material
and energy balance, as well as equipment depreciation costs. The performance-
to-cost ratio is the key to success in commercialization of the new nanoproduct.
• Environmental and safety limitations—emphasis should be put on careful
assessment of health and safety as well as environmental issues associated with
the nanomaterials, which is imperative before introducing the technology in the
industry.
• Compatibility, consistency and reliability in volume production—it is possible
to get good compatibility, consistency and reliability in volume production of
polymeric nanocomposites. However, particle size distribution control may
cause problems because nanofillers show tendency to agglomerate authorization
of the final products for common use—commercializing selected end-use
products may take a longer time, mainly due to stringent approval of e.g.
European Commission or US Environment Protection Agency. Generally, the
products containing new nanomaterials require a long series of positive tests to
fulfill all the formal requirements.
7 Conclusions
Polymer nanocomposites represent a new class of multiphase materials containing

dispersion of nano-sized fillers such as nanoclays, nanotubes, nanofibers etc.
within the polymer matrix. These multifunctional nanocomposites not only exhibit
excellent mechanical properties, but they also show outstanding combinations of
optical, electrical, thermal, magnetic and other physico-chemical properties. It is
believed that the molecular level interactions between the nanoparticles and
polymer matrices along with the presence of very high nanoparticle-polymer
interfacial areas play a major role in influencing the physical and mechanical
properties of nanocomposites [2–5, 11, 13–16, 18–20]. Among nanofillers,
nanoclays offer a reduction in relative heat release, excellent dispersion and ex-
foliation, excellent flame retardant synergy, and reduced weight [3, 5, 17, 20, 41,
44–54]. The use of thermoplastics-based nanocomposites fabricated by processing
methods has been steadily growing, especially in automotive applications, largely
due to the material’s low cost, high performance, low density, longer shelf life,
easy dispersion and ability to recycling [3, 5, 11, 13, 15, 17, 18, 20–22]. A market
research report states that world nanocomposites market is forecast to reach 1.3
billion pounds by the year 2015, and growth in the nanocomposites market will be
driven by robust demand in automotive and aerospace markets. By 2020, the
automotive sector is expected to become the third-largest market for polymer
nanocomposite applications, with over 15 % of the market [98–100].
However, the scaling up of the fabrication process of polymer nanocomposites

still requires increased attation. Techniques for preparation of polymer/montmo-
rillonite nanocomposites on industrial scale need to be optimized, taking into
account important technological problems occurring during the processing both on
equipment and materials side.
Acknowledgments This work was partially funded by the European Commission (FP7 Project
CP-FP; Project Reference: 228536-2) and by the National Science Centre in Poland under
contract UMO-2011/01/M/ST8/06834.
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Influences of Morphology and Doping
on the Photoactivity of TiO2
Nanostructures
Nasser A. M. Barakat and Muzafar A. Kanjwal
Abstract Compared to the bulk, the nanoscale provides special characteristics for
the functional materials. Moreover, the nanostructural morphology has also dis-
tinct influences. Enormous efforts have been devoted to the research of TiO2
material, which has led to many promising applications. Beside the morphology
impact, doping of titanium dioxide nanostructures by pristine metal nanoparticles
(e.g. Ag, Pt, … etc.) revealed distinct improvement in the photocatalytic activity.
Although the doping process can remarkably improve the photoactivity, it has also
noticeable influences on the crystal structure. In this chapter, the important
parameters affecting the photocatalytic activity of TiO2 are discussed; morphology
and silver doping. Also, effect of sliver-doping on the crystal structure and the
nanofibrous morphology is investigated. Moreover, the influence of the tempera-
ture on the photodegradation process using Ag-doped TiO2 nanostructures will be
addressed. Two morphologies were introduced; nanoparticles and nanofibers. The
nanofibers were synthesized by electrospinning of a sol–gel consisting of titanium
isopropoxide, silver nitrate and poly(vinyl acetate). The silver nitrate amount was
changed to produce nanofibers having different silver contents. The nanoparticles
were prepared from the same sol-gels, however instead of spinning the gels were
dried, grinded and sintered. The experimental and analytical studies indicate that
doping by silver reveals to form anatase and rutile when the silver nitrate content
in the mother solution was more than 3 wt%. The rutile phase content is directly
proportional with the AgNO3 concentration. Negative impact of the silver-doping
N. A. M. Barakat (&)
Organic Materials and Fiber Engineering Department, Chonbuk National University, Jeonju
561-756, Republic of Korea
N. A. M. Barakat
Chemical Engineering Department, Minia University, El-Minia 61111, Egypt
M. A. Kanjwal
Technical University of Denmark, DTU Food, Soltofts plads, B 227 2800 Kgs Lyngby,
Denmark

106 N. A. M. Barakat and M. A. Kanjwal
on the nanofibrous morphology was observed as increase the silver content caused
to decrease the aspect ratio, i.e. producing nanorods rather nanofibers. However,
silver-doping leads to modify the surface roughness. In contrast to the known
influence of the temperature on the chemical reactions, in case of the nanofibrous
morphology of Ag-doped TiO2, the temperature has negative impact on the
photoactivity.
1 Introduction
In chemistry, photocatalysis is the acceleration of a photoreaction in the presence

of a catalyst. In catalyzed photolysis, light is absorbed by an adsorbed substrate. In
photogenerated catalysis, the photocatalytic activity depends on the ability of the
catalyst to create electron–hole pairs, which generate free radicals (e.g. hydroxyl
radicals: •OH) able to undergo secondary reactions. Its practical application was
made possible by the discovery of water electrolysis by means of titanium dioxide.
The commercially used process is called the advanced oxidation process (AOP).
There are several ways the AOP can be carried out; these may (but do not nec-
essarily) involve TiO2 or even the use of UV light. Generally the defining factor is
the production and use of the hydroxyl radical. Generally, the semiconductors are
used as photocatalysts. Like other solids, semiconductor materials have electronic
band structure determined by the crystal properties of the material. The actual
energy distribution among the electrons is described by the Fermi energy and the
temperature of the electrons. At absolute zero temperature, all of the electrons
have energy below the Fermi energy; but at non-zero temperatures the energy
levels are filled following a Boltzmann distribution.
In semiconductors the Fermi energy lies in the middle of a forbidden band or
band gap between two allowed bands called the valence band and the conduction
band. The valence band, immediately below the forbidden band, is normally very
nearly completely occupied. The conduction band, above the Fermi level, is
normally nearly completely empty. Because the valence band is so nearly full, its
electrons are not mobile, and cannot flow as electrical current.
However, if an electron in the valence band acquires enough energy to reach the
conduction band, it can flow freely among the nearly empty conduction band
energy states. Furthermore it will also leave behind an electron hole that can flow
as current exactly like a physical charged particle. Carrier generation describes
processes by which electrons gain energy and move from the valence band to the
conduction band, producing two mobile carriers; while recombination describes
processes by which a conduction band electron loses energy and re-occupies the
energy state of an electron hole in the valence band.
In a material at thermal equilibrium generation and recombination are balanced,
so that the net charge carrier density remains constant. The equilibrium carrier
density that results from the balance of these interactions is predicted by
Influences of Morphology and Doping on the Photoactivity 107
thermodynamics. The resulting probability of occupation of energy states in each

energy band is given by Fermi–Dirac statistics.
Fast electrons/holes recombination is the main dilemma facing the semicon-
ductors photocatalysts in general and titanium oxide in particular. Incorporation of
noble metal nanoparticles (NPs) into the titania dielectric matrix is a recent
strategy to overcome this problem and simultaneously improve the photocatalytic
activity of titanium oxide [1, 2]. Doping with foreign metal nanoparticles can
produce high Schottky barrier that facilitates electron capture [3]. The capture of
electrons postulate to produce a longer electron–hole pair separation lifetime, and
therefore hinder the recombination of electron/hole pairs and enhance the transfer
of holes and possibly electrons to O2 adsorbed on the TiO2 surface. Afterwards,
excited electrons migrate to the metal, where they become trapped and the elec-
tron/hole pair recombination is suppressed. Therefore, many investigations have
reported the enhancement of photoactivities in both liquid and gas phases [4, 5].
Moreover, this incorporation provides an absorption feature due to the surface
plasmon resonance (SPR) occurring over the visible range of the spectrum [6].
Particularly, silver and gold nanoparticles are more familiar because of their color
varieties in the visible region, which is attributed to oscillations of the electrons at
the surface of the nanoparticles [7]. Silver is the most common metal used to
modify titania, because its d-s band gap is in the UV region and does not damp out
the plasmon mode as strongly as gold [8, 9]. Titania-modified-silver particles have
raised extensive interest due to their applications in photocatalytic degradation
[10]. The researchers have intensively studied how silver provides titania distinct
photocatalytic activity, the mechanism has been well explained in previous reports
[11–13]. Moreover, some researchers have concluded that incorporation of silver
in titanium dioxide leads to increases in the total surface area of the prepared
titanium dioxide [14, 15]. This can be considered an additional benefit of utilizing
silver-loaded titanium oxide in the field of photocatalytic degradation. Therefore,
many researchers have practically demonstrated that the degradation rates of the
dyes can be enhanced by the deposition of silver on titanium dioxide [16–18].
In the last decades, nanostructural materials have been intensively investigated
because of their high surface area, which strongly affects their physiochemical
properties. Different shapes have been introduced. Of the reported nanostructure
shapes, special attention has been paid to one-dimensional forms such as nanorods,
nanowires, and nanofibers. This is due to their potential applications in the nan-
odevices [19–21]. Nanofibers have received special consideration due to their high
axial ratio, good mechanical properties, and their manageable and novel physical
properties.
Compared to nanoparticles, nanofibers have small surface area which might be
considered a negative impact upon using as catalyst in the chemical reactions.
Therefore, if the morphology has no impact, the nanoparticles will have higher
catalytic activity. Moreover, for the same surface activity, the temperature should
have the same influence on both formulations. In most of the chemical reactions,
positive effect of the temperature on the reaction rates is a prevailing impression.
Temperature is a measure of the kinetic energy of a system, so higher temperature
implies higher average kinetic energy of molecules and more collisions per
unit time. This hypothesis might be true in the normal cases, however the
nanostructures usually have unexpected behaviors compared to the bulk scales.
In this chapter, the aforementioned facts have been investigated for the
Ag-doped TiO2 nanophotocatalyst. Two nano-formulations have been utilized;
nanofibers and nanoparticles. Silver-grafted titanium oxide nanofibers have been
synthesized using the electrospinning of silver nitrate/titanium isopropoxide/
poly(vinyl acetate) sol–gel. However, the nanoparticulate form has been obtained
by calcination of a ground powder prepared from the same electrospun sol–gels.
Metal-doping may also have an influence on the titania crystal structure leading to
distinct improving in the application fields [22, 23]. Therefore, effect of the silver-
doping on the crystal structure, the morphology and the photocatalytic activity of
TiO2 nanofibers will be discussed in this chapter.
2 Nanofibers
Nanofibers are an exciting new class of material used for several value added
applications such as medical, filtration, barrier, wipes, personal care, composite,
garments, insulation, and energy storage. Special properties of nanofibers make
them suitable for a wide range of applications from medical to consumer products
and industrial to high-tech applications for aerospace, capacitors, transistors, drug
delivery systems, battery separators, energy storage, fuel cells, and information
technology [24, 25].
If the diameters of polymer fiber materials are shrunk from micrometers to
submicrons or down to nanometers, there appear several amazing characteristics
such as very large surface area to volume ratio (this ratio for a nanofiber can be as
large as 103 times of that of a microfiber), flexibility in surface functionalities,
and superior mechanical performance (e.g. stiffness and tensile strength)
compared with any other known form of the material. These outstanding prop-
erties make the polymer nanofibers to be optimal candidates for many important
applications [26].
Generally, polymeric nanofibers are produced by an electrospinning process
(Fig. 1). Electrospinning is a process that spins fibers of diameters ranging from
10 nm to several hundred nanometers. This method has been known since 1934
when the first patent on electrospinning was filed. Fiber properties depend on field
uniformity, polymer viscosity, electric field strength and DCD (distance between
nozzle and collector). Advancements in microscopy such as scanning electron
microscopy has enabled us to better understand the structure and morphology of
nanofibers. At present the production rate of this process is low and measured in
grams per hour.
Another technique for producing nanofibers is spinning bi-component fibers
such as Islands-In-The-Sea fibers in 1–3 denier filaments with from 240 to possibly
Fig. 1 Schematic representation of electrospinning process
as much as 1,120 filaments surrounded by dissolvable polymer. Dissolving the

polymer leaves the matrix of nanofibers, which can be further separated by
stretching or mechanical agitation.
The most often used fibers in this technique are nylon, polystyrene, polyacry-
lonitrile, polycarbonate, PEO, PET and water-soluble polymers. The polymer ratio
is generally 80 % islands and 20 % sea. The resulting nanofibers after dissolving
the sea polymer component have a diameter of approximately 300 nm. Compared
to electrospinning, nanofibers produced with this technique will have a very nar-
row diameter range but are coarser.
In the electrospinning process, the solution is held at the tip of a capillary tube
by virtue of its surface tension. The electrical potential applied provides a charge
to the polymer solution. Mutual charge repulsion in the polymer solution induces a
force that is directly opposite to the surface tension of the polymer solution. An
increase in the electrical potential initially leads to the elongation of the hemi-
spherical surface of the solution at the tip of the capillary tube to form a conical
shape known as the Taylor cone [27]. A further increase causes the electric
potential to reach a critical value, at which it overcomes the surface tension forces
to cause the formation of a jet that is ejected from the tip of the Taylor cone. The
charged jet undergoes bending instabilities and gradually thins up in air primarily
due to elongation and solvent evaporation [28]. The charged jet eventually forms
randomly oriented nanofibers that can be collected on a stationary or rotating
grounded metallic collector of the electrospinning set up [29].
2.1 Metallic Nanofibers
In recent years, ceramic material with effective control at the nanometer scale has
been actively pursued as a problem of materials science and engineering. In
particular, the preparation of 1D ceramic nanostructures such as fibers, wires, rods,
belts, tubes, spirals, and rings has received great interest owing to their potential
applications in many vital areas of technologically such as electronics, photonics,
and mechanics [30, 31]. A large number of chemical and/or physical methods,
mostly based on the bottom-up and template directed routes, have been demon-
strated for producing 1D ceramic nanostructures with various compositions by
controlling the nucleation and growth processes. Top-down approaches such as
photolithography, soft lithography and electrospinning have also been exploited to
fabricate 1D ceramic nanostructures [30, 32–35]. Moreover, electrospinning of
vital materials are fascinating in the field of implantology. Electrospinning of
metallic nanofibers has been largely limited due to availability of proper solvent
and desired viscosity for bending instability during electrospinning process.
Ceramics are usually considered to be not directly spinnable although it is possible
(at least, in principle) to electrospun ceramic nanofibers from their melts at
extremely high temperatures. Like conventional spinning processes for generating
ceramic fibers. Preparation of ceramic fibers by electrospinning has to rely on the
use of spinnable precursors or by using a blending template containing colloidal
sol [36]. The fabrication of ceramic nanofibers consists of three major steps:
• Preparation of an inorganic sol or a solution containing a matrix polymer
together with an alkoxide, salt, or polymer precursor.
• Electrospinning of the solution to generate composite nanofibers consisting of
the matrix polymer and precursor. The spinning experiments are usually per-
formed in a well-controlled environment at room temperature.
• Calcination, sintering, or chemical conversion of the precursor into the desired
ceramic at an elevated temperature, with concomitant removal of all organic
components from the precursor fibers.
As compared with the bulk metals, these nanofibers have been approved to be
an excellent templates for the bottom based applications. This potentiality is the
basis for superior properties like less weight, high area to volume ratio, improved
durability and bioactive interfaces [37–41].
2.2 Modification of Titania Nanofibers
Currently, the heterogeneous photocatalysis has arised as an alternative econom-

ical and harmless technology for removal of organic impurities. In such processes,
the illuminated semiconductors absorb light and generate electronic species which
leads to complete oxidation of organic components in waste waters. Titanium

dioxide is considered an interesting material because of its optical, electrical and
photochemical properties [42, 43]. However, for practical applications the
photocatalytic activity and photoresponse behavior of titanium dioxide are very
much needed to be further improved [5, 44]. Recently studies have focussed to
modify the surface of titanium dioxide to improve its efficiency for photocatalytic
activity and to use in solar cells [5, 45]. Incorporation of noble metal nanoparticles
into the titania dielectric matrix is a modern strategy to improve the photocatalytic
character of titanium dioxide. This incorporation is providing an absorption feature
due to surface plasmon resonance (SPR) occurring over the visible range of the
spectrum [6]. In particular, silver and gold metals are the most popular materials
do have strong SPR character [46, 47]. Moreover, the nanoscale noble metals are
usually classical high-performance heterogeneous catalysts [43, 48]. Silver is the
most common metal used to modify titania that is because of its d-s band gap is in
the UV region and does not damp out the plasmon mode as strongly as for gold [8,
9]. The titania modified-silver particles have raised an extensive interest due to
their applications in photocatalytic degradation [10]. The researchers have inten-
sively studied how silver provides titania distinct photocatalytic activity; the
mechanism was well explained [11–13, 49–52]. Many formulations have been
introduced for titania/silver composite, for instance, nanoparticles [53], and thin
films [54–56].
As it is well known, the surface to volume ratio is an important feature for any
catalyst. Accordingly, 1D nanostructures are expected to strongly modify the
photocatalytic activity. Among all 1D nanostructure, nanofibers do have especial
interest due to large surface area to volume ratio. In the field of metal oxides
nanofibers; electrospinning is the most widespread.
3 Experimental Section
3.1 Materials
Silver nitrate (99.8 assay), methylene blue dihydrate dye (95.0 assay), N,N-
dimethylformamide (DMF, 99.5 assay), and rhodamine B dye were obtained from
Showa, Co. Japan. Titanium (1V) isopropoxide (Ti(Iso), 98.0 assay) was pur-
chased from Junsei Co. Ltd., Japan. Poly (vinyl acetate) (PVAc,
MW = 500,000 g/mol) was obtained from Aldrich, USA. These materials were
used without any further purification.
3.2 Preparation of Nanofibers and Nanoparticles of Ag/TiO2

Composite
3.2.1 Nanofibers
The electrospinning process was utilized to prepare the silver-grafted titania

Nanofibers (NFs). Typically, a sol–gel was prepared by mixing titanium iso-
propoxide (Ti(Iso)) and poly(vinyl acetate) (PVAc, 14 wt% in DMF) with a
weight ratio of 2:3, respectively, and then few drops of acetic acid were added
until the solution became transparent. The mixing process was carried out at 25 C
using magnetic stirrer rotating at 150 rpm. To prepare sol–gels containing different
contents of silver, silver nitrate solutions in DMF were mixed with proper quan-
tities of the prepared Ti(Iso)/PVAc solution to prepare final solutions containing
0.5, 1.0, 1.5, 2.0 and 2.5 wt% AgNO3. Afterwards, these solutions were homo-
geneously mixed under stirring conditions for 10 min at 25 C and moderate
stirring speed. A high voltage power supply (CPS-60 K02V1, Chungpa EMT Co.,
Republic of Korea) was used as the source of the electric field. The sol–gel was
supplied through a plastic syringe attached to a capillary tip. A copper wire
originating from the positive electrode (anode) connected with a graphite pin was
inserted into the sol–gel and the negative electrode (cathode) was attached to a
metallic collector covered with polyethylene sheet. Briefly, the solution was
electrospun at 6 kV and 15 cm working distance (the distance between the needle
tip and the collector). The electrospinning process was carried out at 25 C in
40 % relative humidity atmosphere. The formed nanofiber mats were initially
dried for 24 h at 80 C in a vacuum and then calcined in air atmosphere at 700 C
for one hour with a heating rate of 5 C/min.
3.2.2 Nanoparticles
Silver nitrate/Ti(Iso)/PVAc solutions having the aforementioned compositions and

preparation procedure were utilized to prepare nanoparticles containing different
silver contents. The process parameters (temperature and stirring) were not
changed. Instead of spinning, the solution was vacuously dried at 80 C for 48 h to
completely remove the solvent. The obtained solid materials were finely grinded
and sintered in air at 700 C for 1 h.
3.3 Photocatalytic Degradation
The photocatalytic degradation of the selected dyes in the presence of Ag-TiO2

nanofibers and nanoparticles was carried out in a simple photo reactor. The reactor
was made of glass (1,000 ml capacity, 23 cm height and 15 cm diameter), covered
with aluminum foil, and equipped with ultra-violet lamp emitting radiations at
365 nm. The initial dye solution and the photocatalyst were placed in the reactor
and continuously stirred to ensure proper mixing during the photocatalytic reac-
tion. Typically, 100 ml of dye solution (10 ppm, concentration) and 50 mg of
catalyst were used. At specific time intervals, a 2 ml sample was withdrawn from
the reactor and centrifuged to separate the residual catalyst, and then the absor-
bance intensity was measured at 664 and 554 nm for methylene blue and rhoda-
mine B dyes, respectively.
3.4 Characterization
Surface morphology of nanofibers was studied by JEOL JSM-5900 scanning

electron microscope (JEOL Ltd, Japan) and field-emission scanning electron
microscope (FESEM, Hitachi S-7400, Japan). The phase and crystallinity were
characterized by using Rigaku X-ray diffractometer (Rigaku Co, Japan) with Cu
Ka (k = 1.54056 Å) radiation over a range of 2h angles from 20 to 100. High
resolution image and selected area electron diffraction pattern were observed by
JEOL JEM-2200FS transmission electron microscope (TEM) (JEOL Ltd., Japan).
The concentration of the dyes during the photodegradation study was investigated
by spectroscopic analysis using HP 8453 UV–visible spectroscopy system
(Germany). The spectra obtained were analyzed by HP ChemiStation software
5890 series.
4 Results and Discussion
4.1 The Photocatalyst Characterization
The polymer is an essential constituent in sol–gels to achieve the electrospinning

process [19, 57–59]. Metal alkoxides are the best candidates to form the gel
structure due to their affinity to hydrolysis and condensation in the polymer matrix.
Because of the well polycondansation property [60, 61], titanium isopropoxide is a
famous precursor to prepare TiO2 nanofibers by using the electrospinning process
and PVAc as a gelling polymer [62]. Addition of silver nitrate does not affect the
nanofibrous morphology [5]. Figure 2a displays the obtained PVAc/Ti(Iso)/
AgNO3 (the later was 2.0 wt% in the electrospun solution) nanofibers. As shown,
good morphology was obtained. It is noteworthy mentioning that all the formu-
lations produced good morphology nanofibers; only slight decrease in the average
fiber diameter with increasing the silver nitrate content was observed due to
increase the electrical conductivity of the electrospun solutions. Calcination did
not affect the nanofibrous morphology for all formulations. Figure 2b represents
the SEM image of the obtained powder from calcination of the electrospun mat
containing 2.0 wt% silver nitrate. As shown, good nanofibers were obtained.
Increase the roughness of the outer surface with increasing the silver nitrate
content in the original electrospun sol–gel was a noticeable observation. Figure 2c
and d display the FE SEM images of the pristine and Ag-containing
(AgNO3 = 2.0 wt%) TiO2 nanofibers, respectively. Big difference between the
surfaces of the investigated nanofibers can be observed. It is noteworthy men-
tioning that the surface roughness was dependent on the silver content, moreover
increase the silver nitrate content more than the maximum value used in this study
(i.e. 2.5 wt%) led to destroy the nanofibrous morphology and produce nanorods
instead. Concerning the nanoparticulate shape, addition of silver nitrate improves
the spherical morphology of the nanoparticles as shown in Fig. 2e and f which
demonstrate the SEM images of the pristine and Ag-doped (2.0 wt%) TiO2
nanoparticles.
To properly investigate the effect of addition of silver nitrate on the surface of
the silver-doped nanofibers, the surface area has been measured by using Bru-
nauer–Emmett–Teller (BET) technique (Micromeritics, Norcross, GA). The
obtained results indicated that the average surface area of the silver-free nanofibers
was about 21.3102 ± 0.1351 m2/g, while, it was 38.8100 ± 0.1324 m2/g for the
nanofibers obtained from calcination of silver nitrate (2 wt%)/Ti(Iso)/PVAc
electrospun nanofiber mats. As can be concluded from these results, the surface
area of the silver containing nanofibers was duplicated compared to the pristine
ones which strongly enhance the photocatalytic activity. For the nanoparticles, it is
clear from the SEM images that addition of silver has negative influence on the
surface area as the average diameter decreases with silver addition (Fig. 2e and f).
XRD is a reliable and widespread identification technique especially for crys-
talline materials. Figure 3 represents the XRD pattern of the nanofibers obtained
from two sol–gels, Ti(Iso)/PVAc and silver nitrate (2.0 wt%)/Ti(Iso)/PVAc. As
shown in both spectra, the results confirm formation of pure anatase titanium
dioxide. The strong diffraction peaks at 2h values of 25.09, 37.65, 38.44,
47.89, 53.89, 55.07, 62.40, 68.70, 70.04, and 75.00 correspond to the crystal
planes (101), (004), (112), (200), (105), (211), (204), (220), (220), and (215),
respectively indicate formation of anatase titanium dioxide [JCPDS card no
21-1272]. In the case of the nanofibers obtained from calcination of silver nitrate/
Ti(Iso)/PVAc mats (Fig. 2, spectra A), in addition to the titanium dioxide peaks,
extra peaks at 2h values of 38.11, 44.29, 64.43 and 77.48 corresponding to the
crystal planes (111), (200), (220), and (311), respectively confirm presence of
silver metal [JCPDS card no 04-0783]. To make it easy, in Fig. 3, we have marked
the peaks corresponding to titanium oxide and silver as A and S, respectively. It is
noteworthy to mention that the morphology did not affect the XRD data (i.e. the
same results have been obtained for the nanoparticles). Therefore, the XRD pattern
of the nanoparticles was not added to simplify and clarify the figure.
Transmission electron microscope analysis is used to investigate the crystal
structure. Figure 3 shows the HR TEM of the obtained Ag-doped TiO2 nanofibers;
A and nanoparticles; B. As shown in these figures, there are some black dots in
Fig. 2 SEM image of the electrospun PVAc/Ti(Iso)/AgNO3 (AgNO3 = 0.2) nanofibers; a the
corresponding sintered nanofibers; b FE SEM images of the pristine; c and Ag-doped TiO2;
d nanofibers, and SEM images of the pristine; e and Ag-doped TiO2 (AgNO3 = 0.2);
f nanoparticles
both formulations which can be considered as the Ag nanoparticles as these dots

have different crystal structures compared to the TiO2 matrices. Both formulations
have good crystallinity as shown in Fig. 4c and d which represent the SAED
patterns of the Ag-doped TiO2 nanofibers and nanoparticles, respectively.
Moreover, the Fast Fourier Transform (FFT) images for both formulations reveal
good crystallinity as shown in the corresponding insets.
Fig. 3 XRD results for the obtained powder after calcination of PVAc/Ti(Iso) and PVAc/Ti(Iso)/
AgNO3 (AgNO3 = 0.2) electrospun nanofibers in air at 700 C
(a) Ag NP (b)
(c) (d)
Fig. 4 HR-TEM image of the Ag-doped TiO2 nanofibers; a and nanoparticles; b and SAED
patterns of the marked areas; c and d the insets show the FFT images of the marked areas
In order to affirm that the silver is present as particles in the TiO2 nanofibers and
simultaneously investigate the nanoparticles appeared in the TEM images, EDX
analysis has been invoked. The analysis has been performed in two different points
as shown in Fig. 5. As shown in this figure and the corresponding insets, there is
big difference in the silver weight percentages between the two chosen points.
Therefore, one can say that the point in Fig. 5a represents a point containing silver
nanoparticles since the silver content at that point is almost 21 %. However,
Fig. 5b might represent almost silver-free point. Taking into consideration that the
electron beam in the EDX analysis has specific width more than the silver
nanoparticle size, the small weight percentage of silver at this point might be
explained as a small part of bordering silver nanoparticles. Actually, these results
match all the previous reports about silver-doped titania nanostructures which
concluded that the silver exists as small nanoparticles in/on the synthesized
nanostructures. Moreover, according to the atomic size, silver-titania system
cannot form solid solution alloy, so, theoretically silver has to be in the form of
nanoparticles within the titania matrix. Well distribution of silver nanoparticles
can be obtained by good mixing of the original AgNo3-Ti(Iso)-PVAc mixture, so,
in this study, the electrospinning process was achieved after obtaining well mixed
solution.
To explain the phase changes during the calcination process of both formula-
tions (i.e. Ti(Iso)/PVAc and silver nitrate-Ti(Iso)/PVAc), we have utilized thermal
gravimetric analysis (TGA). Figure 6 shows the obtained TGA results in all cases,
Fig. 5 EDX analysis at two different points, the insets represent the corresponding elemental
weight percentages
along with the first derivatives curves were plotted to precisely extract the useful
information. Figure 6a represents TGA results for Ti(Iso)/PVAc nanofiber mats, as
shown in this figure; two peaks are observed in the first derivative plot. According
to the thermal properties of titanium isopropoxide, the first peak (at *325 C) can
be explained as decomposition of this organometallic compound into titanium
Fig. 6 TGA results in oxygen atmosphere for Ti(Iso)/PVAc (a) and silver nitrate-Ti(Iso)/PVAc
nanofiber mats (b)
dioxide. Because of the calcination process has been performed in air atmosphere,
the second peak (at *434 C) can be explained as complete elimination of PVAc
that also matches our previous work in the same polymer [5]. However, in case of
silver nitrate- Ti(Iso)/PVAc (Fig. 6b), there are observable change; as shown in
this figure, the rate of degradation is comparatively low compared with the first
case. Also, there are two main peaks were obtained, a broad peak at *286 C and
another one at 445 C. According to the thermal properties of silver nitrate [59],
and Ti(Iso) (as seen in Fig. 6a), the first peak can be investigated as simultaneous
decomposition of silver nitrate and Ti(Iso). However, the second peak represents
the decomposition of PVAc polymer. There is another peak at low temperature
(*60 C) it might be explained as evaporation of the combined moisture with the
sample. Another observation can be noticed by comprising the thermal decom-
position of the two formulations is increase the final inorganic residuals in case of
the silver nitrate-Ti(Iso)/PVAc than the silver-free case, this increase represents
the silver NPs.
4.2 Effect of Silver Doping on the Photoactivity

of the Titania
To investigate the influence of the silver doping on the photoactivity of titanium

oxide, photodegradation of some organic dyes was performed as explained in the
experimental section.
4.2.1 Methylene Blue Dihydrate dye
To safely estimate the dye concentration in the distilled water, the absorbance
intensities of the utilized methylene dye have been measured for many dye/dis-
tilled water solutions. The UV absorbance spectra for different concentrations of
dye solutions (starting from 1 to 8.75 mg/l) were measured within the range of
500–800 nm. Figure 7a reveals the obtained results. As shown in this figure, the
absorbance curves have maximum value at almost 664 nm. Moreover, the maxi-
mum measured absorbance intensities were linearly increased with increasing of
the dye concentration as shown in Fig. 7b which represents the relationship
between the dye concentration and the measured absorbance at 664 nm. As shown
in this figure, the absorbance varies linearly with the dye concentration in good
model. Statistical analyses of this curve indicated high accuracy of the exploited
linear model since the coefficient of determination; R2 of this model was 0.9989
which reveals excellent precision and reproducibility of this calibration curve.
Theoretically, as mentioned in the introduction section some studies have
explained the role of silver in enhancing the photocatalytic activity of titania.
Generally, these studies have drawn this conclusion. The Ag nanoparticles
Fig. 7 Absorbance spectra at different concentrations of methylene blue dye solutions within a
range of 500–800 nm (a), and the relationship between the absorbance intensity and
concentration of the dye at wavelength of 664 nm (b)
deposited on TiO2 surface act as electron acceptors, enhancing the charge sepa-
ration of electrons and holes and consequently the transfer of the trapped electron
to the adsorbed O2 acting as an electron acceptor. The sufficient dye molecules are
adsorbed on the surface of Ag-TiO2 than on the TiO2 surface, increasing the
photoexcited electron transfer from the sensitised dye molecule to the conduction
band of TiO2 and consequently increasing the electron transfer to the adsorbed O2.
Experimentally, the pure titania and silver-doped titania nanofibers have been
invoked as photocatalysts in degradation of methylene blue dye, Fig. 8 shows the
obtained results. As shown in this figure, incorporating of silver in titanium oxide
nanofibers reveals to significant increase in the degradation rate of this dye. As can
be observed in this figure, within 10 min more than 92 % of the dye has been
degraded, moreover, the dye completely eliminated after almost two hours. This
interesting result comes from exploiting the advantage of the nanofibrous shape as
well as the benefit of incorporating of silver in titanium oxide. However, in case of
pure titanium oxide nanofibers, almost 50 % of the dye has been oxidized after
30 min and the dye was almost disappeared from the solution after 6 h. Actually,
even in case of pure titanium nanofibers, the obtained results are satisfactory
compared with the other photocatalyst [63].
4.2.2 Methyl Red Dye
By the same aforementioned fashion, the wavelength corresponding to maximum

absorbance intensity in case of methyl red dye has been estimated. Figure 9a
shows the relationships between the absorbance intensity and the wavelength for
many dye aqueous solutions (from 1 to 8.75 ppm) within wavelength range of
300–600 nm. As shown in the figure, the wavelength matching maximum
Fig. 8 Photocatalytic degradation of methylene blue dye in presence of pure TiO2 and Ag-TiO2
nanofibers
absorbance intensity for all dye concentrations is 428 nm. Moreover, there is very
good linearity between the dye concentration and the absorbance intensity at this
wavelength as shown in Fig. 9b. A single calibration model was adequate to
represent all the data points in Fig. 9b with very low mathematical errors
(R2 = 0.999). Therefore, one can confidently apply in this calibration curve
(Fig. 9b) to estimate the concentration of any unknown methyl red dye aqueous
solution after measuring the absorbance intensity for this solution at 428 nm.
Fig. 9 Absorbance spectra at different concentrations of methyl red dye solutions within a range
of 300–600 nm (a), and the relationship between the absorbance intensity and concentration of
the dye at wavelength of 428 nm (b)
It is worth noting that methyl red decay is only due to photocatalysis as already
published results showed practically no dye removal by only UV radiation within
300 min [42]. Accordingly, it is difficult to completely remove this dye within
relatively short reaction time; e.g. several hours [42]. Figure 10 reveals the
obtained results after utilizing the prepared TiO2 and Ag/TiO2 nanofibers as
photocatalysts to oxidize the methyl red dye. As shown in this figure, the behavior
of this dye is completely different than methylene blue, in contrast to that dye; the
same removal percentage (i.e. 92 %) was obtained after almost 3 h. Actually, this
result is also very satisfactory since according to our best knowledge, no one has
reached to such decay percentage using any photocatalyst. Moreover, this result
affirms the role of silver in enhancement of the behavior of titanium oxide as
photocatalyst since the nanofibrous shape was not enough to eliminate this dye as
shown in Fig. 10. Almost 50 % of the dye is remaining after 7 h, this decay
efficiency is not rejected compared with the other catalysts [64].
4.3 Effect of Morphology
The effect of the fibrous morphology has been investigated by studying the rates of
degradation of methylene blue dye using the two formulations as photocatalyst.
The obtained results have strongly recommended utilizing this composite in
nanofibrous form. Figure 11 represents the effect of nanostructure shape on the
Fig. 10 Photocatalytic degradation of methyl red dye in presence of pure TiO2 and Ag-TiO2
nanofibers
photocatalytic activity of pure titanium oxide. As shown in this figure, the nano-
fibrous morphology does have great effect. Titanium oxide nanoparticles could not
catalyze the photocatalytic reaction to remove the dye even after almost 12 h,
65 % of the original dye was remaining in the solution after such long reaction
time. However, the high surface area to volume ration which is the mean feature of
nanofibers was the mean reason to get such interesting result compared with
nanoparticles. As shown in Fig. 6, all the dye was oxidized and eliminated within
6 h.
Theoretically, some studies have explained the role of silver in enhancing the
photocatalytic activity of titania. Generally, these studies have drawn this con-
clusion: The Ag nanoparticles deposited on TiO2 surface act as electron acceptors,
enhancing the charge separation of electrons and holes and consequently the
transfer of the trapped electron to the adsorbed O2 acting as an electron acceptor.
The sufficient dye molecules are adsorbed on the surface of Ag-TiO2 than on the
TiO2 surface, increasing the photoexcited electron transfer from the sensitized dye
molecule to the conduction band of TiO2 and consequently increasing the electron
transfer to the adsorbed O2.
Experimentally, the silver-doped titania nanofibers and nanoparticles have been
invoked as photocatalyst in degradation of methylene blue dye, Fig. 12 shows the
obtained results. As shown in this figure, incorporating of silver in titanium oxide
nanofibers reveals to significant increase in the degradation rate of this dye. As can
be observed in this figure, within 10 min more than 92 % of the dye has been
Fig. 11 Photocatalytic degradation of methylene blue dye in presence of pure TiO2

nanoparticles
Fig. 12 Photocatalytic degradation of methylene blue dye in presence of Ag-doped TiO2

nanofibers
degraded, moreover, the dye completely eliminated after almost two hours. This
fantastic result comes from exploiting the advantage of the nanofibrous shape as
well as the benefit of incorporating of silver in titanium oxide. However, in case of
Ag-doped titanium oxide nanoparticles, almost 80 % of the dye has been oxidized
after 12 h and the dye did not completely disappeared from the solution.
The results obtained from Figs. 11 and 12 support the pervious works reported
the advantages of doping of titanium oxide by silver nanoparticles and simulta-
neously strongly recommend utilizing this interesting photocatalyst in nanofibrous
shape.
4.4 Effect of Temperature
Photocatalysis is the acceleration of a photoreaction in the presence of a catalyst.

In catalyzed photolysis, light is absorbed by an adsorbed substrate. In photogen-
erated catalysis, the photocatalytic activity depends on the ability of the catalyst to
create electron–hole pairs, which generate free radicals (hydroxyl radicals: •OH)
able to undergo secondary reactions. Its comprehension has been made possible
ever since the discovery of water electrolysis by means of the titanium dioxide.
Figures 13, 14, 15, 16 and 17 represent the photodegrdation of rhodamine B
using Ag-doped TiO2 nanoparticles obtained from sol-gels contain 0.5, 1.0, 1.5,
2.0 and 2.5 wt% AgNO3, respectively at different temperatures (5, 15, 25, 45 and
55 C). As shown in these figures, increase the silver content in the doped
nanoparticles enhances the photoactivity of the utilized photocatalyst. As it is
known, increase the reaction temperature improves the photodegration efficiency.
Molecules at a higher temperature have more thermal energy. Although collision
frequency is greater at higher temperatures, this alone contributes only a very
small proportion to the increase in rate of reaction. Much more important is the
fact that the proportion of reactant molecules with sufficient energy to react
(energy greater than activation energy: E [ Ea) is significantly higher. Accord-
ingly, the dye photodegradation modified linearly with temperature increase. The
best temperature was found to be 55 C, at this temperature the maximum
decolorization efficiencies at the utilized reaction time (3 h) were 65, 74, 84, 86
and 100 % for the photocatalyst obtained from sol-gels contain 0.5, 1.0, 1.5, 2.0
and 2.5 wt% AgNO3, respectively. It is noteworthy mentioning that the investi-
gated photocatalyst has good performance only under the UV irradiation as normal
light has no impact as shown in Fig. 17.
Table 1 shows the rate of the rhodamine B photodegradation (mg/min) at
different temperatures and silver contents. As shown in the table, the maximum
rate is not always obtained at the maximum temperature; it depends on the silver
content. At the lowest silver content (i.e. 0.5 wt%), the highest rate was obtained at
15 C. Increasing the silver content shifts the maximum rate to be at 25 C for the
samples obtained from sol-gels having 1.0 and 1.5 wt% silver nitrate. However, at
the higher silver contents the best rate was obtained at 45 C. Overall, the
Fig. 13 Effect of temperature on the degradation rate of rhodamine B dye using Ag-doped TiO2
nanoparticles having 0.5 wt% AgNO3 under UV irradiation
nanoparticles having 2.5 wt% AgNO3 under UV irradiation, and also at room temperature under
the normal light
maximum degradation rate is corresponding to the samples obtained from the

sol-gels having 1.0 and 1.5 wt% silver nitrate at the room temperature (0.0356 mg/
min). As aforementioned, besides enhancing the activation energy, increase the
temperature leads to increase the kinetic energy of the dyes molecules which
modifies the collisions with the catalyst surface. If the catalyst surface is very
active so numerous free radicals will be present in the thin film surrounding the
catalyst nanoparticles, so fast cracking reactions of the dye molecules will take
place, otherwise the molecules will escape without degradation. Therefore, for the
low silver content NPs, the surface is not so active so relatively low temperature
(15 C) is preferred to provide suitable time for dye molecules to react with the
available •OH radicals. Increase the temperature leads to escape the molecules.
More increase in the silver content results in more activation of the NPs surfaces,
so low contact time is enough to degrade the dye molecules in the thin layer
surrounding the catalyst NPs. Accordingly, the maximum degradation rates were
obtained at 45 C for the samples having high silver contents (last two columns in
Table 1). At 55 C, the kinetic energy is high enough to liberate the dye molecules
from the active zones before degradation so low degradation rate was obtained.
However, the number of the degraded dye molecules is high in the beginning of
the reaction (the first 10 min) which makes the quantitative degradation is more at
55 C. For instance after 10 min, at 55 C, the eliminated dyes were 35, 38 and
55 % for the nanoparticles obtained from sol-gels containing 0.5, 1.5, and 2.5 wt%
silver nitrate, respectively. It is noteworthy to mention that the fast initial degra-
dation in the first 10 min (Figs. 13, 14, 15, 16, 17) made the total elimination of
the dyes linearly dependent on the temperature. However, after this initial decli-
nation, the photodegrdation rate becomes temperature independent as shown in
Table 1.
In contrast to the nanoparticles, influence of temperature was different in case of
Ag-doped TiO2 nanofibers. Figures 18, 19, 20, 21 and 22 represent the photode-
grdation of rhodamine B using Ag-doped TiO2 nanofibers obtained from elec-
trospun nanofiber mats contain 0.5, 1.0, 1.5, 2.0 and 2.5 wt% AgNO3, respectively
at different temperatures. As shown in these figures, on contrary to the nanopar-
ticulate morphology, the photodegrdation efficiency was temperature-dependent
only at low silver content (0.5 wt%, Fig. 18) as the best degradation was obtained
at the highest temperature. Moreover, the amount of the eliminated dyes was
Table 1 Rate of rhodamine B dye removal (mg/min) using Ag-doped TiO2 nanoparticles
Temperature (C) AgNO3 content (wt%)
0.5 1.0 1.5 2.0 2.5
5 0.0250 0.0269 0.0313 0.0356 0.0200
15 0.0313 0.0288 0.0331 0.0325 0.0269
25 0.0294 0.0356 0.0356 0.0300 0.0269
45 0.0200 0.0263 0.0325 0.0319 0.0300
55 0.0181 0.0256 0.0294 0.0306 0.0250
Activation energy 3,625.32 1,885.29 1,989.84 1,800.2 315.337
nanofibers having 0.5 wt% AgNO3 under UV irradiation
gradually and regularly increases with the temperature increase. For the nanofibers
obtained from electrospun mats having 1.0 wt% silver nitrate, the optimum
reaction temperature was 45 C as shown in Fig. 19. However, for the remaining
formulations the optimum temperature was 25 C; Figs. 20, 21 and 22. For all
formulations, 5 C reaction temperature is the worst conditions as the lowest
degradation was obtained at this temperature. Moreover, contrary to the nanop-
articulate morphology, starting from silver nitrate content of 1.0 wt% in the
electrospun nanofibers mats, the photodegradation cannot be mathematically
correlated with the reaction temperatures as shown in Figs. 19, 20, 21 and 22.
These obtained results can be explained by the higher activity of the nanofibrous
Ag-doped TiO2 compared to the nanoparticulate morphology especially at high
silver contents. Beside the desorption process and kinetic energy, it is possible also
that the temperature affects the e–h pairs transfer and lifetime.
Figure 23 represents a conceptual illustration to explain the influence of the
temperature on the photodegradation of the rhodamine B molecules using Ag-
doped TiO2 nanoparticles and nanofibers. In case of nanoparticles, the surface
activity is not high so increase the temperature has the normal impact on the
chemical reactions and enhances the degradation process in general by modifying
the activation energy. However, in case of the nanofibers having high silver
content, the surface is very active so instant degradation for the dye molecules
takes place at the thin film surrounding the nanofibers. Therefore, increase the
temperature which leads to increase the molecules kinetic energy has positive
impact in the beginning as it helps to move the molecules to the active zones.
nanofibers having 2.5 wt% AgNO3 under UV irradiation, and also at room temperature under the
normal light
However, more increase in the temperature leads to produce kinetic energy able to
move away the dye molecules from the active zones before achieving the
degradation process. Therefore, for the nanofibers obtained from electrospun mats
having silver nitrate more than 1.5 wt% the optimum temperature is 25 C
followed by 45 C and then 55 C which means inverse relationship between the
photodegradation and the temperature due to increase the kinetic energy of the
molecules. In summary, in case of nanofibers, the temperature affects the photo-
degradation process from the kinetic energy point of view. However, in case of
nanoparticles, beside the kinetic energy, temperature can enhance the activation
energy which improves the photodegradation process.
Based on the introduced hypothesis; the initial rate should show a positive
temperature effect over the nanofibers with high silver content. However, some
results (Fig. 13) do not match this expected behavior because the experimental
plan was established to detect the first concentration after 10 min. Because the
surface is very active, it is believed that if the first samples, in case of nanofibers,
were drawn after very short time (e.g. 2 min) the initial rate will be found
temperature dependent.
Figure 24 displays the photodegradation of the methylene blue dye using
Ag-doped nanoparticles; (A) and nanofibers; (B) at the optimum temperatures (i.e.
55 and 25 C, respectively). As shown in the figure, the nanofibers have distinct
performance compared with the nanoparticles at all silver contents. As shown in
Fig. 23 Schematic diagram illustrates the influence of the temperature on the photodegradation
process in case of using the Ag-doped TiO2 nanoparticles and nanofibers
the figure, 92 % from the dye was degraded in 10 min when Ag-doped TiO2
nanofibers obtained from electrospun mats containing 2.0 wt% silver nitrate were
used as photocatalyst. As aforementioned in the introduction section, silver-doping
is a known strategy to enhance the photocatalytic activity of the titanium oxide
nanostructure. Therefore, the photocatalytic activity of the both utilized
formulations was strongly enhanced upon silver addition as shown in all the
obtained results.
The results obtained in Fig. 24 supports the aforementioned hypothesis about
the strong activity of the nanofibers surfaces compared to the nanoparticles.
Therefore, for the same silver content, distinct difference in the photodegradation
performance was obtained as shown in all results. A proposed explanation for this
finding can be as follow: as the photodegradation process mainly bases on elec-
trons transfer through the photocatalyst so the structure providing high surface to
volume ratio is expected to have better performance because it supplies good
electron mobility. Mathematically, it is known that the particulate shape (sphere)
has the lowest surface to volume ratio. Therefore, the nanofibrous shape provides
more space for the electrons which reflects higher activity compared to the
nanoparticles.
4.5 Influence of Silver Doping on the TiO2 Crystal Structure
Titanium oxide has three popular crystal structures; anatase, rutile and brookite.
Anatase is a polymorph with the two other minerals. The minerals rutile and
brookite as well as anatase all have the same chemical formula, TiO2, but they
have different structures. Rutile is the more common and the more well known
mineral of the three, while anatase is the rarest. Anatase shares many of the same
or nearly the same properties as rutile such as luster, hardness and density.
However, due to structural differences, anatase and rutile differ slightly in the
crystal habit. The phase change from anatase polymorph of titania to rutile one has
been the subject of considerable interest and the focus of many groups’ activities
over the years. Figure 1 shows the effect of silver-doping on the crystal structure of
the obtained powder after the calcination process. In case of silver-free solution,
the results affirm formation of pure anatase titanium dioxide, existence of strong
diffraction peaks at 2h values of 25.09, 37.65, 38.44, 47.89, 53.89, 55.07,
62.40, 68.70, 70.04 and 75.00 corresponding to the crystal planes of (101),
(004), (112), (200), (105), (211), (204), (220), (220) and (215), respectively
indicates formation of anatase titanium dioxide [JCPDS card no 21-1272]. Addi-
tion of small amount of silver nitrate (2 wt%) did not affect the crystal structure of
the titania, however pure silver metal was formed due to decomposition of the
silver nitrate upon heating. The extra peaks at 2h values of 38.11, 44.29, 64.43
and 77.48, corresponding to the crystal planes of (111), (200), (220) and (311),
respectively affirm presence of silver metal [JCPDS card no 04-0783]. In Fig. 25,
the main peaks of anatase and silver were marked as A and S, respectively.
Fig. 24 Photodegradation of methylene blue dye using different Ag-doped TiO2 in nanopar-
ticulate; a and nanofibrous; b at 55 and 25 C, respectively
Increase the silver nitrate content to 3 wt% in the original electrospun solution led
to partial phase change in the titania crystal structure. The standard peaks of rutile
can be observed at 2h values of 27.45, 36.09, 41.23, 54.32, 56.64, and 69.08
corresponding to the crystal planes of (110), (101), (111), (211), (220), and (301),
respectively [JCPDS card no 21-1272]. Interestingly, the results indicate that

increase the amount of silver enhances formation rutile phase as shown in Fig. 1
(the main rutile peaks were marked by R letter). Addition of 5 wt% silver nitrate
led to increase the rutile content to be higher than the anatase. According to the
XRD data, the ratio of rutile to anatase is *75 and 440 % when the added silver
nitrate was 3 and 5 wt%, respectively.
4.6 Influence of Silver Doping on the Morphology
The electrospinning technique involves the use of a high voltage to charge the
surface of a polymer solution droplet and thus to induce the ejection of a liquid jet
through a spinneret. Due to bending instability, the jet is subsequently stretched by
many times to form continuous, ultrathin fibers. It is widely used for production of
many polymeric nanofibers. Moreover, the electrospinning process has been
exploited to produce metal oxides nanofibers by calcination of electrospun mats
obtained from completely miscible sol–gel solutions. Electrospinning of a sol–gel
composed of Ti(IsO) and PVAc/DMF solution has been carried out in our lab in
Fig. 25 Effect of silver content on the crystal structure of TiO2

Fig. 26 Effect of silver content on the nanofibrous morphology of TiO2
previous study [62], the resultant electrospun nanofibers have good morphology.
Addition of silver nitrate to the sol–gel does not affect the morphology [5].
Accordingly, well morphology electrospun nanofibers mats were obtained from
AgNO3/Ti(Iso)/PVAc solutions at all the utilized AgNO3 contents (data are not
shown). Figure 26 shows the morphology of the resultant powder after the
calcination process. As can be observed in Fig. 26a and b which demonstrate the
obtained product from silver-free electrospun solution, well and smooth TiO2
nanofibers were obtained, these nanofibers composed of pure anatase as could be
concluded from the XRD results (Fig. 25). Incorporation of small amount of silver
does not have considerable impact on the nanofibrous morphology as shown in
Fig. 26c and d which represent the FE-SEM images of the powder obtained from
calcination of an electrospun solution containing 2 wt% AgNO3. However, the
surface became little rough (Fig. 26d).
5 Conclusion
Ag-doped TiO2 nanofibers can be prepared by calcination of electrospun nanofiber

mats obtained from electrospinning of titanium isopropoxide, silver nitrate and
poly(vinyl acetate) sol-gels. Also, drying, grinding and calcination of the same sol-
gels lead to produce Ag-doped TiO2 nanoparticles. The obtained nanostructure is
having both of antase and rutile phases if the silver nitrate content is more than
3 wt%. Rutile phase content can be increased by increasing the silver content in
the original electrospun solution. However, the nanofibrous morphology is
strongly affected by the silver-content, excess silver causes to destroy the 1D
structure. Silver-doping of the titanium oxide nanofibers greatly enhances the
photocatalytic activity of this interesting material. The temperature has positive
impact on the photodegradation when the photocatalyst is exploited in the form of

nanoparticles due to modification of the kinetic and the activation energies.
However, in case of the nanofibrous morphology, the temperature has negative
impact due to the super activity of the surface compared to the nanoparticles.
Increase the temperature leads to enhance the kinetic energy of the dyes molecules
which leads to escape the molecules from the active zones surrounding the
nanofibers. Overall, this study strongly recommends utilizing using the
photocatalyst in the form of nanofibers at room temperature as the maximum
degradation can be obtained at these conditions.
Acknowledgments This work was financially supported by the Ministry of Education, Science
Technology (MEST) and National Research Foundation of Korea (NRF) through the Human
Resource Training Project for Regional Innovation and ‘‘Leaders in Industry-University
Cooperation’’. We thank Mr. T. S. Bae and J. C. Lim, KBSI, Jeonju branch, and Mr. Jong- Gyun
Kang, Centre for University Research Facility, for taking high-quality FESEM and TEM images,
respectively.
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Foam-Glass-Crystal Materials
O. V. Kazmina and B. S. Semukhin
Abstract This chapter presents a comprehensive study of the structure, physical

and mechanical properties of FGCM obtained from natural siliceous materials. The
scientific principles of controlled formation of FGCM macrostructure and tech-
nological aspects of its production have been formulated in this chapter. At this, the
strength of foamed materials exceeds the strength of the foamglass 3–4 times as
much due to the effect of nanoscale crystals in a vitrified matrix. It has been shown
that the physical and mechanical properties of foamglassceramic material depend
on the number and the size of a crystalline phase. The increase of mechanical
strength as compared to the foamglass can be provided by the particle sizes of a
crystalline phase of less than 1 lm. Maximum strength depending on the volume
rating of the residual crystalline phase accounts for 25 % for less than 1 lm size,
and 5–7 % at a size decrease down to 300 nm. With the increase of the crystalline
phase size up to 10 lm and higher, the compressive strength of material decreases.
1 Introduction
The problems of energy saving are the foremost in the industrial and construction
sectors of economics in all developed countries. The analysis of the experience
shows that one of the most effective ways to address the energy saving is the use of
high-performance heat-insulating materials. Currently, the promising building
materials are materials which combine high heat-proofing and structural
O. V. Kazmina (&)
National Research Tomsk Polytechnic University, 30 Lenin Avenue, Tomsk, Russia634028,
B. S. Semukhin
Institute of Strength Physics and Materials Science of the Siberian Branch of RAS, 2/4
Akademichesky Avenue, Tomsk, Russia634021,

144 O. V. Kazmina and B. S. Semukhin
properties, fire safety and durability. The significant scientific and practical
experience of their production and use was acquired. At present, there is a vast
literature on heat- and sound-insulating construction materials. It covers such
aspects as technological, environmental, physical and chemical production of these
materials.
One of the high-efficient heat-insulating materials that meet the requirements of
environmental safety is foam glass.
Industrial waste utilization and reduction of industrial atmospheric emissions is
closely connected with technical and economic problems of resource and energy
saving as well as environmental protection aspects. Foam glass production is one
of the efficient trends of utilization of both industrial and domestic waste glass. At
the same time, the problem of cullet recycling is relevant as before, because it is so
far one of the most hardest to utilize hard domestic waste.
The amount of cullet required for foam glass production is obtained by the
traditional glass technology including glass manufacturing in industrial furnaces.
The glass melting process is connected with generation of a considerable amount
of gaseous dust air and chimney gas emissions containing end products of fuel
combustion (CO2, NxOy and others), and stack solids (B2O3, Fe2O3, As2O3).
Therefore, taking into account the number of production and economic features of
glass manufacturing, the foremost task is a pre-synthesis of quenched cullet from
natural or industrial raw materials using energy-saving technology in order to
escape the glass melting process. Low-temperature synthesis of quenched cullet is,
on the one hand, economically feasible due to the absence of such energy-intensive
glass manufacturing operations as fining and homogenization of the glass mass. On
the other hand, this is the way to lower hazardous emissions in terms of furnace
end gases.
Foam glass produced on the basis of glass cullet is composed of 100 % silicate
glass which is not, practically, influenced by chemical reagents, is not a nutrient
medium for fungus, mold, and is an ideal barrier for insects and rodents. Resis-
tance of foam glass to putrefaction and the absence of a nutrient medium for mold
and spread of mold and fungus are especially important when the foam glass is
used in closed nonaerated space of roofs, walls, and basements. The absence of
organic matter ensures the escaping of situations connected with the destruction of
heat-insulating materials under the influence of the bioactive environment. Due to
the specific structure of the foam glass with closed impermeable pores, at negative
or variable temperatures and actuation of steam migration inside the material, a
possibility of accumulation of water particles and steam is excluded as well as
their condensation on the surface of interpore partitions which can be destructed in
the weaker areas as a result of water and glass interaction. Therefore, one of the
most important properties of the base glass is its chemical resistance.
Chemical resistance of glass is its capability to withstand the destructive effect
of water, moisture, atmospheric gases, salt solutions, and various chemical
reagents. Chemical resistance of glass mainly depends on its chemical composi-
tion, particularly, on the content of silicon and alkali metal oxides. Introduction of
silicon oxide into glass considerably increases the its resistance while alkali metal
Foam-Glass-Crystal Materials 145
oxides decrease it. When changing the glass composition, its chemical properties
are also changed. As a rule, potash soda-ash glasses increase chemical resistance
of glass.
At this stage, the study of ecotoxicological indicators of FGC (foam-glass-
crystal materials), which is produced from natural and industrial raw materials
based on low-temperature synthesis of quenched cullet, is conducted in compar-
ison with the commercial types of foam glass synthesized from secondary glass
cullet, e.g. FOAMGLAS (Pittsburgh Corning www.foamglas.com). The eco-
toxicological assessment procedure should pay a special attention to the study of
toxic substances effect on the environment which can emit from the material while
in operation.
FOAMGLAS emits no harmful substances, such as formaldehydes, styrenes,
or fire-proofing compounds, fibres, chlorofluorocarbons (CFC/HCFC) etc. that are
detrimental to health. Ecological and biosafety of FOAMGLAS offers optimum
construction solutions not only for rooms where a high degree of air purity is
required (hospitals, museums, schools, offices, waiting rooms, high-tech produc-
tion facilities, etc.) but also in locations where there are special bacteriological and
hygienic requirements (slaughterhouses, cheese factories, dairies, industrial
kitchens, canteens, restaurants, swimming pools, etc.). All approved accessory
products for the systems also aim to satisfy low-emission standards.
The BTU institute (Buro fur technischen Umweltschutz, Reiskirchen, Germany
www.btu-umwelt.de) has gathered data on different parameters (e.g. length of
service-life, primary energy content, price, thermal conductivity, costs of disposal
or recycling and technical or application polyvalence) of the principal industrially-
manufactured insulation products in the market. By applying a mathematical
formula and with the weighting coefficients (per category from 1 to 5, with 1 being
‘‘negative’’ and 5 ‘‘very positive’’), an examination of the parameters under con-
sideration leads to different results per group of products and is expressed by the
profitability index (R). The higher the R-value, the better the product evaluation.
For FOAMGLAS the profitability index—a characteristic value for ecological
and economic evaluation, involving a number of parameters—leads to the value
45.5. This result positions FOAMGLAS amongst the leading products in overall
economic/ecological assessment.
FGC falls within the scope of the Law of the Russian Federation (the Technical
Regulations of the Safety of buildings and facilities), which claims the following:
Building materials and products must not extent damage effect on humans and the
environment; they must not contain and emit harmful substances in such con-
centrations or combinations that could influence directly or indirectly humans, or
animals, or plants; concentration of harmful substances in the air of working area
and habitable rooms must not exceed the normative values stated by the RF
legislation in the field of sanitary-epidemiological welfare of population.
Physicotechnical properties of foam glass are specified mainly by its production
technique, chemical composition and foaming mixture, the kind and the quantity of
gasifier, sponging and fritting modes. Changing these factors one can obtain material
of different density, strength, heat conductivity, water absorption [1-3]. Depending
Fig. 1 Flow chart of the Preparation of the raw materials

powder mode of foam glass
production (two-stage Foamglass melting (1400 – 1500
process)
Production of quenched cullet
Drying of quenched cullet
Preparation of foaming substance
Foaming (800 – 900
Withdrawing of blocks and setting them on the annealer conveyor
Annealing (600
Processing and packing of blocks
Quality control
on its application, foam glass is classified into heat-insulating, sound-insulating and

specific high-temperature. European production widely practises heat-insulating
foam glass with density of 200 kg/m3. Foam glass production technique includes
silicate glass grinding, mixing with foaming additive of carbonic or carbonate type
and thermal treatment of the mixture at 750–850 C temperatures.
Foam glass industrial production is mainly based on the powder mode of two-
stage process, the flowsheet of which is given in Fig. 1 [4]. The advantages of the
two-stage production mode are as follows: minimum sponging time; a complete
use of fritting furnace space due to minimum clearance between the glass blocks
arranged; the minimum number of forms to be returned to production upon a
completion of the sponging process neglecting the long cycle of foam glass frit-
ting. Figure 2 illustrates the plan of the foam glass area designed by the Glamaco
Company (Germany).
The global experience shows that it is not always feasible to utilize foam glass
in the form of blocks or plates. In a number of cases, the foam glass is used in the
form of gravel or crushed stone for building, e.g. as heat-insulating bulk material
or concrete filler. A great experience has been accumulated in the field of utilizing
foam-glass crushed stone Schaumglas Schotter and gravel Poraver. Production of
small granules of heat-insulating material is always more profitable from the
viewpoint of heat exchange. In producing block-like foam glass, up to 80 % of the
length of the tunnel furnace and, as a consequence, up to 80 % of time is spent on
the slow cooling of material. The quenching and productivity improvement result
in considerable internal tensions and destruction of blocks. It is the principle of
quenching which foam-glass crushed stone Schaumglas Schotter production is
being based on: the foam glass is leaves the furnace at a rather high speed, then
additionally cooled, and as a result of this crushed stone is obtained.
Fig. 2 Plan of the foam glass area in the two-stage mode of production designed by the Glamaco
company (Germany)
Raw material used to obtain foam glass according to the classic scheme is
broken glass, the composition of which meets the specific requirements. Firstly,
they use glasses of a wide melting range, the so-called ‘long’ glasses. Secondly,
the glass must contain a component which at the process temperatures would
interact with carbon so as to provide gasification. At the same time, broken glass
still remains one of the most difficultly utilized components of hard domestic
waste. For example, in 2001 the percentage of its recycling in the developed West
European countries ranged from 24 to 92 %. Only profiled broken glass undergoes
the effective recycling while the low-grade one is stored at hard domestic waste
grounds. It leads to the inevitable interaction between the glass and precipitation
which results in scavenging of Na+ ions from the glass surface and formation of
alkaline solutions. Especially, it concerns small fractions which possess the largest
specific surface and, therefore, define scavenging of the alkaline component to a
great extent that negatively influences the environment.
Thus, profiled broken glass of the certain composition is employed to manu-
facture the qualitative foam glass; its lack is made up by the traditional glass
technology. The glass production requires substantial material and energy
expenditures. Therefore, taking into account a number of technological and eco-
nomic glass manufacturing features, the foremost task is to provide the preliminary
synthesis of the quenched cullet from the natural or anthropogenic raw materials
using the energy saving technology at temperatures not above 950 C escaping the
power-intensive process of glass melting.
This chapter presents a comprehensive study of the structure, physical and
mechanical properties of FGCM obtained from natural siliceous materials.
2 Physical and Chemical Principles of the Production

of FGC
A foam-glass-crystalline material is an amorphous porous material that contains

nanostructural units and exhibits increased strength characteristics as compared to
the conventional foam glass manufactured from a glass cullet. The possibility of
controlling the structure of foam-glass-crystalline materials is determined by the
chemical and granulometric compositions of the initial batch; the nature of the basic
glass forming component of the batch, the technology used for preparation of the
batch, which brings into operation of the mechanisms and effects of mechanical
activation of the mixture; and the regime of heat treatment of the batch under the
conditions providing the low-temperature synthesis of the glass granulate.
The glass granulate is the initial raw material for the subsequent foaming and
manufacturing of foam-glass articles with specified characteristics. According to
the phase composition, this intermediate product is a glassy material containing the
residual quartz crystals. The properties of foam-glass-crystalline materials depend
not only on the composition and structure of the phases of the glass granulate,
which are formed in this material, but also on the size and mutual arrangement of
the structural units at the microscale level.
A two-stage method for producing foam glass via the intermediate product
(quenched cullet) synthesized by thermal treatment of the mixture of the certain
composition was developed at Tomsk Polytechnic University [5]. This product
acts as the raw material for the following sponging and obtaining foam-glass-
crystal products with the pre-set characteristics. According to the phase compo-
sition the quenched cullet represents a vitrified product with residual crystal
inclusions which define the density and strength of the end items. The principal
procedure for obtaining foam-glass-crystal materials is given in Fig. 3, which
outlines three main technological stages, two of which relate to the quenched
cullet. The idea of the technology developed lies in the following principles:
• Special preparation of raw materials allows synthesizing a glass ceramic at
temperatures not over 950 C which is the raw material for the foam glass;
Controlling the formation of nano and microstructure of the interpore partition

allows regulating the strength and density of the end item. Relatively low tem-
peratures of the glass phase synthesis carried out according to the designed mode,
promotes not only energy consumption decrease, but also that of the carbonic acid
release. The working operation of the mixture compaction makes possible to lower
the air pollution of the working area as well as the general dust emission to the
atmosphere.
Compositions of container glasses or the like are considered to be the optimal
for foam glass manufacture. The content of oxides required for these glasses
consists of the following elements (mas. %): SiO2 67–72; Al2O3 1–6; CaO 7–11;
MgO 1–4; Na2O 14–15. It has been experimentally stated that the most perspective
Fig. 3 The principal

procedure for obtaining Preparation and Preparation and
foam-glass-crystal materials measuring of basic measuring of additional
materials materials
Mixing of raw materials
Compaction of batches
(dragade, extrusion,pressing)
Heat -processing of batches

and synthesis of quenched
cullet
Grinding of the quenched cullet
Mixing with gas - forming agent
Foaming
Final product
raw material is the breakage of a dark green bottle while less manufacturable is the
breakage of float-glass. Table 1 gives typical compositions of silicate glasses used to
manufacture foam glass in different countries. Oxides included in the glass com-
position influence the sponging mode, namely: the temperature, the process duration
and also such properties as crystallization, viscosity and surface tension [6].
Table 1 Chemical composition of glasses used for foam glass production

Composition Content, mass. % Country
SiO2 Na2O Al2O3 CaO MgO B2O3
1 72–73 15.5–16.5 0.5–1 6–6.5 3.5–4 – Russia
(73) (16.1) (0.8) (6.3) (3.8)
2 55–72 11–18 3–16 9–12 – Czech
(64.8) (14.8) (9.7) (10.7)
3 72–74 13–17 0–2 8–12 – – Great Britain
(73.7) (15.2) (1) (10.1)
4 70–72.7 14 2–7 4.9–7.6 3 0–3.6 France
(70.5) (14) (4.5) (6.3) (2.9) (1.8)
In brackets given are average values translated into 100 % glass composition
The use of the raw materials alternative to the broken glass significantly
expands the technological possibilities of the foam glass production. The diverse
natural and/or anthropogenic feed stock can be utilized as raw materials. The
composition and properties of siliceous and silica-alumina raw materials allow
synthesizing the quenched cullet on their basis with the following processing until
the porous material will be obtained. Controlling the component composition of
the mixture and the temperature conditions for thermal treatment, heat-insulating
materials can be obtained being rather various in their properties.
The analysis of scientific publications and research findings provided have
shown that in order to obtain a low-temperature quenched cullet, the choice of the
mixture composition should be carried out in relation to the following conditions:
• The amount of glass formers’ oxides and alkali metal oxides in the quenched
cullet must be sufficient for a sustainable glass formation, i.e. the content of
SiO2 is in the range of 60–75, and the content of alkali metal oxides is in 13–22
mass % range;
• The number of the glass bath must not be less that 70 % that is necessary to
provide plastic state of the mass at the sponging stage;
• The liquid phase must be of the optimal viscosity (103–106 Pa•s) within the
sponging range;
• The temperature for the liquid phase formation (glass bath) must not exceed
950 C.
With a purpose to select the basic glass composition and diminish the amount of
preliminarily experiments so as to obtain the quenched cullet, carried out was the
analysis of state diagrams of the ternary system Na2O–CaO–SiO2 which is the
basis for a production of the industrial glasses of more oft-used compositions,
namely: container glass, sheet glass, etc. In accordance with the state diagram the
industrial silicate glass area is close to the equilibrium field of crystals of wol-
lastonite, devitrite, tridymite. It is these phases which are often demonstrated in
glass crystallization. Almost all industrial compositions get one elementary phase
triangle Na2O 9 2SiO2–Na2O 9 3CaO 9 6SiO2–SiO2 and begin to melt at

725 C that corresponds to the low-temperature system eutectic.
The analysis of the diagram has shown that the following three groups of
compositions correspond to the above stated conditions: (1) compositions with the
varying ratio of the basic oxides and the fixed amount of SiO2 (73 %); (2) com-
positions with the varying content of CaO and SiO2 at the fixed amount of the
alkaline component (21 %); (3) compositions with the varying content of Na2O
and SiO2 at the fixed amount of alkali-earth metal (5 %) [7].
The research findings have shown that the optimal glass content appropriate to
obtain the foam glass under the low-temperature technology, is the composition
with rather high content of SiO2 (72–74 mass %) and the ratio of basic oxides
CaO/Na2O within the range of 0.2 7 0.9 that corresponds to the sufficient vis-
cosity of the glass bath and stable glass formation.
For test experiments the compositions characterized by the ratio of the basic
oxides were selected within the following limits: the amount of Na2O ranges from
14.5 to 21 %; the amount of CaO ranges from 5 to 13 %. The state diagram of
Na2O–CaO–SiO2 system illustrates that the given compositions limit the area of
glass formation with the various component ratio.
The change of the composition along the line connecting points 1 and 2 is
accompanied by the decrease of Na2O and the increase of the melting temperature
which does not exceed 950 C.
The first composition is eutectic with melting temperature of 725 C; in the
second composition the share of the liquid phase forming in the temperature range
of 800–950 C changes from 45 to 80 %. For all that, one can expect that real
temperatures of mixture treatment will be lower due to the impurity substances
presented in raw materials. To obtain the quenched cullet based on siliceous raw
materials the following two boundary compositions were chosen (mass %):
SiO2—74; CaO—5; Na2O—21 and SiO2—73; CaO—11; Na2O—16.
To synthesize the glass phase of the chosen compositions the two-component
mixture is required which includes the siliceous and alkaline material in the form
of soda ash. In the lack of alkali-earth oxides in raw materials, the mixture is
corrected by the additional introducing of chalk or dolomite.
The adequacy of siliceous raw material for quenched cullet production is
defined by three main indicators: chemical, phase and granulometric compositions.
In this case, siliceous materials with the following oxide content (mass %) are the
most adequate for quenched cullet production: silicon not less than 83; aluminum
up to 7; the total amount of alkali-earth oxides up to 13; ferrum not over 10.
The phase content of siliceous materials is of significant meaning for low-
temperature synthesis of the glass phase. The presence of amorphous component
SiO2 creates favorable background for solid-phase reactions and allows lowering
temperature of glass synthesis in comparison with crystalline silica. In this case,
the most optimal are high-silica amorphous rocks because the silicate glass is an
amorphous material which contains over 70 % of SiO2. However, it should be
taken into consideration that silicate glasses which contain coloring oxides tend to
be crystallized, for example, ferric oxide at the repeated thermal treatment. The
presence of the residual crystal phase in the quenched cullet may promote crys-
tallization which is promoted as well by the high specific surface of initial mix-
tures. Therefore, it is important to take into account the qualitative ratio between
the crystal and amorphous phase components in the siliceous mixture component.
Below given are the experimental findings for siliceous raw materials which
meet the stated requirements in terms of such materials as sand, marshallite,
diatomite and flask (Table 2). The chemical composition of these materials is
represented by rather a high content of SiO2 and the presence of impurities which
are not harmful because of their inclusion in the glass composition and taking into
account in the mixture calculating.
The experiment data showed that the residual content of crystals remains at the
level of 10–23 %; the largest amount of the glass phase has the quenched cullet
based on marshallite and flask. The mixture based on the material with amorphous
SiO2 shows more higher chemical activity at the stage of silicate and glass
formation.
It has been stated that with the increase of the mixture treatment temperature
the content of the crystal phase decreases for all compositions. In case of using
diatomite and flask, the temperature decreases down to 850 C with the further
stabilization of the residual silica amount. Obviously, it is connected with rela-
tively low temperature of the mixture melting and the early approach of high-
Table 2 Properties of siliceous raw materials and quenched cullet produced on their basis
Indicators Siliceous raw materials
Silica Marshallite Diatomite Flask
sand
Chemical composition, mass %:
SiO2 98.15 95.7 86.44 83.00
Al2O3 ? TiO2 0.73 2.10 5.30 5.25
CaO ? MgO 0.09 1.4 1.27 3.52
FexOy 0.05 0.27 1.60 2.72
Phase composition, volume, %:
Crystal forms SiO2 98 95 14 13
Amorphous opal – – 70 57
Silica-alumina crystal phases 2 5 16 30
Specific surface of prepared rock, cm2/g 3,484 5,500 14,510 16,150
Maximum temperature of mixture treatment, C: Thermal treatment of mixture
Composition (I) 930 875 830 810
Composition (II) 880 840 850 825
Crystal phase amount for quenched cullet, mass Quenched cullet properties
%:
Composition (I) 16 1 13.7 2.65
Composition (II) 23 10.38 14.92 6.14
Plastic state temperature of quenched cullet, C:
Composition (I) 800 748 777 740
Composition (II) 850 823 845 841
viscosity liquid phase which takes disjoining effect and lowers the dissolution of
crystal SiO2. The glass formation process for sand mixtures is not complete (the
amount of crystal phase is 23 %). Thus, it is advised to treat the mixture at higher
temperatures or provide the additional preparation of the mixture using mechanical
activation.
Thus, in order to obtain the quenched cullet at relatively low temperatures one
can utilize fine-dispersed siliceous materials in the capacity of the mixture com-
ponent taking into account the following factors:
• The use of quenched cullet with the glass phase amount of over 80 % allows
obtaining foam-glass-crystal material of up to 250 g/cm3 density; 3 MPa
strength and 6 % water absorption;
• The amount of the glass phase of the quenched cullet increases along with the
increase of amorphous component in the siliceous mixture component.
3 Foam-Glass-Crystal Materials Structure
In this section, the experimental results of the analysis of FGC structure on dif-
ferent structural levels are presented. To determine the structure of the samples
obtained, the optical and electron microscopy was used. The elemental composi-
tion of interpore partitions was detected with of high resolution scanning electron
microscope JSM-7500FA and equipped with X-ray microanalyzer. Before
recording, the samples were covered with a thin platinum layer. Recording was
carried out at the following modes: accelerating voltage of the electron beam of
10–15 kV; working distance of 20–50 mm; and magnification up to 100,000 times.
The X-ray structural analysis of the phase composition of quenched cullet and
foamed material was carried out using DRON-3 M diffractometer with Cu Ka
radiation with monochromatization of a diffracted beam by a pyrolitic graphite
crystal.
The energy characteristics of a submicron crystalline phase differ from those of
the starting material [8]. A maximal enhancement in the strengthening of material
might be expected if the crystalline phase microstructure is far from equilibrium.
According to Academician N. P. Lyapishev, a material having specific properties
would be composed of crystallites or of a mixture of nanometer-sized crystals and
amorphous phase. Indeed, the foam glass material manufactured from glass
granulate is in conformity with the latter principles [9].
The experimental dependence illustrated in Fig. 4 was obtained for the test
samples, which had a predetermined content of residual crystalline phase (5 % on
the average) and differed in the size of crystalline phase particles. By assuming
that the minimal critical size of crystalline phase particles is 10 nm, the maximal
theoretical strength was calculated for foam glass material; the value obtained is
5.0 MPa. In the case of foam glass whose amorphous matrix contains no crys-
talline phase this value is not greater than 1.5 MPa [10].
Fig. 4 The strength of foam

glass material versus particle
size of crystalline phase
The particle size of residual crystalline phase can be no further reduced;

therefore, one can employ an alternative method for strengthening of amorphous
matrix by changing its internal structure. Compressive strength values were
obtained experimentally for all the test samples of foam glass material. This data
suggests that an enhancement in the strength of materials (up to 4.3 MPa) was
achieved due to the occurrence in their interpore partitions of spherical formations
(spheroids).
High resolution electron microscope images show spheroids having sizes of
60–160 nm, which occur in the amorphous matrix of these materials. No forma-
tions of this kind were found to occur in the interpore partitions of common foam
glass and glass ceramics whose matrix contains residual quartz particles having
size [200 nm (Fig. 5). Figure 5 clearly illustrates a complex hierarchy of single
spheroids and groups of spheroids. An X-ray dispersion analysis suggests the
occurrence of nonuniformly distributed silicon in the amorphous matrix of the
interpore partition: the maximal silicon concentration is observed in the vicinity of
interpore partition and the minimal, within the interpore partition (Fig. 6). The
formation of spheroids would evidently cause redistribution of silicon in the in-
terpore partition. It is thus concluded that the main silicon-containing structural
elements are nanospheroids which gather mostly in the vicinity of interpore
partition.
It is thus found that the structural changes of a strengthened foam glass material
are due to a change in the structure of its amorphous matrix rather than to the
occurrence and structure of residual crystalline phase. This conclusion seems
inconsistent with the conventional scheme discussed in the literature [11-13].
However, the experimentally observed behavior of the glass ceramic is in accord
with a structure, which enables minimization of the energy of the entire material
volume at the expense of the main (amorphous) component.
In the course of foaming process, the structure of amorphous matrix would
change spontaneously; in so doing, spheroids are formed. Here a remark is in
Fig. 5 The electron

microscope image of
spheroids in the interpore
partition of foam glass
material
Fig. 6 Silicon content

distribution in the interpore
partition
order: when dealing with minerals, spheroids are called ‘globules’. The experi-
mental evidence for the occurrence of globules in silica and the mechanisms
involved in their formation are discussed elsewhere [14]. It is assumed that a
spherical globule has a loosely packed body, while its core has a close-packed
arrangement of SiO4 tetrahedrons. The general aspect of a globule is that of a 3D
particle having a quartz- or crystobalite- type structure; on its surface are arranged
unidimensional SiO chains, i.e. mono-, di- and trimers of silicic acid or sodium
silicate. Such a globule is taken to be an intermediate state between crystalline and
amorphous matter. Abundant experimental evidence for silica globule formation is
available [15, 16]. X-ray diffraction analysis and thermography data suggests that
the globule structure is a set of randomly distributed nanocrystallites and amor-
phous areas.
Using IR spectroscopy technique, investigations were carried on for the test

samples of silica gel and synthetic amorphous aluminosilicate. The spectra
obtained show a band 1,200 cm-1, which corresponds to globule formation [14].
This suggests that on the crystal surface have appeared fragments of SiO4 tetra-
hedrons, which make an angle of 180o with one another; some of these fragments
are composed of two or three tetrahedrons joined together to make a kind of chain.
The IR spectra obtained for glass ceramic samples are found to show a new line
1,249.6 cm-1, which is absent from the IR spectra of foam glass. On the base of IR
spectra and micrographs obtained one can evidently assume that the amorphous
component of the interpore partition has a globular structure. It is for the first time
that globules are discovered in the amorphous matrix of foam glass material. It is
these globules that are responsible for a sudden enhancement in the strength of
foam glass material. It is emphasized that the microstructure of interpore partition
is composed of amorphous matrix, which contains residual quartz particles (B5 %)
having size *200 nm and globules having size B100 nm.
The strength of amorphous materials is generally attributed to the action of
several mechanisms, with the main mechanisms being shearing and local jumps. In
the former case, the deformation is assumed to involve shearing of one amorphous
cluster (globule) against another to cause dissipation of energy [17]. In the latter
case, it is assumed that a jump-wise change of atoms positions would occur within a
cluster (globule). It was proposed recently that, in addition to the above mecha-
nisms, one should taken into account another factor, which might also be respon-
sible for material strengthening, i.e. nanostructure formation within the deformation
bands [18-22]. In our experiments the strengthening of foam glass materials is
largely due to two processes: (1) a decrease in the particle size of residual crys-
talline phase and (2) formation of nanospheroids (globules) in the amorphous
matrix. In the former case, an enhancement in the strength of material is B3 MPa
and in the latter case, one can achieve theoretical strength B5 MPa. In the course of
deformation, the dissipation of energy would mainly occur in material areas con-
taining close-packed globules, with the volume fraction of globules being B95 %.
A new type of deformation strengthening has been observed for the first time.
This involves spontaneous formation of nanometer-sized spherical globules within
the amorphous matrix of the deforming material. The model of strengthening
proposed for amorphous materials in is validated by the experimental results
discussed herein.
4 Mechanical Properties
Foamglass is one of the universal high-performance heat and sound-insulating

materials whose scope of use as a structural material is impartially limited by the
compressive strength indicator (not over 1.5 MPa) that depends on the nature and
structure of material, i.e. ‘glass foam’ with the pore partition thickness up to
50 mkm.
The foam glass-crystal material high-strength characteristics as compared to the

traditional foam glass technology based on the use of cullet. The increase of
mechanical strength of foam glass allows widening its scope of use as a structural
material.
The research findings of the fracture process of foam glass-crystal samples
obtained in vitro as well as the relation between the structure and mechanical
strength are discussed in this Report.
There are two extreme cases of a body behavior at the external load application.
In the first case, which corresponds to an ideal solid, deformation is proportional to
the stress imposed. The second extreme case is viscous fluid for which the
deformation rate equals to the applied load divided by the coefficient of viscosity.
Amorphous solids are neither perfectly elastic nor perfectly viscous ones and
combine both elasticity and viscosity properties. It means that complete defor-
mation of the amorphous solid is likely to consist of two parts—elastic and
viscous. In case of foam glass, this phenomenon appears to the specific degree
because the ‘classical’ glass is fractured in perfectly brittle way according to the
Griffiths’ model, while the foam glass and the foam glass-crystal material display
both elastic and viscous components.
To analyze the mechanical properties, and specifically to define the tensile
ultimate strength of foam glass, some tests were conducted by means of the uni-
versal machine ‘Instron 1185’ with the load range between 0–100 N and
0–100 kN. The measurement accuracy was ±0.5 % of the display value, or
±0.25 % of the load scale used. In compliance with the recommendations given by
the Russian State Standards (UOCTs), P EH 826–200 ‘‘Heat-insulating products
used in construction. Method of compression characteristics’ detection’’, tests
were carried out at rate of 2 mm/min. Foam glass samples in the form of rectangles
or cubes underwent the test for compression down to their complete fracture with
registering strain diagram in the automatic mode. For the comparative analysis
three kinds of samples were chosen, namely: foam glass-crystal materials,
industrial foam glass and laboratory foam glass obtained from cullet.
Figure 7 presents the generalized view of dependencies r–f(e) which shows that
the dependence characters for foam glass samples obtained from cullet are similar,
while those ones of the foam glass-crystal material are different. The value of the
tensile ultimate strength of the foam glass-crystal samples is considerably higher
(2–3 times) as compared to the foam glass. This significant difference can be
explained by the material structure including the size of pores and interpore
partitions, the composition and structure of the amorphous component.
To describe the deformation curve of the foam glass-crystal material the syn-
ergetic approach was applied, which was described by Prof. Olemsky in his work
on fluid vitrification [23]. It was shown in this work that within the synergetic
equations the modified Maxwell equation is in compliance with the experiment for
the viscoelastic medium:
r ¼ r=sr þ g r e T ð1Þ
Fig. 7 Compression test Foam - glass - crystal

materials
curves of foam glass Industrial foam - glass
materials 6
Laboratory foam-glass
5
3
σ, MPa
2
1
0
F
0,12
0,10
0,08
H 0,06
0,04
0,02 ε
0,00
The first summand is responsible for the dissipative process of stress relaxation
to the equilibrium value, and for the microscopic Debye time of 10-12 s at that.
This time appears in the well-known Zhurkov formula which describes the
interrupting time and rupture stress rp relation [24]:
s ¼ s0 exp½ðU0 c rp Þ ¼ k T ð2Þ
The second summand of Eq. (1) defines the self-organization process.
Thus, the elementary deformation curve r (e) includes not one but two sections.
The first section is elastic, Hookian, and has a wider slope angle; the second
section is more gradient and responsible for plastic deformation processes. Taking
into account the deformation module defect at transition from Hookian stage to the
plateau of the plastic flow adequately reflects the vitrification process in terms of
synergistic concepts. In the case described, the deformation curve of the foam
glass-crystal material actually consists of two segments specified by the suggested
synergetic model and Zhurkov’s model (Fig. 8).
It should be noted that in compression testing of foam glass, the abrupt fraction
of samples typical for brittle materials has almost never been observed. With the
increase of the load the sample becomes deformed, and at the same time, thin
partitions of cells are sequentially fractured on the fixed thrust face. The received
glass powder is pressed into the anew fractured cells.
The elemental composition of interpore partitions was detected by the electronic
microscope JSM-7500FA equipped with the power-dispersion microanalyzer Edax.
It is shown in the figure that nearby the interpore partition the silicon concentration
is the highest while in the centre it is minimal. This high content of silicon must
result in formation of crystal inclusions of SiO4 in the boundary layer of the in-
terpore partition. The presence of crystal phase in amorphous matrix increases the
strength of the interpore partitions. In applying the load to the sample during the
compression test process, the partitions collapse.
Fig. 8 Deformation curve 6

(by time) of the foam glass-
crystal material 5
σ, MPa σð
3
0
0 200 400 600 800 1000
t, s
The relation of grain size and strength for non-deformed materials is similar to
Hall–Petch relation for the yield strength of ductile metals: if average grain size
could be decreased even further to the nanometer length scale the yield strength
would increase as well. However, in case of porous materials, this correlation
should take place rather between the sizes of interpore partitions than the pores
themselves because all mechanical properties of the material depend on the
properties of partitions themselves.
Figure 9 illustrates the curve of average size of the interpore partition in the
foam glass-crystal material depending on stress. One can see that this dependence
is similar to Hall–Petch relation.
The important feature of cellular material affecting the mechanical strength is
the porosity character that includes spatial arrangement of pores (packing),
Fig. 9 Dependence of the

average size of the interpore 4,5
partition upon the ultimate
strength 4,0
3,5
σ, Ì Pà
3,0
2,5
2,0
1,5
20 30 40 50 60 70 80 90 100 110
l, mkm
distribution of pores by their size (pore combination of various sizes), the form and
the thickness of interpore partitions.
The pore shape is the parameter which characterizes a degree of deformation of
spherical pores into regular polyhedrons. One can judge about the degree of pore
deformation according to the cellular porosity bulk: the 75–80 % excess indicates
the possibility of transition from spherical pores to polyhedrons. The higher
porosity the more regular polyhedrons should be. The system tends to such
porosity parameters that provide formation of pores with a dense smooth surface.
The porosity increase is achieved at various sizes and aspheric shapes of pores.
Products with more homogenous honeycomb structure of pores possess higher
strength. A polydisperse character of pore distribution by their sizes provides the
high probability of uniform location of smaller pores between the larger ones.
It is worth noting, that the pore distribution by sizes in the foam glass-crystal
material is similar to that one of the structural elements presented in nanocrys-
talline materials. This distribution of hierarchically subordinate microvolumes of
materials should have an impact on strength properties (Fig. 10).
At the same time, the size and the shape of pores are connected with mechanical
properties. Figure 11 presents the diagram of the pore size (average value
according to the image) depending on the definite fracture stress. This linear
dependence has the high correlation coefficient.
Thus, the defect structure of pore types in cellular materials can characterize the
performance of foam glass products. At the load applied to cellular materials the
pressure transmits along the partitions of pores which form arches. Due to this, the
structure of linearly loaded material always has the bulk stress state. It is known
that at big arch sizes high stresses occur. Arch sizes in the structure of cellular
articles are in direct relation to the pore sizes. Therefore, cellular materials possess
higher strength characteristics when they have pores of smaller sizes, all other
conditions being equal.
Fig. 10 Pore distribution by

the sizes in the foam glass-
crystal material Data: Data1_B
40 Model: Gauss
Chi^2 = 4.69656
R^2 = 0.99117
y0 2.0157 ±1.19022
30 xc 0.4767 ±0.01553
w 0.50574 ±0.03276
A 26.89852 ±2.02103
N
20
10
0
0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0
d, mm
Fig. 11 Dependence of the 7

average pore size on the
ultimate strength of the foam
6
glass-crystal material
σ , MPa
4
1
0,5 0,6 0,7 0,8 0,9 1,0 1,1
d, mm
However, the analysis of micrographs illustrating the foam glass-crystal

materials obtained from mixtures of diverse compositions makes obvious the
advantage of location of spherical pores of two different diameters, the so-called
two-modal filling manner. This layout implies filling of the free space between the
spherical pores of larger sizes with those ones of smaller sizes. It can be seen well
in Fig. 12 which represents the microstructure of various foam glass-crystal
materials.
Moreover, modification of pore shapes, i.e. the tendency to a honeycomb dis-
tribution of hexagonal pores can considerably increase the mechanical properties
of cellular material. Figure 13 illustrates two pictures of materials with different
pores and different ultimate strengths.
According to the research findings in relation to the fracture process of foam
glass-crystal samples obtained in vitro it has been stated:
• foamglass-crystal samples have higher strength as compared to the foamglass
obtained from cullet;
3,35 МPа 2,51 МPа 3,61 МPа 4,8 МPа
Fig. 12 Sizes and shapes of pores belong to various foam glass-crystal materials and the
corresponding strength
3,41 МPа 3,67 МPа
Fig. 13 Hexagonal shape of pores of the foam glass-crystal materials and their strength
• the fracture mechanism for foamglass-crystal samples is well described by the

synergetic models of deformation of a quasi-viscous (amorphous) solid;
• the relation between the interpore partitions of foamglass-crystal material and
the ultimate strength is similar to Hall–Petch relation;
• the fracture stress is in direct proportion to the pore size whose diminishing
raises the strength of cellular materials.
5 Conclusion
The scientific principles of controlled formation of FGCM macrostructure and

technological aspects of its production have been formulated in this chapter. A
novelty of research findings is consisted in the development of physic-chemical
principles of obtaining materials by a formation of nano and microcrystalline
phase in a vitrified matrix of the silicate system. This method allows using a wide
range of natural and industrial raw materials without glass melting unlike the
traditional foam glass production. At this, the strength of foamed materials exceeds
the strength of the foam glass 3–4 times as much due to the effect of nanoscale
crystals in a vitrified matrix.
It has been shown that the physical and mechanical properties of foam glass
ceramic material depend on the number and the size of a crystalline phase. The
increase of mechanical strength as compared to the foam glass can be provided by
the particle sizes of a crystalline phase of less than 1 lm. Maximum strength
depending on the volume rating of the residual crystalline phase accounts for 25 %
for less than 1 lm size, and 5–7 % at a size decrease down to 300 nm. With the
increase of the crystalline phase size up to 10 lm and higher, the compressive
strength of material decreases.
The FGC technology can be recommended as a safe technology for a large-
scale industrial introduction. The research of this technology justifies both the
safety of methods and high quality of products. At the same time, the problem of
energy efficiency of technology have been solved (lowering energy costs by 1.3
times) and decrease of hazardous emissions to the atmosphere at the production
stage (by 2 times on average).
Production of materials using this technology is supposed to be carried out at
temperatures 850–900 C what is significantly lower as compared to keramzit
technology (1,150–1,200 C) and traditional cullet-based foam glass
(1,400–1,500 C).
The development of compositions and technology of FGC which combines heat-
insulating and constructive properties widens the nomenclature of construction
products and facilitates the problem solving of heat-insulating material production
which meet the requirements of fire and environmental safety.
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High Temperature Polymer
Nanocomposites
K. Balasubramanian and Manoj Tirumalai
Abstract The chapter on High Temperature Polymer Nanocomposites mainly

covers the advancements made in the research on varied composite materials and
their novel innovations for high temperature applications. The chapter begins with
a prelude on existing polymers of thermoplastic or thermosets and also a combi-
nation of the two to exploit the dual advantage of both high temperature ther-
moplastics and thermosets. The polymer composites are developed and
implemented for varied temperature regimes in the range of 120–250C,
250–350C specially suited for aerospace applications. Further research work is
under progress to explore the material suitable for temperatures above 350C. The
initial section explains on the applicability of polymer composites having matrices
such as either liquid crystalline polymer, cyanates, polyimides or bismaleimides
which are reinforced with either the carbon, glass or aramid fibres especially
continuous fibre which provides improved material and physical properties. The
polymer-composites are assessed for performance of the matrices and the com-
posites not only for their strength or stiffness but also for their resistance to
cracking, minimum loss of weight, brittleness due to cross-linking and other
properties that may degrade the performance of the composites over the long
period of high temperature applications. This section mentions on the literature
reviews having come up with research in progress on other types of resins for high
temperature applications namely the oligomers such as the acetylene terminated
polyimides or the norbornene terminated polyimides. The second section is con-
cerned with the polymer-nanocomposites for high temperature applications. In this
section, the role of nanofillers in the enhancement of composite properties is
discussed. The various forms of nanofillers are the nanoclay, nanofibres, carbon
K. Balasubramanian (&)
Head: Materials Engineering, DIAT(DU), Girinagar, Pune, Maharashtra 411025, India
M. Tirumalai
Department of Airforce, MILIT, Girinagar, Pune, Maharashtra 411025, India

166 K. Balasubramanian and M. Tirumalai
nanotubes, Polyhedral OligoSilsesquioxanes (POSS) and nano-oxides where they

reinforce polymer chain at molecular scale as against the carbon fibres of
macroscopic scale seen in polymer-composites. In a nanocomposite the thermal
properties depends on the filler’s nature, rate and dispersion in a matrices. The
applications have been as fire retardant materials or for re-entry applications in
aerospace vehicles. Research on nanofillers is still at its nascent stage that ample
scope is available for exploring the potential of various nanofillers for high tem-
perature applications and as fire retardant materials. Some polymer thermosets such
as PMR-15 (Polymerization from Monomeric Reactants) are the most extensively
used resin for applications where long term thermal stability is required at 300C.
This section dwells on other progress under way in the field of nanocomposites as
high temperature nanocomposites. The last section presents a review on advanced
materials for high temperature applications, especially applicable for the next
generation aerospace vehicles. The issues concerning adhesives for joining of
surfaces exposed to high temperatures, the effective role of nano-fillers for
improving fracture toughness at high temperature etc. It is seen that the most
promising resin for high temperatures has been the polyimides (315C). This resin
has high Tg (400C) and other good characteristics such as good micro cracking
resistance, low moisture absorption and low toxicity. There are various grades of
polyimides under development. Overall, the chapter provides a glimpse on the
effective developments in the field of polymer-composites and nanocomposites for
high temperature applications especially for aerospace vehicle and automotives.
1 Prelude on Polymer Composites for High Temperature

Applications
1.1 Introduction
1. The appearance of polymers in 19th century and the popularity of composites

since last decade has revolutionised the scope of materials with substitution of
metals and non-ferrous alloys by polymer-composites. The area of application
has been from the least significant parts of aerospace vehicles, medical equip-
ments, household equipments, technology equipments for automobiles, and other
science and engineering products to the most significant parts [1]. The application
has been progressively being made for high temperature requirements [2–7].
2. The application of fibre reinforced composites has been mainly seen on aero-
space vehicles where the parts are subjected to a temperature range of
150–400 C. The parts affected with such temperature range are the airframe
skin, the aero-engine parts and the surrounding areas, and the parts exposed to
hyper velocity or supersonic speeds. The commonly used matrices are the liquid
crystalline polymers, cyanates, polyimides and bismaleimides [2, 8, 5, 6, 9]. The
High Temperature Polymer Nanocomposites 167
matrices are reinforced with carbon, glass or aramid fibres especially continuous
fibre which provides improved material and physical properties [2, 8, 9]. The
epoxy based carbon or the glass or the aramid composites have been extensively
used for load bearing structural applications on the aircraft. The future gener-
ation aircraft or any other high temperature applications of the range of
120–400 C [5] would require the matrices to withstand the brunt of the high
temperatures based on the area of application. In case of aircraft the high
temperature zones have been the aircraft skin of supersonic/hypersonic aircraft,
the leading edges of the wing and control surfaces and around the aero-engine
regions even at the exhaust end where high exhaust plumes are exposed on the
exhaust plates which are subjected to temperature stresses and strain.
1.2 High Temperature Composite Specialty
3. The matrices which are most popular will be the polyimides. The polymer
matrices-composite behaviour depends on the interfacial bondage. The com-
posite needs to retain properties at high temperatures, maintain glass transition
temperature (*300 C) without being affected by the presence of the moisture
i.e. low moisture absorption of nearly 4 %, retain thermal stability, overcome
ageing affects and do not get affected by oxidation. The polymer matrices are
developed in the high temperature ranges viz, 120–250 C, 250–350 C and
350 C and above [5].
4. The polymer matrices such as the cyanate esters (CE), BMI, phenolics,
polyimides have been used for temperature application between the range
120–250 C, for the range 250–500 C the polyimides are found suitable and
for temperatures beyond 350 C the research is in progress to find the required
material [5].
5. The epoxies were found to mostly suit for a temperature application of 135 C
limits. The BMI has been found to be thermally stable and having thermo-
oxidative stability [6]. The various mechanical properties of a Polymer Com-
posite Matrices as applicable to mainly aircraft structures have been the tension
providing the longitudinal modulus (GPa)/strength (MPa), transverse modulus
(GPa)/strength (MPa), the compression also providing the longitudinal modulus
(GPa)/Strength (MPa) and transverse modulus (GPa)/strength (MPa). The car-
bon fibre has the Young’s Modulus given in the range 220–230 GPa, Ultimate
Tensile Strength 3 GPa. Over the period the advancement in polymer composite
research has been in improving these properties by performing structural
modifications in the polymers like the bismaleimides by reducing the cross-link
density and having cross-linking through chain extension. The properties are
further refined for damage tolerance by adding fine particles of polyimides
which are high temperature materials. The primary structures which are sub-
jected too high temperatures due to kinetic heating during flight have such
composites of carbon/bismaleimide that can sustain a temperature of 180 C.
1.3 Research Review on High Temperature Composites
6. Promising work is in progress at various countries to improve the thermal

stability and curing behaviour of high temperature polymer-composites. In one
such example, is the research going on with the addition of amines with
bismaleimides/carbon. The other areas of application of high temperature
composites have been especially on aerospace vehicles for the radomes, stealth
aircraft composites, antennae covers where the surface temperature are high
and need to be contained. The Cyanate esters though less superior than the
bismaleimides have better dielectric properties and low absorption of moisture.
The field has been further expanding from the usage of epoxies as matrice
material to thermoplastics. Of the two types of thermoplastics namely the
amorphous or the crystalline, it is seen that the crystalline thermoplastics are
finding large applications. The crystalline thermoplastic show slow decrease in
modulus above Tg (Glass Transition Temperature). The thermoplastics show
high fracture toughness (1–2.5 kJ/m2) and impact strength. Thermoplastics
have shown lower compressive strength than the thermosets, however the
resistance to environmental effects and better inter laminar shear stress show
better applications especially for area of impact and compression. The dual
properties of both amorphous and crystalline thermoplastics have been
extracted when combined; examples are PEEK, PEI etc [8, 5].
7. The process of improving the high temperature polymer performance is by
polymerising more of aromatic heterocyclic units and minimise the aliphatic
contents. In the temperature range of 250–350 C, the groups of polyimides
have been used be it the condensation or the addition types. Most of these are
commercially available in United States. The condensation type has certain
drawback due to volatiles that skill is required to produce low void composites.
8. The polyimides resins obtained through the polymerisation of monomer reac-
tants have been taken for composite applications exposed to high temperatures
in the range of 260–288 C. Therefore in polyimides of condensation types, the
reduction in aliphatic content has improved the thermo-oxidative stability and
improved toughness due to reduced crosslinking.
9. The thermoplastic matrices under high temperature applications yield to
cracking and loss of weight and are subjected to repeat thermal cycling. The
compressive and shear properties of the matrices get adversely affected with
high temperature exposures.
10. Long term applications of polymer-composites for high temperature appli-
cations need to assess the performance of the matrices and the composites not
only for their strength or stiffness but also for their resistance to cracking,
minimum loss of weight, brittleness due to cross-linking and other properties
that may degrade the performance of the composites over the long period of
high temperature applications. The high temperature polymer-composites
have been extensively researched for applications on aero-space vehicles
especially for the skin, aero-engine parts and engine areas (nozzle, liners etc.,)
and the re-entry requirements for the space vehicles (ablative materials) and
armament ammunitions (anti ballistic missiles). The research is mainly seen
to improve composite composition by improved matrices synthesisation,
selection of matrix material with compatible fibre reinforcement, catalysts,
additives and solvents to achieve higher glass transition temperature and other
mechanical properties useful for prolonged high temperature applications. The
degradation due to ageing needs to be considered for improving the materials
properties for longer application endurance with time.
11. The other mostly used thermoset-composite will be the phenolics which
though are not suitable for load bearing structure are found applicable for high
temperature applications especially as ablative and erosion resistance mate-
rials in composite form with carbon fibre/silica reinforcements. The other
improvement in thermal property will be the char yield which normally is
assessed for 70 % at a high temperature depending on the resin composition.
Several works are in progress toward this to improve the temperature limits
for the char yield of 70 %. The experiments of phenolic-carbon or silica have
shown this property at 700 C with the resin cured by functional groups like
maleimides propogylether and phenyl ethynyl while the resin has shown
further improvements with cyanates with the temperature limits raising up to
1,000 C.
12. Literature reviews have come up with research in progress on other types of
resins for high temperature applications namely the oligomers such as the
acetylene terminated polyimides or the norbornene terminated polyimides
which are experimented for suitable replacement as matrices for the phenolics.
The process limitations and cost economy has held back the actual applica-
tions. As on date, the research still continues on these other oligomers to arrive
at cost effective and better polymer-composites for high temperature
applications.
13. Therefore polymer-composites have found its usage for various high tem-
perature applications especially connected to aerospace vehicles have been the
aircraft skin, engine nacelles, panels, firewalls, engine ducts, nozzle liners,
ablative materials, fins for ammunition stores (missiles), cases for helicopter
gear box etc. The temperature applications cover a range of 150–250 C i.e.
the aircraft skin areas and 250–350 C for the engine areas. The thermo-
plastics such as BMI, CE, and Thermoplastic Polyimides are for lower tem-
perature applications (150–250 C) and the toughened polymerisation of
monomer reactants and the oligomers are for higher temperature ranges
(250–350 C). The latest research on liquid crystalline polymers and pht-
halonitrile are found to be the latest resins of interest for high temperature
applications which are cost effective and less complex in processing with
possible adaptation for fine tuning with the autoclave moulding followed for
epoxy composites.
14. The applications may be extended to any other field of science and engi-
neering such as the automotives, the ships, thermal and nuclear engineering
[10, 11] etc.
2 Polymer-Nanocomposites for High Temperature

Applications
2.1 Introduction
1. The polymer composites gave an insight to the various mixtures of polymers

with primary reinforcements such as the carbon, glass or the aramid fibres and
the silicates for the high temperature applications. The search for improved
material properties for varied science and engineering applications gave rise to
the birth of nanofillers as substitutes for carbon fibres and other forms of
composite reinforcements [12]. The nanofillers are of the size less than 100 nm
which are functionalised or surface modified for better interfacial adhesion with
the bulk matrices which may be either thermoplastic or thermosets.
2. The nanofillers due to their superior multi-functional properties are being
researched as an effective replacement for the exiting carbon fibres and other
primary structural reinforcement materials under application for high temper-
ature applications [13, 14]. The drawbacks in polymer–composite mixture of
process or synthesisation complexity and cost have been taken care in the use of
polymer-nanocomposites. There are several literatures available that describes
the nanofiller synthesisation, characterisation and properties [15, 16] along with
the [17, 18], various applications of these nanocomposites (polymer-nanofiller)
in medical, bio-engineering [17, 18], automotive, civil engineering, nuclear and
thermal plants and maximum in aerospace vehicles.
3. The polymer-nanocomposites have been even researched as repair agent for
high temperature polymer-composites. One such example is the Bisphenol E
Cyanate Ester with alumina nano-particles (*40 nm) [19]. The repair of
laminate composites are undertaken by use of such polymer-nanocomposites by
injecting low viscosity polymer-nanocomposites which provides desired
toughness and better mechanical properties. The filler will have high Tg
([270 C) and decomposition temperature which permits the repair of high
glass transition temperature composites.
2.2 High Temperature Nanocomposite Salients
4. The various forms of nanofillers are the nanoclay, nanofibres, carbon nano-
tubes, Polyhedral OligoSilsesquioxanes (POSS) and nano-oxides. The nanof-
illers reinforce polymer chain at molecular scale as against the carbon fibres of
macroscopic scale seen in polymer-composites. One of the significant appli-
cations of polymer-nanofiller composites have been as an effective fire retardant
material. Nano-composites therefore are a group of nano materials wherein a
nanoparticle is dispersed in a matrices resin or multi-phases. The nanoparticle
Fig. 1 Nanofiller scale [20]
could be of 1D (a plate) or a 2D (tubes and fibres) or a 3D (nano-metric silica

beads) sized nano particle of dimension \100 nm (Fig. 1) [20].
5. The effect in significant properties is achieved by addition of nanofillers in the
range of 1–10 wt%. These nanofillers may be mixed in addition to the con-
ventional additives and composite fillers such as carbon black, carbon fibres,
silicates etc. The nanoalumina as a filler for repair of composites and the nano
antimony tin oxides as good fire retardant material have been found suitable for
high temperature applications.
6. The blend of polymers-nanofillers is seen to be better whenever the nanofillers
are surface modified or functionalised for good interfacial adhesion and cross-
linking. The nanofillers when added either forms regions in the resin matrix
forming multi-phases or the polymers intercalates between the nanofillers or
exfoliates and disperses throughout the polymer resin (Fig. 2) [21, 20].
2.3 Research Review on Nanocomposites for High Temperature

Applications
7. It is seen from the literatures that functionalisation of carbon nanotubes with

Poly (acryloyl chloride), PACL reacts well with epoxy monomers that the
epoxy grafted CNT adheres well to the epoxy resin matrices that the nano-
compsoite formed has better thermal–mechanical properties. This is achieved
with low wt% addition of CNTs (i.e. 0.1 to 1 wt%). Experiments have shown
Fig. 2 Three main types of layered nanofiller (say silicates) in polymer matrix [21]
that the addition of Multi Walled CNTs (0.5 %) in epoxy resins have improved
the Tg from 167 to 189 C.
8. In a nanocomposite the thermal properties depends on the filler’s nature, rate,
and dispersion in a matrices. The combination of traditional composite fibres
with nanocomposites has proved to be more beneficial with capabilities to
sustain larger temperature range than the traditional composites. One such
example is the addition of organophile montmorillonite.
9. The high temperature polymers are usually composed of aromatic or hetero-
cyclic rings which are blended by flexible linking groups. The literature studies
have brought out that high temperature polymers have high Tg and good
mechanical properties. The chemical structures of commonly used high tem-
perature polymers as brought out in the previous sections are shown in Fig. 3a–d
[5, 19, 22].
10. PMR-15 (Polymerization from Monomeric Reactants) thermoset polymer is
the most extensively used resin for applications where long term thermal
stability is required at 300 C. This polymer has its own disadvantages such as
complex processing with high cure temperature needs and toxic starting
materials. Group of Cyanate esters is the other popular polymer which is
finding applications in the high temperature applications especially for aero-
space and microelectronics sectors.
11. The various research objectives on the high temperature nanocomposites have
been the following [19]:
Fig. 3 Chemical structure for high temperature thermosetting polymers. a Epoxy resin: MY270.
b Bismaleimide: 4,40 -bismalimidodiphenyl methane. c PMR polyimide: PMR-15 resin. d Cynate
ester: 2,20 -bis(4-cyanatophenyl)propane [5, 19, 22]
11.1. Curing Kinetics of Polymer. This is investigated by Differential

Scanning Calorimetry. In this many reaction models are taken to model
isothermal curing. The model is analysed for activation energy and
reaction orders.
11.2. The Effect of Nanofillers on the Curing Kinetics of Polymer. In this
the cure kinetics of polymer with varying loadings of nanofiller is tes-
ted. The catalyst is not added to the mix. The isothermal curing of the
polymer/nanocomposite is determined.
11.3. Rheology and Dynamic Mechanical Analysis of polymer/nanocom-
posites. Nanofillers are functionalised which are characterised by using
Fourier Transform IR and Thermogravimetric Analysis (TGA). The
dispersion of functionalised nanofillers in the polymer matrices is found
to be good. Here, the rheology and rheokinetics of the polymer sus-
pension is evaluated. The Dynamic Mechanical Analysis determines the
thermo-mechanical properties for nanocomposites with bare nanofiller
and functionalised nanofiller. The change in glass transition temperature
is found and the dispersion is seen in a transmission electron microscope.
11.4. Creep Behaviour of Nanocomposite. The creep property of nano-
composite is studied through tensile creep testing using DMA. The
tensile creep interval is measured at isothermal conditions. The tem-
perature time superposition principle predicts the long term creep
behaviour in a high temperature environment.
12. The nanofiller having increased number of hydroxyl groups on the surface will
have greater catalytic effects on the cured polymer. The addition of nanofillers
will bring about a change in chemistry, curing, crystalline structure, and
matrix chain mobility.
2.4 Applications
13. One such application of high temperature conditions will be as ablative

materials in nozzles of high speed space vehicles. The selection of filler
irrespective of micron or nano size is of importance. The selection of com-
posites/nanocomposite should be such that there is proper bonding of the
ablative material with the metal substrate of the nozzle and also serve
the purpose of correct transfer of the hot gases of the propellant through the
nozzle without damage to the metal structure. The process of manufacture of
this ablative material will govern the adequacy of the density, percent resin
content, compressive strength, inter laminar shear strength, thermal conduc-
tivity, coefficient of thermal expansion, and tensile strength. The example of
such a material showing adequate properties for high temperature ablative
material is the Carbon-phenolics [23]. This carbon fibre of micron size when
replaced by nanofiller will enhance the composite properties many folds due
to the better interfacial adhesion between the matrix and the filler with the
generation of large surface area and high aspect ratio. Also the thermal con-
ductivity improves due to low percolation thresholds which could be further
improved by functionalising the nanofillers. The other ablative materials used
depending on the location in the Solid Rocket Motor (SRM) nozzle are the
Glass cloth-phenolic and the Silica cloth–phenolic. The ablative properties of
C-Ph material can also be improved by adding zirconium diboride particles as
additives (Fig. 4) [24].
14. In common a high temperature material especially of nanocomposites show
improved thermal stability and high Hot Distortion Temperature (HDT). The
thermal stability is improved by commonly incorporating nanoclay into the
polymer matrix as it performs as a superior insulator and mass transport
barrier to the volatile products generated during decomposition.
15. The research literatures have brought out that the elastic and thermal prop-
erties of CNTs vis-a-vis carbon reinforcing fibres have been found to be nearly
four times high. The CNTs are uniquely stiff fibres with tensile strength
ranging above 50 GPa with the strength to weight ratio being nearly four
times larger than the carbon reinforcing fibres. The SWCNT has a greater
strain as compared to any other structural material unlike the negligible strain
seen in polymer-composite material where the fracture is sudden without prior
sign of failure. The thermal conductivity is also high in the range of
1,750–5,800 W/mK.
Fig. 4 Ablative materials in a solid rocket motor of a nozzle [24]
16. Layered silicates as fillers. Nanocomposites are layered with silicates of a

thickness of around 1 nm. The aspect ratio (length to thickness) is high over
1,000 due to the lateral dimension ranging wide. The layer forms gap between
them leading to interlayer. The interlayer distances are increased by the
exchange of cationic surfactants thereby reducing the action of these layers
form stacks with a gap in between them called the interlayer or the gallery.
Isomorphic substitution within the layers (Mg2+ replaces A13+) generates
negative charges that are counterbalanced by alkali or alkaline earth cations
situated in the interlayer [20] (see Fig. 5). The inorganic cations within the
interlayers can be substituted by other cations. The exchanges with cationic
surfactants, such as bulky alkylammonium-ions, increase the spacing between
the layers and reduce the surface energy of the filler. Therefore these modified
fillers (called organoclays) are more compatible with polymers and form
polymer-layered silicate nanocomposites. Montmorillonite, hectorite and
saponite are the most commonly used layered silicates [21, 20, 25,26, 17, 18].
17. Nanoclay has been widely researched as potential nanofiller for flame retar-
dancy [14]. The nanocomposite materials such as the organoclay plus alu-
minium oxide and series of polypropylene plus organoclay have found
applications as flame retardant materials. These materials have been com-
mercialised. Even the nanofillers like the CNTs or any other alternatives as the
Graphite Oxides or the Graphenes have been experimented to enhance the
mechanical, electrical and flammability properties of the otherwise traditional
polymer-composites. The graphene nanofillers in range of ceramics have
improved their toughness making them suitable for high performance struc-
tural applications.
Fig. 5 Layered silicates [21, 20]
18. The nanoceramics are finding its foothold as candidates for high temperature
applications. The reasons of having nanocomposites over traditional polymer-
composites are for their following benefits: -
(a) Improved strength, modulus and dimensional stability.
(b) Higher thermal stability and HDT (Heat Distortion Temperature).
(c) Better flame retardant properties and low smoke emissions
19. Nanoceramics have shown to have the abovementioned properties and a
suitable material for engine applications subjected to temperatures of around
1,400 C with strength maintained at 300 MPa. The material also exhibits
negative creep rate a desirable property for high temperature applications. The
other salients exhibited by nanoceramics over the traditional polymer-ceramic
composites are the high resistance to oxidation, sub-critical crack growth and
thermal shocks.
20. Nanocomposites such as SiC (Silicon Carbide)/Si3N4 (Silicon Nitride) com-
posites, are another material exhibiting improved strength, creep and fracture
toughness [10, 11, 27–32]. The material retains strength at higher temperatures
and has good resistance to creep. The Fig. 6 shows the microstructure of
polycrystalline Silicon Carbide (SiC)-Silicon Nitride (Si3N4) nanocomposites.
The structure contains filler Si3N4 of 0.8–1.5 lm and the polymer SIC of
200–300 nm. The grain boundary thickness is seen to be around 50 nm. The
other similar types of nanocomposites suitable for high temperature applica-
tions or under research will be the Graphene or Graphite Oxide/SiC, carbon
nanofibres/SiC-Aluminium Oxide (Al2O3)/and TiN-Si3N4.
21. The ongoing research on nanoceramics at Multiphysics Laboratory at Purdue
mainly focuses in understanding the performance of high temperature based
nanoceramics especially of nitrides and carbides. The materials so developed
will be helpful for power generation applications, nuclear applications, and
aerospace applications.
22. The research work is focusing on following areas.
(a) To develop materials of low conductivity by studying effects of material
morphology changes on thermal conductivity using simulation techniques
such as Molecular Dynamics (MD).
(b) To develop ceramic nanocomposites (nitrides and carbide based) capable of
withstanding high temperature environments even meant for nuclear applica-
tions. The advanced ceramic nanocomposites materials are researched to have
the capability to withstand temperatures of the order of approx 1,800 K and
Fig. 6 Actual microstructure

of a SiC-Si3N4
nanocomposite [31]
above [33]. The usage of such materials is experimented for various functions
like the Multi-functional material or as structures for extreme temperature
applications (Nuclear) [10, 11] or as sensors in high temperature zones.
23. The other area of research in nanodomain for high temperature applications
have been the nanocomposites of amorphous (Si, O and C) with nano SiC or C
fillers [30]. The research has shown that these materials have required prop-
erties and characteristics for a wide range of high temperature usage. The
nanocomposite exhibits ceramic like properties of negative creep rate and
anti-oxidant. The Fig. 7 shows one of the applications of PyroSic. The pyroSic
have been found much better than the conventional CFRPs.
24. The pyrolysis of pre-ceramics has been found to be simple as compared to the
conventional processing of CFRP. The tooling and process are seen to be less
complex as compared to Ceramic Matrix Composites.
25. The other processes evolved for improvement of ablative resistance of com-
posites such as the C-Phenolics has been by introduction of Zirconium dib-
oride particles [34, 35]. Sufficient research is in progress on this subject with
various combinations of nanofiller added to C-Ph composites to improve
ablation resistive property and also provide reduced smoke emission [23, 35].
The resistance is due to the formation of oxides of Zirconium and Barium. The
research in this field has shown that the ablative rate has been higher as
compared to Carbon fibres in C-Ph composites. The ablative resistance
properties have been improved by adding modified phenolics in the C-Ph
matrix [34–39]. The modification is obtained by treating with boric acid or
POSS (Poly Oligomeric Silsequioxanes), or H3PO4. This treatment gives a
reduced erosion rate thereby retarding ablation. Research has seen further
improvements in linear ablation rate by having composites of SiC Ceramic,
carbon fibres and boron modified phenolics. The Nanosilica powder modified
rayon-based composites show better ablation resistance, reduced thermal
conductivity and higher ILSS (inter-laminar shear strength) at a controlled
quantity. In this, process of improvement involves the modification of either
carbon fibres or the phenolics. Researchers find that the effects of ZrB2 on the
ablation performance of C–Ph composites are still unclear. The research
Fig. 7 Exhaust duct made

out of PyroSic
Fig. 8 Surface temperatures of Z C-Ph composites and C-Ph composites (a) the ablated surface
(b) the back surface [35]
papers have shown that the linear ablation rate of Z C-Ph composite has
reduced by 79 % compared with the un modified C-Ph composite [35]. The
ablation surface though at higher temperature during ablation process the back
surface temperature is found to be lower by 100 C as compared to unmod-
ified composites. This is shown in the Fig. 8. Therefore this material may
become the main material for high temperature structural applications.
26. The other promising research for better ablative material or as heat shields for re-
entry applications has been the resol type phenolic resin with kaolinite and
asbestos cloth nanocomposite [40]. The material has been tested for an external
heat flux of 8 9 109 W/m2 and 3,000 K. The material was tested for its ablation,
charr formation and thermal degradation performance for its usage as heat
shields. The temperature is withstood by the formation of a strong refractory
char on the insulator surface. Insulator later degrades to a char layer at higher
temperatures due to pyrolysis. Recent advances in polymer layered silicate
nanocomposites are seen as potential ablative materials [41, 42]. The reason
being on pyrolysis, the organo–inorgano nanostructure reinforcing the polymer
are transformed into a uniform ceramic char, leading to increased resistance to
oxidation and mechanical erosion in comparison with composite materials.
27. Ablation performance. Experiments on ablation performance of composites
(asbestos-Ph) and nanocomposites (Asbestos-Ph-Kaolinite) [40] have shown
the following:-
(a) The back surface temperature of a nanocomposite is found approx 43 %
lower than composites (Fig. 9) [40].
(b) The Heat Release Rate (HRR) and mass loss @ 80 KW/m2 (Fig. 10) [40]
show that to some stage i.e. up to 100 s of the Oxy-acetylene flame test both
composites and nanocomposites behave thermally same. After 100 s, with
the surface temperature increasing to 1,000 C the rate of mass loss and HRR
reduces for a nanocomposite. The nanocomposites show a reduction of nearly
35 % HRR and 22 % mass loss.
Fig. 9 Temperature distribution of back surface (composite and nanocomposite) [40]
Fig. 10 Comparison of HRR and mass loss @ 80 KW/m2 [40]
3 Advanced Thermal Protection Materials for Next

Generation Aerospace Vehicle Designs
3.1 Introduction
1. The research is under progress at NASA to establish high temperature materials

for various aerospace applications such as the structures, adhesives that are used
for bonding of composites and the thermal protection system namely fire retar-
dants (coatings). The work is progressing to reduce the thickness of the thermal
protection system by having high temperature resistant structures and adhesives.
3.2 Review on Advanced Materials for High Temperature

Applications (HTA)
2. The high temperature adhesives are those that have the working temperature
ranging from 315–400 C (600–700 F). The adhesive must also satisfy the
bond-line temperature requirement between the TPS-substrate of being above
the traditional limit of 250 C. The adhesive’s bond-line (Fig. 11) integrity
needs to be maintained for high temperatures and high heating rates [43].
3. The structure which is of honeycomb structure has graphite or aluminium-
epoxy face sheet and aluminium honeycomb. This material may be improvised
by using nanofillers with low wt% loadings and deriving many fold benefits of
thermo-mechanical properties. The thickness of the thermal protection system
depends on the allowable temperature for the bond line. The research will be
with the aim to increase the bond line temperature ([250 C) so as to reduce
the TPS and hence increase the payload with overall reduction in structural
weight. The need for high temperature adhesives will be to withstand high
temperatures for short period of time and for one or more loading cycles. The
test on adhesive bonding with substrate is carried out to check whether the
failure will be due to pure adhesive peeling off from substrate surface which is
the adhesive failure or the failure of the adhesive which demonstrates the
cohesive failure. The desirable test is to check the cohesive failure which
speaks more on the bond line integrity. Some clippings of the NASA tests are
shown below at Figs. 12 and 13.
4. The primary requirement of the adhesive is to retain some if not all of its
strength at high temperatures. Polymer-composites such as Polyimides group,
Cyanate ester group, BMI have shown good strength at high temperatures and
the properties profoundly improve when nanofillers such as nanoclay, nanoa-
lumina, nanotubes etc. are added.
Fig. 11 Aerovehicle structure [43]

Fig. 12 Adhesive failure

[43]
Fig. 13 Cohesive failure

[43]
5. The high temperature structures mainly of carbon reinforced fibres with resin
for polymer-composites may be replaced with nanofillers or additionally added
to the existing phases for strength improvement. The limiting factor at high
temperatures is the performance of matrices and their interfacial binding with
the nanofillers or the composite fibres. The most promising resin for high
temperatures have been the polyimides (315 C). This resin has high Tg
(400 C) and other good characteristics such as good micro cracking resistance,
low moisture absorption and low toxicity. There are various grades of polyi-
mides under development.
6. The applicability of a material depends on its performance during the coupon
tests which are carried out for determining the tensile strength/modulus, shear
strength/modulus (Fig. 14), for laminates the de-lamination at high temperatures
which is seen in case of CFRP composites [43],
7. The other type of resin which is less complex for processing will be the
modified polycyanates. The ablators for advanced temperature systems have
been the silicon based or the phenolic based with nanofllers or high grade of
fibres to increase the stiffness and strength.
8. The potential impact of advancing composites will replace the usage of metals
to composites for high temperature applications especially in the field of
aerospace vehicles. A typical impact of materials is given in Fig. 15 [44].
9. The use of high temperature composites/nanocomposites will definitely reduce
the weight of the structure and increase the payload capacity for useful
requirements of space research. The high temperature capabilities will make it
possible to have entire aerospace vehicles to be of composites. An example of a
Fig. 14 Effect of temperature on shear strength on three different laminates [43]
Fig. 15 Impact of change in materials with time [44]
engine nacelle of an aero-vehicle of becoming fully composite is shown in

Fig. 16 [44].
10. The challenge ahead is to select the right material for the required high
temperature applications. The nanocomposites/composites/hybrid materials
etc. are the various many options available which will replace the position of
metals in a structure and systems in all fields of science and engineering.
Fig. 16 Impact of advanced composite materials [44]
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Energy Absorption and Low-Velocity
Impact Performance of Nanocomposites:
Cones and Sandwich Structures
James Njuguna, Sophia Sachse and Francesco Silva
Abstract The increasing need for high performance structures, in the energy and
transport industry, demands a continuous development of new engineering mate-
rials. Unique mechanical properties together with low specific weight can be
achieved by the combination of various constituent materials into one macroscopic
composite material. Coupling of the high strength reinforcement with supporting
matrix creates a novel material with the improved characteristics, which could never
be obtained using either of the constituents separately. These types of materials are
particularly desirable in structures where a high strength to weight ratio is of great
importance. In this chapter, two case studies are provided one on nanophased
sandwich composites with polyurethane/layered silicate foam cores and the other on
thermoplastic glass-fibre and nano-silica reinforced nanocomposites.
1 Introduction
Over the last decade increased amount of research in the field of composite
materials proved that addition of nano-sized fillers, rather than micro-sized fillers,
can significantly enhance mechanical properties of the polymeric materials.
Composite material is usually defined as a ‘nano’, if one of the constituents
possess at least one dimension in the range of 1–100 nm. The unique properties, of
the material reinforced with nano-particles, come from the large number of
interfacial effects, existing due to the high surface-area-to-volume ratio of the
J. Njuguna (&)
Institute for Innovation, Design & Sustainability, Robert Gordon University,
Aberdeen AB10 7GJ, UK
S. Sachse F. Silva
Cranfield University, MK43 0AL Cranfield, Bedfordshire, UK

188 J. Njuguna et al.
reinforcement. For the spherical nano-particles and nano-fibres this ratio is irre-
versibly proportional to their radius, and its value can be even up to 1,000 m2/g. In
case of light weight structures, the most widely used nano-reinforcements are
silica based particles, due to their good mechanical properties and high thermal
stability [1].
Up to date, research works have been conducted to study the influence of the
nano-particles on the mechanical behaviour of polymer composites. Several fac-
tors influencing the enhancing capabilities of the nano-reinforcements were
studied in the literature [2–4]. This includes key parameters such as shape and size
of nano-fillers, matrix and reinforcement material, interfacial strength and inter-
phase characteristics, as well as volume fraction and quality of dispersion within
the matrix. Mechanical properties and energy absorption characteristics of nano-
composites have been mainly characterized by means of tensile, flexural or Izod
impact testing.
2 Energy Absorption of Composite Materials
Modern vehicle structures must be able to withstand severe impact loads, at the
same time providing safety of the occupants. That is why structural materials used
for crashworthy applications must be characterized by the energy absorption
capability. In order to ensure survivability of the accident, structure has to dissi-
pate energy in a controlled manner. This is limited by the two factors: induced
decelerations and maintaining of a survival space for occupants during a crash [5].
Energy absorbed throughout a collision is defined by the area under the load–
displacement curve as shown in Fig. 1 [6].
Analyzing the above graph we can notice that the energy absorbed can be
controlled by the value of the force and the deflection. The maximum peak load is
limited by the occupants’ tolerance and the maximum deflection is limited by the
geometry of the structure. In an idealized energy absorbing system induced load
should be constant and just below the human tolerance limit. In reality design of
Fig. 1 General load–

displacement curve [6]
Energy Absorption and Low-Velocity Impact Performance of Nanocomposites 189
Fig. 2 Various structural

responses [6]
crashworthiness structure is always a compromise and trade off. As an example

three different structural responses are compared in Fig. 2. In the scenario with
very stiff structure induced peak loads can highly exceed allowable limit. In such
case occupants will suffer high decelerations while deformations of the structure
are small. In case of the weak structure induced peak loads are strongly reduced
but large deformations can crash the occupants causing serious injuries or even
death. The third scenario is a compromise with the moderate value of the force and
acceptable deflections not affecting occupants’ space. In this scenario energy
absorbed by the structure is maximized but within the limits of allowable load and
deformation.
Traditionally metallic materials have been applied for the crashworthy struc-
tures due to their ability to sustain plastic deformations. In contrast, composite
materials do not exhibit plastic deformations as they are usually brittle. However,
if they are properly designed, they can absorb high amounts of impact energy by
the progressive failure and delamination.
In order to facilitate a comparison of various crashworthiness materials, several
measuring parameters are commonly used, and the most important ones are the
specific energy absorption (SEA) parameter and the energy absorption efficiency.
The specific energy absorption (SEA) parameter is defined by the amount of
energy absorbed per unit mass of crushed material.
R
energy absorbed Fdx
SEA ¼ ¼
crashed mass mc
where F—load, x displacement.
The energy absorption efficiency (EAE) is defined by the ratio of the area under
the load–displacement (true energy absorbed) curve to the rectangular area formed
by the maximum load and maximum displacement (perfect energy absorbed).
energy absorbed
EAE ¼ 100
max load max displacement
The most widely used method to evaluate the ability of a composite material to
absorb the energy, is axial collapse of a structural elements. This technique has
been applied by many researchers, on various composite materials.
The ability of a composite structure to absorb energy is highly dependent on the
mode of fracture. Materials which fail in a progressive manner, with extensive
delamination and fragmentation, are able to absorb much higher energies than those
materials which tend to fail in a brittle manner. Farley [7–9] found that thermoset
composites reinforced with glass and carbon fibres fail progressively in fragmen-
tation and splaying modes. On the other hand, thermoset tubes reinforced with
Kevlar, failed in a progressive folding mode. Mamalis et al. [5] who studied poly-
ester cones, cylinders and tubes, reinforced with random orientated glass fibres,
divided failure of the samples into four modes: progressive crushing with micro-
fragmentation (Mode I), brittle fracture with catastrophic failure (Mode II and III,
depending on the crack form), Progressive folding and hinging, similar to the
metallic tubes (Mode IV). The authors observed that significant influence on fracture
mode has geometry of the sample. Conical and square tubes with small semi-apical
angles (5–15) tend to fail in a stable Mode I, whereas samples with large semi-
apical angles (20–30) were found to fail in a brittle Mode II. They also found that
wall thickness, related to number of composite layers, has direct influence on the
mode of failure. The collapse mode for large semi-apical angel samples has changed
from stable to unstable, with increasing wall thickness. In case of small angel
samples, the collapse mode remained the same with increased thickness of the wall.
3 Energy Absorption in Nanocomposites
Modern vehicle structures must be able to withstand severe impact loads, at the
same time providing safety of the occupants. For this reason, structural materials
used for crashworthy applications must be characterized by the energy absorption
capability. Energy absorbed throughout a collision is controlled by the value of the
force and the deflection. The maximum peak load is limited by the occupants’
tolerance and the maximum deflection is limited by the geometry of the structure.
In the scenario with very stiff structure induced peak loads can highly exceed
allowable limit and occupants will suffer high decelerations while deformations of
the structure are small. In case of the weak structure induced peak loads are
strongly reduced but large deformations can crash the occupants causing serious
injuries or even death. The third scenario is a compromise with the moderate value
of the force and acceptable deflections not affecting occupants’ space. In this
scenario energy absorbed by the structure is maximized but within the limits of
allowable load and deformation.
The most widely used method to evaluate the ability of a composite material to
absorb the energy, is axial collapse of a structural elements. The experiments
presented in the literature vary in geometry and material of the specimen, as well
as parameters of the impact such as: velocity and energy. The most often used
geometries of crash-samples are: cylinders, cones and square tubes [5, 7–11]. The
materials which have been investigated extensively include: carbon, Kevlar and
glass as fibre materials; and epoxy [7–9], PEEK [12], polyester [5] and vinylester
[10] as matrix materials.
Low cost thermoplastic polymers, such as polypropylene (PP) and polyamide
(PA), are widely used in the aerospace industry because of their good mechanical
performances, processing properties and low cost. However, their application as
structural materials is limited due to their low impact resistance [13]. Incorporation
of various nano-sized filers like; nano-particles (SiO2, TiO2, WS2, CaSiO3, Al2O3),
carbon nanotubes, and clay nano-plates; can be an appropriate solution to this
problem [14]. Injection moulded, short fibre-reinforced thermoplastic composites
are the most prevalent composite materials as thermoplastic nano-reinforced
structures. Several important factors influencing energy absorption capability of
nanocomposites are summarized in the followings:
• Particles stiffness: The particles stiffness influences the mechanical properties of
polymer matrix nanocomposites. For instance, the impact response of the high
density polyethylene with addition of elastic rubber and rigid calcium carbonate
(CaCO3) particles was investigated by means of notched Izod impact testing
[15, 16]. The results showed that addition of 22 vol. % of elastic rubber causes
an increase in notch toughness more than 16 times. However, a decrease by
50–60 % in the Young’s modulus and yield stress by 40–50 %, was observed in
relation to the net polymer.
• Particles geometry: Addition of Al2O3 nano-whiskers, glass fibres and wallas-
tonite into polymer matrix improves the fracture toughness significantly, while
incorporation of the plate shaped particles of nanoclay, into the same matrix
material, was found to decrease it [17]. Favourable effect on the impact
toughness was also observed after the addition of amino-functionalized multi
wall carbon nano tubes [18] or small amounts of single wall carbon nano tubes
[19]. Moreover, it was observed by Kireitseu [20] that the composite impact
toughness and stiffness are highly dependent on the modulus of nano-tubes.
• Volume fraction and inter-particle distance: Important influence on the impact
toughness of nano-composites has the inter-particle distance s, independently of
the reinforcement geometry. Its value is closely related to the concentration u
and average size of the particles d [21]. Zhang et al. [21] found, that if inter-
particle distance is smaller than average particle size d, then composite tough-
ness increases significantly, as it are presented in Fig. 3. This phenomenon can
be explained by the fact, that distance between particles is small enough to build
around them, a three dimensional network of interphase region.
• Effects of particles size: Effect of particles size on the mechanical properties of
the polyurethane foams was studied by Javni et al. [22]. Incorporation of nano-
sized filler was found to increase the compression strength of the foam, and to
decrease its rebound resilience. On the other hand the addition of micro-sized
fillers was found to lower the hardness and compression strength, at the same
time leading to an increase in rebound resilience. This indicates that foams
Fig. 3 Improvements in mechanical properties due to the inter-particle distance [21] and energy
dissipation against average radius of the filler [23]
reinforced with nano-particles are able to absorb higher amounts of impact

energy. According to the analytical studies carried out by Chen et al. [23],
energy dissipation due to the interfacial debonding is highly dependent on the
size of particles. The material ability to dissipate energy increases significantly
with increasing size of the particles up to 140 nm, whereas particles bigger than
that indicate gradual decrease in the material performances.
4 Sandwich Composites
Sandwich composites are widely used in wind turbines, automotive bumpers,

aircraft engine nacelle, on wings for fuel tanks protection, tail plane panels for
protection of stones and pebbles on take-off and landing, naval ships, human vests
and helmets for ballistic protection, automotive for collision and heat protection.
Unfortunately, any composite materials are susceptible to impact and the damage
can be big and tend to increase in time- Research has shown that damage initiation
thresholds and damage size on sandwich composites, primarily depend on the
properties of the core materials, face sheets, and the relationship between the
properties of the cores and those of the facings. Much of the earlier research on
sandwich composites under impact loading focused on the honeycomb core
(Nomex, glass thermoplastic or glass-phenolic) sandwich constructions. A key
problem in the honeycomb sandwich constructions is the low core surface area for
bonding. Consequently, expanded foams, (often thermoset) are nowadays pre-
ferred to achieve reasonably high thermal tolerance, though thermoplastic foams
are also used. In turn, the response of foam core sandwich constructions to impact
loading has been studied by many researchers [24–26]. Accordingly, it is now well
understood that the response of the foam core sandwich composites strongly
depend on the density and the modulus of the foam.
Foams are defined as materials containing gaseous voids surrounded by a
denser matrix, which is usually a liquid or solid. Polymer foams can also be
defined as either closed cell or open cell foams. In closed cell foams, the foam cells
are isolated from each other and cavities are surrounded by complete cell walls.
In open cell foams, cell walls are broken and the structure consists of mainly ribs
and struts. Generally, closed cell foams have lower permeability, leading to better
insulation properties. Open cell foams, on the other hand, provide better absorptive
capability. One-step reactive foaming is typical for thermoset polymers. A good
example is PU/clay nanocomposite foams, where a physical blowing agent such as
pentane is used with monomers and clay nanoparticles. Reaction exotherm leads to
a temperature jump and foaming. Most nanocomposite foams to date are synthe-
sized via a two-step process: the nanocomposite is synthesized first and followed
by foaming. Readers interested in the synthesis of PU/clay foams are referred to
available literature such as Refs. [27, 28] (literature related to the reactive
extrusion foaming of various nanocomposites is also covered). Polymeric foams
have been widely used as packing materials because they are lightweight, have a
high strength/weight ratio, have superior insulating properties and high energy
absorbing performance.
A possible way of improving the properties of foam materials is through the
inclusion of small amounts of nanoparticles (like carbon nanotubes and nanofibres,
TiO2, nanoclay, etc.) to improve the foam density and modulus properties. Up to
now, montmorillonite nanoclays are the best candidate for foam reinforcement due
to ease in processing, major thermal–mechanical properties enhancement, wide
availability and are relatively cheap [2, 3]. Likewise, polyurethanes (PU) are core
materials of choice due to their tailorable and versatile physical properties, ease of
manufacture and their low costs. Unfortunately, the use of thermoplastic resins
filled with nanoparticles to construct either laminates or foams is relatively new.
Moreover, the use of nanoparticles in such laminates or foams in sandwich
composite construction is in its infancy but realistic and beneficial. For instance,
by using less than 5 % by weight nanoclay loadings, significant improvement on
the foam properties (failure strength and energy absorption) can be realised with
over 50 % increase in the impact load carrying capacity over the neat foam
sandwich [29, 30]. However, since most current research concentrates on the
processing and characterization of nanophased foams and evaluation of static
properties only, materials data on impact behaviour, failure mechanisms due to
impact and impact-structure–property relations is missing. For wide usage of
nanophased foams in the sandwich constructions and reduction of weight (while
maintaining the same level of protection), proper understanding of their impact
behaviour at both high- and low-velocity impact is required.
4.1 Fabrication of Sandwich Panels with Nanophased Cores
Polyurethane foam with various different weight percentages (up to 10 %) of

nanoclay have been prepared. The low weight percentages are targeted for infusion
to avoid the agglomeration of nanoparticles common in high concentrations.
Preparation of the PU systems modified with MMT consists of three steps—first,

polyol blend (polyether RF-551) and polyester (T-425R) mixture from Alfasystems,
Brzeg Dolny, Poland, was stirred with powdered MMT (Optibent 987, Süd Chemie
AG, Moosburg, Germany). Then catalyst (N,N-dimethyl cyclohexylamine), water
and surfactant (SR-321, Union Carbide, Marietta, GA) were added in order to
prepare the polyol premix (component A). In the next step n-pentane as a physical
blowing agent was added to component A. Component B was polymeric 4, 4’-
diphenylmethane diisocyanate (PM 200). It was added to component A and the
mixture was stirred for 10 s with an overhead stirrer. Finally, the prepared mixtures
were dropped into a mould. All the experiments were performed at ambient tem-
perature of ca. 20 C.
The sandwich beam samples are fabricated from aluminium face sheets
(aluminium grade 24,139, Young’s modulus of 79 GPa, 2 mm thick) and the
above manufactured 20 mm thick nanophased polyurethane rigid foams. Firstly,
the aluminium faceplates were pre-treated and polished. Later they are degreased
using acetone for 2 min before applying the adhesive (DP-100 supplied by 3 M@).
The surfaces are then dried and the adhesive applied evenly on the foam surface
using a glue gun, and the metal skin is laid on top for each side at a time. This is
repeated for the other side of the foam after allowing for 24 h of curing time. Once
the adhesive is applied the sandwich samples are cured for a further period of 24 h
in a press. Basically, the samples are laid on the base of the press between two
thick metal plates to ensure pressure is distributed evenly all through the structure.
The finished products are 5 specimens of sandwich beams of length 140 mm and
width 100 mm for each.
4.2 Low Velocity Impact Tests
All the low impact tests were conducted using an instrumented falling weight
impact tester, type 5. The device is equipped with impulse data acquisition system
that can acquire data points. Using this machine, impact energy and velocity can
be varied by changing the mass and height of the dropping weight. The velocity of
the tup is measured just before it strikes the specimen. It is also fitted with
pneumatic rebound brake, which prevents multiple impacts on the specimen.
During the testing, the specimen is held in the fixture placed at the bottom of the
drop tower which provided a clamped circular support span (Fig. 1). The weight of
cross-head is maintained at a specific value and it is guided through two smooth
guide columns. The impactor end of the drop mass is fitted with an instrumented
tup with hemispherical end having a capacity to record the transient response of
the specimens. To carry out the impact tests, sandwich composite samples
(140 9 100 mm) are placed between the clamps and heights adjusted depending
on the desired energy level. The projectile had a 20 mm diameter hemispherical
tip. The impact force history obtained during the test was measured using a piezo-
electric load cell located above the impactor tip. The amplified signals from the
load cell were recorded by the computer. The height is the distance between the tip
of the indenter and the top surface of the sample held between the clamps. Once
the height required to attain a particular energy level is known, the indenter is
moved accordingly to that height before it is dropped on the specimen for the test.
4.3 Results and Discussions
The impact response of sandwich structures with and without nanoclay core and
nanophased face sheets were evaluated. Several samples of each set were tested at
different energy levels. Transient data including time, load, energy, velocity and
deflection were collected for each sample as functions of time. Figure 4 compares
typical load and deflection versus time curves for the four specimen types at 45 J
impact energy level.
The peak loads were 3,560 N for neat cored sandwich and for 2.5 % MMT
loaded core sandwich composites. A slight improvement of *300 N was observed
in peak load for both 5 and 7.5 % MMT loaded samples, indicating that higher
MMT loading samples performed better than the lower MMT loaded ones.
The energy absorption at failure point was recorded as 32.5, 32.5, 43.4 and 44 J
for 0, 2.5, 5 and 7.5 % MMT loading respectfully. The energy absorption in any
material under impact loading is mainly through the elastic deformation in the
initial stage with some energy absorbed through friction. Once, the energy level is
Fig. 4 Comparison of load versus time graph obtained from first impact
beyond the level required for maximum elastic deformation, the structure then
dissipates the excess energy in the form of either plastic deformation in case of
ductile materials or through various damage mechanisms in the case of brittle
materials. As can be seen on Fig. 5, it is evident that the absorbed energy at peak
load was within a close range for all samples.
The deflection at peak load is a qualitative indication of the stiffness of the
material. The same applies to their maximum deflection recorded, averaging
around 2.1 mm but minor diversity between the specimens was found. As
expected, the peak loads and deflections were similar at low impact energy. These
current results were in contrast to related published work in the literature which
reported that at 45 J, the neat core sandwich structures had higher deflection at
peak load on nanophased core and fibre-reinforced sandwich composites [30]. The
literature further reported that the total time and the time to peak load were also
higher for the neat core sandwich samples [30]. However, it should be noted that
the work was based on fibre-reinforced composites as face sheets whereas alu-
minium face sheets have been used in the current work. In the latter case, there was
no perforation on the face sheets by the indent striker. It is also apparent that we
will need to undertake future tests at higher energy levels above the 45 J thresholds
the current tests were conducted at.
Fig. 5 Energy versus time graph obtained from first impact

A detailed examination revealed no debonding of the skin and core or crack

development into the foam cross-section at the mid-plane of the structures over the
range of energies considered. This demonstrated the importance of a proper
selection of adhesive for particular foams. Typically, core fracture takes place
when defects exist in the adhesive layer and at the skin/adhesive/core interfaces or
where poor adhesion occurs between the skin and the adhesive. In our case, DP-
100@ is a thin film and highly viscous. When a one-step process is used to cure the
facings to the core, localized cell wall collapse and cell coalescence occur, leading
to non-uniform thickness and weaker cores near the skin/core bondline. In such
cases, the problem is caused by the high pressure required to cure the facings. In
the current work, therefore, a thin layer application was employed followed by
compression during bonding hence minimising potential defects in the materials at
fabrication stage. Nevertheless, a microscopic inspection revealed some small
debonding for both 5 and 7.5 % samples along the skin/foam interface edges in the
structure width after the first impact tests. This failure may be attributed param-
eters that are direct indications of the stiffness of the samples rather than just the
adhesive failure. It follows that at impact, as the dented aluminium face sheet
yielded inwards, the back face remained intact and no deformations were observed
along the cores length. However, debonding occurred along the sandwich com-
posite edges (face plate, width-wise) to make up for the bending displacements
thereby forcing the edge lines to split along the skin/core interface. The core at the
midsection experienced compression forces but there were no signs of cracks
formation for all samples even under microscopy. This may be related to reactive
foams and their microcellur cells collapsing to absorb load instead of expected
cracks and fracture characteristics, as widely reported in the literature.
Since sandwich structures are often used as energy absorbing structures in
damage susceptible areas, we decided to conduct a second drop weight impact
recurrence on the previously impacted samples in order to closely replicate
repetitive occurrences. Such scenarios are common between structural inspection
periods or in incidences where the damage was missed during normal inspection
routines. Interestingly, we found out that the nanophased samples recorded sig-
nificantly higher peak loads than the neat PU cored ones. As can be seen from
Figs. 6 and 7, a difference of over 1,000 N in peak load was observed for the
7.5 % samples as compared to that of neat PU foam samples.
It was further noted that the neat foam samples had the highest energy intake at
failure point, in agreement with previous observations by Hosur et al. [24]. Still,
there was no visible cracking deformation on the surface of the reactive foam cores
along the length of the structures. The only visible debonding and crack formation
was along the width of the structures which, as eluded to earlier on, may be
associated to bending deformation on the face plate due to impact loads. Further
investigations by microscopy are currently underway to investigate the level of
damage on the microcellular cores’ cross-sections in conjunction with in-depth
morphology studies.
Fig. 6 Load versus time graph obtained from second impact test
5 Thermoplastic Nanocomposites
Numerous researches have been conducted to study the influence of nano-particles

on the mechanical behaviour of polymer composites. Several factors influencing
the enhancing capabilities of the nano-reinforcements were studied in the litera-
ture. This includes key parameters such as: shape [31] and size [32] of nano-fillers,
matrix and reinforcement material [33, 34], interfacial strength and interphase
characteristics [35], as well as volume fraction [21] and quality of dispersion
within the matrix [36].
For the purpose of measuring the energy absorption in composite structures,
tube crashing experiments are the most prevailing. The ability of a composite
structure to absorb the energy was found to be highly dependent on the mode of
fracture. Materials which fail in a progressive manner, with extensive delamination
and fragmentation, are able to absorb much higher energies than those materials
which tend to fail in a brittle manner. Farley [7–9] found that thermoset composites
reinforced with glass and carbon fibres fail progressively in fragmentation and
splaying modes. On the other hand, thermoset tubes reinforced with Kevlar, failed
in a progressive folding mode. Mamalis et al. [5] who studied polyester cones,
cylinders and tubes, reinforced with random orientated glass fibres, divided failure
of the samples into four modes: progressive crashing with micro-fragmentation
(Mode I), brittle fracture with catastrophic failure (Mode II and III, depending on
Fig. 7 Energy-time graphs after second impact test
the crack form), progressive folding and hinging, similar to the metallic tubes
(Mode IV).
Regarding nanocomposite structures there is a lack of crash experiments con-
ducted on these materials presented in the literature [14]. Energy absorption
characteristics of these materials have been mainly characterized by means of
compression [37], flexural [38] and Charpy or Izod impact testing [17]. The
relationship between mechanical properties of nanocomposite material and energy
absorption characteristics of nanocomposite structure is not fully understood. This
work therefore aims to correlate changes in the mechanical properties of the
material with induced fracture modes and ability of the structure to crash pro-
gressively, after the addition of secondary reinforcement.
5.1 Fabrication of Cone-Shaped Nanocomposites Structures
Preparation of the nano and glass reinforced polymer composites was conducted in
three main steps: preparation of the nano-composites granulate, mixing and
extrusion of the nano and glass reinforced composite granulate and injection
moulding of the macro-sample. The flow chart showing the preparation process is
shown in Fig. 8.
Fig. 8 Material
compounding and test sample
manufacturing
In order to warrant the highest homogeneity of the composition, nano-rein-

forcement and polymeric matrix, all in solid (powder) form, were premixed before
extrusion. This activity was performed by the use of a turbomixer with rotatory
blades. The pre-mixing phase consisted of two steps, the first one at lower speed
(1,500 rpm) and the second one at higher speed (3,000 rpm). This choice was
made in order to ensure the maximum homogeneity of the premix and, on the other
hand, to subject the polymer to a small temperature stress, to improve binding
between polymeric matrices and added reinforcements. Subsequently the premixed
materials were fed into a twin-screw extruder at a constant predefined rate.
5.2 Crashing Behaviour
Crashing behaviour and energy absorption characteristic of the polymer com-

posites were studied by means of quasi-static compression and dynamic impact
tests. Figure 9 show the variation of load with increasing crashed length of the
conical structure. Comparing the load–displacement curves, several important
comments can be made. In all conducted experiments the initial slope of the load
curve is approximately linear. This is associated with the elastic deformation of the
structure [39–41]. The first extremism of the curve indicates maximum load
supported by the structure, which depends on the material strength. After that
point, a sudden drop in load is observed due to the formation of the cracks.
Subsequently, a progressive crashing occurs, what is visible as following sharp
load peaks. Analyzing the obtained results we can note, that magnitude of the load
peaks depends on the crashing characteristic of the material and testing speed. It
could be seen that all PA composites and neat PPGF composite, tested under the
quasi-static load, had bigger secondary peaks than the initial one. On the other
hand, the same materials, tested under the dynamic conditions, induced signifi-
cantly lower secondary peaks. This difference is associated with the mechanism of
cracks propagation. If the crack propagates along the height of the cone, as it can
be seen in Figs. 9 and 10, then the load required to crash the sample can be smaller
(a)
T=2 T=14
(b)
T=2 T=14
Fig. 9 Crushing characteristics of nanofilled cones. High speed camera records (a) PA/GF/MMT
(b) PA/GF/SiO2
Fig. 10 Dynamic collapse mode in: (a) PP/GF (b) PP/GF/SiO2 (c) PP/GF/MMT (d) PP/GF/GS
(e) PA/GF (f) PA/GF/SiO2 (g) PA/GF/MMT (h) PA/GF/GS
than that required to form the initial crack. The opposite situation exists if prop-
agation of the crack stops quickly after the formation, and new cracks have to be
initiated in order to crash the sample.
5.3 Energy Absorption Characteristics of Nanocomposite

Structures
By relating the energy absorption characteristic with the propagation of the crack,
it can be seen that materials that fail in a progressive manner, are able to absorb
much higher energies than those with large continuous cracks. Furthermore, the
mean crashing load in these materials is either on the same or higher level than the
initial peak, what causes that the area under the load–displacement curve is
significantly bigger.
Analyzing the results listed in Tables 1 and 2, we can note that crashing
characteristic under dynamic load are different from those subjected to quasi-static
compressive load.
All materials absorbed similar amount of impact energy, whereas energy
absorbed during the quasi-static test is different in each material. This discrepancy
is caused by the fact that each material failed with a different crashing length under
the impact loading, while under the static loading the crashing length is constant in
all experiments
Regarding the loads induced during the impact, we can note that mean crashing
load was much closer to the initial peak, in case of all PP composites, what has a
direct influence on the amount of energy absorbed by the structure. In case of PA
materials the mean crashing load was significantly smaller than the initial peak,
indicating weaker impact-energy absorption capabilities. Conclusions
Nanophased reactive polyurethane cores were manufactured and then used to
fabricate sandwich structures. It has been found that the incorporation of MMT
resulted in higher number of PU cells with smaller dimensions and higher
anisotropy index (cross-sections RI and RII). The obtained materials exhibited
Table 1 Quasi-static crashing characteristics

Material Crash Collapse Initial Mean Energy Specific Change
length mode peak crashing absorbed energy (SE) in SE (%)
(mm) (kN) load (kN) (kJ) [kJ/kg]
PPGF 86 III 29.74 34.75 2.993 49.4
PPGF + SiO2 86 III 26.59 17.86 1.489 24.4 -50.7
PPGF + MMT 86 III 24.75 15.39 1.294 21.2 -57.0
PPGF + GS 86 I 22.06 17.66 1.652 26.3 -46.9
PAGF 86 III 47.66 50.44 4.339 58.1
PAGF + SiO2 86 III 44.61 45.66 4.156 54.5 -6.1
PAGF + MMT 86 III 54.59 40.65 3.232 42.9 -26.2
PAGF + GS 86 III 55.10 45.74 4.117 51.7 -11.0
Table 2 Dynamic crashing characteristics

Material Crash Collapse Initial Mean Energy Specific Specific
length mode peak crashing absorbed energy energy
(mm) (kN) load (kN) (kJ) (kJ/kg) increase (%)
PPGF 29.79 I 22.99 14.19 0.365 23.6 –
PPGF + SiO2 31.4 I 25.72 15.41 0.376 22.6 -4.2
PPGF + MMT 36.02 I 20.02 12.86 0.401 20.5 -13.0
PPGF + GS 35.03 I 26.28 13.52 0.403 20.7 -12.3
PAGF 60.5 II 19.99 5.64 0.356 7.7 -
PAGF + SiO2 57.56 III 26.51 8.98 0.432 9.8 27.0
PAGF + MMT 62.61 II 38.82 4.48 0.376 7.7 0.1
PAGF + GS 22.03 III 40.42 15.58 0.320 22.3 188.5
improved parameters in terms of thermal insulation properties. The investigation

revealed that nanophased sandwich structures were capable of taking higher peak
loads than those made of neat polyurethane cores when subject to low-velocity
impact. This was especially true for multi-impact recurrences within the threshold
loads and energies studied. It is proposed to investigate the threshold load that
initiates delamination damage in the sandwich laminate which is a particularly
important property of polymer composite components exposed to water and/or
moisture and subjected to low energy impact.
Thermoplastic polymer glass-fibre and nano-silica reinforced composites were
investigated as an alternative to polymer glass-fibre composites. The effect
of matrix and reinforcement material on the energy absorption capabilities of
composite structures was studied in details. The axial dynamic and quasi-static
collapse of conical structures was conducted using high energy drop tower, as well
as Instron electro-mechanical testing machine. The impact event was recorded
using high-speed camera and the fracture surface was investigated with scanning
electron microscopy (SEM). Attention is directed towards the relation between
micro-fracture process and crack propagation mechanism, and energy absorbed by
the structure.
The obtained results indicate an important influence of filler and matrix material
on the energy absorption capabilities of the polymer composites. A significant
increase in specific energy absorption is observed in polyamide 6 reinforced with
nano-silica particles and glass-spheres, whereas addition of montmorillonite
caused a decrease in that property. On the other hand, very little influence of the
secondary reinforcement on the energy absorption capabilities of polypropylene
composites was found.
Acknowledgments The authors would like to acknowledge the European Commission financial
support through the FP7 Project- CP-FP, Project Reference No.: 228536– 2. Support from
Research Councils Unite Kingdom (RCUK) and the Engineering and Physical Sciences Research
Council (EPSRC) equipment pool is also acknowledged.
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Predictions of Energy Absorption
of Aligned Carbon Nanotube/Epoxy
Composites
D. Weidt and Ł. Figiel
Abstract The potential of aligned CNT/epoxy nanocomposites towards energy

absorption applications was demonstrated using finite element modeling. For that,
two cases studies were carried out: (1) prediction of crack resistance characteristics
of epoxy reinforced with aligned double-walled CNTs (DWCNTs), and (2)
prediction of rate-dependent compressive response of epoxy filled with aligned
single-walled CNTs (SWCNTs). It was found that reinforcing epoxy with CNTs
can significantly reduce the crack driving force in epoxy and increase strains to
failure as a result of the damage propagation at the CNT–epoxy interphase. Par-
ticularly, enhancements of shear stiffness, shear strength and mode II fracture
energy of CNT–epoxy interphases via CNT functionalization and minor increases
of low sp3-bond densities in the interwall phase of DWCNTs were shown to
increase the crack resistance of the nanocomposite. Furthermore, it was found that
the linear and nonlinear compressive deformations and thus the energy absorption
characteristics of epoxies can be significantly affected by the presence of CNTs.
Specifically, the initial stiffness was increased and the post-yield behaviour of the
nanocomposite showed enhanced strain stiffening, both with increasing CNT
loading and increasing CNT aspect ratio. Additionally, a combined effect of aspect
ratio and volume fraction on energy absorption characteristics was found. This
suggests that the average aspect ratio of CNTs should be carefully selected in order
to maximise the energy absorption for the given CNT volume fraction.
D. Weidt Ł. Figiel
Department of Mechanical, Aeronautical, and Biomedical Engineering/Materials and
Surface Science Institute, University of Limerick, Limerick, Ireland
Ł. Figiel (&)
Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,
Sienkiewicza 112 90-363 Łódź, Poland

208 D. Weidt and Ł. Figiel
1 Introduction
Carbon fibre reinforced epoxy laminates are commonly used to build lightweight
structures due to their excellent strength/stiffness to weight ratios, and good fatigue
and corrosion resistance (when compared to metals). As a result, they have a wide
range of applications in transport (aerospace, automotive) and energy-generation
(wind and tidal turbines) sectors. Unfortunately, they frequently behave as brittle
materials under various types of impact loading as they cannot absorb/dissipate
enough energy. This is especially important for laminates used in aircraft industry,
which experience a considerable number of impact events during their service life.
As a result, matrix cracks can develop due to the brittle nature of epoxy. In
combination with a weak interlaminar strength, further opening of these matrix
cracks can cause delaminations, and lead to catastrophic failure of the laminates
and their structures.
Over the last two decades, attention in composites research has been shifted to
nanofillers such as carbon nanotubes (CNTs). The reason for this is that CNTs
exhibit exceptional mechanical properties (e.g. stiffness, resilience) [7, 18]. Fur-
thermore, nanoreinforcements possess a specific surface area several orders of
magnitude larger than the conventional microfillers [16]. Hence, an enormous
interface area is available to enhance the interaction between the matrix and
reinforcement at low CNT concentrations. Convinced by the potential of advanced
nanoscale reinforcements several researchers used CNTs to improve the damage
and failure resistance of CFRP laminates. Various approaches have been pursued,
and they include enhancement of the mechanical performance of composite
matrices [24]. Others have used CNTs to strengthen the interface between the
CFRP pre-preg lamina [13], or have grown them on the microfibre surfaces to
produce a stitching effect [23]. We believe that the incorporation of a CNT/epoxy
nanocomposite coating onto the laminate surface can help to enhance overall
energy absorption characteristics of the laminates. This is expected to have two
different origins: (1) enhanced ductile deformation of epoxy in compression due to
presence of CNTs and (2) CNT crack bridging mechanisms [12, 22, 25] accom-
panied by CNT pull-out and interface debonding.
Therefore, in order to demonstrate the potential of aligned CNT/epoxy nano-
composites towards energy absorption applications, computational studies were
performed in this contribution. In particular, two case studies were investigated:
(1) crack resistance characteristics of the CNT/epoxy nanocomposites with aligned
double-walled CNTs (DWCNTs) in the vicinity of a matrix crack, and (2) rate-
dependent compressive response of CNT/epoxy systems with aligned single-
walled CNTs (SWCNTs). In particular, the influence of different properties of
CNT–CNT and CNT–epoxy interphases on the normalized total energy release
rate at the matrix crack tip and damage propagation along interphases were
investigated in case (1). In case (2), the nanocomposite behaviour at various strain
rates ranging from quasi-static to impact rates was predicted and the effects of
CNT volume fraction and CNT aspect ratio on the macroscopic compressive
Predictions of Energy Absorption of Aligned Carbon Nanotube/Epoxy Composites 209
stress–strain response were investigated. Those predictions were compared with

the response of unfilled epoxy, and the normalized energy absorption character-
istics of the nanocomposites in the absence of interphases and interphase damage
were evaluated.
2 Energy Absorption of Aligned CNT/Epoxy

Nanocomposites in Tension
2.1 Modelling Approach
An increased energy absorption in impact areas dominated by tensile stresses is

expected to be caused by CNT crack bridging mechanisms accompanied by CNT
pull-out and interface debonding. Hence, a problem of a stationary matrix crack in
the vicinity of a DWCNT was studied to investigate the effect of interphase (CNT–
epoxy and CNT–CNT) properties on the fracture parameter.
Carbon nanotubes in matrix systems provide load transfers similar to conven-
tional short fibre composites. Lourie and Wagner [15] observed the formation of
damage doublets in adjacent straight carbon nanotubes embedded in a polymer
matrix. Such damage clusters usually occur in traditional non-continuous fibres
reinforced composites due to a redistribution of stress from a failed fibre to its intact
neighbour. The authors followed that the fundamentals of continuum mechanics of
fibre composites hold to some degree in carbon nanotubes embedded in polymer
matrices. The same was assumed in our computational study where continuum
finite element (FE) modelling was applied. The continuum approach adopted here
offers a compromise between accuracy and computational time when compared to
molecular simulations. The FE software ABAQUS/Standard was used.
An axisymmetric unit cell with a circumferential matrix crack of length a was
used in this work, as shown in Fig. 1. This represents a plausible scenario, where a
matrix crack approaches a ‘forest’ of aligned (locally or globally) carbon nano-
tubes without yet touching of their surfaces. A CNT volume fraction, defined as
volume ratio between a solid representation of the CNT and RVE, of *1.28 %
was assumed. A CNT aspect ratio of LCNT/RCNT = 50 was considered here, where
CNT length LCNT = 500 nm, and CNT radius RCNT = 5 nm. This aspect ratio is
relatively small compared to typical aspect ratios of CNTs. However, it corre-
sponds to a lower reinforcing limit (worst case scenario), where a debonding
length and CNT-bridging effect is small. The Young’s modulus and Poisson’s ratio
of the epoxy were assumed to be 2.5 GPa and 0.4 respectively. The Young’s
modulus of the CNT was assumed to be 3.36 TPa [19]. The model symmetry
resulted in modelling of only one half of the axisymmetric cell. The matrix crack
was modelled as a sharp circumferential crack perpendicular to the axis of the
CNT. Interphases between adjacent CNT walls and CNT and epoxy matrix were
incorporated into the model to account for different CNT–CNT and CNT–epoxy
Fig. 1 Schematic view on the 2D axisymmetric RVE. LRVE = 291 nm, RRVE = 41 nm,
LCNT = 500 nm, RCNT = 5 nm, TCNT = 0.1 nm [19], TIP = 0.24 nm, a = 18 nm
interactions. CAX4 (4-node bilinear axisymmetric quadrilateral elements) and

COHAX4 elements (4-node axisymmetric cohesive elements) were used. The
stress transfer from the matrix to the top edges of CNT walls was assumed to
be negligible, therefore no bonding at the interface between top CNT edges and the
matrix was modelled.
CNT–CNT and CNT–epoxy interactions were modelled using the cohesive
zone concept through bilinear traction–separation laws (see Fig. 2). Those laws
include damage initiation, damage propagation and failure. The damage initiation
criterion used here is based on the maximum nominal stress value in shear or
normal direction. Damage propagation is represented in terms of the stiffness
degradation, and described using a linearly decaying function. The complete set of
interphase parameters is shown in Table 1. It was assumed that modes I and II can
Fig. 2 Traction separation

law; Energy release rate Gc;
Strength S; Stiffness K;
Displacement at damage
initiation Di; Displacement at
failure Df
Table 1 Cohesive zone parameters for the interphases (mode II)

Interphase Shear Shear sp3-bond Energy Damage initiation Failure
strength stiffness density* release rate displacement displacement
S [MPa] K [MPa/ f [%] GIIC[MPa nm] Di [nm] Df [nm]
nm]
A 30 20 – 50 1.5 3.333
B 30 100 – 50 0.3 3.333
C 30 100 – 150 0.3 10
D 30 100 – 100 0.3 6.667
E 90 100 – 150 0.9 3.333
F 120 100 – 150 1.2 2.5
G 30 180 – 50 0.167 3.333
O 5 10 0.00019 2.5 0.5 1
P 25 50 0.00097 12.5 0.5 1
Q 250 500 0.00966 125 0.5 1
R 2500 5000 0.09659 1250 0.5 1
*
In this work sp3-bond density f was calculated from G = G0f for the given shear stiffness
K (cases O-R) and the interwall thickness 0.34 nm, where G0 = 1760 GPa (see [6]) – values of
f in Table 1 correspond approximately to 1, 6, 58 and 580 sp3-bonds respectively
be separated. Moreover, shear strength, shear stiffness and energy release rate in
mode I were assumed to be twice as much of their counterparts in mode II, while
damage initiation displacement Di and failure displacement Df in mode I and mode
II were assumed to be of same value.
Parameters of the cohesive law were defined by considering results of molec-
ular and experimental studies reported in the literature, and a short summary is
given here. Ganesan et al. [10] estimated interfacial fracture energies between 50
and 250 MPa nm from pull-out experiments. A discrepancy can be found between
interfacial shear strength from molecular predictions and experiments. Molecular
simulation results predicted the interfacial shear strength for non-functionalised
CNTs within polymer to be around 2.7 MPa [9], while from pull-out experiments
shear strengths of *30 MPa for non-functionalised and *150 MPa for func-
tionalised MWCNTs were found [3]. Therefore, the shear strength value was
chosen to be based on the experimental investigation of Barber et al. [3]. Various
combinations of CNT–epoxy interphase are denoted by letters from A to G (see
Table 1). They are used to capture the shear strength range (*30–150 MPa) and
fracture energy range (*50–250 MPa nm), as described above.
In addition, short summary of properties for the CNT–CNT interwall bonding
reported in the literature is given as follows. Cumings and Zettl [8] estimated
through controlled and reversible telescopic extension of MWNTs using trans-
mission electron microscopy the static friction force per surface area of contact
smaller than 6.6 9 10-15 N/Å2 and the dynamic friction force per surface area of
contact smaller than 4.3 9 10-15 N/Å2. These values are negligible small and
correspond to an interwall shear strengths of around 0.5 MPa. In another experi-
mental work, it was shown that the interwall shear resistance can be enhanced
through irradiation of MWCNTs, which leads to sp3-bonds [17]. The grade of

irradiation may be reflected by the interwall sp3-bond density. It is also possible
that standard CVD provide MWCNTs with covalent sp3-bonding [1, 2]. Hence, the
range of shear stiffnesses reflect variations in the sp3 interwall bond density, which
is defined as the number of sp3-bonds divided by the number of carbon atom-pairs
in the DWCNT system [6] (see the footnote of Table 1). It is noteworthy to
mention that those sp3-bonds can damage the mechanical performance of CNTs.
However, no effect of the interwall bond density on the mechanical properties (i.e.
axial Young’s modulus) of the CNT walls was assumed in this work. Various
combinations of CNT–CNT interwall bonding are denoted by letters from O to R
(see Table 1).
The virtual crack closure technique (VCCT), which is based on assumptions of
linear elastic fracture mechanics (LEFM), was used to determine the total energy
release rate (TERR). According to this technique the work necessary to extend the
crack from a ? Da to a ? 2Da is the same as the work required to close the crack
from a ? Da to a (see Fig. 3). It is assumed that crack extension from a ? Da to
a ? 2Da does not significantly alter the total energy release rate [14]. Applied
tensile loads and model geometry imply that the total energy release rate is equal
to the mode I energy release rate GI, i.e. no mode II was assumed to be present
here. The computation was carried out at a post-processing stage, by calculating
the reaction force Fj2 at node j, the displacement gk2 of node k in x2 direction and
TERR at each increment of applied displacement:
F2j gk2
TERR ¼ : ð1Þ
pDað2RRVE 2a DaÞ
Fig. 3 Scheme of
computation of TERR
2.2 Results and Discussion
The effect of the epoxy/CNT interphase shear stiffness on TERR for different
combinations of interphase properties is shown in following Fig. 4. The first letter
(A-G) refers to properties (Table 1) of the CNT–epoxy interphase and the second
letter (O-R) corresponds to properties of the interwall phase. The composite TERR
is normalised against TERR of the same axisymmetric model made of unfilled
epoxy. The normalised TERR is then plotted as a function of applied strain to track
the evolution of the normalised TERR with the applied load.
The CNT–epoxy interphase shear stiffness significantly affected normalised
TERR at the beginning of strain until approximately 2 % of strain. In this range, a
higher value of shear stiffness produced a lower value of normalised TERR, which
is directly related to a lower intensity of the stress field around the matrix crack
tip—all this is caused by the increased stress transfer from the matrix to the
nanofiller. Hence, if the matrix crack is in the vicinity of functionalised CNT–
epoxy and sp3-bonded CNT–CNT interphases, the fracture parameter is reduced.
Then, all interphase combinations that possess the weakest interwall phase
(denoted by O) revealed a fracture parameter jump around 1 % of strain. Damage
initiated in the interwall phase at the start of the jump, and subsequently the first
cohesive zone element failed completely. Fracture propagation in the interwall
Fig. 4 Effect of CNT-epoxy interphase shear stiffness on TERR

phase continued (final failure of 60–70 % of the interwall phase) until the onset of
failure in a first cohesive zone element in the CNT–epoxy interphase. At that point
of around 0.02 applied nominal strain a local minimum of TERR was observed.
Then, as damage and failure progressed in the CNT–epoxy interphase, the slope of
TERR increased with increasing applied nominal strain. At larger applied strains
the normalised TERR tended to uniformity slightly above 1, because of full deb-
onding of the CNT–epoxy interphase, where the model behaves as an unfilled
epoxy. A value of 1 was passed at around 0.045 of applied strain, which lies out of
the investigated range in Fig. 4. At this level of strain around 80 % of the CNT–
epoxy interphase has failed.
It is noteworthy to mention that the graph reveals a nonlinear relationship
between the shear stiffness of CNT–epoxy interphase and fracture parameter
TERR. In particular, a significant decrease of energy release rate was achieved
from interphase A to B (AR and BR), no further significant decrease was found
from B to G (BR and GR). A similar saturation governs the effect of sp3-bond
density—a decrease of the fracture parameter was observed when increasing the
sp3-bond density from 0.00019 to 0.00097 %. Further increase did not provide
significant improvements. This is shown to be dominant at smaller magnitudes of
applied nominal strain.
The decrease in TERR, especially pronounced for BP, BR, GP and GR between
applied nominal strain values of 0.005 and 0.013, is probably caused by a stress
redistribution within the matrix at the CNT end. The constraints on the matrix at
the CNT end were relaxed due to the localized stiffness degradation of cohesive
elements. As a result further applied nominal strain primarily strained this matrix
region, while the rest of the model was hardly affected. Temporarily, this led to a
less pronounced increase of TERR for the composite. Normalisation with TERR of
pure epoxy resulted then in a local decrease of TERR. The less dominant reduction
of TERR with interphases of lower shear stiffnesses (AP, AQ, AR) would support
this explanation, because the matrix is less constrained in those cases.
Before fracture in the CNT–epoxy interphase occured, the sp3-bond density of
the interwall phase have had a larger effect on the energy release rate when
combined with stiff CNT–epoxy interphases. This combined effect was further
pronounced for BP, BR, GP and GR by a decrease of normalised TERR with
increasing strain between applied nominal strain magnitudes of 0.005 and 0.013.
The effect of the CNT–epoxy interphase shear strength on TERR is shown in
Fig. 5a. The interphase shear strength (considering only the mode II traction–
separation law) increased from 30 to 90 to 120 MPa for C, E and F respectively.
Again, according to the pull-out experiments of [3] 30 MPa corresponds to non-
functionalised CNTs and 120 MPa may correspond to functionalised CNTs.
It was found that the shear strength of the CNT–epoxy interphase affected
damage in the interwall phase—whereas for C, interwall damage/fracture occurred
only in combination with interwall phase O, the CNT–epoxy interphase E exhibited
interwall damage in combination with O and P. However, for visualisation purposes
curves that possess damage in the interwall phase are excluded in Fig. 5.
Fig. 5 Effect of a CNT–epoxy interphase shear strength and b CNT–epoxy fracture energy on
TERR
The graph shows, how the CNT–epoxy interphase shear strength influenced the
position and shape of the minimum. When increasing the CNT–epoxy interphase
shear strength, the minimum of TERR was compressed and shifted to larger strain
values. Significant improvements are visible from 30 to 90 MPa, but the difference
between 90 and 120 MPa is negligibly small, which suggests that there will be no
significant difference in the stress field near the crack tip. The larger applied strain
value localising the minimum was caused by the increase in interphase shear
strength that allowed the interphase to last longer. The smaller magnitude of the
minimum for larger interphase shear strength values (90, 120 MPa) can be
attributed to the larger stress that was carried by the CNT.
The effect of the CNT–epoxy interphase fracture energy on TERR is shown in
Fig. 5b. From interphase B to D to C the mode II interphase fracture energy
changed from 50 to 100 to 150 MPa nm respectively. The graph shows how the
CNT–epoxy interphase mode II fracture energy affected the normalized TERR at
later stages of strain due to the delay of failure in the CNT–epoxy interphase—
smaller values of the interphase fracture energy (associated with the smaller
separation at failure) resulted in an accelerated interphase damage propagation and
failure, thus causing an increase of stresses at the crack tip, and hence the increase
of TERR. For all interphase combinations, damage in the CNT–epoxy interphase
started at around 0.005 of applied strain. The start of failure was delayed from
1.8 % (BP) to 3.0 % (DP) and to 4.3 % (CP) of applied nominal strain with
increasing fracture energy. Additional increase in strain of 0.5 % led to a failure of

38 % (BP), 20 % (DP) and 14 % (CP) of the CNT–epoxy interphase. Enhancing
the fracture energy of the interphase from 50 to 100 MPa resulted in a significant
decrease of the fracture parameter between 0.015 and 0.03 of applied nominal
strain.
In summary, the cases studied above show that various combinations of CNT–
CNT and CNT–epoxy interphase properties lead to a reduction of stresses near the
tip of a stationary matrix crack when compared with pure epoxy. As expected, the
most efficient reduction of fracture parameter is caused by strong interphases,
which lead to an improved stress transfer from the matrix to CNTs, and hence to
reduction of stresses at the crack tip.
3 Prediction of Energy Absorption Characteristics

of Aligned CNT/Epoxy Nanocomposites Under
Compressive Loading
3.1 Modelling Approach
The ductility of epoxy in compression suggests that the energy absorption charac-
teristics of CNT/epoxy can be improved through a CNT-enhanced nonlinear
deformation of the matrix in zones undergoing compression. Hence, this study was
focused on the prediction of the compressive macroscopic stress–strain response of
the CNT/epoxy nanocomposite at strain rates ranging from quasi-static to impact
rates. In particular, the emphasis was on the effect of CNT aspect ratio and volume
fraction on energy absorption characteristics. An idealised aligned morphology of
CNTs was investigated in this work to obtain an initial insight into the rate-dependent
response of aligned CNT/epoxy nanocomposites. A rate-dependent constitutive
model for epoxy was implemented into a finite element (FE) framework, and com-
bined with the representative volume element (RVE) and numerical homogenisation.
Predictions of nanocomposite behaviour for different rates were compared with pure
epoxy, to demonstrate the effect of CNT aspect ratio and CNT volume fraction on
energy absorption characteristics of CNT/epoxy nanocomposites.
In order to capture the macroscopic response of the nanocomposite it was
assumed that the CNT morphology is globally periodic and that the macroscopic
deformation is uniform. This enabled the application of the RVE concept. A
simple axisymmetric RVE, including a single-walled CNT embedded in an epoxy
matrix, was proposed because of its simplicity. The single-walled CNT was
modelled as an effective continuum fibre in this work (see Fig. 6). The elastic
properties of the effective continuum CNTs were obtained by homogenizing dis-
eff
crete versions of CNTs. The effective Young’s modulus ECNT was derived based
on the axial CNT direction [21], as model and loading conditions used in this study
suggest that this is a good approximation, and it is given by:
2
eff 2RCNT TCNT TCNT
ECNT ¼ ECNT 2
; ð2Þ
RCNT
where RCNT is the CNT radius, TCNT is the CNT wall thickness and ECNT the
Young’s modulus of the CNT—based on a tubular cross section. A Young’s
modulus of ECNT = 3.36 TPa for a discrete CNT was used to obtain the effective
modulus of the homogenised CNT. This value is higher than commonly used, but
it was calculated using elastic shell theory for a smaller (than usual) wall thickness
i.e. TCNT = 0.1 nm and Poisson’s ratio of m = 0.2 [19]. The effective Young’s
modulus of homogenised CNTs was calculated as 133.056 GPa.
It is noteworthy to mention that different geometries of CNTs were compared
(discrete and effective, capped and uncapped) to investigate shape of CNT ending.
As a result, negligible differences were found for the stress–strain response of
RVEs simulated with (1) solid, homogenised isotropic CNT cylinder and (2)
discrete, tubular isotropic CNT cylinder exhibiting a circular cap at the CNT
ending (see Fig. 6).
Perfect bonding between CNTs and the matrix was assumed in this work.
Hence, a possible debonding and pull-out of CNTs from the matrix was excluded
as possible energy dissipation/absorption mechanisms. As a result, nonlinear
deformation of the epoxy matrix was expected to be the major cause of energy
absorption for the nanocomposite.
The non-linear and rate-dependent matrix behaviour was represented using a
physically-based constitutive model proposed and validated by Buckley et al. [5]
for thermosetting resins. The model accounts for the strain softening and adiabatic
Fig. 6 2D Axisymmetric RVEs for aligned CNT/epoxy nanocomposites

heating effect (active upon applied impact loads), and enabled capturing basic
phenomena of epoxy matrices subjected to varying strain rates. The mechanical
constitutive behaviour was implemented as a user subroutine UMAT (ABAQUS/
Standard), with the model parameters obtained by [4] for the standard bisphenol A
resin.
Matrix and CNTs were discretized using up to 3000 CAX8 (8-node biquadratic
axisymmetric quadrilateral) elements. Uniform displacement boundary conditions
were applied to the axisymmetric RVE in the y-direction, i.e. a uniform defor-
mation of the right edge in the x-direction was enforced by setting the corre-
sponding nodal displacements (right edge) as equal to the top right corner node of
the RVE (using the ABAQUS’ ‘*Equation’ command). The vertical movement of
the RVE was constrained at the bottom as shown in Fig. 6.
Then, the macroscopic true (Cauchy) stresses in the longitudinal direction were
predicted based on the sum of reaction forces and the current cross-sectional area
of the RVE. The normalized energy absorption was calculated as the ratio of areas
under the stress–strain curves for the nanocomposite and for pure epoxy up to
13 % of applied nominal strain.
3.2 Results and Discussion
Predicted compressive stress–strain curves and energy absorption characteristics of

CNT/epoxy nanocomposites subjected to different strain rates are shown and
discussed in this section. The CNT aspect ratio was changed by varying the CNT
length LCNT of the axisymmetric RVE. Variations in CNT volume fraction in the
axisymmetric CNT were obtained by changing the dimensions of the RVE with
LRVE-LCNT/2 = RRVE-RCNT. CNT volume fractions refer to a nanocomposite
composed of a hexagonal packing.
Effects of the CNT volume fraction (VF) and varying strain rates on the stress–
strain response are shown in Fig. 7. As expected, the incorporation of CNTs into
epoxy produced a considerable stiffening effect in the linear portion of the curve—
the Young’s modulus of the nanocomposite increased by around 15, 30, 46 and
77 % compared to pure epoxy for volume fractions of 0.5, 1, 1.5 and 2.5 %
respectively. Hence, CNT volume fraction exhibited almost a linear effect on the
Young’s modulus of the nanocomposite. As expected, no change in the nano-
composite Young modulus was predicted with increasing strain rate. This is
because the constitutive model for epoxy used in this work does not account for
the rate-dependent stiffness. However, experimental data across a wide range of
compressive strain rates for an RTM-6 epoxy system reported in [11] shows that
there is no significant change in Young’s modulus up to true strain rates *103 s-1.
The latter is greater than the maximum magnitude of nominal strain rates con-
sidered in this work, as the true strain rate e_ M is related to the applied (nominal)

strain e_ MðappÞ through e_ M ¼ e_ MðappÞ = 1 þ eMðappÞ
Fig. 7 Predicted stress–strain curves for pure epoxy and nanocomposites for different CNT
volume fractions VF and applied strain-rates; CNT aspect ratio AR = 50
The stiffening effect on the stress–strain response caused by the CNT volume
fraction continued beyond the elastic limit. In particular, for the given magnitude
of applied strain, a gradual increase in the macroscopic true stress with CNT
volume fraction was predicted, while the onset of nonlinear deformation was
shifted to a slightly lower value of applied strain with increasing CNT volume
fraction. In all cases a higher yield stress, defined here as the stress of the transition
zone between the elastic and nonlinear behaviour, was predicted, when compared
with the pure epoxy. The post-yield strain softening, which have been predicted
and validated experimentally for the pure epoxy [4], was no longer present mac-
roscopically for volume fractions equal to or greater than 1 %. Furthermore, an
increase in the CNT volume fraction resulted in an increased post-yield strain-
hardening effect.
Effects of CNT aspect ratio (AR) and varying strain rates on the stress–strain
response were also investigated (see Fig. 8). As expected, the predicted trends
were found to be in a qualitative agreement with the effects of varying CNT
volume fraction. However, quantitatively, only a slight increase of the nano-
composite modulus was predicted with increasing CNT aspect ratio within the
investigated range from 50 to 250. As indicated by different curves, the effect of
CNT aspect ratio on the stress–strain response tended to saturate with increasing
aspect ratio—less significant improvement of the overall stress–strain response
was obtained for aspect ratios greater than 100 within the simulated strain range.
However, in general there was an enhanced post-yield behaviour (increasing strain
stiffening) with increasing CNT aspect ratio, which suggests that energy absorp-
tion characteristic can be enhanced only at large deformations. Again, the major
contribution to that comes from the enhanced nonlinear deformation (strain stiff-
ening) of the matrix caused by the presence of CNTs.
Fig. 8 Predicted stress–strain curves for pure epoxy and nanocomposites (axisymmetric RVEs)
for different CNT aspect ratios AR and strain-rates; CNT volume fraction VF = 0.5 %
Hence, assuming that the energy absorbed by the material system can be rep-
resented by the area under the stress–strain curves, it is postulated that the
improved post-yield behaviour of the nanocomposite can largely contribute to the
improved energy absorption of the CNT/epoxy nanocomposite in compression.
This increase in energy absorption characteristics results from an enhanced non-
linear deformation (pronounced by strain stiffening) of the matrix, caused by the
presence of CNTs.
Therefore, normalised energy absorption characteristics were then evaluated
based on the compressive stress–strain curves. Areas under those curves were
evaluated up to strains of *13 %, both for the nanocomposites and matrix, at two
strain rates (1 9 10-3s-1 and 1 9 103s-1), and with different volume fractions
and aspect ratios. Our predictions are shown in Fig. 9, where generally, the nor-
malised energy absorption was enhanced due to the presence of CNTs at both
strain rates.
A significant correlation between CNT volume fraction and energy absorption
characteristics was found. An increase in CNT volume fraction contributed to a
considerable increase in normalised energy absorption under quasi-static loading
(1 9 10-3s-1). This was especially the case for CNT aspect ratios greater than
150. There exists a significant combined effect of CNT volume fraction and aspect
ratio. In comparison, predictions for a volume fraction of 0.5 % did not show such
a significant increase in the normalised energy absorption with increasing aspect
ratio than predictions for a volume fraction of 1.5 %.
In summary, our results suggest that CNTs can be used to enhance the nonlinear
response of epoxies under compression to improve their energy absorption char-
acteristics. The main contribution comes from the strain stiffening effect occurring
Fig. 9 Predicted normalised

energy absorption
characteristics as a function
of CNT aspect ratio and CNT
volume fraction for quasi-
static 1910-3 s-1 (a) and
high strain rates 19103 s-1
(b). The normalised energy
absorption characteristics at
the data points (crosses) were
used to determine the
coefficients of the nonlinear
regression functions via the
least squares method
in the post-yield regime. The effect is improved with the increasing CNT volume
fraction, which should be used for a carefully selected average CNT aspect ratio to
maximize the energy absorption of CNT/epoxy nanocomposites. Results of our
studies hold under the assumption that the nonlinear matrix deformation is the
primary energy absorption mechanism. However, future studies will include other
possible damage mechanisms such as debonding [20] and pull-out of CNTs from
the matrix, which will enhance our predictions of energy absorption.
4 Conclusions
Finite Energy absorption characteristics of CNT/epoxy nanocomposites were

investigated numerically in this work. In particular, computational studies were
performed to investigate the potential of aligned CNT/epoxy nanocomposites
towards structural energy absorption applications, as impact-resistant coatings for
advanced composite laminates. In particular, two case studies were investigated:
(1) crack resistance characteristics of the CNT/epoxy nanocomposites with aligned
double-walled CNTs (DWCNTs) in the vicinity of a matrix crack, and (2) rate-
dependent compressive response of CNT/epoxy systems with aligned single-
walled CNTs (SWCNTs). The findings of these studies can be summarized as
follows:
(1) The fracture parameter (total energy release rate) of a stationary matrix can
be significantly reduced due to the presence of a CNT. Furthermore, the value of
that fracture parameter depends on the properties of CNT–epoxy and CNT–CNT
interphases such as shear strength, shear stiffness and fracture energy. Whereas the
shear stiffness significantly reduced the fracture parameter at early stages of
applied strain, the interphase shear strength and fracture energy contributed to its
reduction at larger applied strains. Premature nanocomposite failure due to the
existence of matrix cracks may therefore be prevented through relevant func-
tionalisations. In particular, the reinforcement of epoxy with CNTs can reduce the
crack driving force and promote larger strains to failure while progressive damage
at the CNT–epoxy interphase takes place. This might be achieved through
enhancements of shear stiffness, shear strength and mode II fracture energy of
CNT–epoxy interphases via CNT functionalisation, and minor increases of low
sp3-bond densities in the interwall phase of DWCNTs.
(2) The compressive behaviour of epoxies can be significantly affected by the
presence of CNTs at different loading rates (from static to impact). In particular,
the initial stiffness and post-yield behaviour of nanocomposites were shown to be
influenced considerably by CNT volume fraction and aspect ratio. In both cases,
increased volume fraction and aspect ratio caused increased strain stiffening. This
led to increased area under the stress–strain curves, which suggests that energy
absorption in compression can be improved by addition of CNTs. The energy
absorption characteristics evaluated from the stress–strain curves were improved
with increasing CNT volume fraction and CNT aspect ratio, both for static and
impact rates. Additionally, a combined effect of CNT aspect ratio and CNT vol-
ume fraction on energy absorption characteristics was found. This suggests that the
average aspect ratio of CNTs should be carefully selected in order to maximise the
energy absorption for the given CNT volume fraction. Our ongoing work on
inclusion of interphase properties into the model will further improve our
description of energy absorption of CNT/epoxy nanocomposites, and give some
new insight into the effect of CNT functionalisation on the compressive response
of the nanocomposites across different strain rates.
Acknowledgments The project is supported by the Irish Research Council (IRC). Computa-
tional facilities and support are provided by the SFI/HEA Irish Centre for High-End Computing
(ICHEC).
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Silver Nanocluster/Silica Composite
Coatings Obtained by Sputtering
for Antibacterial Applications
Cristina Balagna, Sara Ferraris, Sergio Perero, Marta Miola,

Francesco Baino, Andrea Coggiola, Daniela Dolcino, Alfio Battiato,
Chiara Manfredotti, Ettore Vittone, Enrica Vernè
and Monica Ferraris
Abstract Bacterial contamination is a critical issue which concerns different

fields related to people and everyday life products and goods. Authors at
Politecnico di Torino developed a new silver nanocluster/silica composite coating
obtained by sputtering able to confer antibacterial properties to several materials.
Silver nanocluster/silica composite coatings were deposited by radio frequency
co-sputtering technique on glasses, ceramics, metals and polymers. The sputtering
method is extremely versatile and suitable for most of substrates, because it does
not require high temperatures which could decrease the mechanical properties of
coated materials (e.g. polymers). The main results will be discussed for each
coated substrate, in terms of characterization techniques, morphology, composi-
tion, antibacterial effect and adhesion to the substrate.
1 Introduction
1.1 Microbial Contamination in Different Fields
Materials with antibacterial properties are more and more requested in several
fields where the risk of microbial contamination is considered a relevant issue,
such as biomedical implants, agricultural/food industry, facilities in crowded
C. Balagna (&) S. Ferraris S. Perero M. Miola F. Baino E. Vernè M. Ferraris

Department of Applied Science and Technology, Institute of Materials Physics
and Engineering, Politecnico di Torino, Corso Duca degli Abruzzi 24 10129 Turin, Italy
A. Battiato C. Manfredotti E. Vittone
Experimental Physics Department/Centre of Excellence Nanostructured Interfaces and
Surfaces, University of Torino and INFN sez, Torino, Via P. Giuria 1 10125 Turin, Italy
A. Coggiola D. Dolcino
Azienda Ospedaliera SS. Antonio e Biagio e Cesare Arrigo, Via Venezia 16,
Alessandria, Italy

226 C. Balagna et al.
places (hospitals, public transportation systems), cell phones, personnel protective

systems as well as aerospace structures [1–3].
Bacterial contamination of surfaces is mainly related to the formation of bio-
film, a complex 3D structure of microorganisms and extracellular materials which
adheres to solid surfaces and makes bacteria more resistant to antimicrobial agents.
Biofilm formation includes the absorption of macromolecules on the surface,
bacterial cell adsorption and adhesion on the conditioned surface, bacterial pro-
duction of biopolymeric substances and cell signaling molecules, cell replication
and growth and bacteria production of polysaccharide matrix [4, 5]. Biofilm
represents a problem from different points of view, i.e. human health (infection
development), industrial processes and equipments (products contamination and
material damage). A brief review of bacterial contamination in different fields is
reported below.
1.1.1 Medical Implants
Implant-associated infection is a widely discussed and studied topic in the medical

field. Despite of systemic antibiotic prophylaxis and special antiseptic operative
procedures, the problem is not completely solved. The development of an infection
can lead to implant failure and need for its removal. The presence of an artificial
material within the body increases the susceptibility to infections. The patient
immune system results compromised and the implant surface constitutes a pref-
erential site for bacterial adhesion. Moreover bacterial susceptibility to antimi-
crobials is reduced in presence of an artificial material [6–10]. The physical–
chemical properties of the implant surface (e.g. roughness, charge, chemical
composition) affect the initial proteins absorption and consequently bacterial
adhesion as well as the biofilm formation [6, 7, 9]. Microbial contamination and
biofilm formation can affect different materials for medical implants, mainly
metals for orthopedic and dental applications [6–8] and polymers for catheters and
abdominal wall repair prostheses [9, 10]. Bacterial contamination issues in oph-
thalmic applications, such as eye surgery and implants, can give significant clinical
problems together with the need for post-surgical additional treatments, both
expensive and stressful for patients.
1.1.2 Home
Microbial contamination of the household environment has recently been reviewed

[11]. Staphylococcus aureus and other staphylococci have been found in different
household areas and surfaces: the kitchen (working surfaces, sink, refrigerator and
sponges), the toilet (cabinet top or shelves, hand towels and taps) the bedroom
(pillows and bedding) but also on toys, television, remote controls, telephones,
door knobs and carpets [11]. The main sources for bacterial contamination have
been individuated as people, animals and environment.
Silver Nanocluster/Silica Composite Coatings Obtained by Sputtering 227
1.1.3 Aerospace
Microbial contamination in space missions is generally limited and maintained

below strict, high quality standard thanks to specific prevention and monitoring
strategies. However it constitutes an extremely tricky topic because of the ham-
pered immune system of the astronauts (due to high working pressure, defined diet,
restricted hygienic practices, microgravity and radiation) [12]. The main bacterial
sources are humans and the contamination can interest air, surfaces, water and
food [13, 14]. As far as surfaces are concerned, microorganisms can adhere onto
materials and then form a structured and resistant biofilm. In space structures
surface bacterial contamination is minimized before the flight start by means of
different surface treatments (e.g. heat, radiation, chemicals) depending on the
material resistance characteristics. In flight contaminations are reduced by using
disinfectant wipes based on quaternary ammonium compounds or a mixture of
quaternary ammonium compounds and hydrogen peroxide. The repeated failure of
the disinfection process may cause the replacement of the contaminated surfaces/
components [12].
1.1.4 Food
Bacterial contamination of food from processing and handling is an extremely

critical issue. In particular for products that cannot undergo any antibacterial
treatment before consumption, such as cheese, they can be the cause of poison, as
reported in the literature [15]. In these case, bacteria can come from the raw milk,
milking machines, farm environment, cheese processing plants and also from
operators [15–17]. The basic rule for prevention of contamination is based on an
effective cleaning and disinfection program (including removal of all residuals
from the surface, application of detergents and disinfectants, removal of all traces
of cleaning products) and an equipment design easy for cleaning (free of dead
ends, corners or cracks and preferably made of stainless steel) [5].
1.2 Silver as Antibacterial Agent
Silver is the most known and documented antimicrobial agent and its powerful
action can be expressed in several forms as metallic film/layer, nanoparticles and
ions [18, 19].
Silver ions (Ag+) can bind to different specific chemical sites (characterized by
thiol groups) causing inactivation and cell death. For example Ag+ can bind to
proteins altering their structure and cause the rupture of cell walls, or to enzymes
preventing their function, or to DNA interfering with cell division and replication
[18, 20].
The antimicrobial properties of silver nanoparticles can be related to their

extremely high surface area that provide silver release. Moreover nanoparticles
can directly attach to the cell surface or enter the cell causing membrane rupture
and cell damage [18]. The formation of pits on the cell wall and the alteration of
cellular structures and function have been documented both for Gram negative
[21] and Gram positive [22] bacteria. It has been observed that the antibacterial
activity of silver nanoparticles depends both on their dimensions and shape [18].
Thanks to the multiplicity of action routes, a reduced resistance development
has been documented for silver in comparison to common antibiotics.
The bactericidal effect of silver has been widely employed in the treatment of
burns, wounds and infection and also in the water purification [18]. Different forms
of silver (e.g. silver nitrate, sulfadiazine, metallic silver) have been considered for
these purposes.
Recently, an increasing interest in silver nanoparticles has been observed [18]
and numerous antibacterial products based on nano-silver can be found [23]. They
include medical devices (masks, tubes, catheters, fillers, diagnosis tools, coat-
ings…), personal care and cosmetics products, textiles and shoes, electronic
devices and domestic appliances (refrigerators, washing machines, mobile
phones…), household products (antibacterial surfaces, paints and cleaning prod-
ucts), filtration devices, food handling and production tools [23]. This widespread
use of nano-sized silver can lead to different routes of exposure to nano-Ag
(mainly inhalation, dermal and oral contact) with possible long-term toxic effects,
due to the exposition to free ion and silver nanoparticles [23].
1.3 Techniques to Obtain Silver-based Coatings
Silver-related antibacterial properties can be conferred to glasses, ceramics, metals

and polymers by means of several techniques such as: absorption on zeolites or in
silica microsphere [24–26], Ag embedding in polymers [27], ion-exchange on Na+/
K+ based glasses [28–36], chemical vapor deposition (CVD) [37, 38], sol gel [27,
40–45], sputtering [46, 47] etc.
Advantages and disadvantages of each technique are listed in Table 1.
Sputtering is one of the most versatile coating methods, suitable for most
substrates, because it does not need high temperatures during process, which could
decrease the mechanical and thermal properties of materials to be coated (e.g.
polymers) [47].
The sputtering technique consists in extracting from a bulk material (target)
some atoms/molecules or clusters of atoms/molecules and deposit them on the
substrate. All the process is performed in vacuum.
Sputtering is one of the most common coating technique and there are several
literature references that describe in details technology and equipments [55].
Nowadays sputtering is widely diffused in industrial processes also because it can
be merged in the industrial process flow as an in-line production technology.
Table 1 Comparison among different techniques suitable to provide antibacterial coatings
Method Process PROs CONs Ref.
Ag doped zeolites or Ag+ absorption on zeolites Low cost, industrial Ag doped zeolites and silica [24–26]
silica microspheres or silica microsphere products microspheres
available, suitable to must be embedded in a
coat matrix to obtain
large surfaces a coating
Low thermo-mechanical
properties of
the polymer matrix
Ag embedded in polymers Ag particles embedded in Low cost, industrial Limited mechanical and [27]
polymers products available, thermal Stability
or synthesis of polymer suitable to coat large due to polymers
containing Ag ions surfaces and
to large scale production
Silver Ionic-exchange Ag +/Na + or Ag +/ Low cost, industrial Suitable only for glasses [28–36]
on glasses K + Ion-exchange products available, containing
on glasses containing suitable to coat large K + or Na +
Na + or K+ surfaces and
to large scale production
Chemical Vapour Reaction of volatile No chemical solution Limited number of suitable [37, 38]
Deposition precursors on the manipulation and waste precursors.
(CVD) of silver or silver substrate in a reaction solution production Expensive technique
Silver Nanocluster/Silica Composite Coatings Obtained by Sputtering
doped coatings chamber, No needing of special and

in vacuum expensive precursor gas
and related
industrial equipments
(continued)
229
Table 1 (continued)
230
Method Process PROs CONs Ref.

Sol gel deposition of Mixing, stirring, gelation Cheap process, suitable for Thermal treatment needed [27, 40–45]
silver doped coatings and drying large scale production for drying and
of organic and inorganic stabilization
precursors containing Time consuming process
silver Possible cracks on the
coating after drying
Sputtering of silver Atomic clusters deposition Suitable for large scale High initial costs for the [46, 47]
or silver doped from a bulk target to the production. sputtering equipment
coatings desired substrate in a Suitable for almost every Substrates must resist
vacuum chamber substrate. under vacuum
Quick, one step process
STOBER method Mixing, stirring, filtering Coating production in one Limited mechanical and [48–50]
and drying of silica and step process. thermal stability due to
silver nanoparticle Easy scaling up process the polymer matrix
precursors, which are Suitable to coat large
then dispersed in a surfaces
suitable carrier
(polymeric) to be used
as coating
MELTING of Ag doped Mixing, melting and Coating in one step process. Unsuitable to coat polymers [28, 39]
glasses pouring of raw High thermal resistance.
materials. Glass bulk/ Suitable for large scale
frit that can be used to production
coat surfaces by a
second process
PAINTING with silver Silver doped polymeric- Suitable to every substrate Suitable only for low [51–54]
doped paints based paints temperature
applications.
Low thermal/chemical/
mechanical stability of
C. Balagna et al.
polymeric paint
In order to obtain antibacterial layers with high thermal, chemical and

mechanical stability ideally on every class of materials, co–sputtering is the pre-
ferred technique [56–63]. For the preparation of silver nanocluster/silica coatings,
two different targets are used at the same time to obtain a composite material with
Ag nanoparticles embedded in a matrix. Modifying the power density applied to
the targets and/or the deposition time, it is possible to tailor the Ag content in the
silica matrix, therefore the coating antibacterial properties, characteristic that is
mandatory for most applications.
2 A New Approach to Confer Antibacterial Properties

to Materials: Sputtering Deposition of Silver
Nanocluster/Silica Composite Coatings onto Several
Substrates
A new approach was developed by authors from Politecnico di Torino [56] to

confer antibacterial power to glasses, ceramics, metals and polymers for different
applications [64, 65]. Silver nanocluster/silica composite coatings were deposited
onto the substrates by means of radio frequency (RF) co-sputtering technique using
two targets, a silica one and a silver one, both placed in the sputtering chamber [56–
63]. The antibacterial silver nanoclusters are well embedded into the silica matrix
which provides good mechanical and thermal resistance together with a suitable
release of silver ions. These coatings allow the reduction of the silver amount and
thereby the risk of toxicity, if compared with pure silver coatings [23, 66]. As
discussed in the introduction, the sputtering technique is a method easy-fitting to all
the classes of materials as the process parameters (deposition time, power on the
targets, pressure, pre-treatment of the samples) can be properly set as a function of
the substrate and the final application. In particular some properties of the coatings,
such as the thickness and the total silver content, could be increased with the
deposition time. The optimization of the silver amount is of primary importance,
especially for materials whose applications are in direct contact with human organs
and tissues, where the risk of a cytotoxic effects is enhanced.
Generally, the temperature reached in sputtering chamber is quite low (maxi-
mum 80 C, even lower with systems for cooling the substrate). This temperature,
or in some case the exposures to high temperatures during sputtering can damage
thermo-sensitive substrates, such as polymers. For these materials, short sputtering
treatments have been optimized. Figure 1 summarizes the influence of the sput-
tering deposition time on the coating characteristics.
In the following sections, an overview about the main techniques for the
characterization and the deposition of silver nanocluster/silica composite coatings
on several substrates will be presented. The materials (silica and sodalime glasses,
different polymers and steel) were chosen because of their suitability for different
applications, from the food industry to biomedical implants, aerospace structures
and personal protective systems.
Fig. 1 Schematic representation of the influence of deposition time on silver amount in the
coating and its effects
2.1 Characterizations and Analysis
There are many different techniques that can be used for characterizing thin films;
the most commonly used in this research are shortly presented below.
Spectroscopy techniques, such as electron dispersive spectroscopy (EDS) and
X-ray photoelectron spectroscopy (XPS), allowed the identification of the coating
composition by measuring the Ag/Si ratio, whereas the size of silver nanoclusters
can be directly observed by transmission electron microscope (TEM) or, indi-
rectly, by UV–visible absorption spectroscopy (UV–Vis), by measuring the
Localized Surface Plasmon Resonance (LSPR). The presence of metallic silver
nanoclusters and/or other crystalline phases was detected by means of X-ray
diffraction (XRD).
The morphology of the coating was studied and analyzed by means of field
emission scanning electron microscopy (FESEM).
The antibacterial behavior of the silver nanocluster/silica composite coating
was verified through the inhibition zone evaluation towards Staphylococcus aureus
strain, a Gram-positive bacteria in accordance with the National Committee for
Clinical Laboratory (NCCLS) [67]. In other specific cases, different bacteria
strains as Gram positive (Bacillus cereus) and Gram negative (Morganella,
Klebsiella pneumonite, Escherichia coli) were tested.
Finally, the mechanical behavior was evaluated in terms of adhesion of the
coating to the substrate through tape test according to the ASTM D3359–97
standard [68] and nanohardness by means of nanoindentation test.
Some thermal treatments were performed in order to control the effect of the
temperature on the coating properties.
2.2 Silver Nanocluster/Silica Composite Coatings on Silica

and Sodalime
Silver nanocluster/silica composite coatings were deposited on silica (SiO2) and

sodalime (SL) glass substrates [57, 58, 61]. The coated substrates have been heated
from 150 to 600 C in order to control the effect of heat treatments on their
properties.
Figure 2 shows the as deposited (AS DEP) and thermal treated (450 C) (TT
450 C) coatings on silica (SiO2) and sodalime (SL) substrates. The coating
thickness ranges from 50 to 300 nm.
The typical brown color of the coating is due to the silver nanoclusters
embedded into the silica matrix [57, 58]. The higher is the coating thickness, and
so the silver amount, the darker is the deposited layer (as in the case of SiO2,
coated by a 300 nm layer). On the other hand, the thermal treatment tends to
bleach the coating. This modification is correlated with an enlargement of na-
noclusters size [57, 58] as confirmed by FESEM and XRD in Fig. 3 (with per-
mission of [58]) and by UV–visible absorption spectra (Fig. 4).
FESEM in Fig. 3 shows the morphology of the coating surfaces, as deposited
(a) and after thermal treatment at 150 C (c), 300 C (e), 450 C (g), and 600 C
(i), on silica substrate [58].
The typical porous structure of the sputtered layers is observable in the as
deposited coating (Fig. 3a). The coating becomes gradually more compact and the
silver nanoclusters, visible as bright dots, decrease in number but enlarge in
dimensions with the increase of thermal treatment temperatures. In fact, the
nanocluster size ranges from less than 7 nm (as deposited coating) to about
20–60 nm (thermally treated coating). It was observed that a treatment from 500 to
800 C decreases the porosity of silica containing silver nanoparticles [69]. In
addition, the XRD patterns in Fig. 3b, d, f, h, l relative to the same samples show
the presence of a broad diffraction band due to the silica substrate and two peaks
due to metallic silver. A gradual increase of silver peaks intensity is directly
influenced by the increment of the treatment temperature.
Figure 4 shows the comparison of UV–visible spectra of coatings on SiO2 and
SL substrates, as-deposited and thermally treated at 450 C. An absorption peak
due to the well-known Localized Surface Plasmon Resonance (LSPR) absorption
of metal silver nanoclusters [61, 70].
Fig. 2 Silver nanocluster/

silica composite layer on
silica (SiO2) and sodalime SL
substrates, as deposited (AS
DEP) and after a thermal
treatment at 450 C (TT
450 C)
Fig. 3 FESEM images and XRD spectra of as deposited silver nanocluster/silica composite
coatings on silica (a, b) and after thermal treatment at: 150 C (c, d), 300 C (e, f), 450 C (g, h),
and 600 C (i, l) (with permission of [58])
Fig. 4 Comparison of UV–Vis absorption spectra of silver nanocluster/silica composite

coatings, as-deposited and treated at 450 C, on silica (SiO2) and soda lime SL substrates. The
uncoated substrates are reported for comparison purposes
In particular, the absorption peak at 414 nm obtained from the silver nano-
cluster/silica composites sputtered on silica substrates, increases from the as
deposited coating to the one treated at 450 C [57]. Both scattering and SPR effects
were produced from the silver nanoclusters embedded into a matrix. The prevalence
of the first or second effects depends on the nanoclusters dimension. The dark color
brown color of the coated samples, noticed in Fig. 2, is a consequence of the
scattering in the case of small nanoclusters. When the nanocluster dimension size
enlarges, the LSPR shifts to at 420 nm of wavelength and increases the absorption,
with a generating bleaching effect resulting in a yellow/orange color.
On the contrary, the curves of coatings deposited on soda-lime glass show a
shift of the absorption peak from 403 to 423 nm, and a decrement in intensity from
the as-deposited coating to the treated one. Elemental depth profiles obtained by
ERDA (Elastic Recoil Detection Analysis) have evidenced, in the case of SL an
effective ionic exchange between Na+ of the substrate and Ag+ of the silver
nanocluster/silica composite coating during thermal treatment [61].
The antibacterial activity of the silver nanocluster/silica composite coating,
tested towards Staphylococcus aureus strain, is observable in Fig. 5. A well visible
inhibition halo of about 4–5 mm is formed around the as deposited coating on
silica substrate. The halo results slightly reduced after the thermal treatment at
450 C. The silver nanoparticles with smaller size have a higher antibacterial
Fig. 5 Antibacterial halo

against S. aureus for the
silver nanocluster/silica
composite coatings, as-
deposited AS DEP and treated
at 450 C (TT 450 C), on
silica (SiO2) and sodalime SL
substrates
behavior because of their larger surface area. When the nanocluster size increases
with the temperature, the antimicrobial efficiency is consequently reduced.
The antibacterial coating deposited on the SL substrate is able to form a very
thin halo of about 1 mm in the case of the as deposited layer. The inhibition zone
around the sample treated at 450 C, is not visible, but the bacteria are not able to
proliferate under it. This different behavior of the two substrates is a direct con-
sequence of the ionic exchange process which occurs between Ag and Na ions of
the sputtered coatings and the soda-lime substrate. The amount of silver is reduced
after ionic-exchange on the coating surface and consequently the antibacterial
power decreases, as discussed previously and in [61, 71].
Another relevant feature to be considered is the adhesion of the coating to the
substrate. The silver nanocluster/silica composite coatings, as deposited and after
the treatment at 450 C, show good cohesion and adhesion to both the considered
substrates (silica [57, 58] and soda-lime [61]). As reported in Fig. 6, no sign of
macroscopic damage or detachment is noticed on the coatings. All the samples can
be classified as 5B (0 % damage) according to ASTM D3359 standard [68] .
The nano-mechanical properties of the coatings before and after thermal
treatment in terms of hardness (Fig. 7 with permission of [61]) and reduced
modulus were tested by nano-indentation tests and compared with those of the
substrates (silica or sodalime glasses). The indentation depth and the maximum
applied load were chosen at 30 or 50 nm and 1 or 5 mN, respectively. The thermal
treatment performed at 450 C significantly improves the hardness of the coating
deposited on the silica substrate (Fig. 7a). Consistently, an opposite effect occurs
with the heated coating deposited on the sodalime substrate (Fig. 7b) in agreement
with the above discussed Na/Ag ionic exchange [61]. The ionic exchange
increases the amount of Na+ which acts as a modifier for the silica matrix of the
coating, thereby reducing the coating mechanical properties [61].
Similar effect has been observed for the reduced modulus which is related to the
coatings Young modulus [61, 72, 73].
Fig. 6 Silver nanocluster/

silica composite coating as-
deposited (AS DEP) and
treated at 450 C (TT
450 C) on silica (SiO2) and
sodalime SL after tape test
(ASTM D3359): the coating
is still well adhered on the
substrates after removal of
the tape
Fig. 7 Hardness of silver nanocluster/silica composite layers on silica a and soda-lime

b substrates, as deposited and after thermal treatment at 450 C (with permission of [61])
2.3 Silver Nanocluster/Silica Composite Coatings

on Polymers
The same co-sputtering technique have been applied to several polymeric sub-
strates, taking into account the limited thermal resistance of some of them
(Table 2).
The thickness of the silver nanocluster/silica composite coating, as previously
discussed, is optimized for each substrate after several preliminary tests according
to the polymer thermo-mechanical resistance and final application. As an example,
an antibacterial coating for a polymer to be used for biomedical implants such as
PP or PMMA, has to be carefully controlled in terms of silver amount in order to
avoid eventual toxicity due to silver release.
The surface of sputtered PMMA (Fig. 8a) was investigated by FESEM,
revealing a porous morphology typical of sputtered silica with Ag nanoclusters
visible as bright spots (Fig. 8b). EDS (Fig. 8c) confirms the composite nature of
the sputtered coating, showing the presence of Ag, Si and oxygen with Ag/Si
atomic ratio of about 0.3.
Table 2 Silver nanocluster/silica composite coatings on several polymeric substrates

Polymer Composition Application Antibacterial
coating
thickness (nm)

Combitherm Multilayer co-extruded film Air bladder for 60
composed of EVOH, PA aerospace
and PE inflatable
modulus
Kevlar fabric Aramidic fibers Aerospace inflatable 300
modulus
Personal protective 50
systems
Nylon film Polyamide Parachute 50
Polypropylene film PP Biomedical implant 60
Polyurethane film PU Biomedical implant 150
Poly(methylmethacrylate) PMMA Biomedical implant 50
(flat substrate)
Fig. 8 Silver nanocluster/silica composite coatings sputtered onto PMMA substrates: a appear-
ance of the coated sample, b FESEM micrograph of the deposited layer (magnification
900000 9), c EDS of the layer
Combitherm film is currently used for food packaging, but also for the air
bladder layer in the aerospace inflatable modulus of the International Space Station
[74, 75].
Figure 9 shows the visual appearance of the Combitherm film before (a) and
after (b) the deposition of silver nanocluster/silica composite coating with a
thickness of about 60 nm. Since the substrate has a low thermal resistance com-
pared to inorganic substrates, a deposition time of only 15 min was chosen to
avoid any damage [60].
The typical brown color of the coating is present also on this substrate, as
discussed before, and reported in [60] where the LSPR typical of the silver
nanoclusters was detected at about 414 nm.
As discussed in the introduction, different kinds of bacteria were discovered
into the International Space Station after long-term missions. For this purpose,
several bacterial species, both Gram positive (Staphylococcus aureus, Bacillus
cereus) and Gram negative (Morganella, Klebsiella pneumoniae and Escherichia
coli), were used for evaluating the antibacterial activity of the silver nanocluster/

Fig. 9 Combitherm film a before and b after the silver nanocluster/silica composite coating
deposition
silica composite coating deposited on the Combitherm substrate. The formed

inhibition halos towards all the chosen bacteria are reported in Fig. 10. The
dimension and morphology of the halo is strongly affected by the sensitivity of the
bacteria strain to silver ions and the structure of their cell wall [76]. The effec-
tiveness of silver ions on E. coli and B. cereus is more evident and a halo of about
2–3 mm is formed around these samples.
As discussed in [60], the most relevant features, i.e. mechanical properties and
air permeability, of the Combitherm for aerospace applications are not signifi-
cantly affected by the antibacterial coating. The transmission rate and permeability
to air remained unchanged and equal to about 14 ml/m2*day and 2 ml*mm/
m2*day*atm, respectively, for the uncoated and coated substrate [60]. Some tested
mechanical properties such as tensile strength and perforation were improved by
the presence of the coating; the tear resistance was not altered after coating [60].
However, the coating was gradually removed during an abrasion test against an
aramidic fabric until the complete elimination after 3,000–5,000 cycles.
Some textiles, such as mimetic aramidic fibers, polyamide and activated carbon
fiber textiles (Fig. 11), have been coated by the antibacterial silver nanocluster/
silica composite layer. The brownish color typical of the antibacterial coating is
not visible on these substrates because of their original color.
Fig. 10 Inhibition halo test against different bacteria of the silver nanocluster/silica composite
coating deposited on Combitherm substrates
Fig. 11 Some textiles coated by silver nanocluster/silica composite coating: a mimetic aramidic
fibers, b polyamide and c activated carbon fiber textiles
However, a pale yellow aramidic fabric becomes darker after the coating
deposition as reported in Fig. 12, for the same reasons discussed in Sect. 2.2
The antibacterial activity and the unchanged mechanical properties of these
textiles after coating deposition have been demonstrated.
2.4 Silver Nanocluster/Silica Composite Coatings on Metals
The sputtering technique has been successfully used to obtain silver nanocluster/
silica composite coatings on metals (aluminum and steel) for different applications
such as food handling industry and space applications.
Figure 13 shows the antibacterial coating deposited on stainless steel before (a)
and after thermal treatment at 450 C (b). The morphology of the sputtered silver
nanocluster/silica coating is the same as reported in [57, 58] with silver
Fig. 12 Aramidic fabric a before and b after antibacterial coating deposition

Fig. 13 Silver nanocluster/silica composite coatings as deposited a and after thermal treatment
at 450 C b on a steel substrate
nanoclusters well embedded in the sputtered silica matrix. The effect of the
thermal treatment, with the increase of nanoclusters size and the consequent
chromatic change, occurs also for these samples, similarly to what observed for the
silica substrates. Moreover a significant improvement in the adhesion and cohesion
of the coating have been measured after the heating, due to a further densification
of the composite coating, as reported in [57] for thermal treated coatings on silica
substrates.
Figure 14 reports inhibition halos against S. aureus for as deposited and ther-
mally treated samples. The antibacterial behavior is evident for the as deposited
samples (at about 5 mm halo) and still present after heating at 450 C (about
1 mm halo).
These results are in accordance with those obtained for coated silica substrate
and confirm the ability of this coating to retain its antibacterial effect after being
heated at 450 C, also on steel substrates.
Silver nanocluster/silica composite coating depositions on aluminum alloys for
aerospace application have also been considered in order to prevent bacterial
contamination. Sputtered aluminum tiles have been tested in two international
experiments. The first one, MARS 500, is an international experiment in which
crewmembers stayed 520 days in a confined environment, simulating the travel to
Mars [77]. The second one (VIABLE) is an activity on the International Space
Fig. 14 Inhibition halo

against S. aureus for as
deposited a and heated
antibacterial silver
nanocluster/silica composite
coatings b (450 C) on
stainless steel
Fig. 15 Silver nanocluster/silica composite coating on aluminum alloys for space application in
the MARS 500 experiment
Station, actually ongoing: it will last 4 years and, together with other scientific
activity, will compare the behavior of different surface treatments and coatings
against bacterial contamination [78]. In both cases the bacterial biofilm formation
on the different surfaces is under investigation.
Figure 15 reports the different tiles under testing. In the fourth row (evidenced
in red) the silver nanocluster/silica composite coating on aluminum tiles. Results
of both tests are under evaluation.
3 Summary and Future Trends
A new antibacterial silver nanocluster/silica composite coating was successfully

deposited on glasses, metals and polymers by co-sputtering technique. The coating
thickness and the amount of silver was easily modulated by sputtering deposition
parameters, according to the substrate properties and final application. The coating
has a brownish color due to the presence of silver nanoclusters which resulted well
embedded in the silica matrix with a typical nano-structured morphology. Nano-
cluster size and coating color could be modified by means of appropriate thermal
treatments. Coating bleaching and increase of the clusters size occur with the
increment of heating treatment. The antibacterial activity against S. aureus and
other bacterial strains was widely demonstrated with the formation of a well-
visible inhibition halo on all coated substrates. The adhesion of the antibacterial
coating resulted satisfactory with all the substrates.
The new silver nanocluster/silica composite coating exhibit an intrinsic

advantage with respect to other antibacterial coatings:
-being silver antibacterial agent different from antibiotics, no development of
bacterial resistance that could compromise the efficiency of the antibacterial effect,
are expected to occur.
-it is possible to tailor the silver content by varying the co-sputtering param-
eters. In such a way it is possible to design the antibacterial effect in terms of both
efficiency (amount of released silver) and life-time (release kinetic of silver).
-thermal and mechanical resistance of the coating is higher than those of
polymer-based alternatives: the antibacterial effect of this coating it has been
demonstrated up to 450 C.
-RF sputtering technique is potentially applicable to substrates with irregular or
curved geometries
A crucial issue to be investigated is the durability of the composite coating after
prolonged contact with biological fluids; in order to overcome this problem,
materials with higher stability in wet environment than silica in the biological
environment will be tested in the future, as suggested in [62] by the authors.
Another aspect deserving accurate investigation is the assessment of the form
and amount of released Ag. Early studies seem to suggest that Ag is released from
the nanoclusters in ionic form rather than as nanoparticles: this is a very significant
characteristic of these coatings, since several in vitro and in vivo studies dem-
onstrated the toxicity of metal nanoparticles [79, 80].
Acknowledgments This activity was funded by Regione Piemonte, Italy (NABLA, Nano-
structured Antibacterial Layers) and by REA (EU Project-NASLA-FP7-SME-2010-1—Project
262209).
The authors kindly acknowledge Dr Giacomo Fucale (Traumatology Orthopaedics and
Occupational Medicine Department, University of Turin, Italy) for antibacterial tests facilities,
and all industrial partners of the projects (Thales Alenia Space—IT, Dipromed, Alce Calidad,
Easreth, Aero Sekur, Reply, KTH Royal Institute of Technology, Bactiguard).
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Recent Advances on the Utilization
of Nanoclays and Organophosphorus
Compounds in Polyurethane Foams
for Increasing Flame Retardancy
Javier C. Quagliano, Victor M. Wittemberg

and Irma C. Gavilán García
Abstract Recent advances on fire retardants utilized in polyurethane foams were

reviewed, mainly focusing on organophosphorus compounds. The application of
nanotechnology for developing novel fire retarded nanocomposites is discussed as
well, focusing in the addition of nanoclays to polyurethanes. The review is focused
on flame retardants known or believed by the authors to be in actual use at the time
of writing, without expanding on recent proprietary or patented information.
Although fire retarded nanocomposite is an increasing area of research, still market
utilization is to be developed.
1 Introduction
All organic polymers are combustible. They decompose when exposed to heat,
decomposition products burn, smoke is generated, and the products of combustion
are highly toxic, even if only CO and CO2 [24]. The use of flame retardants to
J. C. Quagliano (&)
Organic Synthesis Division, Applied Chemistry Department, Instituto de Investigaciones
Científicas y Técnicas para la Defensa (CITEDEF), Avenue Juan Bautista de Lasalle 4397
B1603ALO Buenos Aires, Argentina
V. M. Wittemberg
Analytical Chemistry Division, Applied Chemistry Department, Instituto de Investigaciones
Científicas y Técnicas para la Defensa (CITEDEF), Avenue Juan Bautista de Lasalle 4397
B1603ALO Buenos Aires, Argentina
I. C. Gavilán García
Faculty of Chemistry, National Autonomous University of Mexico (UNAM), Mexico,
Mexico

250 J. C. Quagliano et al.
reduce the flammability of polymers and production of smoke or toxic products

during their combustion has become an important aspect of the research, devel-
opment, and application of new materials. Among polymers, cellular materials like
polyurethanes possess a high surface area per unit mass and this resulted in almost
complete pyrolysis of combustible matter [20]. Polyurethanes, in the absence of
flame retardants, are extremely combustible.
There are four main chemical groupings of flame retardants. These are inor-
ganics (e.g. aluminum trioxide and magnesium hydroxide), nitrogen-based
organic, organophosphorus (e.g. phosphate esters), and halogenated flame retar-
dants [3]. Considering a broader range of applications as with plastics and textiles,
fire retardants fall into several distinct classes (1) alumina trihydrate (2) haloge-
nated compounds usually used in combination with antimony oxide (3) borax and
boric acid and (4) the phosphorus nitrogen and phosphorus halogen compounds
[25]. Respect to their reactivity with polymers, fire retardants are classified in
reactive and additive. Polyurethane foam is one area where phosphorus flame
retardants are often used due to their effectiveness [44].
Recently, nanotechnology has been described as the next great frontier of
materials research because nanocomposite formation brings about improved mate-
rial performance, including enhanced mechanical, thermal, optical, dimensional,
and barrier performance properties [14]. This technology has also been developed
for polyurethanes. Regarding fire retardancy, polyurethane nanocomposite prepa-
ration methods were reviewed, including characterization of the composites, thermal
stability and combustion behaviour [9, 22, 43].
2 Fire Retardants in Polyurethanes
Because of the banning of pentabromodiphenyl ether (PBDE) in Europe and vol-

untary withdrawal of this product from the market in the US, the polyurethane (PU)
industry is searching for a more environmentally acceptable low-scorch alternative.
For polyurethane foams, the most commonly used flame retardants include chlo-
rinated phosphate esters that provide cost-effective performance at a significant
disadvantage in thermal resistance (scorch resistance) [26]. Also a mixture of an
alkyl tetrabromobenzoate and a triaryl phosphate has been used commercially for
the purpose of avoiding scorch. Both halogenated and halogen-free solutions are
being considered but the PU industry now seems to have a preference for the
halogen-free products, generally containing phosphorus [18]. Progress in flame
retardancy of polyurethane and polyisocyanurate foams was also reviewed by
Levchik and Weil [17, 19]. Major progress in the area of flame-retardant PUs in
recent years is found in the field of phosphorus- or silicon-containing products,
especially reactive ones. Inorganic additives remain of great interest, especially in
PU-based intumescent coatings [40].
Organophosphorus compounds have a long history of use as fire retardant in
polymers in general and particularly polyurethanes. Since the advent of polyvinyl
Recent Advances on the Utilization of Nanoclays 251
chloride (PVC) in the 30, tricresyl phosphate was known as a fire retardant for this
plastic. Later it was shown that the o-isomer is neurotoxic, and tricresyl phosphates
made from m,p-cresol continued to be used. Several other alkyl phenyl and dialkyl
phenyl phosphates were developed [41]. Many other organophosphorus fire
retardants include halogens, such as halo alkyl phosphates. Tris(1,3-dichloro-2-
propyl) phosphate (TDCPP) or tris(chloroisopropyl) phosphate (TCPP) have been,
and are currently, extensively used. This later has substantially reduced volatility
and is more stable than TDCPP. There was some earlier use of tris(2,3-dibromo-1-
propyl) phosphate but that compound was removed from the market when it was
found to be mutagenic and carcinogenic. The chlorine analogs were found not to
share that problem. Also, chlorinated alkyl phosphate, available as AMGARD V6
is utilized in polyurethanes. Tetrabromophthalic anhydride and its derivative diol
are reactive flame retardants mainly used in polyurethanes. Also tribromone-
opentyl alcohol is used as a reactive flame retardant for polyurethanes. Its high
solubility in urethanes allows reaction of the single hydroxy functionality to form
pendant urethane groups [26]. Generally phosphorus appears to act as an acid
precursor in the solid phase to induce decomposition pathways that result in a
reduced combustion and an increase in charring.
A huge amount of research was done in the last two decades to develop low-
toxicity fire retardants for polyurethanes. Aromatic phosphates are another type of
flame retardants which are currently used in polyurethane foam found in home
furnishings. However, there is also the concern of exposure to aromatic phosphates
[3].
The leading method for flame retarding rigid foam is to use additives, although
reactive diols are occasionally employed where there is some special requirement.
The leading additives are tris(2-chloroethyl) phosphate (now less used) and tris
(1-chloro-2-propyl) phosphate [40]. Altogether, several types of fire retardants
have been utilized in polyurethanes: both organic, as for example melamine [28],
melamine polyphosphate and melamine cyanurate [26, 34] and inorganic, such as
alumina trihydrate [27]; zinc borate [42]; zinc stearate (not used as a flame
retardant but as a miscibility adjuvant) [23] and expanded graphite [13]. Among
organics, organophosphorus compounds in polyurethanes, we found oligomer
phosphates [1]; phosphonates like dimethyl methylphosphonate (DMMP) and
oligomer phosphonates; phosphine oxides and other less common such as pyro-
phosphoric lactone as fire retardant coating [11] and 5,5,50 ,50 ,500 ,500 -hexamethyltris
(1,3,2,-dioxaphosphorinanemethan)amine 2,20 ,200 -trioxide (XPM-1000 from
Monsanto), advocated to be used in flame-retardant polyurethanes formulations
[45]. Oligomeric cyclic phosphonates are utilized in rigid polyurethanes foams,
and have been known since more than 50 years. They have excellent thermal and
hydrolytic stability and are extensively used. On the other side, oligomeric chlo-
roalkyl phosphonates such as Antiblaze 78 (Mobil) and Phosgards, once used in
rigid PU foams, are not utilized in the market because of environmental and
toxicological reasons [36]. Phosphazenes, both cyclic and polymeric, have been
examined for their application as flame-retardant materials. A blend of poly
[bis(carboxylatophenoxy)-phosphazene] with polyurethane precursors resulted in a
urethane foam which exhibited increased thermal stability relative to the pure
polyurethane [2]. An aromatic-substituted cyclic phosphazene, 2,4,6-triphenoxy-
2,4,6-tri-(hydyoxyethoxy) cyclotriphosphazene (TPTHCP) was synthesized and
used as a flame retardant to improve the flame retardancy of PU foams. Self
extinguishing foam could be obtained when the phosphorus content was
1.5–2.0 wt% [10]. However, they are not utilized in practical applications. Sivriev
et al. [31] synthesized a phosphorus- and nitrogen-containing polyol by conden-
sation of tetrakis(hydroxymethyl)phosphonium chloride with diethanolamine. The
effects of the structure and the content of the phosphorus- and nitrogen-containing
polyol on properties of the polyurethanes, especially resistance to combustion,
have been investigated. They demonstrated that the new phosphorus and nitrogen-
containing polyol is an efficient flame retardant for rigid polyurethane foams.
However, more recent research on these materials was not continued. There is
abundant literature in this area regarding fire retardancy, and utilization is driven
by a balance of cost and performance.
Phosphine oxides have been found highly effective in polypropylene [38].
Research on these compounds has continued. A phosphorus and nitrogen-con-
taining polyol has been synthesized by condensation of tetrakis(hydroxymethyl)
phosphonium chloride with diethanolamine. The newly synthesized polyol-
tris[N,N-bis-(2-hydroxyethyl)aminomethyl] phosphine oxide (TPO) has been used
in the preparation of rigid polyurethane foams with reduced flammability [31].
Phosphine oxides are expensive and this significantly limits their application [26].
It was shown early in fire retardant development that for a given series of
related structures, either aliphatic or aromatic, the phosphates and phosphonates
were superior to the phosphites (which are often hydrolytically sensitive) [6].
Novel organophosphorus fire retardant methyl-DOPO: 9,10-dihydro-9-oxa-
methylphosphaphenthrene-10-oxide, which is a phosphinate, was considered for
flexible polyurethane foam although more usually used in epoxy laminates. At
temperatures where urethanes depolymerize, methyl-DOPO releases low molec-
ular weight species like HPO, CH3PO, or PO2. These species are able to scavenge
the H- and OH-radicals in the radical chain reactions of the flame [16].
Some researchers synthesized inherent flame retardant polyurethanes contain-
ing phosphorus that can react with isocyanate. Phosphorus-containing polyure-
thanes were synthesized by the reaction of phosphorus-containing diisocyanates
and diols. Some newer phosphorus containing polyurethanes have highly flame
retardant properties; the LOI values of these polyurethanes are around 29–33 [10].
A phosphorus- and nitrogen-containing polyol [polyol-bis(hydroxymethyl)-N,
N-bis(2-hydroxyethyl) aminomethylphosphine oxide, AMPO] was used in the
preparation of rigid polyurethane foams and were compared to polyurethane foams
prepared on the basis of the commercially available flame retardant diethyl-N,
N-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol 6). The polyurethane
foams with AMPO exhibit a slight increase in the resistance to combustion
(oxygen index) and a noticeable improvement in the thermal and mechanical
properties [30].
The influence of several fire retardants on compressive strength and fire

behaviour of rigid polyurethane foams was studied with ammonium polyphosphate,
melamine cyanurate, alumina trihydrate, borax, and expanded graphite. In general,
the cell size decreased, and compressive strength increased, as filler percentage was
increased. One exception to this trend was borax, which led to a significant loss in
compression strength of PU when it was added at the 15 % level [5].
3 Polymer-Layered Silicate Polyurethane Nanocomposites
Polymer-layered silicate nanocomposites are a new type of material, based on

smectite clays usually rendered hydrophobic through ionic exchange of the sodium
interlayer cation with an onium cation. They may be prepared via various synthetic
routes comprising exfoliation adsorption, in situ intercalative polymerization and
melt intercalation [12].
The use of nanoclays in polymers to impart fire retardancy to polyurethanes has
been subject to numerous investigations, including preparation, properties and uses
of this new class of materials. Nanoclays are interesting materials that are nano-
metric in only one dimension: they are formed by sheets of few nanometeres thick
to hundred thousands nanometers long. There are many investigations about the
use of clays both alone or with other compounds to flame retard polyurethanes.
These compounds usually contain phosphorus, nitrogen or both, and are added to
the polyol component of PU. Although the increasing research on nanocomposites
for its fire retardant properties, very often polymer nanocomposites exhibit low
flammability in terms of peak of heat release but fail other tests such as UL-94
rating and limiting oxygen index (LOI). This can be overcome combining nano-
particles with conventional fire retardants [7].
Wang and Pinnavaia [37] have synthesized intercalated nanocomposites based
on elastomeric PUs. They used an organomontmorrillonite modified with dode-
cylamine or octadecylamine swollen in a polyol and then cross-linked with an
isocyanate prepolymer. PU elastomeric matrices exhibit a sizeable increase in
tensile stress at break upon the addition of small quantities of nanofillers. Pro-
cessing, structure and properties of polyurethane/clay nanocomposites were
studied by Cao and coworkers [8]. They found that the morphology and properties
of PU nanocomposites and foams greatly depend on the functional groups of the
organic modifiers, synthesis procedure and molecular weight of the polyols
because of the chemical reactions and physical interactions involved. A novel
intumescent flame retardant, namely montmorillonite (MMT) modified with a
compound containing phosphorus–nitrogen structure (called c-MMT), was pre-
pared by ion exchanging of the nanometer Na-montmorillonite (Na-MMT) with a
phosphorus-nitrogen compound. The results showed that the addition of flame
retardant c-MMT enhanced the thermal stability and flame retardancy of poly-
urethanes significantly. The authors concluded that exfoliated montmorillonite
incorporated into polyurethane systems by in situ polymerization enhanced the
thermal stability and flame retardancy of PU significantly [15]. Also, the nanoscale
morphology of segmented polyurethane (SPU) nanocomposites containing various
proportions of organomodified montmorillonite (MMT) was reported [21].
Nanoparticles such as organoclay MMT and carbon nanotubes in thermoplastic PU
were reported to act mainly in a physical way (no chemical interactions) rein-
forcing intumescent char [7]. Mechanical properties of nanoclay-PU composites
were studied. Data obtained from the compressive stress–strain curves revealed
that the strength and modulus of polyurethane foam increase by addition of
organoclay up to 1 wt% and then decrease [35]. Thirumala et al. [33] found that
the compressive strength of organoclay/organically modified nanoclay (OMC)
filled PU foam (PUF) increased up to 3 parts per hundred of polyol (php) by
weight of OMC loading and then decreased. Dynamic rheological studies were
performed on thermoplastic PU (TPU) with the incorporation of organoclay,
showing increased dynamic viscosity and storage modulus, which was attributed to
the formation of an interphase between soft and hard segments of the TPU matrix
and effective dispersion of the organoclay [4].
Incorporation of commercial and laboratory-prepared nanoclays in a TDI-based
polyurethane was done in our laboratory. Organically-modified clays interchanged
with cetyl trimethyl ammonium bromide (CTAB) were incorporated in the polyol
component of the PU at a high shear mixing rate (in situ intercalative polymeri-
zation), resulting in an exfoliated clay, which is nanometric in one dimension. This
nanoclay, when dispersed in the polyurethane, resulted in the same fire retardancy
rating (UL-94) than when the polyurethane was treated with a commercial nanoclay
[29]. These results are in agreement with those obtained by Huang et al. [15].
The influence of surface-modified nanoclay on the self-organized nanostructure
of segmented polyurethane composites was investigated [21]. Local researchers
have studied the mechanical properties of montmorillonite-filled polyurethane
foams and found an enhancement in the mechanical properties for the PUF sample
at 5 wt% of MMT [32].
4 Commercial Applications
Despite the huge amount of literature existent in this field, which we have only
reviewed in a condensed way, it is important to stress that fire retardant additives
should not jeopardize polyurethane performance in general uses. The choice of
suitable polymeric flame-retardants has to be restricted to species that allow
retention of the advantageous mechanical properties of the polyurethane.
Commercial applications were thoroughly reviewed by Levchik and Weil [18].
Tris(2-chloroisopropyl) phosphate and tris(dichloroisopropyl) phosphate are ade-
quately stable in many formulations and have been used widely in polyurethanes.
A non-halogenated phosphorus additive, which has had usage in rigid polyure-
thane foam for a long time, is dimethyl methylphosphonate (DMMP). It contains
25 wt% phosphorus (near the maximum possible for a phosphorus ester) and it is
therefore highly efficient on a weight basis as a flame retardant. Triaryl phosphates,

specifically triphenyl phosphate, isopropylphenyl diphenyl phosphate, tricresyl
phosphate and trixylenyl phosphate all find some use in rigid foam formulations.
Although reactive phosphorus- or halogen-containing fire retardants are on the
market, it is believed that the use of additives is dominant in both rigid and flexible
polyurethanes. From an environmental point of view, the reactive or reacted-in flame
retardant has less likely to become an air and water pollutant in contrast with additive
flame retardants. A good compromise is an oligomeric additive that has no vapor
pressure or water-solubility, thus also meeting the environmental requirements.
Among reactive fire retardants, the Exolit OP 5xx series for polyurethanes in
manufactured by Clariant. They are reactive flame retardants which integrate into
the polyurethane matrix like a polyol. They show no migration, are more effective
than the usual additive flame retardants and have only a minimal impact on the
material properties. The three largest markets are transportation, furniture and
carpet backing. Carpet backing uses mostly alumina trihydrate (ATH) as the
flame-retardant additive, the other markets use an ever-increasing variety of
approaches. A major fraction of the flexible polyurethane foams used in furniture
is flame retarded. Additives are the dominant means, although much research has
been expended on reactives.
When slightly volatile additives such as tris(1,3-dichloro-2-propyl) phosphate
are used as flame retardants in automobile seating foams, there is often a detectable
fogging of the inside of the windshield if the passenger compartment of the vehicle
is warm. Other components of the foam, such as the catalysts and surfactants can
also contribute to the fogging. There are various industry tests for windshield
fogging. Where the monophosphate fails this test, it is usual to use diphosphates or
oligomeric phosphates or phosphonates. The most widely used non-fogging flame
retardant is tetrakis(2-chloroethyl) 2, 2-bis(chloromethyl)-1,3-propanediyl
diphosphate.
The commercial development of several phosphorus-containing diols occurred in
response to the need to flame-retard rigid urethane foams used for insulation in the
transportation and construction industry. The earliest produced was a diol obtained
from propylene oxide and dibutyl acid pyrophosphate [38]. A commercially
significant phosphorus diol is diethyl bis(2-hydroxyethyl)aminomethylphosphonate
(a trade mark for this chemical is Fyrol 6), especially useful in spray foams.
It is synthesized by reaction of diethanolamine, formaldehyde and diethyl phosphite.
It is stable in polyol-catalyst mixtures and imparts humid-aging resistance to foams.
This is a reactive flame retardant, as the diol structure permits permanent incorpo-
ration of the phosphonate group into the urethane foam. The phosphonate linkage is
on a side chain rather than in the backbone of the polyurethane, which increases the
hydrolytic stability [39]. Most recent non-halogenated polyols containing phos-
phorus are utilized, as Clariant’s hydroxy-terminated ethyl phosphate oligomer, as
well as brominated diols.
5 Conclusions
Organophosphorus flame retardants are in an active state of development driven by

their good performance and also by environmental and regulatory problems with
the brominated flame retardants. Literature sources were mostly taken from the
publications from the last decade, with reference to previous ground older publi-
cations. Nanoclay incorporation into polyurethane foams for increasing flame
retardancy appears to be a new area for development of commercial future
products, the same as with other industrial polymers. Current publications show
that nanoclays exert improved flame retardant properties mainly when acting
synergistically with conventional fire retardants.
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Ecological Assessment of Nano Materials
for the Production of Electrostatic/
Electrochemical Energy Storage Systems
M. Weil, H. Dura, B. Simon, M. Baumann, B. Zimmermann,

S. Ziemann, C. Lei, F. Markoulidis, T. Lekakou and M. Decker
Abstract Electrochemical double layer capacitors, also known as supercapacitors

are considered as a promising option for stationary or mobile electric energy
storage. At present lithium ion and nickel metal hydride batteries are used for
automotive applications. In comparison to this type of batteries supercapacitors
possess a high specific power, but a relatively low specific energy. Therefore, the
goal of ongoing research is to develop a new generation of supercapacitors with
high specific power and high specific energy. To reach this development goal
particularly nano materials are under investigation on cell level. In the presented
study the ecological implications (regarding known environmental effects) of
carbon based nano materials are analysed using Life Cycle Assessment (LCA).
Major attention is paid to efficiency gains of nano material production due to
scaling up of such processes from laboratory to industrial production scales.
Furthermore, a developed approach will be displayed, how to assess the envi-
ronmental impact of nano materials on an automotive system level over the whole
life cycle.
M. Weil (&) H. Dura B. Simon M. Baumann B. Zimmermann

S.Ziemann M. Decker
Karlsruher Institute of Technology (KIT), Institute of Technology Assessment and Systems
Analysis (ITAS), POB 3640 76021 Karlsruhe, Germany
M. Weil B. Simon
Helmholtz Institute Ulm for Electrochemical Energy Storage, Hermann-von-Helmholtz-
Platz 1 76344 Eggenstein-Leopoldshafen, Germany
C. Lei F. Markoulidis T. Lekakou
Department of Mechanical Engineering Sciences, University of Surrey,
Guildford GU2 7XH, UK

260 M. Weil et al.
1 Introduction
Electro mobility is considered as one of the most promising technologies for

replacing fossil fuelled mobility. Depending on the electricity generation mixture
of a region, electric cars can have already today an environmental advantage
against petrol cars [1]. With a growing share in regenerative production of electric
energy this advantage will substantially increase, particularly when synergy effects
of the progressively merging energy and transport networks will appear. The key
element of an electric vehicle is the energy storage system. At present for hybrid
and full electric vehicles commonly nickel metal hydride and lithium based bat-
teries are used. If electro mobility is to succeed there are a number of obstacles to
be overcome including great improvements in energy density, peak power, life
time (calendar and cycle stability), operation temperature and costs. Furthermore,
the energy storage systems should rely on available resources [2], be easily
recyclable and should have an overall good environmental performance. None of
the present energy storage systems fulfil the requirements sufficiently, that means
all electrochemical and electrostatic storage systems needs significant further
improvement. Nevertheless supercapacitors belong to a group of very promising
energy storage systems, which could enable the breakthrough for full electric or
hybrid power trains.
2 Double Layer Capacitor
Within the group of capacitors the electrochemical and electrostatic (dry) capac-
itors can be basically distinguished (Fig. 1). The electrostatic capacitor with no
electrolyte has no importance for energy intensive mobile or stationary
Fig. 1 Classification of
capacitors
Ecological Assessment of Nano Materials for the Production 261
Fig. 2 Specific energy and specific power of various energy storage systems
applications, due to its relatively low capacity, which is in the range of a few
microfarads or lower. In contrast, the capacity of electrochemical double layer
capacitors is thousands of times higher.
Thus double layer capacitors are a very promising candidate as an alternative
energy storage system in automotive applications.
They have the advantage of high power density, high cycle stability, high
calendar life time, a broad temperature range for operation and rely only on good
available raw materials like carbon. However, they are facing a number of prob-
lems including low energy density and high cost.
In Fig. 2 the performance regarding power and energy density of capacitors,
supercapacitors and batteries are shown (c.f. [3]). In this way, supercapacitors can
be considered as a link between electrostatic capacitors and electrochemical bat-
teries. Also regarding the cycle life time supercapacitors take a centre position
between electrostatic capacitors and electrochemical batteries.
Despite of the high price and the low energy density, there are some first
applications of supercapacitors in vehicles. Buses for public transport in the USA,
Russia and China are already in use with no traction batteries, but with superca-
pacitors as the only electric energy storage system [4].
262 M. Weil et al.
But to enable the mobility with supercapacitors (with low energy density) all
the bus stops are equipped with an induction charge stations. The induction
charging avoids is the physical need of a wire and plug connector. In this way the
buses can be recharged very simple at each stop through induction.
3 Improved Supercapacitors by Nano Materials
3.1 Performance Implications by the Use of Nano Materials
The structure of a super capacitor is related to the structure of a battery encom-

passing current collectors, high surface area electrodes, an electrolyte and sepa-
rator. However, the energy is not stored chemically but electrostatically in an
electric double layer (EDL) forming at the interface between the electrodes and the
electrolyte as depicted in Fig. 3 [5]. Thus, the amount of energy stored is pro-
portional to the surface area of the electrode [6], the higher the surface area, the
greater the specific energy. Since carbonaceous nano materials offer great surface
areas at low specific weight and volume, their application for supercapacitor
electrodes is increasingly being investigated. As already shown in Fig. 3 sup-
ercapacitors have a very good power density, but need great improvement in
energy density in order to increase their applicability for automotive energy
storage.
To overcome the stated problem a second generation of electrochemical double
layer capacitors is under development.
Often research largely focuses on the development of high area electrodes. This
may be achieved using carbonaceous nano materials, as these offer high surface to
volume and weight ratio.
The EU project ‘‘Autosupercap’’ focuses on the development of supercapacitors
with high power and high energy density while reducing weight and costs. To
achieve these ambitious goals different kinds of carbon based nano objects for the
production of the electrodes are being investigated and tested [7].
Fig. 3 Simplified drawing of

the electric double layer [18]
The energy and power performance of the capacitor as well as the lifetime are
strongly influenced by the internal resistance. The internal resistance is the product
of the carbon material itself, the carbon particle–particle contact, and the carbon-
current collector contact [7].
Normally carbon based aerogels and powders are used for the synthesis of
electrodes. A major improvement of the electrode resistance can be achieved by
using conducting additives, such as black carbon or carbon nanotubes [8].
In both ways the intelligent use of nano materials may improve the techno-
logical performance of the supercapacitor.
At present there a several investigations which focus on the use of graphene or
graphene derivate for the development of high performance electrochemical
double layer capacitors [9, 10]. A research group at the University of Alberta and
the National Research Council of Canada have synthesized a new graphene
material with a sponge-like structure. They could show, that this material, which
has a 3D macroporous structure, can be used for the manufacturing of double layer
capacitors electrodes. The produced capacitors with these new electrodes on a
laboratory scale have an incredible ultrahigh power density of approximately
48,000 W/kg, and provide still a relatively high energy density of 7.1 Wh/kg [10].
3.2 Production of Nano Materials and Their Environmental

Implications
High performance carbonaceous nano materials may be produced by three

methods: arc discharge, laser ablation and chemical vapour deposition (CVD). The
arc discharge method and laser ablation are based on vaporization of carbon
feedstock. In the arc method two carbon rods are placed in inert gas or liquid
nitrogen. A high temperature discharge between the two rods causes a vaporization
of the surface of one of the carbon rods while deposition takes place on the other.
In laser ablation vaporization of graphite rods is attained using a dual pulsed laser
and a subsequent thermal treatment. Due to the underlying principal of evaporation
of the carbon source, these two production approaches appear to be difficult for up
scaling to an industrial level [11].
Chemical Vapour Deposition (CVD) on the other hand has the greatest
potential for large scale production. In a batch process, plates containing a catalyst
are placed on the bottom of a reaction chamber, which is filled with a synthetic gas
mixture. Upon heating, the gas reacts with the catalyst forming nanotubes on the
catalyst surface [12]. A further development of the CVD process uses a fluidized
bed reactor and allows the continuous and mass production of CNTs [13].The
production of nano materials is very often a energy and resource intensive process,
which may partially explain the high price of these products. Using such materials
increases the efforts for the production of the supercapacitor. To reach a net
environmental and economic gain the efforts for the production have to be at least
264 M. Weil et al.
compensated if not significantly outweighed by a better environmental perfor-

mance during the use phase and at the end of life treatment of a nano enabled
supercapacitor.
In this regard an environmental assessment of the entire life cycle is a key
element. But until today only few LCAs exist on the production of nano materials
[14]. That means the real environmental impacts of such materials are neither well
assessed nor well understood. Furthermore, there is a need for additional models
that describe adequately the paths of release and effects of nano materials
throughout their life cycle [15]. This problem is further enhanced by the high
variability of nano materials even within one material group, i.e. a multi walled
carbon nano tube (MWCNT) is not necessarily comparable to another MWCNT.
The associated environmental impact depends on several factors including pro-
cesses of synthesis, purification and dispersion as well as functionalization. In this
study it is the goal to investigate the environmental impact of commonly used
carbon based nano materials for electrode production.
4 LCA Methodology, System Boundary and Approach
Life cycle assessment (LCA) offers a methodological framework for a consistent

assessment and comparison of different technological systems with respect to
various types of environmental impacts. According to the framework set forth by
DIN EN ISO 14040 [16] and 14044 [17] a LCA is comprised of four work
packages starting with a goal and scope definition followed by a life cycle
inventory (LCI) and life cycle impact assessment (LCIA). The fourth work
package, the evaluation is included as an iterative process which is performed
during all three prior stages. In the first step the objective of the study is to be
stated and further details explained including information on how the study will be
performed, the functional unit, system boundaries as well as allocation methods
and impact categories used. The LCI is purely descriptive documenting all input
and output flows into and out of the earlier defined system. In a subsequent step,
the LCIA is performed in order to determine environmental repercussions on the
basis of the flow network.
For the presented work the cumulated energy demand (CED) is displayed and
used as a screening indicator for environmental burdens as it depicts the direct and
indirect energy used e.g. from use of raw materials.
The considered system boundaries of the investigated nano materials are from
‘‘cradle to gate’’, meaning all pre chains of the production process are included. A
general problem of LCA investigations for nano materials is the complexity, which
is described in [12], but more often also the restricted access to detailed data
regarding the production process [18]. It has to be stated that at present LCA can
not consider and evaluate the potential human toxicity and ecological impact of
nano objects and materials.
5 LCA Results of Carbonaceous Materials on Nano

and Micro Scale
The raw materials, the production technology and energy requirements of the
investigated carbon derivates are quite different, thus it was expected to identify
the f0 differences also in the LCA results. The calculated CED values for the
different carbonaceous materials and production procedures are shown in Fig. 4.
Most striking is the extremely high energy intensity of SWCNT production by
laser ablation creating an energy demand of more than 200.000 MJ/kg, more than
twice as much as SWCNT produced by CVD. MWCNT cause a much smaller
CED, although this also strongly depends on the production method applied.
Although significant reductions may be achieved with the fluidized bed and CVD
production processes, in comparison with the production of black carbon and
activated carbon both types of the carbon nano materials create a relatively high
CED, from 4 fold larger (MWCNT fluidized bed) up to approximately 4 orders of
magnitude larger (SWCNT laser ablation).
Another problematic issue regarding the production of MWCNT by a fluidized
bed reactor is the tendency to have high impurities and agglomerations of CNTs,
which might cause in addition (for some application fields) further efforts for
purification and dispersion. There exist some evidences, that the purification and
dispersion of nano objects can cause a relatively high environmental impact, in
Cumulative Energy Demand [MJ/kg] > 200000
SWCNT (laser ablation, high purity,

laboratory scale) own data
SWCNT (CVD) based on [21] ~ 900000
CNT (CVD, fluidized bed, carbon monoxide)

464
[24]
MWCNT (CVD , floating catalyst, with

~770
purification, baseline) based on [23]
MWCNT (CVD, fluidized bed, without

~165
purification) [22]
Activated Carbon based on [19] and own

92
assumptions
Black Carbon [20] 89
0 40000 80000 120000 160000 200000
Fig. 4 Comparison of different carbon based materials for electrode production regarding the
cumulative energy demand (CED)
266 M. Weil et al.
some cases even significantly higher than the production itself, depending on the
considered life cycle impact category [12].
6 Assessment of Nano Materials on Automotive System

Level
The focus on the production phase is not sufficient for an ecological and economic
evaluation of nano materials and to understand their inherent value.
In order to assess the economic and environmental effects of the use of nano
materials in new developed supercapacitor the whole life cycle of a use case has to
be considered. For this the life cycle models regarding an automotive application
have to cover the production phase, use phase, and end of life phase.
In Fig. 5 the system boundary for an ecological assessment of a supercapacitor
is shown. It is obvious that the production of carbon based nano materials is just
one process of a long process chain. Thus there is a potential danger, that the
positive and negative contribution of nano materials reaches not a high signifi-
cance, due to the dominance of other processes.
But only by considering the whole life cycle the net value of nano materials
with respect to economic and ecological aspects can be evaluated. Furthermore,
regarding the results, general statements are not possible, due to the strong
dependency of the application field. Thus, this kind of prospective evaluation has
to be conducted for each single nano material and for each application field of
supercapacitors.
7 Summary and Outlook
Present available electrochemical double layer capacitor technology is too

expensive and the energy density is too low for a broad mass application in electric
vehicles. The next generation of electrochemical double layer capacitors, which
are under development, uses particularly nano materials to improve the technical
performance and reduce costs. It could be shown, that the production of carbon-
iferous materials on nano scale can have a significant environmental impact.
Certainly the environmental impact of nano materials depends on several factors,
but the upscale of the synthesis process from laboratory to industrial scale looks
very promising in significantly reducing economic and ecological efforts and
related impacts. Unfortunately the scale up process of nano particle production
might have an important influence on the quality of the nano materials. The quality
losses may cause a higher use of the nano materials or cause further efforts for the
improvement of their quality, e.g. by an additional dispersion or purification
process. To evaluate the possible environmental and economic savings due to the
improved technical performance, the supercapacitor has to be investigated on a
Fig. 5 System boundaries for life cycle assessment of supercapacitors
product system level. This will be conducted in the future for a simulated auto-
motive application with measured data from a test rig. By the consideration of the
whole life cycle the real value (in respects of economic and ecological savings) of
nano materials applied in energy storage systems can be assessed.
268 M. Weil et al.
Acknowledgments This research was funded by the European Commission FP7 project
‘‘AUTOSUPERCAP’’. We would like to express our sincere gratitude also to Regina Fischer and
Prof. Dr. Manfred Kappes from the KIT, Division of Physical Chemistry of Microscopic Systems,
Germany.
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Engineering Materials

James Njuguna Editor

For further volumes:

ISSN 1612-1317 ISSN 1868-1212 (electronic)

Library of Congress Control Number: 2013954843

Springer-Verlag Berlin Heidelberg 2013

Printed on acid-free paper

Springer is part of Springer Science+Business Media (www.springer.com)

Absorption and Low-Velocity Impact Performance of Nanocomposites: Cones and

Dispersion Methods of Carbon Nanotubes for the Development

Thermoplastic Nanocomposites with Carbon Nanotubes . . . . . . . . . . . 19

Graphite-Based Nanocomposites to Enhance

Optimization and Scaling up of the Fabrication Process of Polymer

Influences of Morphology and Doping on the Photoactivity

Foam-Glass-Crystal Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143

High Temperature Polymer Nanocomposites . . . . . . . . . . . . . . . . . . . 165

Energy Absorption and Low-Velocity Impact Performance

Predictions of Energy Absorption of Aligned Carbon

Silver Nanocluster/Silica Composite Coatings Obtained

Recent Advances on the Utilization of Nanoclays

Ecological Assessment of Nano Materials for the Production

C. Manteca Martínez, A. Yedra Martínez and I. Gorrochategui

Abstract Composites use is increased worldwide quickly because they present

C. Manteca Martínez A. Yedra Martínez (&) I. Gorrochategui Sánchez

J. Njuguna (ed.), Structural Nanocomposites, Engineering Materials, 1

The use of advanced composite materials is becoming increasingly popular in the

3 Nanomaterials Dispersion Within Thermosetting Resin

Fig. 1 Sonication equipment

Currently, different methods are being used to disperse nanomaterials into

Fig. 2 Rotating disc to disperse particles in different matrices

4 Three-Roll Milling Process

Table 1 Example of dispersion parameters

4.2 Preparation of Samples

Fig. 5 Scheme of manufacturing nanocomposite

The introduction of nano-particles into thermoset polymer as additives involves

5 Samples Characterization and Potential Applications

5.1 Dispersion Characterization

There are several characterization techniques to determinate the structure and

Fig. 8 Raman spectrum 4000

Fig. 9 Distribution map of UP/0.1 % MWCNT

5.2 Mechanical Characterization

Fig. 10 Distribution maps of MWCNT/polyester composites: a MWCNT 0.5 wt%. b MWCNT

[14]. Figure 11 depicts the tensile behavior of nanocomposites under ambient

Tensile Modulus (GPa)

Fig. 12 Delamination failure mode of a tensile test specimen

427 444 424 426 30

addition of carbon nanotubes. Depending of nanoreinforcements content the

Fig. 14 Bending specimen. a Fibre fracture. b Interphase shear failure

5.3 Structural Application: Panel Sandwich

Structural sandwich panels are products used primarily in order to perform

Fig. 15 Sandwich panel

Sandwich panels have been developed with improved mechanical performance

1. ACCIONA company: Web www.acciona.es

Shyam Sathyanarayana and Christof Hübner

Abstract The potential impact of light-weight structures with multifunctional

J. Njuguna (ed.), Structural Nanocomposites, Engineering Materials, 19

Table 1 Areas of possible applications for different nanofillers

2 Carbon Nanotubes: An Overview

2.1 Structure of CNT