Hydrothermal synthesis of nanocrystalline

ZrO2-8Y2O3-xLn2O3 powders (Ln = La, Gd, Nd, Sm):

crystalline structure, thermal and dielectric properties
Radu Robert Piticescu, Anca Elena Slobozeanu, Sorina Nicoleta Valsan,
Cristina Florentina Ciobota, Andreea-Nicoleta Ghita, Adrian Mihail Motoc,
Stefania Chiriac, Mythili Prakasam

To cite this version:

Radu Robert Piticescu, Anca Elena Slobozeanu, Sorina Nicoleta Valsan, Cristina Florentina Ciob-
ota, Andreea-Nicoleta Ghita, et al.. Hydrothermal synthesis of nanocrystalline ZrO2-8Y2O3-xLn2O3
powders (Ln = La, Gd, Nd, Sm): crystalline structure, thermal and dielectric properties. Materials,
2021, 14 (23), 7432 (21 p.). �10.3390/ma14237432�. �hal-03482599�

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 materials
Article
Hydrothermal Synthesis of Nanocrystalline ZrO2-8Y2O3-xLn2O3
Powders (Ln = La, Gd, Nd, Sm): Crystalline Structure, Thermal
and Dielectric Properties
Radu-Robert Piticescu 1, * , Anca Elena Slobozeanu 1, *, Sorina Nicoleta Valsan 1 , Cristina Florentina Ciobota 1 ,
Andreea-Nicoleta Ghita 1 , Adrian Mihail Motoc 1 , Stefania Chiriac 1 and Mythili Prakasam 2

1 National R&D Institute for Non-Ferrous and Rare Metals, INCDMNR-IMNR, 102 Biruintei Blvd.,
077145 Pantelimon, Romania; [email protected] (S.N.V.); [email protected] (C.F.C.);
[email protected] (A.-N.G.); [email protected] (A.M.M.); [email protected] (S.C.)
2 CNRS, Université de Bordeaux, ICMCB, UMR 5026, 87 Avenue du Docteur Schweitzer,
CEDEX, 33608 Pessac, France; [email protected]
* Correspondence: [email protected] (R.-R.P.); [email protected] (A.E.S.)

Abstract: Zirconium dioxide (ZrO2 ) is one of the ceramic materials with high potential in many
areas of modern technologies. ZrO2 doped with 8 wt.% (~4.5 mol%) Y2 O3 is a commercial powder
used for obtaining stabilized zirconia materials (8 wt.% YSZ) with high temperature resistance and



good ionic conductivity. During recent years it was reported the co-doping with multiple rare earth

 elements has a significant influence on the thermal, mechanical and ionic conductivity of zirconia,
Citation: Piticescu, R.-R.; due complex grain size segregation and enhanced oxygen vacancies mobility. Different methods have
Slobozeanu, A.E.; Valsan, S.N.; been proposed to synthesize these materials. Here, we present the hydrothermal synthesis of 8 wt.%
Ciobota, C.F.; Ghita, A.-N.; (~4.5 mol%) YSZ co-doped with 4, 6 and 8 wt.% La2 O3 , Nd2 O3 , Sm2 O3 and Gd2 O3 respectively. The
Motoc, A.M.; Chiriac, S.; crystalline phases formed during their thermal treatment in a large temperature range were analyzed
Prakasam, M. Hydrothermal by X-ray diffraction. The evolution of phase composition vs. thermal treatment temperatures shows
Synthesis of Nanocrystalline
as a major trend the formation at temperatures >1000 ◦ C of a cubic solid solutions enriched in the
ZrO2 -8Y2 O3 -xLn2 O3 Powders
rare earth oxide used for co-doping as major phase. The first results on the thermal conductivities
(Ln = La, Gd, Nd, Sm): Crystalline
and impedance measurements on sintered pellets obtained from powders co-doped with 8 wt.% Y
Structure, Thermal and Dielectric
and 6% Ln (Ln = La, Nd, Sm and Gd) and the corresponding activation energies are presented and
Properties. Materials 2021, 14, 7432.
https://doi.org/10.3390/ma14237432
discussed. The lowest thermal conductivity was obtained for La co-doped 8 wt.% YSZ while the
lowest activation energy for ionic conduction for Gd co-doped 8 wt.% YSZ materials.
Academic Editor: Paweł Głuchowski
Keywords: rare-earths doped zirconia; hydrothermal synthesis; crystalline structure; thermal
Received: 11 October 2021 conductivity; impedance spectroscopy
Accepted: 26 November 2021
Published: 3 December 2021

Publisher’s Note: MDPI stays neutral 1. Introduction

with regard to jurisdictional claims in
Zirconium dioxide (ZrO2 ), also known as zirconia and zirconium oxide, is a ceramic
published maps and institutional affil-
material of great technological importance due to its advanced multidimensional prop-
iations.
erties, such as: high mechanical strength, chemical inertness, high temperature stability,
low thermal conductivity, corrosion resistance, high ionic conductivity and biocompati-
bility [1,2]. These properties lead to different applications in areas such as gas sensors [3],
solid-oxide fuel-cell [4], catalysis [5], thermal barrier coating [6], medical prosthesis [7] and
Copyright: © 2021 by the authors. memory devices [8].
Licensee MDPI, Basel, Switzerland. Zirconia is found in several polymorphic forms depending on the temperature condi-
This article is an open access article
tions: monoclinic (m), tetragonal (t) and cubic (c) phases. At temperatures below 1100 ◦ C,
distributed under the terms and
the monoclinic phase of pure ZrO2 is the stable form. From 1100 ◦ C up to 2370 ◦ C, pure
conditions of the Creative Commons
ZrO2 has a tetragonal structure, while at temperatures from 2370 ◦ C up to 2706 ◦ C (the
Attribution (CC BY) license (https://
melting point) it exists as cubic phase. On cooling, the cubic-tetragonal and tetragonal-
creativecommons.org/licenses/by/
monoclinic transformations are accompanied by both a decrease in theoretical density and
4.0/).

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Materials 2021, 14, 7432 2 of 21

an expansion of the volume between 3–5%. Therefore, due to the high stresses during the
cooling period, pure zirconia undergoes the formation of micro-cracks, strongly affecting
its mechanical properties. To prevent these inconveniences, several oxides, such as MgO,
CaO and Ln2 O3 (Ln: all transition metals from the lanthanum series in the periodic table of
elements) are added to the zirconium oxide to stabilize the tetragonal and/or cubic phases
when cooled to sintering temperature. The doped materials thus obtained are generally
called partially stabilized zirconia (t or c + t phases are formed) or stabilized zirconia (only
c phase formed) [9–12]. The doping elements do not affect only the structural and mechani-
cal properties but also opto-electronic and phonon behavior due to the compensation of
differences between the valence of doping elements and Zr+4 matrix with oxygen vacancies
according to the rule of charge neutrality [13].
It was shown that using rare earth oxides (REOs) as dopants may avoid grain size
coarsening due to interface segregation in doped zirconia ceramic, enhancing its thermo-
mechanical properties. It has been theoretically proposed that the grain boundary energy
may be correlated with dopant concentration is close to zero, enhancing stability of nano-
materials. The absolute grain boundary energy of Gd-doped nanocrystalline ZrO2 vs. grain
size can reach a quasi-zero energy state (0.05 J/m2 ), when a critical dopant enrichment is
achieved, until a temperature threshold where the dopant re-dissolves in the crystalline
bulk [14].
The oxygen vacancies formed due to RE ions dopants were reported to improve
the ionic conductivity in a co-doped sintered ((Y0.75 La0.25 )1−x Gdx )0.18 Zr0.82 O2−δ system
and the energy values for the bulk and grain boundary conductions are strongly re-
lated to the ionic radii of the trivalent REs ions and the vacancy concentrations at lower
temperatures [15]. Fine-grained ceramics based on solid solutions ZrO2 -xLn2 O3 (where
Ln = Sm and Yb) were obtained by the colloidal chemical synthesis of the powders followed
by spark plasma sintering. The addition of lanthanides stabilized the structure and no
phase transformation occurred during heating, ensuring a high density of the ceramic
obtained [16].
The use of ZrO2 doped with mixed REOs is considered as a challenge in designing
of SOFCs membranes with high ionic conductivity, long-term temperature performance
stability, density and long-term reliability (high strength and high durability). It was
reported that co-doping ZrO2 with Y2 O3 and CeO2 led to high temperature stabilization
of tetragonal ZrO2 with 6–9 nm crystallite sizes [17]. (ZrO2 )0.85 (REO1.5 )0.15 (RE = Y, Sc)
solid solutions in pure cubic fluorite structure obtained by a citrate gel method have been
proposed as materials with promising properties for SOFCs applications [18].
In the present paper we investigate the thermal conductivities and dielectric properties
of ternary ceramic materials from the system ZrO2 -8Y2 O3 -xLn2 O3 powders (Ln = La, Gd,
Nd and Sm, x = 4, 6 and 8 wt.%) obtained by the hydrothermal method as a first step in
developing new materials with controlled thermal and ionic conductivities.
Different physical, chemical and combined routes were used for nanopowders’ syn-
thesis. The chemical reactions for nanomaterials’ synthesis may take place in a solid, liquid
or gaseous state. The main advantage of solid-state reactions is the easy control of the
composition, but high activation temperatures are required for grain boundaries’ diffusion
which may lead to excessive grain growth. In liquid or gas phase synthesis reactions, the
activation energy is many orders of magnitude lower and the synthesis of nanostructured
materials can be achieved at lower temperatures avoiding powders coarsening. However,
the control of the final chemical composition is more challenging.
Obtaining zirconia nanoparticles has been achieved by hydrothermal [19], spray
pyrolysis [20], co-precipitation method [21], sol-gel [22], microwave irradiation [23], com-
bustion [24], ball milling [25], pyrolysis [26], spray pyrolysis [27] and hydrolysis [28], each
method developed with the aim to fulfil specific applications.
Hydrothermal process can be defined as a heterogeneous and homogeneous chemical
reaction in the presence of a solvent (aqueous or non-aqueous) above room temperature
and at pressures higher than 1 atm. in a closed system. These main characteristics lead
Materials 2021, 14, 7432 3 of 21

also to a process with a low environmental impact. Under a hydrothermal reaction, the
reactants, in the presence of a mineralizer or solvent, go into solution as complexes due to
chemical transport reactions. The hydrothermal process is versatile and takes place in a
single step with a minimum energy consumption. Nanosized materials can be obtained
in situ, without involving post-synthesis treatment. The presence of surfactants plays an
important role in the preparation of highly dispersed, oriented and self-assembled particles
of complex or multicomponent materials [29]. The value of the isoelectric point and pH
influences the inorganic surface modification in the presence of a surfactant.
The in-situ deprotonation of water molecules from the coordination sphere of metallic
ions due to high temperatures and pressures in hydrothermal solutions produces homoge-
neous nucleation sites for the crystallization of the new phases [30]. The particles’ growth
is further controlled by adsorption/desorption and chemical reactions at the interfaces that
are topo-chemical processes strongly depending on the interface/surface characteristics. A
remarkable advantage of the hydrothermal synthesis is the increased solubility product of
compounds in water at elevated temperatures and pressures and the enhanced chemical
reactivity of usually insoluble reagents [29]. ZrO2 materials doped with different rare
earth oxides (REOs) have been recently studied as candidates for new thermal barrier coat-
ings [31,32] for different industrial applications [33–35]. At the time they were identified,
in the eighteenth and nineteenth centuries, they were considered relatively rare compared
to other elements. The term “rare” is actually somewhat misleading; for example, they are
more common than lead, copper, gold or silver. REEs are relatively common in the Earth’s
crust, but the fact that they are mixed with many other minerals in different concentrations
in the soil makes extraction difficult to achieve [36–38]. Usually, because they have similar
ionic radii and a trivalent charge, REEs are found together in the Earth’s crust, with the
exception of Europium, which can occur in a state of valence Eu2+ or Cerium as Ce4+ [39].
The two largest sources of REE combined in mineral deposits are monazite and bastnaesite.
Monazite is a phosphate mineral while bastnaesite is a fluorinated carbonate mineral
containing different REEs [40]. The world’s reserves of rare earths are about 120 million
metric tons, of which 36.67% are located in China. Significant reserves are also held by
the United States, Australia, Brazil, India and Malaysia [41]. China has won a monopoly
not only on reserves but also on rare earth production. This has led to a global supply
risk since 2010 [42]. Therefore, the European Commission has identified them as critical
materials with a significant supply risk, as they play an important role in a number of
modern technologies [43]. Different methods were proposed to obtain mixed REOs-doped
ZrO2 powders.
Mekala and co-workers used the coprecipitation method to synthesize Ce-doped
ZrO2 and Dy doped ZrO2 . The nanoparticles thus synthesized showed the tetragonal
(t-ZrO2 ) and monoclinic (m-ZrO2 ) phase and the decrease of the crystal size by Dy and Ce
doping. Doping with RE elements had different effects on both size (undoped ZrO2 had a
nanoparticle size of about 12 nm, Dy doping led to a particle size of 9 nm and ZrO2 doped
with Ce had the smallest particle size at 6 nm) and morphology [44].
The co-precipitation method was also used by Lei Guo et al. to synthesize 1 mol%
RE2 O3 and 1 mol% Yb2 O3 co-doped 3.5 mol% Y2 O3 stabilized ZrO2 (1RE1Yb-YSZ, RE = La,
Nd, Gd and Yb) powders, alternative TBC material. The study showed that Re2 O3 ((RE = La,
Nd, Gd and Yb) and Yb2 O3 co-doping has an obvious influence on the thermal conductivity
and phase stability of YSZ ceramics for TBC applications. YSZ doping with lower ionic
RE has beneficial effects on phase stability, but has a limited effect on reducing thermal
conductivity. Therefore, the study reported that among the compounds investigated,
1Gd1Yb-YSZ showed better phase stability and lower thermal conductivity [45]. ZGYbY:
ZrO2 -9.5Y2 O3 -5.6Yb2 O3 -5.2Gd2 O3 powder, as a new material for TBC applications, was
synthesized by a chemical co-precipitation method to increase phase stability of YSZ at
higher temperatures, above 1200 ◦ C. The result of the heat treatment at 1300 ◦ C for 50 h
indicated ZGYbY powder exhibited excellent stability due to the complete retention of
the t ’zirconia tetragonal phase and the transition from tetragonal to monoclinic phase
Materials 2021, 14, 7432 4 of 21

upon cooling while YSZ powder decomposed into two new phases, including cubic and
monoclinic zirconia. These results make ZGYbY a promising material for TBC applications
in new generations of turbines [46].
Chao Chen et al. used the chemical coprecipitation method and the calcination method
to obtain the powders xSc2 O3 -1.5Y2 O3 -ZrO2 (x = 4.5, 5.5 and 6.5, in mol%) and 4.5 mol%
Y2 O3 -ZrO2 in order to test the samples for hot corrosion in molten salts Na2 SO4 + V2 O5
(50/50 %gr.). An excellent hot corrosion resistance was obtained for those ScYSZ ceramics
with a higher Sc2 O3 content, such as 6.5Sc1.5YSZ [47].
ZrO2 YO1.5 -TaO2.5 powders were prepared by Pitek et al. by inverse co-precipitation of
mixed solutions. The zirconium-based material stabilized with 16.6% YO1.5 + 16.6% TaO2.5
is tetragonal and has phase stability up to at least 1500 ◦ C [48].
Leila Sun et al. obtained, by a co-precipitation technique, ZrO2 doped with 7.5 mol%
Sc2 O3 and Gd2 O3 (ScGdSZ). Samples co-doped with Gd3+ ·3.7Sc2 O3 and 3.7 Gd2 O3 co-
doped ZrO2 (in mol%) had the lowest thermal conductivity, which was 20% lower than
7.5 ScSZ and 40% lower than 4, 5 YSZ, respectively [49].
Solution combustion method using Glycine as a fuel, was used by H. C. Madhusudhana et al.
to synthesize Gd doped ZrO2 (1–9 mol%). In the case of the 7% mol sample of Gd
doped ZrO2 , the results of the impedance spectroscopy show good dielectric proper-
ties with a very high dielectric constant (ε0 = 345) and also a high alternative conductivity
(σac = 0.06837 S·cm−1 ) at 10 MHz, suitable for solid oxide fuel cell applications [1].
Using the solid-state reaction method, X. Song and co-workers obtained ZrO2 -Ta2 O5 -
Y2 O3 -Ln2 O3 (Ln = Nd, Sm or Gd) powders to investigate the effects of rare earth oxides on
thermal structure and properties. There have been significant improvements in thermal
conductivity by the addition of rare earth oxides Ln2 O3 , but also a decrease in grain
growth and specific thermal capacity. Gd2 O3 showed the best efficiency for thermal
conductivity [50].
The solid-state reaction method was used by Wang and co-workers to obtain dense
x mol% ZrO2 -Gd3 NbO7 (x = 0, 3, 6, 9, 12). It was observed that the thermal conductivity of
ZrO2 -Gd3 NbO7 is much lower, at 1.21–1.82 (W·m−1 ·K−1 ) from 25 to 900 ◦ C, compared to
La2 Zr2 O7 (1.50–2.00 W·m−1 ·K−1 ), Y2 SiO5 , 8YSZ (2.50–3.00 W·m−1 ·K−1 ), ZrO2 -DyTaO4 ,
ZrO2 -Y2 O3 -Ta2 O5 and Yb2 O3 [51].
The introduction of Sm2 O3 and Yb2 O3 into zirconia results in a higher shrinkage
intensity and a lower sintering activation energy. This energy is determined by the influence
of Sm3+ and Yb3+ ions on the diffusion properties of the granule boundaries and by the
ratio between the atomic radii of zirconium and lanthanide [16].
Hydrothermal synthesis was one of the methods successfully used for obtaining ZrO2
doped with different REOs.
Nanoparticles of zirconia doped with erbium Er3+ and ytterbium Yb3+ have been
synthesized by Jasso and co-workers [52,53] using the hydrothermal route. The XRD
analysis for the synthesized samples revealed the face cantered cubic phase of the particles
with nanometric crystal size ~ 10 nm.
Powder of zirconia doped with terbium Tb3+ were synthesized by Ramos-Guerra et al. [54]
by hydrothermal route using different types of stabilizing agents in order to evaluate their
influence on the structural and luminescent properties.
The hydrothermal synthesis method was also used by Gionco and co-workers [55] to
manufacture nanostructured rare-earth (Ce and Er) doped zirconia nanoparticles in order
to evaluate their potential as solar light photocatalysts.
Recently, in order to understand the crystallization mechanism of 5% yttrium stabi-
lized tetragonal zirconia, Song et al. [56] used the hydrothermal technique, starting from
precursors with different zirconium coordination.
8YSZ doped with different concentrations of Eu3+ was synthesized by the hydrother-
mal method. It was concluded based on the combination of crystal structure and photolu-
minescence spectroscopy that 3 mol% Eu3+ ions in 8YSZ is the optimal concentration [57].
Materials 2021, 14, 7432 5 of 21

Ce and Er doped ZrO2 (from 0.5 to 10 mol% on an oxide basis) were successfully
synthesized by the hydrothermal method [58] in order to investigate the photocatalytic
activity caused by the sun. By introducing rare earth ions, the tetragonal (Ce and Er) and
cubic (Er, 10 mol%) phases were stabilized.
Nanoparticles with polymorphic phases (m-ZrO2 , t-ZrO2 and c-ZrO2 ) from the ZrO2 -
Me2 O3 system (where Me = Y, Eu, Tb, Sm and Er) with crystallite size in the range 5–25 nm
in the form of (spheres, hollow spheres, rods and star structures) with luminescence
properties were obtained by the hydrothermal route [59].

2. Materials and Methods

2.1. Hydrothermal Synthesis
This paper aims to obtain zirconium-based powders doped with 8 wt.% (~4.5 mol.%)
Y2 O3 (further abbreviated 8 wt.% YSZ) and co-doped with controlled amounts of La, Nd,
Sm and Gd and study the crystalline phase modification after thermal treatment in the
temperature range 400–1400 ◦ C, thermal conductivities and ionic conductivities to further
assess their potential applications in high temperature thermal barrier coatings (TBC).
The 8 wt.% Y2 O3 -ZrO2 composition was selected based on their commercial use as feed
powder in obtaining TBCs in aeronautics or gas turbines [60]. Thus, different REO dopants
(4/6/8 wt.% La, 4/6/8 wt.% Nd, 4/6/8 wt.% Sm, 4/6/8 wt.% Gd) were added to the ZrO2
doped with 8% Y2 O3 , obtaining a number of 12 initial powders further denominated MxZY
4/6/8La, MxZY 4/6/8Nd, MxZY 4/6/8% Sm and MxZY 4/6/8% Gd respectively.
All nanostructured powders were synthesized in a one-step process by the hydrother-
mal method at moderate temperatures (max. 250 ◦ C) and pressures (max. 40 atm). The
temperature was selected based on the estimation of the reaction enthalpy (∆H), reaction
entropy (∆S), Gibbs free energy (∆G) and equilibrium constants (log K) for the hydrother-
mal reactions:

0.984Zr(+4a) + 0.08Y(+3a) + 0.08Ln(+3a) + 4.416OH(−a)

(1)
= 0.984ZrO2 + 0.04Y2 O3 + 0.04Ln2 O3 + 2.208H2 O

where: Ln-La, Nd, Sm and Gd, (a) denominates the ionic species in aqueous solutions
and the stoichiometric coefficients correspond to the highest 8 wt.% Ln as dopants. The
estimation has been done using the HSC Chemistry v.10 software and database (Outotec,
Pori, Finland). The results are presented in Figure 1a–d. The values obtained for the
enthalpies, entropies and Gibbs free energies in Figure 1a–c are very close for the four
lanthanides considered in this thermodynamic study, with a difference < 1 kcal.
The synthesis was made from high purity raw materials: Y2 O3 > 99%—Merck,
Darmstadt, Germany, La2 O3 ≥ 99.9%—Roth, Karlsruhe, Germany, Nd2 O3 ≥ 99.9%—
Alfa Aesar, Kandel, Germany, Sm2 O3 ≥ 99.9%—Alfa Aesar, Gd2 O3 ≥ 99.9%—Alfa Aesar.
Kandel, Germany, Zirconium tetrachloride (ZrCl4 99% Merck) was used as raw material
for preparing an aqueous Zr (IV) stock solution with programmed Zr concentration. The
dissolution of REOs precursors in ZrCl4 solution was done under vigorous mechanical
stirring until a homogenous clear solution was obtained. Ammonia solution (NH3 25%
p.a., Chimreactiv S.R.L.) agent was added as mineralizing until an alkaline suspension
with pH ~ 9 was obtained. The suspension thus obtained was transferred to a Teflon
vessel of a sealed hydrothermal autoclave reactor (5 L capacity, Berghoff Products + Instru-
ments GmbH, Berghoff, Germany) and subjected to the hydrothermal process, followed
by controlled water cooling with the help of a coil inserted in the reaction vessel. A solid
precipitate formed, was filtered and washed three times with distilled water to remove
soluble impurities and was dried in an oven at 100 ◦ C to constant weight.
Materials 2021, 14, 7432 6 of 21

Figure 1. (a) Enthalpies of reactions (1), (b) entropies of reactions (1), (c) Gibbs free energy of reactions (1), (d) equilibrium
constants of reactions (1). Series 1 corresponds to La3+ , series 2 to Nd3+ , series 3 to Sm3+ and series 4 to Gd3+ .

A working scheme for an understanding of the entire research activity that has been
carried out in this paper is presented in Figure 2.
After the hydrothermal synthesis process, for the assessment of phase stability, the
powders MxZY 4/6/8% La, MxZY 4/6/8% Nd, MxZY 4/6/8% Sm and MxZY 4/6/8% Gd,
were subjected to calcination at various temperatures (400 ◦ C/800 ◦ C/1000 ◦ C/1200 ◦ C/
1400 ◦ C, respectively) for 60 min and their phase compositions were analyzed.

2.2. Characterization Methods

REO-co-doped ZrO2 powders were chemically analyzed by inductively coupled
plasma optical emission spectrometry (Agilent 725 ICP-OES, Agilent Technologies Inc.,
Colorado Springs, CO, USA) according to ASTM E 1479-99 (2011).
Materials 2021, 14, 7432 7 of 21

Figure 2. Schematic workflow of the study.

The microstructure of REO-doped ZrO2 powders was examined using a BRUKER D8

ADVANCE X-ray diffractometer (Bruker AXS GmbH, Karlsruhe, Germany) with monochro-
matic Kα radiation, using the Bragg-Brentano diffraction method. Scans were obtained
in the range 2θ 4–74◦ with a step size of 0.02◦ every 2.5 or 6 s. To identify the phases
contained in the samples, the data processing was performed using the software pack-
age DIFFRAC.SUITE.EVA launched 2016 by Bruker AXS Company, Karlsruhe, Germany;
SLEVE + 2020 and the ICDD PDF-4 + 2020 database published by the International Center
for Diffraction Data (ICDD).
The morphology of the powder samples was investigated by scanning electron mi-
croscopy (SEM) using a high-resolution microscope Quanta 250 (FEI Company, Eindhoven,
The Netherlands), incorporated with Energy Dispersive X-Ray Spectrometer, produced by
EDAX (Mahwah, NJ, USA), consisting of ELEMENT Silicon Drift Detector Fixed, Element
EDS Analysis Software Suite APEX™ 1.0, EDAX, Mahwah, NJ, USA.
The room-temperature thermal conductivity was measured using the hot disk method
(TPS 2200 Hot Disk, Hot Disk AB, Göteborg, Sweden) on pairs of cylindrical pellets
(approximate 20 mm diameter and 5 mm height) thermal treated at 1200 ◦ C. A 2 mm
diameter Kapton sensor (code 7577) sandwiched between the two cylindrical replicate
samples was used to generate heat and monitor the temperature evolution of the sample.
The thermal conductivity was calculated using the data processing software developed by
the manufacturer.
Materials 2021, 14, 7432 8 of 21

Impedance spectroscopy measurements were performed on Probostat equipment

(NORECS, Oslo, Norway) placed into a vertical tubular furnace (ELITE, Leicestershire,
UK). As impedance analyzer an Array M3500A instrument (Array, Nanjing, China) was
used in order to measure in AC mode. Impedance measurements were conducted in a fre-
quency interval between 1 kHz and 100 kHz. Temperature range was established between
200 ◦ C and 900 ◦ C at a 100 ◦ C interval. For analysis and impedance data fitting, NOVA
2.1 software from Methrom Autolab. (Metrohm Autolab B.V., Utrecht, The Netherlands)
was used.
Differential scanning calorimetry coupled with thermal gravimetry analysis (DSC-TG)
has been performed on a SETARAM SETSYS Evolution equipment (SETARAM Instrumen-
tation, Caluire, France) in inert atmosphere. Samples were introduced in alumina crucibles
and heated with a heating rate of 10 K/min up to 1450 ◦ C, then cooled to room temperature
with the same rate. The experimental data were processed with the help of Calisto software
v.1.097 (SETARAM Instrumentation, Caluire, France).

3. Results
3.1. Chemical Analysis
The chemical analysis of the powders synthesized under hydrothermal conditions
is in accordance with the designed compositions. The concentration of Zr, Y and Ln in
mother liquor resulting from the filtering of the hydrothermal reaction products and in the
wash-waters was in all cases <10−3 g·L−1 .

3.2. XRD Analysis

The XRD spectra of initial and thermal treated samples are presented in Figure 3a–d.

Figure 3. Cont.
Materials 2021, 14, 7432 9 of 21

Figure 3. Cont.
Materials 2021, 14, 7432 10 of 21

Figure 3. (a) XRD spectra of 8 wt.% YSZ powders co-doped with 4, 6 and 8 wt.% La2 O3 thermal treated at different
temperatures; (b) XRD spectra of 8 wt.% YSZ powders co-doped with 4, 6 and 8 wt.% Nd2 O3 thermal treated at dif-
ferent temperatures; (c) XRD spectra of 8 wt.% YSZ powders co-doped with 4, 6 and 8 wt.% Sm2 O3 thermal treated at
different temperatures; (d) XRD spectra of 8 wt.% YSZ powders co-doped with 4, 6 and 8 wt.% Gd2 O3 thermal treated at
different temperatures.

The qualitative phase analysis is presented in Table 1.

Table 1. Qualitative phase analysis of ZrO2 co-doped with 8 wt.% Y2 O3 and 4/6/8 wt.% Ln2 O3 powders initials and
after calcination.

Phase Composition
Sample % Dopant
Initial 400 ◦C 800 ◦ C 1000 ◦ C 1200 ◦ C 1400 ◦ C
C-(ZrO2 )SS 1 C-(ZrO2 )SS 1
C-(ZrO2 )SS 1
C C-(ZrO2 )SS 1 C-(ZrO2 )SS 1 M-(ZrO2 )SS M-(ZrO2 )SS
4 M-(ZrO2 )SS
M M-(ZrO2 )SS M-(ZrO2 )SS T-(ZrO2 )SS T-(ZrO2 )SS
T-(ZrO2 )SS
Pyr Pyr
C-(ZrO2 )SS 2 C-(ZrO2 )SS 2
C-(ZrO2 )SS 2
C C-(ZrO2 )SS 2 C-(ZrO2 )SS 2 M-(ZrO2 )SS M-(ZrO2 )SS
MxZY-La 6 M-(ZrO2 )SS
M M-(ZrO2 )SS M-(ZrO2 )SS T-(ZrO2 )SS T-(ZrO2 )SS
T-(ZrO2 )SS
Pyr Pyr
C-(ZrO2 )SS 3 C-(ZrO2 )SS 3
C-(ZrO2 )SS 3
C C-(ZrO2 )SS 3 C-(ZrO2 )SS 3 M-(ZrO2 )SS M-(ZrO2 )SS
8 M-(ZrO2 )SS
M M-(ZrO2 )SS M-(ZrO2 )SS T-(ZrO2 )SS T-(ZrO2 )SS
T-(ZrO2 )SS
Pyr Pyr
C C-(ZrO2 )Ss 4 C-(ZrO2 )SS 4 C-(ZrO2 )SS 4
4 C-(ZrO2 )SS 4 C-(ZrO2 )SS 4
M-(ZrO2 )SS M-(ZrO2 )SS M-(ZrO2 )SS
C-(ZrO2 )SS 5
C-(ZrO2 )SS 5 C-(ZrO2 )SS 5
6 C M-(ZrO2 )SS C-(ZrO2 )SS 5 C-(ZrO2 )SS 5
MxZY-Nd M-(ZrO2 )SS M-(ZrO2 )SS
T-(ZrO2 )SS
C-(ZrO2 )SS 6
C-(ZrO2 )SS 6 C-(ZrO2 )SS 6
8 C M-(ZrO2 )SS C-(ZrO2 )SS 6 C-(ZrO2 )SS 6
M-(ZrO2 )SS M-(ZrO2 )SS
T-(ZrO2 )SS
Materials 2021, 14, 7432 11 of 21

Table 1. Cont.

Phase Composition
Sample % Dopant
Initial 400 ◦C 800 ◦ C 1000 ◦ C 1200 ◦ C 1400 ◦ C
C-(ZrO2 )SS 7 C-(ZrO2 )SS 7 C- (ZrO2 )SS 7
C C-(ZrO2 )SS 7 C-(ZrO2 )SS 7
4 M-(ZrO2 )SS M-(ZrO2 )SS M-(ZrO2 )SS
M M-(ZrO2 )SS M-(ZrO2 )SS
T-(ZrO2 )SS T-(ZrO2 )SS T-(ZrO2 )SS
MxZY-Sm C C-(ZrO2 )SS 8 C-(ZrO2 )SS 8
6 C-(ZrO2 )SS 8 C-(ZrO2 )SS 8 C-(ZrO2 )SS 8
M M-(ZrO2 )SS M(ZrO2 )SS
C C-(ZrO2 )SS 9 C-(ZrO2 )SS 9
8 C-(ZrO2 )SS 9 C-(ZrO2 )SS 9 C-(ZrO2 )SS 9
M M-(ZrO2 )SS M-(ZrO2 )SS
C-(ZrO2 )SS 10
C C-(ZrO2 )SS 10 C-(ZrO2 )SS 10 C-(ZrO2 )SS 10 C-(ZrO2 )SS 10
4 M-(ZrO2 )SS
M M-(ZrO2 )SS M-(ZrO2 )SS T-(ZrO2 )SS T-(ZrO2 )SS
T-(ZrO2 )SS
C-(ZrO2 )SS 11
C C-(ZrO2 )SS 11 C-(ZrO2 )SS 11 C-(ZrO2 )SS 11 C-(ZrO2 )SS 11
MxZY-Gd 6 M-(ZrO2 )SS
M M-(ZrO2 )SS M-(ZrO2 )SS T-(ZrO2 )SS T-(ZrO2 )SS
T-(ZrO2 )SS
C-(ZrO2 )SS 12
C C-(ZrO2 )SS 12 C-(ZrO2 )SS 12
8 M-(ZrO2 )SS C-(ZrO2 )SS 12 C-(ZrO2 )SS 12
M M-(ZrO2 )SS M-(ZrO2 )SS
T-(ZrO2 )SS
Abbreviations used: C—Cubic Yttrium Zirconiu Oxides, PDF 01-077-2286; M—Monoclinic ZrO2 Baddeleyite, PDF 00-036-0420;
C-(ZrO2 )SS 1 —Cubic (La0.07 Y0.14 Zr0.79 )O1.9 , PDF 04-011-8534; M – (ZrO2 )SS —Monoclinic ZrO2 Baddeleyite, PDF 00-036-0420; T-(ZrO2 )SS
—Tetragonal, PDF 01-078-3348; Pyr-Cubic RE2 Zr2 O7– La2 Zr2 O7, PDF 04-017-6784; C-(ZrO2 )SS 2 —Cubic (La0.11 Y0.14 Zr0.75 )O1.88, PDF 04-
011-8534; C-(ZrO2 )SS 3 —Cubic (La0.14 Y0.14 Zr0.72 )O1.86 , PDF 04-011-8534; C-(ZrO2 )SS 4 —Cubic (Nd0.07 Y0.14 Zr0.79 )O1.9, PDF 04-011-8534;
C-(ZrO2 )SS 5 —Cubic (Nd0.11 Y0.14 Zr0.75 )O1.88 , PDF 04-011-8534;.C-(ZrO2 )SS 6 —Cubic (Nd0.14 Y0.14 Zr0.72 )O1.86, PDF 04-011-8534; C-(ZrO2 )SS 7 —
Cubic (Sm0.07 Y0.14 Zr0.79 )O1.9 86 , PDF 04-011-8534; C-(ZrO2 )SS 8 —Cubic (Sm0.11 Y0.14 Zr0.75 )O1.88 86, PDF 04-011-8534; C-(ZrO2 )SS 9 —Cubic
(Sm0.14 Y0.14 Zr0.72 )O1.86 , PDF 04-011-8534; C-(ZrO2 )SS 10 —Cubic (Gd0.07 Y0.14 Zr0.79 )O1.9, PDF 04-011-8534; C-(ZrO2 )SS 11 —Cubic (Gd0.11
Y0.14 Zr0.75 )O1.88 , PDF 04-011-8534; C-(ZrO2 )SS 12 —Cubic (Gd0.14 Y0.14 Zr0.72 )O1.86, PDF 04-011-8534.

The crystallite sizes of the initial hydrothermally synthesized powders have been
calculated from the broadening of [111] peak of the cubic phase using the Scherrer formula:

Kλ
d= (2)
β cos θ

where d is the mean size of the crystalline domains; K is a dimensionless shape factor, with
the typical value of about 0.9; λ is the X-ray wavelength; β is the line broadening at half
the maximum intensity (FWHM), after subtracting the instrumental line broadening, in
radians; and θ is the Bragg angle. The results are presented in Table 2.

Table 2. Mean crystallite sizes of the initial hydrothermally synthesized ZrO2 doped powders.

Sample % Dopant d (nm) Sample % Dopant d (nm)

4 6 4 5.4
MxZY-La 6 7 MxZY-Sm 6 5.6
8 7 8 5.1
4 6.3 4 5.7
MxZY-Nd 6 6 MxZY-Gd 6 5.7
8 5.7 8 5.6

All initial hydrothermal powders consist of cubic Yttrium Zirconium Oxide as the
major phase and monoclinic M-ZrO2 (Baddeleyite) as the secondary phase, with the
exception of 8 wt.% YSZ co-doped with Nd that consists only of the cubic phase.
All samples thermally treated at 400 ◦ C and 800 ◦ C have a similar phase composition.
The major phase is a solid substitution solution with the cubic structure of ZrO2 (C-(ZrO2 )ss )
in which Zr+4 is isomorphically substituted by Ln+3 in similar proportions.
Materials 2021, 14, 7432 12 of 21

With increasing thermal treatment temperatures, a secondary solid solution with

tetragonal symmetry (T-(ZrO2 )SS ) specific to intermediate temperatures is formed. At
1200 ◦ C and 1400 ◦ C the formation of pyrochlore structures (Pyr-RE2 Zr2 O7 where RE—Y
and Ln) is observed. However, for samples MxZY-Nd with 4, 6 and 8 wt. Nd at 1200 ◦ C
and 1400 ◦ C, MxZY-Sm with 6 and 8 wt.% Sm at 1000 ◦ C, 1200 ◦ C and 1400 ◦ C and MxZY-
Gd with 8 wt.% Gd only the cubic solid solution (ZrO2 )SS -(Ln0.14 Y0.14 Zr0.72 )O1.86 phase
was observed.

3.3. SEM Analysis

Scanning electron microscopy images show that nanopowders with irregular shapes
are formed in all systems and no significant grain growth is observed after calcination.
Figure 4 presents, as an example, the morphology of 8 wt.% YSZ powders co-doped with
6% Ln2 O3 as obtained by hydrothermal process and after calcination to 1000 ◦ C. The grain
sizes of all samples are summarized in Table 3.

Figure 4. Cont.
Materials 2021, 14, 7432 13 of 21

Figure 4. SEM images for 6% MxZYLn powders as obtained and calcined at 1000 ◦ C. (a) MxZY-6La initial powders;
(b) MxZY-6La calcined 1000 ◦ C powders; (c) MxZY-6Nd initial powders; (d) MxZY-6Nd calcined 1000 ◦ C powders;
(e) MxZY-6Sm initial powders; (f) MxZY-6Sm calcined 1000 ◦ C powders; (g) MxZY-6Gd initial powders; and (h) MxZY-6Gd
calcined 1000 ◦ C powders.

Table 3. Grain sizes of 4, 6, 8% MxZyLn powders, initial and calcinated at 1000 ◦ C.

Concentration of Dopant (%)

Sample
4 6 8
Initial 2.20–42.81 nm 2.14–14.53 nm 1.91–24.37 nm
MxZYLa
Calcined 1000 ◦C 1.29–17.55 nm 1.68–9.72 nm 1.51–20.25 nm
Initial 2.35–68.34 nm 2.02–52.31 nm 1.83–14.54 nm
MxZYNd
Calcined 1000 ◦ C 1.45–14.60 nm 1.91–12.91 nm 1.45–14.60 nm
Initial 2.65–11.49 nm 2.05–30.48 nm 1.62–18.73 nm
MxZYSm
Calcined 1000 ◦ C 1.36–17.71 nm 1.76–22.06 nm 1.55–13.83 nm
Initial 2.71–58.39 nm 1.78–52.27 nm 12.41–19.08 nm
MxZYGd
Calcined 1000 ◦C 1.26–16.96 nm 1.35–20.69 nm 1.52–23.3 nm

3.4. DSC Analysis

Thermal analysis was used to analyze the thermal stability of powder and phase
transformations during thermal treatment of hydrothermally synthesized powders. As
an example, the TG and DSC graph of the MxZy4%Gd powder heated from ambient
temperature to 1450 ◦ C is shown in Figure 5, with the specification that the graphs of the
other powders are similar. The mass losses for each individual system revealed in the TG
curve are shown in Table 4.
Materials 2021, 14, 7432 14 of 21

Table 4. Mass losses (wt.%) for MxZy%Ln powders.

Sample H2 O Loss Total Loss Sample H2 O Loss Total Loss

MxZY4% La 5.142 8.46 MxZy4% Sm 4.876 8.243
MxZY6% La 5.164 9.406 MxZy6% Sm 4.733 7.979
MxZY8% La 6.68 11.42 MxZy8% Sm 5.924 9.985
MxZY4Nd 4.859 8.168 MxZy4% Gd 4.095 8.224
MxZY6Nd 4.693 8.132 MxZy6% Gd 4.994 7.987
MxZY8Nd 6.299 10.233 MxZy8% Gd 5.295 8.352

Figure 5. DSC-TG analysis of MxZY4% Gd powder.

3.5. Thermal Conductivity

The thermal conductivity at room temperatures for ZrO2 co-doped with 8 wt.% Y and
6 wt.% Ln (Ln = La, Sm, Nd, Sm and Gd) are presented in Figure 6. The values obtained
are in the range of 0.305 W/mK for La co-doped pellets to 0.38 W/mK for Gd co-doped
pellets. The values are similar with those measured by Shi et al. for 4 wt.% RE2 O3 (RE = La,
Yb, Ce and Gd) and Y2 O3 co-doped ZrO2 powder synthesized by a sol–gel method [61].
Thermal conductivities of RE-YSZ (RE = La, Yb, Ce and Gd) tetragonal powders were
0.5181, 0.4215, 0.4851, 0.5187 and 0.5347 W/mK, respectively. Other thermal properties are
given in Table 5.

Table 5. Thermal properties of ZrO2 co-doped with 8 wt.% Y-6% Ln (Ln = La, Nd, Sm, Gd).

Th. Conductivity Th. Diffusivity Volumetric Spec. Heat Spec. Heat

Sample
(W/m·K) (mm2 /s) (MJ/m3 ·K) (MJ/m3 ·K)
MxZY-6%La 0.3049 ± 0.0079 0.2603 ± 0.0075 1.1715 ±0.0104 0.4048 ± 0.0036
MxZY-6%Nd 0.3276 ± 0.0004 0.2899 ± 0.0018 1.1297 ± 0.0077 0.3502 ± 0.0023
MxZY-6%Sm 0.3923 ± 0.0019 0.2766 ± 0.0053 1.4185 ± 0.0216 0.3987 ± 0.0060
MxZY-6%Gd 0.3799 ± 0.0012 0.2799 ± 0.0084 1.3577 ± 0.0379 0.3809 ± 0.0106
Materials 2021, 14, 7432 15 of 21

Figure 6. Thermal conductivity for ZrO2 co-doped with 8 wt.% Y-6% Ln (Ln = La, Nd, Sm, Gd).

3.6. Impedance Spectroscopy

Figure 7a–d presents the Nyquist plots for samples ZrO2 co-doped with 8 wt.% Y2 O3
and 6 wt.% Ln2 O3 (Ln = La, Sm, Nd, Sm, Gd) measured at 300, 400, 500 and 600 ◦ C
respectively. It may be observed that at temperatures below 500 ◦ C only one semi-circle
is presented. In the spectra registered at 500 ◦ C a second semi-circle emerged and the
formation of two semi-circles is clearly seen in all spectra from 600 ◦ C. The two semi-circular
arcs observed at 600 ◦ C indicate the grain and grain boundary contribution respectively [62].
The values obtained for the conductivity of samples analysed were further used to calculate
the activation energy of the conduction according to the equation:

σT = σ0 exp (−Ea/kT) (3)

where Ea is the activation energy for electrical conduction, σ is electrical conductivity, σ0

pre-exponential factor, k is Boltzmann constant and T is temperature, from the Arrhenius
plot presented in Figure 8. Activation energy calculated from the slopes of the least-squares
fit of lnσ vs 1000/T in the temperature range 300–600 ◦ C (573–873 K) are presented in
Table 6.
Table 6. Activation energy of conduction for ZrO2 co-doped with 8 wt.% Y2 O3 -6% Ln2 O3 (Ln = La,
Nd, Sm and Gd).

Sample Ea (eV)
MxZY-6%La 1.12
MxZY-6%Nd 1.21
MxZY-6%Sm 1.17
MxZY-6%Gd 1.09
Materials 2021, 14, 7432 16 of 21

Figure 7. (a) Nyquist plots for samples ZrO2 co-doped with 8 wt.% Y2 O3 and 6 wt.% Ln2 O3 at 300 ◦ C; (b) Nyquist plots for
samples ZrO2 co-doped with 8 wt.% Y2 O3 and 6 wt.% Ln2 O3 at 400 ◦ C; (c) Nyquist plots for samples ZrO2 co-doped with
8 wt.% Y2 O3 and 6 wt.% Ln2 O3 at 500 ◦ C; and (d) Nyquist plots for samples ZrO2 co-doped with 8 wt.% Y2 O3 and 6 wt.%
Ln2 O3 at 600 ◦ C.

Figure 8. Arrhenius plots for ZrO2 co-doped with 8 wt.% Y2 O3 and 6 wt.% Ln2 O3 at 600 ◦ C.
Materials 2021, 14, 7432 17 of 21

4. Discussions
The hydrothermal method provides an efficient route to obtain ZrO2 nanopowders
with controlled chemical composition by co-doping with Y, La, Nd, Sm and Gd. SEM
analysis shows the formation of ceramic powders with irregular shape and grain sizes
in the range 1.3–70 µm with no significant grain growth during thermal treatment at
temperatures up to 1000 ◦ C.
All initial hydrothermally synthesised powders consist of a mixture of Cubic Yttrium
Zirconium Oxide as the major phase and Monoclinic ZrO2 with the typical structure
of natural mineral Baddeleyite, excepting initial powders doped with 4, 6 and 8 wt.%
Nd2 O3 where only the cubic phase was formed. These results confirm previous results [63],
showing that the hydrothermal synthesis of yttria-doped zirconia nanopowders favours the
stabilization of the cubic phase at low temperatures, induced by the uniform distribution
of temperature and pressure during the nucleation process.
After thermal treatment at 400 ◦ C, the phase composition is homogenized and all
samples consist of the mixture of cubic and monoclinic phases previously mentioned.
DSC-TG analysis confirm that around 400 ◦ C the hydroxyl groups from the precipitated
powders are removed and a fully crystalised powder is formed. With further increase the
thermal treatment temperature to 1000 ◦ C, a tetragonal ZrO2 solid solution is formed as a
new phase in all powders, excepting 8 wt.% YSZ co-doped with 6 and 8 wt.% Sm2 O3 .
At 1200 ◦ C and 1400 ◦ C the formation of a new cubic solid solutions and pyrochlore
structures (Pyr-RE2 Zr2 O7 where RE—Y and Ln) is observed. The phase compositions ob-
tained at high thermal treatment temperatures are in good agreement with those predicted
from the study of phase diagrams briefly summarised in [64].
In the case of 8 wt.% YSZ co-doped with 4, 6 and 8 %wt. Nd2 O3 , 8YSZ co-doped with
6 and 8 wt.% Sm2 O3 and 8 wt.% YSZ co-doped with 8 wt.% Gd2 O3 , a cubic solid solution
was observed as single phase. The evolution of crystalline phases vs. composition and
temperature shows a clear trend toward the formation of cubic solid solutions with different
compositions depending. The higher stability of cubic zirconia with increasing temperature
is well known and is explained by the lower surface energy of the cubic symmetry. The
cubic phases formed in the 8 wt.% YSZ-co-doped with 4, 6 and 8 wt.% Ln2 O3 (Ln = La, Nd,
Sm and Gd) can be classified into three types of solid solutions, depending on the dopant
concentration: (Ln0.07 Y0.14 Zr0.79 )O1.90 ; (Ln0.11 Y0.14 Zr0.75 )O1.88 and (Ln0.14 Y0.14 Zr0.72 )O1.86 .
The increase in dopant concentration leads to decreasing the height and widening of
diffraction maxima. These results could be explained by the following fact: the increase
of the dopant concentration favours the introduction of micro-tensions at the level of the
elementary cell and the formation of nanometric crystallites. More detailed works and
deconvolutions are further needed to evaluate these changes induced in the elementary
cell in a multiphase material.
The low thermal conductivity of 8 wt.% YSZ co-doped with 4, 6 and 8 wt.% Ln2 O3
may be related to the complex phase composition and the formation of cubic pyrochlore
that was reported as low thermal conductive materials [65]. However, the results obtained
by the hot disk method should be further checked with other standardized methods, such
as flash DSC.
Impedance spectrometry indicates that at about 600 ◦ C the migration of the charge
carriers take place through different mechanisms, due to the modification of the grain
boundaries and bulk contributions vs. dopant used, leading to the decrease of the total
electrical resistance of samples with increasing temperature. The dopants modify the
grain resistance and grain boundary behaviour within the studied frequency range. This
is in accordance with previous studies showing that in the case of doping with Gd the
conductivity presents a rapid increase with temperature [66]. The formation of complex
cubic solutions in the case of co-doping 8 wt.% YSZ with LnO3 is enhanced by the ratio
between Ln3+ ionic radii and Y3+ ionic radius leading to modification of the intergranular
energy and grain boundaries diffusion properties [16].
Materials 2021, 14, 7432 18 of 21

With increasing temperature, the grain boundary contribution becomes the conduction
limiting step. The activation energies have values of the same order of magnitude for all
8 wt.% YSZ-6 wt.% Ln2 O3 samples studied, with a lower value of 1.09 eV for 6 wt.%
Gd co-doped materials. Compared to the experimental results presented in [67] where
activation energies for bulk conductivity of YSZ doped with 1 and 2 wt.% Yb and Gd were
in the range 0.68–0.84 eV, it may be considered that the higher concentration of co-doping
elements, the higher association of vacancies concentrations with lattice defects, influencing
the total conductivities of materials. These results will be further used to understand the
structure modification induced by co-doping ZrO2 with various Rare Earth Oxides.
The influence of the sintering procedure (classic uniaxial pressing followed by air
sintering and spark plasma sintering) is a work in progress to validate the experimental
results regarding thermal conductivities and optimise their processing to assess their
potential applications as materials for high temperature TBCs.

5. Conclusions
Zirconia powders co-doped with 8 wt.% Y2 O3 and 4/6/8 wt.% Ln2 O3 (Ln = La, Nd,
Sm and Gd) were obtained by hydrothermal synthesis in one-step process at moderate tem-
peratures (max. 250 ◦ C) and pressures (max. 40 atm). Nanocrystalline powders consisting
of cubic Yttrium Zirconium Oxide as a major phase and monoclinic M-ZrO2 (Baddeleyite)
as a secondary phase were obtained, excepting YSZ doped with Nd that consist only of
a cubic phase. The phase evolution of powders during thermal treatment in the range
400–1400 ◦ C shows the progressive formation of different solid solution by isomorphically
substitution of Zr4+ with Ln3+ . A cubic ZrO2 solid solution is the major phase and sec-
ondary phases with generic formula (Ln0.07 Y0.14 Zr0.79 )O1.90 ; (Ln0.11 Y0.14 Zr0.75 )O1.88 and
(Ln0.14 Y0.14 Zr0.72 )O1.86 are formed depending on the dopant concentration.
At temperatures 1200 ◦ C and 1400 ◦ C, the formation of cubic solid solutions with
Pyrochlore structures (Pyr-RE2 Zr2 O7 where RE—Y and Ln) is observed for all compositions,
with the exception of samples co-doped with 4, 6 and 8 wt.% Nd, 6 and 8 wt.% Sm and
8 wt.% Gd, when only the cubic (ZrO2 )SS -(Ln0.14 Y0.14 Zr0.72 )O1.86 phase was observed.
Low values of the thermal conductivities were measured by the hot plate method
at room temperature. The impedance spectroscopy allowed calculation of the activation
energy of conduction for zirconia powders co-doped with 8 wt.% Y2 O3 and 6 wt.% Ln2 O3 ,
with the lower value 1.09 eV for Gd co-doped materials.
Further works are in progress to correlate the thermal conductivities and activation
energies with the complex structures induced by each co-doping element and assess the
potential applications in TBCs.

Author Contributions: Conceptualization, R.-R.P. and A.M.M.; methodology, S.N.V.; validation,

C.F.C. and M.P.; investigation, A.-N.G., A.E.S. and S.C.; writing—original draft preparation, A.E.S.
and S.C.; writing—review and editing, R.-R.P. and A.E.S.; supervision, R.-R.P. and A.M.M.; project
administration, R.-R.P. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by UEFISCDI Romania in the frame of contract PN-III-P2-2.1-
PED-2019-2175 ID 503 AEROCOAT and UEFISCDI Romania and TUBITAK Turkey in the frame of
ERAMIN III Program, Project ID 38 RETECH.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding authors.
Acknowledgments: We thank Viorel Badilita for fruitful discussions regarding XRD results.
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2021, 14, 7432 19 of 21

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