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Ceramics International 44 (2018) 2485–2490

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Chemical and nanoindentation study of diffusion during sintering of T


12Ce-ZrO2/3Y-ZrO2 powder layers

J.J. Roaa,b, , M. Turon-Vinasa,b, D. Tovara,b, J. Ledesmac, M. Angladaa,b
a
CIEFMA-Materials Science and Metallurgical Department, Barcelona School of Engineering (EEBE)-Universitat Politècnica de Catalunya, 08019 Barcelona, Spain
b
Research Center in Multiscale Science and Engineering. Barcelona School of Engineering (EEBE)-Universitat Politècnica de Catalunya, 08019 Barcelona, Spain
c
ScienTec Ibérica, 28290 Madrid, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Tetragonal zirconia polycrystals doped with 3% mol of yttria (3Y-ZrO2) exhibit excellent mechanical properties
12Ce-ZrO2/3Y-ZrO2 interface and biocompatibility. However, under humid environments, their surface structural integrity is degraded by
Diffusion aging (low temperature degradation). Co-doping with Ceria by starting from mixtures of 3Y-ZrO2 and 12Ce-ZrO2
Chemical analysis powders can increase the resistance to low temperature degradation. In this study, systematic chemical and
Wavelength dispersive spectrometry
nanomechanical measurements have been conducted in powder multilayers of the12Ce-ZrO2/3Y-ZrO2 system
Micromechanical properties
after sintering at different temperatures (from 1400 to 1600 °C) during 2 h in order to measure the distribution of
diffusion of stabilizer solutes. The results indicate that the diffusion process zone at the 12Ce-ZrO2/3Y-ZrO2
interface increases with sintering temperature by following an Arrhenius equation. Measuring the hardness by
nanoindentation through the diffusion zone gives similar activation energy at high sintering temperatures. At
low sintering temperatures, nanoindentation has not enough resolution at low sintering temperatures for the
sintering time used.

1. Introduction but is often studied by accelerated aging tests in autoclave at 134 °C


under 2 bar pressure. During aging, water species induce the t → m
Tetragonal polycrystalline zirconia doped with 3% molar yttria (3Y- transformation at the free surface which slowly progresses inside the
ZrO2) has excellent physical and chemical properties, which makes it a material [4], leading to a t → m surface transformed layer. The main
prospective candidate for being used in different fields of engineering effect is to degrade the surface mechanical properties, as for example
and in dentistry. One characteristic property of 3Y-ZrO2 is an enhanced the wear resistance. A study of the mechanical properties of this de-
fracture toughness with respect to other ceramic oxides. The reason for graded layer was carried out by Camposilvan et al. [5] by extracting
the high toughness is related to transformation toughening which takes and testing micro-cantilevers from the degraded surface by means of
place by means of a martensitic phase transformation from the me- the focused ion beam technique. He found that the strength of this layer
tastable tetragonal (t) to the monoclinic (m) crystal structure [1]. The was several times smaller than the non-degraded material.
transformation is accompanied by a change in shape and volume in- The resistant to LTD can be easily improved by doping with ceria
crease of around 4%, which closes the crack when it is activated by the instead of yttria. Thus ceria ceramics like 10 or 12Ce-ZrO2, for example,
stress in front of a crack [2]. By contrast, if the critical stress for t-m are fully resistant to LTD and much tougher than 3Y-ZrO2, but their
transformation is reached on the free surface of components stressed in hardness and strength are significantly lower. Co-doping with yttria, or
bending, it can initiate fracture and, hence, reduce its structural relia- other stabilizers, can reduce the grain size, so that hardness and
bility. The transformation is triggered when the change in bulk che- strength can be increased, but paying a penalty for fracture toughness
mical free energy is sufficient to overcome the surface energy of the and, depending on the composition, for the resistance to LTD [6].
new interface and the strain energy [3]. Moreover, the distribution of main stabilizers after sintering at
A weak feature of 3Y-ZrO2 is the phenomenon known as low tem- 1450 °C for 2 h was found inhomogeneous, not only because of che-
perature degradation (LTD) or also referred to as “aging” that originates mical segregation to the grain boundaries (GBs), but also due to a non
in contact with water. This process takes place at different temperatures homogenous distribution of stabilizers inside the grains [6]. However,


Corresponding author at: CIEFMA-Materials Science and Metallurgical Department, Barcelona School of Engineering (EEBE)-Universitat Politècnica de Catalunya, 08019 Barcelona,
Spain.
E-mail address: joan.josep.roa@upc.edu (J.J. Roa).

http://dx.doi.org/10.1016/j.ceramint.2017.10.226
Received 15 September 2017; Received in revised form 27 October 2017; Accepted 30 October 2017
Available online 31 October 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
J.J. Roa et al. Ceramics International 44 (2018) 2485–2490

the results presented in Ref. [6] are not conclusive to assert the extent profile and three different profiles across the interface were conducted.
of the diffusion process between the 3Y-ZrO2 and 12Ce-ZrO2 particles. The distance between each measurement was kept constant and equal
Within this context, the aim of the paper is to compare the effect of the to 2 µm, with counting times that ensured a statistical uncertainty lower
sintering temperature on the interdiffusion between 12Ce-ZrO2/3Y- than 1%.
ZrO2 compacted powder layers and relate the change in composition
during diffusion with the change in nanohardness. The sintering tem-
2.3. Micromechanical characterization
peratures studied are from 1400 to 1600 °C. In doing so, advanced
microscopy techniques, as Electron Probe Microanalysis (EPMA) using
Mechanical properties (mainly hardness, H) at the micrometric
Wavelength Dispersive Spectrometry (WDS) and Field Emission Scan-
length scale were determined by means of nanoindentation. The na-
ning Electron Microscopy (FESEM) have been used.
noindentation tests were performed with the nanoindenter iNano® from
Nanomechanics Inc., Oak Ridge (USA) equipped with a Berkovich tip
2. Experimental procedure indenter. Nanoindentation curves were analyzed using the Oliver and
Pharr method [9,10], and all the experiments were performed in dis-
2.1. Samples preparation placement controlled mode. The indenter shape was carefully cali-
brated for true indentation depth as small as 25 nm by indenting fused
The starting commercial powders used in the preparation of the silica sample of known Young's modulus, 72 GPa [11].
specimens were 12Ce-ZrO2 (ZrO2 with 12 mol% CeO2, CEX-12 SD), 3Y- Two different sets of experiments at the micro- and nanometric
ZrO2 (ZrO2 with 3 mol% Y2O3, HSY-3FSD), both with small con- length scale were performed. First, the hardness for each individual
centrations of Al2O3 (about 0.25 wt%) and there were supplied by phase was determined at a maximum penetration depth of 1000 nm (or
Daiichi Kigenso Kagatu Kogyo, Japan. until reaching the maximum applied load of the loading cell, 45 mN)
Layers of 12Ce-ZrO2/3Y-ZrO2 were prepared by depositing one through a homogeneous indentation array of sixteen imprints (4 by 4).
powder in a mould, uniaxially pressing to 100 MPa and repeating the The distance between them was kept constant and equal to 50 µm in
process with the other powder. The layers formed in this way were later order to avoid any overlapping effect. The hardness profile through the
sintered at different temperatures (1400, 1450, 1500, 1550 and 12Ce-ZrO2/3Y-ZrO2 interface was measured by performing a line with
1600 °C) for 2 h in air atmosphere. A field emission scanning electron an array of 210 indentations regularly spaced and at with 200 nm of
microscopy (FESEM) image of the interface investigated for a specimen maximum displacement into surface. The equivalent diameter of the
sintered at 1400 °C is depicted in Fig. 1 as example. Periodicity of the indents was about 1400 nm. Thus, the indentations were performed
multilayers is controlled by the amount of powder deposited per layer; with a spacing distance of 5 µm to avoid any overlapping effect. In this
thus, resulted in a constant bilayer (λ) period of around 800 µm. way, in the hardness versus distance profile, each point was averaged
Before chemical and micromechanical characterization, the speci- over three different measurements. The error bars represent the stan-
mens were firstly ground and polished using silicon carbide papers, dard deviation.
followed by diamond suspensions until 3 µm, and a final step using
colloidal silica. The final surface was carefully cleaned ultrasonically
with acetone for 15 min and dried with pure air. 3. Results and discussion

3.1. Chemical analysis


2.2. Chemical analysis: wavelength dispersive spectrometry
Fig. 2 shows WDS quantitative chemical concentration profiles for Y
Electron probe X-ray microanalysis (EPMA) using wavelength dis- and Ce through the layer interface for each sintering temperature.
persive spectrometry (WDS) was conducted in three different regions These profiles clearly exhibit a diffusion zone around the interface
per each specimen through the 12Ce-ZrO2/3Y-ZrO2 layer interface after (marked by vertical dashed lines) with a width ranged between 4.9 and
sintering using a JEOL JXA-8230 microprobe. The X-ray profiles were 17 µm depending on the sintering temperature. The chemical compo-
recorded in high-resolution mode, using a channel width of 1 eV. sition away from the interface remains constant and consistent with the
Electron currents were selected to ensure that counting rates were less nominal composition, 4.3 and 13.5 wt% for the Y and Ce content, re-
than 104 counts s−1. More information about the protocol followed to spectively.
conduct this analysis can be found elsewhere [7,8]. It is known that in powder mixtures there is important diffusion
For each sample, at least ten measurements along the interface according to the results reported by Nakahira et al. [11] for 12Ce-ZrO2/
3Y-ZrO2 sintered at 1400 °C for 4 h and post-hot isostatic pressing (HIP)
treatment at 1350 °C in Air/O2 atmosphere, where most of grains
contained Ce and Y, so that co-doping was generated at this small scale.
Very close to the interface between layers the process of sintering
takes place at the same time that diffusion of stabilizers among the
particles. In a given layer, depending of the distance to the initial in-
terface, sintering will be affected in a more or less degree by the dif-
fusion of the stabilizer of the contiguous layer. This effect may be strong
just at the interface, but as far as the distance to the interface increases
the particles will be sintered with less influence of the stabilizer of the
contiguous layer. Particles of powders far away from the interface will
sinter independently of the presence of the other powder.
As diffusion depends on temperature throughout the diffusion
coefficient, the equations for the concentration of stabilizers at different
sintering temperatures will depend on diffusion during sintering and in
the sintered state. For a fixed concentration, if we assume that diffusion
Fig. 1. FESEM micrograph of the multilayer 12Ce-ZrO2/3Y-ZrO2 interface sintered at is controlled by an effective diffusion coefficient, Deff, the width of the
1450 °C. The green arrow shows the direction where the chemical and mechanical ex- process zone, w, at different temperatures for a fixed sintering time of
periments were conducted.
2 h can be written as:

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Fig. 2. Chemical profiles determined by WDS through the 12Ce-ZrO2/3Y-ZrO2 interface for each sintering temperature: (a) 1400 °C, (b) 1450 °C, (c) 1500 °C, (d) 1550 °C and (e) 1600 °C.
The vertical dash lines delimit the diffusion region.

w 2~Deff ·t (1) subsequent diffusion of the stabilizers will occur in a much larger grain
size.
By taking logarithms:

lnw = lnA − Qeff /RT (2) 3.2. Mechanical analysis

then ln w should be linear with 1/T and the slope should give the ef- 3.2.1. Micromechanical properties for each constitutive layer
fective activation energy for diffusion, Qeff, divided by the gas constant, In order to provide reference values before the diffusion process the
R. This value of Qeff can be considered as an effective activation energy hardness of the 12Ce-ZrO2 and 3Y-ZrO2 sintered at the same tempera-
for diffusion of the stabilizers in this complex process. At low sintering ture that used for the 12Ce-ZrO2/3Y-ZrO2 interface systems was mea-
temperatures diffusion of the stabilizers will be favored by the sintering sured. Fig. 3 shows the hardness histogram as a function of the sintering
process itself and by the existence of one smaller grain size which en- temperature for both materials. It can be appreciated that the 3Y-ZrO2
hances the effect of grain boundary diffusion. By contrast, at high material is harder than the 12Ce-ZrO2. Two different trends can be
temperature, since sintering will take place more rapidly, the distinguished depending on the sintering temperature, being the border

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3.2.3. Hardness profile through the 12Ce-ZrO2/3Y-ZrO2 interface


Fig. 5 a-e exhibits the hardness profile through the 12Ce-ZrO2/3Y-
ZrO2 interface for each sintering temperature, from 1400 to 1600 °C.
The profile is changing from the initial stepwise function to a smooth
transition from the “hard” 3Y-ZrO2 to the “soft” 12Ce-ZrO2, which is
mainly related to the diffusion of Y and Ce as revealed by chemical
analysis. Far from the diffusion zone, the hardness values observed in
each profile are similar to those reported in Fig. 3.
Hardness is not only dependent of the solute concentration, it de-
pends also on grain size. Therefore, at a specific distance from the in-
terface on the 3Y-ZrO2 (12Ce-ZrO2) side, hardness will be dictated by
the concentration of stabilizer as well as by the grain size achieved. As
with the chemical concentration analyzed in Section 3.1, we plot the
width of the change in hardness in terms of temperature of sintering.
The width over which these changes have taken place will depend in
principle of the diffusion coefficient and grain size. However, one
should take into account several additional factors. First, at the lowest
temperature, the presence of a higher amount of porosity in the sintered
layers may decrease the hardness. Secondly, the indentations are se-
Fig. 3. Hardness histogram for each layer (12Ce-ZrO2 and 3Y-ZrO2) determined at
parated one of each other 5 µm, so that the technique is limited when
1000 nm of maximum displacement into surface as a function of the sintering tempera-
ture. the diffusion process zone is of about this small size. Thirdly, at the
highest sintering temperatures the nanoindentation imprint may be
contained inside only one grain or in very few grains, so that the scatter
line at around 1500 °C. For the 3Y-ZrO2 system the hardness increases
might be larger and the average value might be not very sensitive to the
as sintering temperature increases until reaching a maximum hardness
grain size.
of around 18.3 GPa for the specimen sintered at 1500 °C. This may be
related to the reduction of sintering defects (mainly porosity) as the
3.3. Diffusion kinetics
sintering temperature increases. Porosity has significant effects on
mechanical properties including hardness, elastic modulus and fracture
The combined study of the hardness and chemical profile across the
toughness. On the other hand, for sintering over 1500 °C, the hardness
12Ce-ZrO2/3Y-ZrO2 interface by using the nanoindentation and WDS
decreases until reaching about 17.2 GPa. This may be related to easier
techniques, respectively, allowed to build a graph of hardness versus Y
activation of t-m transformation with grain growth, but not to the
concentration for the different studied samples (Fig. 6). It can be no-
presence of cubic phase since this phase is harder than the tetragonal
ticed that the hardness is mainly determined by the concentration of
phase [12]. This reduction in hardness may be related to the larger
yttria, while is not very sensitive to concentration of ceria. Ceria may
tetragonal grains present and to the impoverishment of stabilizer of the
have an indirect effect on hardness as contributing to grain growth and
tetragonal phase when partition takes place with the appearance of the
making the t-m transformation easier.
stabilizer rich cubic phase. Since the hardness remains constant (around
The activation energy can be estimated by plotting the logarithm of
17 GPa) at sintering temperatures of 1550 and 1600 °C, in spite of the
the diffusion width versus the inverse of the sintering temperature.
increasing presence of cubic phase, this means that the remaining tet-
Fig. 7 shows such Arrhenius plot obtained with data of the diffusion
ragonal phase becomes slightly softer. This trend is in agreement with
width experimentally determined by WDS (Fig. 2) and by na-
the values measured in [13].
noindentation (Fig. 5). As can be observed, there is a good correlation
For the 12Ce-ZrO2 system, the behavior is slightly different.
between both measurements at high temperature, but important de-
Minimum hardness (11.4 GPa) is achieved at 1400 °C and maximum
viations can be found in the graph corresponding to nanoindentation at
hardness at 1550 °C (14 GPa), which only slightly changes around this
the lowest temperatures mainly at 1400 °C. This can be explained by
last sintering temperature. Since fast grain growth already occurs at
the limitation in the spatial resolution of the technique when the width
1550 °C, the reason for this relative insensitivity to grain size might be
of the process zone is too narrow (similar to separation between na-
related to the t → m transformation becoming less sensitive to the grain
noindentation imprints).
size after a critical grain size is achieved. Furthermore, another possi-
Qeff determined from the fitting of the experimental values to an
bility could be associated to Ce reduction, from Ce+4 to Ce+3, at high
Arrhenius equation is 305.4 kJ/mol with a correlation parameter R2
temperature and concomitant segregation to grain boundaries as pre-
equal to 0.957. Qeff is lower than the activation energies for grain
viously observed by Roa et al. [6].
boundary and lattice diffusion in 3Y-ZrO2, which are about 460 [14]
and 580 kJ/mol [15], respectively. However, it should be noticed that
3.2.2. Indentation size effect the diffusion flow in the present case takes place partly during the
Possible indentation size effect (ISE) or tip defect were evaluated by sintering process, which can assist diffusion by the sintering diffusion
plotting P/S2 (where P is the applied load and S is the stiffness) versus mechanisms.
the displacement into surface, h, for the 12Ce-ZrO2 (Fig. 4a) and 3Y-
ZrO2 (Fig. 4b) layers, at all the sintered temperature investigated. This 4. Conclusions
parameter is independent of the contact area. Then, it does not depend
on the calibration of the tip. As it may be observed from the resulting In this study we have characterized the chemical and nanomecha-
graphs, P/S2 data are independent of the displacement into surface nical stability of 12Ce-ZrO2/3Y-ZrO2 multilayers compacted powders
employed for all the sintering temperatures as the latter gets deeper through the interface when they are sintered at different temperatures.
than 25 nm. However, for penetration depths shallower than 25 nm, the From the analysis of the experimental results, the following conclusions
values are strongly affected by length scale effects (i.e. superficial have been drawn:
roughness, etc.) or ISE. In order to avoid any scale or size effects, pe-
netration depth was kept constant for the nanoindentation tests done (i) Nanoindentation is a suitable technique to measure the diffusion
through the interface and equal to 200 nm. layer through the 12Ce-ZrO2/3Y-ZrO2 interface with a high

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Fig. 4. P/S2 ratio against displacement into surface for the 12Ce-ZrO2 (a) and 3Y-ZrO2 (b) sintered at the different temperatures investigated here.

Fig. 5. Hardness profiles through the 12Ce-ZrO2/3Y-ZrO2 interface for each sintering temperature: (a) 1400 °C, (b) 1450 °C, (c) 1500 °C, (d) 1550 °C and (e) 1600 °C. The vertical dash
lines delimit the diffusion region.

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(ii) It is shown by both methods that at high temperatures the diffusion


zone between 12Ce-ZrO2 and 3Y-ZrO2 layers follows an Arrhenius
behavior.

Acknowledgements

Authors greatly acknowledge the MAT2014-60720-R supported by


the Spanish “Ministerio de Economía y Competitividad”. Furthermore,
we are grateful to “Secretaria d’Universitats i Recerca de la Generalitat
de Catalunya” for financial support (2014-SGR-130).

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