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