Pressureless Sintering of (Y0.2Gd0.2Er0.2Yb0.2Lu0.2)2Zr2O7 High-entropy Ceramic and Its High Temperature CMAS Corrosion Resistance

doi:10.15541/jim20240256

Abstract

Abstract:

Rare-earth zirconates (REZs) have attracted attention in the field of thermal barrier materials because they are more resistant to calcium-magnesium-aluminum-silicon oxide (CMAS) corrosion than yttria stabilized zirconia (YSZ). High-entropy design of zirconates is an effective method to enhance CMAS corrosion resistance, but currently the ability of its corrosion resistance still does not meet the growing requirement. In this work, a solid-state reaction technique was used to synthesize high-entropy rare-earth zirconate (HE-REZ) (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ powder with a single-phased defect fluorite structure, and pressureless sintering (PLS) combined with cold isostatic pressing (CIP) technique was used to efficiently prepare bulk samples. The phase composition, microstructure, element distribution, thermal and mechanical properties were studied, focusing on the CMAS corrosion resistance. According to the results, under the same CMAS corrosion environment at 1300 ℃, the corrosion depth of HE-REZ with a relative density of 98.6% is only 2.6% of 7YSZ and 22.6% of Gd₂Zr₂O₇ (GZO). The synergistic effect of zirconates' chemical inertness and high-entropy materials' sluggish diffusion accounts for this exceptional corrosion resistance. The obtained HE-REZ shows higher hardness and Young's modulus, larger coefficient of linear expansion, and lower thermal conductivity than ever, making its mechanical and thermal properties superior to GZO. All these outcomes demonstrate the good application potential of (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ in the field of thermal barrier materials.

Key words: high-entropy ceramic, thermal barrier material, zirconate, pressureless sintering, CMAS corrosion resistance

CLC Number:

TQ174

FAN Wenkai, YANG Xiao, LI Honghua, LI Yong, LI Jiangtao. Pressureless Sintering of (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ High-entropy Ceramic and Its High Temperature CMAS Corrosion Resistance[J]. Journal of Inorganic Materials, 2025, 40(2): 159-167.

Figures/Tables 12

Fig. 1 Phase composition of rare-earth zirconates (REZs) (a) XRD patterns of HE-REZ vs. other REZs with P indicating pyrochlore structure and F indicating defect fluorite structure; (b) Raman spectrum of HE-REZ; (c, d) XRD patterns of HE-REZ synthesized at different temperatures

Table 1 Shannon ionic radii of some cations

Element	Coordination number	Valency	Ionic radius/pm
Zr	6	+4	72.0
Lu	8	+3	97.7
Yb	8	+3	98.5
Er	8	+3	100.4
Y	8	+3	101.9
Gd	8	+3	105.3
Sm	8	+3	107.9
Nd	8	+3	110.9
La	8	+3	116.0

Table 2 Summary of some properties of bulk ceramic samples prepared in this work

Sample	Preparation method	Relative density/%	Average grain size/μm	Corrosion depth (1300 ℃, 10 h)/μm
HE1	SPS	99.7	7.20±3.20	18±2
HE2	PLS	95.4	2.60±0.80	45±5
HE3	CIP+PLS	98.6	2.40±0.60	28±3
GZO	CIP+PLS	98.3	2.70±0.80	124±8
7YSZ	CIP+PLS	97.2	0.36±0.14	1070±10

Fig. 2 Macroscopic and microscopic morphologies and EDS analyses of HE-REZ bulk ceramic (HE3) prepared by CIP+PLS (a) Photo of bulk sample; (b) SEM image of surface; (c-h) EDS element mappings of Fig. (b)

Fig. 3 Crystalline morphologies and CMAS corrosion depths of HE-REZ bulk samples with different relative densities (a, b) HE2 (by PLS); (c, d) HE3 (by CIP+PLS); (e, f) HE1 (by SPS)

Fig. 4 Corrosion depths and Si distributions of bulk ceramic synthesized by CIP+PLS under the same CMAS corrosion condition (a) HE-REZ (HE3); (b) GZO; (c) 7YSZ

Fig. 5 Crystalline morphologies of control groups (a) GZO; (b) 7YSZ

Fig. 6 Morphology and element distribution in the reaction zone of HE-REZ after CMAS corrosion (a) SEM image of reaction zone; (b-f) EDS element mappings of Fig. (a); (g-i) Partial enlarged images showing hexagonal apatite crystals (yellow box)

Fig. 7 CMAS corrosion kinetics of HE-REZ bulk ceramic (a-e) SEM images of HE-REZ after CMAS corrosion for different time; (f) Mathematical relationship between corrosion depth (H) and corrosion time

Fig. 8 Schematic diagram of CMAS corrosion kinetics for HE-REZ ceramic (a) RE3+ diffusing into CMAS; (b) ZrO2 forming; (c) Apatite precipitating out as RE3+ saturated

Fig. 9 Mechanical properties of HE-REZ, GZO and 7YSZ bulk ceramics

Fig. 10 Thermal properties of HE-REZ and GZO bulk ceramics (a) Thermal conductivity; (b) Linear expansion in temperature range of 30-1200 ℃

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Pressureless Sintering of (Y_0.2Gd_0.2Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ High-entropy Ceramic and Its High Temperature CMAS Corrosion Resistance

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