构型熵提高稀土锆酸盐CMAS耐蚀性的作用

doi:10.7527/S1000-6893.2025.32302

Abstract

Abstract:

To investigate the influencing factors of CMAS corrosion resistance in rare-earth zirconates， seven low-， medium-， and high-entropy rare-earth zirconates RExZO （RE = Y， Ho， Dy， Er， Gd， Yb， Tm； x = 1-7） were prepared， and their CMAS corrosion behaviors at 1 300 ℃ were systematically studied. Results indicate that rare-earth zirconate materials undergo dissolution damage upon contact with CMAS at high temperatures， accompanied by the formation of a new apatite phase. The high-entropy structure facilitated the development of a dense reaction layer composed of apatite and fluorite phases through a “dissolution-reprecipitation” mechanism， significantly reducing the maximum infiltration depth from 80.6 μm for RE1ZO to 30.9 μm for RE7ZO （a 61.7% reduction）. Influenced by ionic radius variations， dissolved rare-earth elements exhibited gradient diffusion into the apatite and fluorite phases. Correlation analyses reveal a significant positive relationship between corrosion depth and optical basicity difference， while showing significant negative correlations with configurational entropy and atomic size disorder. First-principles calculations and XPS results further confirm that high configurational entropy reduces the Gibbs free energy and oxygen vacancy concentration of rare-earth zirconates while enhancing elemental binding energy， thereby improving structural stability. Based on these findings， an optimization strategy for designing CMAS-resistant rare-earth zirconates is proposed： priority should be given to material combinations featuring low optical basicity difference， high configurational entropy， and high atomic size disorder.

Key words: rare-earth zirconate, configurational entropy, CMAS corrosion, thermal barrier coating, high-entropy ceramic

CLC Number:

V254.2

Shihua ZHANG, Kunying DING, Zhongshen DONG, Jianhai YU, Yubo SUN, Tao ZHANG, Jiaxi YUAN, Jintao LU. Role of configurational entropy in enhancing CMAS corrosion resistance of rare-earth zirconates[J]. Acta Aeronautica et Astronautica Sinica, 2026, 47(5): 432302.

Figures/Tables 20

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References 44

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样品	稀土元素类型	平均离子半径R_A/nm	构型熵ΔS_mix/（J∙K^-1）	尺寸无序度δ_R
RE1ZO	Y	1.019	0	0
RE2ZO	Y，Ho	1.017	0.69R	0.002
RE3ZO	Y，Ho，Dy	1.020	1.10R	0.004
RE4ZO	Y，Ho，Dy，Er	1.016	1.38R	0.008
RE5ZO	Y，Ho，Dy，Er，Gd	1.024	1.61R	0.016
RE6ZO	Y，Ho，Dy，Er，Gd，Yb	1.017	1.79R	0.021
RE7ZO	Y，Ho，Dy，Er，Gd，Yb，Tm	1.014	1.95R	0.021

样品	平衡晶格常数/Å	精修晶格常数/Å	理论密度/（g∙cm^-3）	实际密度/（g∙cm^-3）	相对密度/%
RE1ZO	5.214	5.208	5.748	4.976	85.2
RE2ZO	5.198	5.210	6.629	5.672	85.6
RE3ZO	5.203	5.218	6.875	5.911	86.0
RE4ZO	5.191	5.209	7.068	5.994	86.6
RE5ZO	5.209	5.232	7.057	5.990	85.4
RE6ZO	5.210	5.225	7.147	5.998	84.5
RE7ZO	5.198	5.215	7.221	6.264	86.8

分类	样品	标记点	含量/%
分类	样品	标记点	RE	Zr	Ca	Si	Al	Mg	O	相
低熵和中熵	RE1ZO	A1	11.37		15.30	21.74			51.59	Apatite
		A2	4.19		14.7	20.02	5.79	6.09	49.20	CMAS
		A3	11.24	35.76	1.28				51.71	Fluorite
		A4	22.62	20.04					57.34	RE1ZO
	RE2ZO	B1	14.50		13.23	22.55			49.73	Apatite
		B2	3.84		14.58	20.67	7.27	5.93	47.71	CMAS
		B3	11.60	37.47	1.72				49.21	Fluorite
		B4	20.83	19.71					59.46	RE2ZO
	RE3ZO	C1	5.65		13.67	22.03			58.66	Apatite
		C2	6.92	31.62	3.14				58.32	Fluorite
		C3	1.21	2.82	13.85	18.20	6.25	3.84	53.83	CMAS
		C4	18.83	19.51					61.66	RE3ZO
	RE4ZO	D1	13.06		11.88	22.54			52.51	Apatite
		D2			19.74	18.62	4.56	6.71	50.37	CMAS
		D3	10.36	34.40	1.41				53.82	Fluorite
		D4	20.76	19.32					59.92	RE4ZO
高熵	RE5ZO	E1	15.31		13.21	23.48			48.02	Apatite
		E2	11.39	36.83	1.23				50.55	Fluorite
		E3	2.13	2.86	13.44	20.00	7.10	3.63	50.84	CMAS
		E4	21.42	27.69					50.89	RE5ZO
	RE6ZO	F1	17.02		11.73	20.80			50.44	Apatite
		F2	11.14	34.37	1.45				53.03	Fluorite
		F3	1.91	0.37	14.23	21.38	6.66	3.52	51.94	CMAS
		F4	22.64	23.50					53.86	RE6ZO
	RE7ZO	G1	17.25		11.23	21.51			50.01	Apatite
		G2	4.39		13.56	19.94	5.42	6.39	50.29	CMAS
		G3	10.14	34.22	1.39				54.25	Fluorite
		G4	22.51	24.38					53.11	RE7ZO
	表面	H1	9.50		27.88	25.48			37.14	Apatite
	表面	H2	5.42		24.36	25.85			44.36	Apatite

样品	标记点	含量/%
样品	标记点	RE	Zr	Ca	Si	Al	Mg	O
RE1ZO	A1	9.33	30.49	1.14				59.04
	A2	6.54		14.93	16.70			61.84
	A3			11.86	21.23	3.49		63.41
	A4					25.38	14.53	60.09
RE2ZO	B1	11.82	29.51	2.10				56.57
	B2	13.01		9.26	16.36			61.37
	B3			14.32	7.51	18.85		59.32
	B4					26.42	15.71	57.87
RE3ZO	C1	9.07	29.26	1.57				60.10
	C2	12.41		12.87	18.74			55.98
	C3			14.61	4.19	15.07		66.13
	C4					24.54	8.24	67.22
RE4ZO	D1	17.39		7.70	19.08			55.83
	D2	13.47	25.79	4.01				56.73
	D3			9.49	14.63	3.37		72.51
	D4					23.43	11.15	65.42
RE5ZO	E1	16.31		7.94	22.95			52.81
	E2	18.59	10.82	7.97				62.62
	E3					27.67	7.56	64.77
RE6ZO	F1	15.29		8.38	18.79			57.54
	F2	13.87	28.07	3.44				54.61
	F3					22.85	9.88	67.27
RE7ZO	G1	11.15		15.20	20.20			53.45
	G2	10.23	32.03	1.87				55.87
	G3					12.94	22.18	64.88

样品	吸附氧/%	空位氧/%	晶格氧/%	空位氧/晶格氧
RE1ZO	6.4	38.8	54.8	0.71
RE2ZO	4.6	38.8	56.5	0.69
RE3ZO	1.4	39.0	59.6	0.65
RE4ZO	5.6	34.7	59.7	0.58
RE5ZO	4.8	34.9	60.3	0.58
RE6ZO	10.5	29.1	60.3	0.48
RE7ZO	10.6	32.1	57.3	0.56

Role of configurational entropy in enhancing CMAS corrosion resistance of rare-earth zirconates

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