RE-Si-Al-O玻璃相对高熵稀土双硅酸盐微结构及耐CMAS腐蚀性能的影响

doi:10.15541/jim20240018

摘要/Abstract

摘要：

环境障涂层是高功重比航空发动机的关键技术, 其目的是阻挡燃气及环境腐蚀介质的侵蚀, 为陶瓷基复合材料热端部件提供有效保护。目前, 高熵稀土双硅酸盐((xRE_1/_x)₂Si₂O₇)是最具潜力的新一代环境障涂层材料。为了进一步提升高熵稀土双硅酸盐的耐高温(1500 ℃)CMAS(CaO-MgO-Al₂O₃-SiO₂)腐蚀能力, 本工作设计制备了一种新型高熵(Y_0.25Yb_0.25Er_0.25Tm_0.25)₂Si₂O₇/RE-Si-Al-O(RE=Yb、Y、La)复相陶瓷。结果表明, 在复相陶瓷中, RE-Si-Al-O玻璃相不仅能够包裹陶瓷晶粒, 而且能够促进稀土双硅酸盐晶粒长大, 减少晶界数量, 使CMAS熔体的渗入通道数量减少。同时, 随着RE-Si-Al-O玻璃相中稀土离子半径增大, 玻璃相更易与CMAS熔盐中的Ca²⁺离子反应, 生成磷灰石相, 降低CMAS熔体的活性, 抑制高温CMAS熔盐对高熵稀土双硅酸盐晶粒的侵蚀, 从而提高高熵稀土双硅酸盐的耐高温CMAS腐蚀能力。在1500 ℃腐蚀48 h后, (Y_0.25Yb_0.25Er_0.25Tm_0.25)₂Si₂O₇/La-Si-Al-O复相陶瓷表面仍残留CMAS熔盐层, 表明该复相陶瓷具有良好的耐高温CMAS腐蚀能力。该复相陶瓷的微结构设计为增强环境障涂层材料在高温CMAS环境下的长期应用提供了一种新的思路。

关键词: 高熵稀土双硅酸盐陶瓷, CMAS腐蚀, RE-Si-Al-O玻璃相

Abstract:

Environmental barrier coating (EBC) is a key material for high power-to-weight ratio aero engine, which can provide effective protection for the hot end components of ceramic matrix composites, and prevent the erosion of gas and environmental corrosive media. At present, high entropy rare earth disilicates ((xRE_1/_x)₂Si₂O₇) are the most promising next-generation environmental barrier coatings. In order to enhance the CMAS corrosion resistance of high entropy rare earth disilicates, a novel high entropy (Y_0.25Yb_0.25Er_0.25Tm_0.25)₂Si₂O₇/RE-Si-Al-O (RE=Yb, Y, and La) multiphase ceramic was designed and prepared. The results show that the RE-Si-Al-O glass phase can not only wrap the ceramic grains, but also exist at the grain boundaries. Moreover, this multiphase ceramics can promote the growth of rare earth disilicate grains, reduce the number of grain boundaries, and decrease the number of diffusion channel of CMAS melt. As the radius of rare earth ion in the RE-Si-Al-O glass phase increases, the glass phase is more prone to react with Ca²⁺ ion in the CMAS melt, generating apatite, reducing the activity of the CMAS melt, inhibiting the erosion of high entropy rare earth disilicate grains by the CMAS molten salt, and thus improving the CMAS corrosion resistance of high entropy rare earth disilicates. After corrosion at 1500 ℃ for 48 h, there is still a residual CMAS layer on the surface of (Y_0.25Yb_0.25Er_0.25Tm_0.25)₂Si₂O₇/La-Si-Al-O multiphase ceramics, indicating that the multiphase ceramics have good resistance to CMAS corrosion. In conclusion, the microstructure design of this multiphase ceramic provides a new approach to improve the long-term application of EBC materials in high-temperature CMAS environments.

Key words: high entropy rare earth disilicate, CMAS corrosion, RE-Si-Al-O glass phase

中图分类号:

TQ174

李刘媛, 黄开明, 赵秀艺, 刘会超, 王超. RE-Si-Al-O玻璃相对高熵稀土双硅酸盐微结构及耐CMAS腐蚀性能的影响[J]. 无机材料学报, 2024, 39(7): 793-802.

LI Liuyuan, HUANG Kaiming, ZHAO Xiuyi, LIU Huichao, WANG Chao. Influence of RE-Si-Al-O Glass Phase on Microstructure and CMAS Corrosion Resistance of High Entropy Rare Earth Disilicates[J]. Journal of Inorganic Materials, 2024, 39(7): 793-802.

图/表 13

图1 (4RE0.25)2Si2O7陶瓷与(4RE0.25)2Si2O7/RE-Si-Al-O复相陶瓷的XRD图谱

Fig. 1 XRD patterns of (4RE0.25)2Si2O7 ceramics and (4RE0.25)2Si2O7/RE-Si-Al-O multiphase ceramics

图2 (4RE0.25)2Si2O7陶瓷与(4RE0.25)2Si2O7/RE-Si-Al-O复相陶瓷的SEM照片及EDS谱图

Fig. 2 SEM images and EDS mappings of (4RE0.25)2Si2O7 ceramics and (4RE0.25)2Si2O7/RE-Si-Al-O multiphase ceramics (a) (4RE0.25)2Si2O7; (b) (4RE0.25)2Si2O7/Yb-Si-Al-O; (c) (4RE0.25)2Si2O7/Y-Si-Al-O; (d) (4RE0.25)2Si2O7/La-Si-Al-O

表1 图2中各点的元素组成(%, 原子分数)

Table 1 Elemental composition of each point in Fig. 2 (%, in atom)

Spot	Y	Yb	Er	Tm	Si	O	Matter
1	4.54	3.55	3.49	3.40	19.29	65.73	(4RE_0.25)₂Si₂O₇
2	4.42	4.31	5.48	4.09	18.99	62.71	(4RE_0.25)₂Si₂O₇
3	4.49	4.19	4.23	4.06	19.27	63.76	(4RE_0.25)₂Si₂O₇
4	5.18	5.69	5.48	5.30	21.41	56.94	(4RE_0.25)₂Si₂O₇
5	4.26	1.84	2.13	2.11	17.51	72.15	(4RE_0.25)₂Si₂O₇

图3 (4RE0.25)2Si2O7/RE-Si-Al-O复相陶瓷中玻璃相的EDS谱图

Fig. 3 EDS patterns of glass phases in (4RE0.25)2Si2O7/RE-Si-Al-O multiphase ceramics (a) (4RE0.25)2Si2O7/Yb-Si-Al-O; (b) (4RE0.25)2Si2O7/Y-Si-Al-O; (c) (4RE0.25)2Si2O7/La-Si-Al-O

图4 (4RE0.25)2Si2O7陶瓷与(4RE0.25)2Si2O7/RE-Si-Al-O复相陶瓷在1300 ℃腐蚀48 h后的截面SEM照片

Fig. 4 Cross-sectional SEM images of (4RE0.25)2Si2O7 ceramics and (4RE0.25)2Si2O7/RE-Si-Al-O multiphase ceramics after corrosion at 1300 ℃ for 48 h (a) (4RE0.25)2Si2O7; (b) (4RE0.25)2Si2O7/Yb-Si-Al-O; (c) (4RE0.25)2Si2O7/Y-Si-Al-O; (d) (4RE0.25)2Si2O7/La-Si-Al-O

表2 图4中各点的元素组成(%, 原子分数)

Table 2 Elemental composition of each point in Fig. 4 (%, in atom)

Spot	Yb	Tm	Er	Y	Si	O	Ca	Mg	Al	La	Matter
1	0.76	0.69	0.71	0.69	22.15	57.64	9.43	0.99	6.94		CMAS
2	2.85	2.78	2.67	2.19	21.16	52.94	13.05		2.36		Ca₂RE₈(SiO₄)₆O₂
3	6.06	5.55	5.23	3.81	21.75	57.60					(4RE_0.25)₂Si₂O₇
4	1.91	1.89	2.02	1.24	23.55	58.21	11.18				CMAS
5	0.61	0.54	0.54	0.46	23.43	58.28	8.82	0.90	6.42		CMAS
6	2.02	1.82	1.84	0.82	24.39	57.84	11.27				Ca₂RE₈(SiO₄)₆O₂
7	5.54	5.11	5.36	3.77	22.74	57.48					(4RE_0.25)₂Si₂O₇
8	0.53	0.61	0.69	0.53	23.82	58.48	9.71		5.63		Yb-Si-Al-O-Ca
9	0.51	0.40	0.52	0.43	22.40	59.87	8.46	0.75	6.66		CMAS
10	1.79	1.90	1.98	0.95	23.72	58.85	10.81				Ca₂RE₈(SiO₄)₆O₂
11	5.98	4.92	4.89	3.56	21.68	58.97					(4RE_0.25)₂Si₂O₇
12	0.37	0.34	0.37	0.23	23.14	59.04	8.50	0.27	7.74		Y-Si-Al-O-Ca
13	0.76	0.71	0.68	0.69	24.75	55.79	9.23	1.01	6.22	0.16	CMAS
14	1.87	1.99	2.07	0.80	26.09	54.97	12.02			0.19	Ca₂RE₈(SiO₄)₆O₂
15	5.98	5.96	5.54	3.02	23.81	55.69					(4RE_0.25)₂Si₂O₇
16	0.22	0.35	0.45	0.21	26.26	57.49	7.13	0.28	6.32	1.29	La-Si-Al-O-Ca

图5 (4RE0.25)2Si2O7和RE-Si-Al-O与CMAS混合后在1300 ℃煅烧反应48 h后的XRD图谱

Fig. 5 XRD patterns of (4RE0.25)2Si2O7 and RE-Si-Al-O mixed with CMAS after calcination at 1300 ℃ for 48 h (a) Mixture of (4RE0.25)2Si2O7 and CMAS; (b) Mixture of RE-Si-Al-O and CMAS

图6 (4RE0.25)2Si2O7陶瓷与(4RE0.25)2Si2O7/RE-Si-Al-O复相陶瓷在1500 ℃腐蚀(a) 24和(b) 48 h后的XRD图谱

Fig. 6 XRD patterns of (4RE0.25)2Si2O7 ceramics and (4RE0.25)2Si2O7/RE-Si-Al-O multiphase ceramics after corrosion at 1500 ℃ for (a) 24 and (b) 48 h

图7 (4RE0.25)2Si2O7陶瓷在1500 ℃腐蚀(a) 24和(b) 48 h后的截面SEM照片

Fig. 7 Cross-sectional SEM images of (4RE0.25)2Si2O7 ceramics after corrosion at 1500 ℃ for (a) 24 and (b) 48 h (c) Partial enlargement of area in (b)

表3 图7中各点的元素组成(%, 原子分数)

Table 3 Elemental composition of each point in Fig. 7 (%, in atom)

Spot	Yb	Tm	Er	Y	Si	O	Ca	Mg	Al	Matter
1	1.39	1.12	1.03	0.84	22.26	54.21	14.35	0.39	4.41	CMAS
2	7.80	8.12	8.21	8.46	14.57	45.43	7.41			Ca₂RE₈(SiO₄)₆O₂
3	8.10	8.39	8.13	4.03	28.68	42.67				(4RE_0.25)₂Si₂O₇

图8 (4RE0.25)2Si2O7/RE-Si-Al-O复相陶瓷在1500 ℃腐蚀24与48 h后的截面SEM照片

Fig. 8 Cross-sectional SEM images of (4RE0.25)2Si2O7/RE-Si-Al-O multiphase ceramics after corrosion at 1500 ℃ for 24 and 48 h (a, d) (4RE0.25)2Si2O7/Yb-Si-Al-O; (b, e) (4RE0.25)2Si2O7/Y-Si-Al-O; (c, f) (4RE0.25)2Si2O7/La-Si-Al-O

图9 (4RE0.25)2Si2O7/RE-Si-Al-O复相陶瓷在1500 ℃腐蚀48 h后局部放大的SEM照片

Fig. 9 Local enlarged SEM images of (4RE0.25)2Si2O7/RE-Si-Al-O multiphase ceramics after corrosion at 1500 ℃ for 48 h (a) (4RE0.25)2Si2O7/Yb-Si-Al-O; (b) (4RE0.25)2Si2O7/Y-Si-Al-O; (c) (4RE0.25)2Si2O7/La-Si-Al-O

表4 图9中各点的元素组成(%, 原子分数)

Table 4 Elemental composition of each point in Fig. 9 (%, in atom)

Spot	Yb	Tm	Er	Y	Si	O	Ca	Mg	Al	La	Matter
1	1.23	0.90	0.84	0.72	23.01	55.92	10.20	0.38	6.80		CMAS
2	6.17	7.43	7.75	8.02	16.47	47.83	6.33				Ca₂RE₈(SiO₄)₆O₂
3	6.92	6.61	6.34	3.64	24.73	51.76					(4RE_0.25)₂Si₂O₇
4	0.34	0.44	0.48	0.21	25.89	54.59	10.73	0.34	6.98		Yb-Si-Al-O-Ca
5	1.01	0.92	0.81	0.74	24.10	55.69	9.65	0.22	6.86		CMAS
6	5.92	6.23	6.52	6.94	16.85	52.31	5.23				Ca₂RE₈(SiO₄)₆O₂
7	5.27	5.35	5.64	3.77	23.11	56.86					(4RE_0.25)₂Si₂O₇
8	0.64	0.69	0.76	0.41	24.03	56.45	9.70	0.43	6.89		Y-Si-Al-O-Ca
9	5.61	5.82	6.15	6.43	15.97	53.99	5.02			1.01	Ca₂RE₈(SiO₄)₆O₂
10	5.81	5.34	5.62	3.50	23.47	56.26					(4RE_0.25)₂Si₂O₇
11	0.39	0.47	0.53	0.23	25.11	56.14	9.01	0.27	7.18	0.67	La-Si-Al-O-Ca
12	1.73	1.82	1.89	1.57	28.54	54.01		0.36	8.17	1.91	La-Si-Al-O

参考文献 40

[1]	刘巧沐, 黄顺洲, 何爱杰. 碳化硅陶瓷基复合材料在航空发动机上的应用需求及挑战. 材料工程, 2019, 47: 1. DOI
[2]	PADTURE N P. Advanced structural ceramics in aerospace propulsion. Nat. Mater., 2016, 15: 804. DOI PMID
[3]	刘大响. 一代新材料,一代新型发动机: 航空发动机的发展趋势及其对材料的需求. 材料工程, 2017, 45: 1. DOI
[4]	ZHU S J, MIZUNO M, NAGANO Y, et al. Creep and fatigue behavior in an enhanced SiC_f/SiC composite at high temperature. J. Am. Ceram. Soc., 1998, 81: 2269.
[5]	CURTIN W A. Theory of mechanical properties of ceramic-matrix composites. J. Am. Ceram. Soc., 1991, 74: 2837.
[6]	任孝旻. 高熵稀土单硅酸盐热障/环境障涂层材料的设计、制备和性能研究. 合肥: 中国科学技术大学博士学位论文, 2022.
[7]	黄璇璇, 郭双全, 姚改成. 航空发动机SiC/SiC复合材料环境障碍涂层研究进展. 航空维修与工程, 2017(2): 28.
[8]	ZHU D M. Durability and CMAS resistance of advanced environmental barrier coatings systems for SiC/SiC ceramic matrix composites. J. Nucl. Mater., 2010, 8: 203.
[9]	POERSCHKE D L, HASS D D, EUSTIS S, et al. Stability and CMAS resistance of ytterbium-silicate/hafnate EBCs/TBC for SiC composites. J. Am. Ceram. Soc., 2015, 98: 278.
[10]	WANG Y, MENG J S, LIU S Y, et al. Environmental barrier coatingschallenges and opportunities. J. Aerosp. Sci. Technol., 2018, 6: 17.
[11]	周邦阳, 崔永静, 王长亮, 等. 稀土硅酸盐环境障涂层研究进展. 材料工程, 2023, 51(12): 12.
[12]	LEE K N, FOX D S, BANSAL N P. Rare earth silicate environmental barrier coatings for SiC/SiC composites and Si₃N₄ ceramics. J. Eur. Ceram. Soc., 2005, 25: 1705.
[13]	王浩宇. 几种稀土硅酸盐环境障涂层的制备、表征与性能研究. 合肥: 中国科学技术大学博士学位论文, 2023.
[14]	孙晓文. 稀土硅酸盐环境障涂层成分结构设计及高温失效机制研究. 天津: 河北工业大学硕士学位论文, 2022.
[15]	MAIER N, RIXECKER G, NICKEL K G. Formation and stability of Gd, Y, Yb and Lu disilicates and their solid solutions. J. Solid State Chem., 2006, 179: 1630.
[16]	LUO Y X, SUN L C, WANG J M, et al. Material-genome perspective towards tunable thermal expansion of rare-earth di-silicates. J. Eur. Ceram. Soc., 2018, 38: 3547.
[17]	王京阳, 孙鲁超, 罗颐秀, 等. 以抗CMAS腐蚀为目标的稀土硅酸盐环境障涂层高熵化设计与性能提升. 金属学报, 2023, 59(4): 523.
[18]	TIAN Z L, ZHENG L Y, LI Z J, et al. Exploration of the low thermal conductivities of γ-Y₂Si₂O₇, β-Y₂Si₂O₇, β-Yb₂Si₂O₇, and β-Lu₂Si₂O₇ as novel environmental barrier coating candidates. J. Eur. Ceram. Soc., 2016, 36: 2813.
[19]	TIAN Z L, REN X M, LEI Y M, et al. Corrosion of RE₂Si₂O₇ (RE=Y, Yb, and Lu) environmental barrier coating materials by molten calcium-magnesium-alumino-silicate glass at high temperatures. J. Eur. Ceram. Soc., 2019, 39: 4245.
[20]	TURCER L R, SENGUPTA A, PADTURE N P. Low thermal conductivity in high-entropy rare-earth pyrosilicate solid-solutions for thermal environmental barrier coatings. Scr. Mater., 2021, 191: 40.
[21]	SUN L C, REN X M, LUO Y X, et al. Exploration of the mechanism of enhanced CMAS corrosion resistance at 1500 °C for multicomponent (Er_0.25Tm_0.25Yb_0.25Lu_0.25)₂Si₂O₇ disilicate. Corros. Sci., 2022, 10: 110343.
[22]	GUO X T, ZHANG Y L, LI T, et al. High-entropy rare-earth disilicate (Lu_0.2Yb_0.2Er_0.2Tm_0.2Sc_0.2)₂Si₂O₇: a potential environmental barrier coating material. J. Eur. Ceram. Soc., 2022, 42: 3570.
[23]	SUN L C, LUO Y X, REN X M, et al. A multicomponent γ-type (Gd_1/6Tb_1/6Dy_1/6Tm_1/6Yb_1/6Lu_1/6)₂Si₂O₇ disilicate with outstanding thermal stability. Mater. Res. Lett., 2020, 8: 424.
[24]	WANG X, HE Y X, WANG C, et al. Thermal performance regulation of high-entropy rare-earth disilicate for thermal environmental barrier coating materials. J. Am. Ceram. Soc., 2022, 2: 18456.
[25]	WOLF M, MACK D E, GUILLON O, et al. Resistance of pure and mixed rare earth silicates against calcium-magnesium- aluminosilicate (CMAS): a comparative study. J. Am. Ceram. Soc., 2020, 103: 7056.
[26]	POERSCHKE D L, JACKSON R W, LEVI C G. Silicate deposit degradation of engineered coatings in gas turbines: progress toward models and materials solutions. Annu. Rev. Mater., 2017, 47: 297.
[27]	DONG Y, REN K, WANG Q K, et al. Interaction of multicomponent disilicate (Yb_0.2Y_0.2Lu_0.2Sc_0.2Gd_0.2)₂Si₂O₇ with molten calcia-magnesia-aluminosilicate. J. Adv. Ceram., 2022, 11: 66.
[28]	CHEN Z Y, LIN C C, ZHENG W, et al. Investigation on improving corrosion resistance of rare earth pyrosilicates by high-entropy design with RE-doping. Corros. Sci., 2022, 199: 110217.
[29]	SUN L C, LUO Y X, TIAN Z L, et al. High temperature corrosion of (Er_0.25Tm_0.25Yb_0.25Lu_0.25)₂Si₂O₇ environmental barrier coating material subjected to water vapor and molten calcium- magnesium- aluminosilicate (CMAS). Corros. Sci., 2020, 175: 108881.
[30]	TURCER L R, KRAUSE A R, GARCES H F, et al. Environmental-barrier coating ceramics for resistance against attack by molten calcia-magnesia-aluminosilicate (CMAS) glass: part II, β-Yb₂Si₂O₇ and β-Sc₂Si₂O₇. J. Eur. Ceram. Soc., 2018, 38: 3914.
[31]	Ahlborg N L, ZHU D M. AHLBORG N L, ZHU D M. Calcium- magnesium aluminosilicate (CMAS) reactions and degradation mechanisms of advanced environmental barrier coatings. Surf. Coat. Technol., 2013, 237: 79.
[32]	GRANT K M, KRÄMER S, LÖFVANDER J P A, et al. CMAS degradation of environmental barrier coatings. Surf. Coat. Technol., 2007, 202: 653.
[33]	WU N N, WANG Y L, TONG Y L, et al. Interaction of ytterbium monosilicate environmental barrier coating material with molten calcium-magnesium-aluminosilicate (CMAS). Corros. Sci., 2023, 211: 110864.
[34]	WANG X, CHENG M H, XIAO G Z, et al. Preparation and corrosion resistance of high-entropy disilicate (Y_0.25Yb_0.25Er_0.25-Sc_0.25)₂Si₂O₇ ceramics, Corros. Sci., 2021, 192: 109786.
[35]	HE Y X, XIAO G Z, WANG C, et al. Improved thermal properties and CMAS corrosion resistance of rare-earth monosilicates by adjusting the configuration entropy with RE-doping. Corros. Sci., 2024, 226: 11664.
[36]	DENG S X, HE G, YANG Z C, et al. Calcium-magnesium- alumina-silicate (CMAS) resistant high entropy ceramic (Y_0.2Gd_0.2-Er_0.2Yb_0.2Lu_0.2)₂Zr₂O₇ for thermal barrier coatings. J. Mater. Sci. Technol., 2022, 107: 259.
[37]	WEBSTER R I, OPILA E J. Viscosity of CaO-MgO-Al₂O₃-SiO₂ (CMAS) melts: experimental measurements and comparison to model calculations. J. Non-Cryst. Solids., 2022, 584: 121508.
[38]	SHIMIZU F, TOKUNAGA H, SAITO N, et al. Viscosity and surface tension measurements of RE₂O₃-MgO-SiO₂ (RE=Y, Gd, Nd and La) melts. ISIJ Int., 2006, 46: 388.
[39]	XIAO G Z, SHEN Q Y, TIAN Y, et al. Investigation on the relation of microstructures and CMAS corrosion resistance of high entropy RE disilicates. Corros. Sci., 2024, 227: 111727.
[40]	HE Y X, WANG X, WANG C, et al. Significantly improved corrosion resistance of high-entropy rare-earth silicate multiphase ceramics against molten CMAS. J. Am. Ceram. Soc., 2023, 106: 2744.