富铝CMAS对稀土硅酸盐环境障涂层的腐蚀行为与机制研究

doi:10.15541/jim20220532

无机材料学报 ›› 2023, Vol. 38 ›› Issue (5): 544-552.DOI: 10.15541/jim20220532

所属专题：【结构材料】热障与环境障涂层(202309)

富铝CMAS对稀土硅酸盐环境障涂层的腐蚀行为与机制研究

范栋¹^,²(), 钟鑫¹(), 王亚文¹, 张振忠²(), 牛亚然¹, 李其连³, 张乐³, 郑学斌¹

1.中国科学院上海硅酸盐研究所, 上海 200050
2.南京工业大学材料科学与工程学院, 南京 211816
3.中国航空制造技术研究院, 北京 100024

收稿日期:2022-09-13 修回日期:2022-10-06 出版日期:2022-10-28 网络出版日期:2022-10-28
通讯作者: 钟鑫, 助理研究员. E-mail: zhongxin@mail.sic.ac.cn;
张振忠, 教授. E-mail: njutzhangzz@126.com
作者简介:范栋(1998-), 男, 硕士研究生. E-mail: fandong1998@126.com
基金资助:
国家科技重大专项(2017-VI-0020-0092);国家自然科学基金(52202075);上海市科学技术委员会科学基金(20ZR1465700)

Corrosion Behavior and Mechanism of Aluminum-rich CMAS on Rare-earth Silicate Environmental Barrier Coatings:

FAN Dong¹^,²(), ZHONG Xin¹(), WANG Yawen¹, ZHANG Zhenzhong²(), NIU Yaran¹, LI Qilian³, ZHANG Le³, ZHENG Xuebin¹

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211816, China
3. Avic Manufacturing Technology Institute, Beijing 100024, China

Received:2022-09-13 Revised:2022-10-06 Published:2022-10-28 Online:2022-10-28
Contact: ZHONG Xin, assistant professor. E-mail: zhongxin@mail.sic.ac.cn;
ZHANG Zhenzhong, professor. E-mail: njutzhangzz@126.com
About author:FAN Dong (1998-), male, Master candidate. E-mail: fandong1998@126.com
Supported by:
National Science and Technology Major Project(2017-VI-0020-0092);National Natural Science Foundation of China(52202075);Natural Science Foundation of Shanghai(20ZR1465700)

摘要/Abstract

摘要：

稀土硅酸盐环境障涂层(EBCs)有望应用于新一代高推重比航空发动机热端部件, 但是服役条件下的熔盐腐蚀成为限制其应用的瓶颈。CMAS组分和稀土硅酸盐的晶体结构等因素对其腐蚀行为产生显著影响。本工作以不同晶型的稀土硅酸盐涂层材料为研究对象, 采用大气等离子喷涂技术制备X1-Gd₂SiO₅、X2-RE₂SiO₅(RE=Y, Er)涂层, 并研究其在富Al₂O₃的CMAS熔盐环境(1400 ℃)的腐蚀行为与机制。结果表明, X2-RE₂SiO₅(RE=Y, Er)涂层耐蚀性能优于X1-Gd₂SiO₅涂层, 这与涂层材料的物相组成和晶体结构的稳定性等因素有关。经CMAS腐蚀25 h后, X1-Gd₂SiO₅涂层表面仅生成磷灰石相; X2-RE₂SiO₅涂层不仅生成磷灰石相, 涂层中的RE₂O₃还与CMAS中的Al₂O₃反应生成石榴石相。生成石榴石相可提高涂层表面CMAS中CaO、SiO₂的相对含量, 促进磷灰石致密层的生成, 从而改善其耐蚀性能。

关键词: 环境障涂层, 稀土硅酸盐, CMAS腐蚀, 腐蚀机理

Abstract:

Environmental barrier coatings (EBCs) are expected to be applied to the hot-section components of a new generation of high thrust-to-weight ratio aero-engines. Rare-earth silicates have been acknowledged as promising alternatives to EBC materials due to their superior high-temperature phase stability, suitable coefficient of thermal expansion, and long durability in water vapor. However, the calcium-magnesium-alumino-silicates (CMAS) molten salt corrosion under service conditions has become a bottleneck that limits the application of rare-earth silicates in EBCs. Factors such as the composition of CMAS and the crystal structures of rare-earth silicates have a significant impact on their corrosion behavior. In this paper, X1-Gd₂SiO₅ and X2-RE₂SiO₅ (RE=Y, Er) coatings with different crystal structures, were prepared by atmospheric plasma spraying (APS) technique. Their corrosion behaviors and mechanisms of the three kinds of coatings under CMAS melt environment at 1400 ℃ were explored. Results showed that the corrosion resistance of X2-RE₂SiO₅ coatings were better than that of X1-Gd₂SiO₅ coating due to their phase compositions and stability of crystal structure. After corrosion by CMAS, X1-Gd₂SiO₅ coating dissolved in CMAS melt and formed apatite phase, while the X2-RE₂SiO₅ coatings not only formed apatite phase, but also formed garnet phase from reaction of the RE₂O₃ in the coatings with Al₂O₃ in CMAS. Formation of generate garnet phase could increase relative content of CaO and SiO₂ in CMAS, and promote formation of dense apatite layer, thereby improving corrosion resistance. This study provides a strategy for designing EBC systems with excellent CMAS corrosion resistance.

Key words: environmental barrier coating, rare-earth silicate, CMAS corrosion, corrosion mechanism

中图分类号:

TQ174

范栋, 钟鑫, 王亚文, 张振忠, 牛亚然, 李其连, 张乐, 郑学斌. 富铝CMAS对稀土硅酸盐环境障涂层的腐蚀行为与机制研究[J]. 无机材料学报, 2023, 38(5): 544-552.

FAN Dong, ZHONG Xin, WANG Yawen, ZHANG Zhenzhong, NIU Yaran, LI Qilian, ZHANG Le, ZHENG Xuebin. Corrosion Behavior and Mechanism of Aluminum-rich CMAS on Rare-earth Silicate Environmental Barrier Coatings:[J]. Journal of Inorganic Materials, 2023, 38(5): 544-552.

图/表 13

表1 等离子喷涂工艺参数

Table 1 Technical parameters used for plasma spraying

Parameter	RE₂SiO₅(RE=Gd, Y, Er)
Primary Ar/(L·min^-1)	43
Secondary H₂/(L·min^-1)	12
Carrier Ar/(L·min^-1)	2.3
Spray distance/mm	230

图S1 CMAS粉体的XRD图谱

Fig. S1 XRD pattern of CMAS powders

表2 CMAS粉体的XRF化学元素组成

Table 2 Chemical compositions of CMAS powders

XRF/(%，in mol)	CaO	MgO	AlO_1.5	SiO₂
CMAS	27.87	8.79	26.22	38.52

图1 粉体与喷涂态涂层的XRD图谱

Fig. 1 XRD patterns of powders and as-sprayed coatings (a) X1-Gd2SiO5; (b) X2-Y2SiO5; (c) X2-Er2SiO5

图2 涂层经CMAS腐蚀4和25 h后的XRD图谱

Fig. 2 XRD patterns of coatings after CMAS corrosion for 4 and 25 h (a) X1-Gd2SiO5; (b) X2-Y2SiO5; (c) X2-Er2SiO5

图S2 喷涂态涂层的表面和截面微观结构

Fig. S2 Surface and cross-sectional microstructures of as-sprayed coatings (a-b) X1-Gd2SiO5; (c-d) X2-Y2SiO5; (e-f) X2-Er2SiO5

图3 涂层经CMAS腐蚀4和25 h后的表面形貌

Fig. 3 Surface microstructures of coatings after corrosion for 4 and 25 h (a-b) X1-Gd2SiO5; (c-d) X2-Y2SiO5; (e-f) X2-Er2SiO5

表3 图3中标记区域的EDS元素组成

Table 3 EDS elemental compositions of the marked regions in Fig. 3

EDS/ (%, in atom)	Gd	Y	Er	Si	O	Ca	Al	Mg
Point 1	20.60	—	—	19.62	51.73	8.02	—	—
Point 2	—	26.04	—	17.55	50.57	5.83	—	—
Point 3	—	—	26.95	15.16	50.78	7.10	—	—
Point 4	—	14.03	—	5.72	52.27	4.01	20.31	3.66

图4 涂层经CMAS腐蚀4 h后的截面形貌

Fig. 4 Cross-sectional microstructures of coatings after CMAS corrosion for 4 h (a, b) X1-Gd2SiO5; (c, d) X2-Y2SiO5; (e, f) X2-Er2SiO5

表4 中标记区域的EDS元素组成

Table 4 EDS elemental compositions of the marked regions in Fig. 4

EDS/(%, in atom)	Gd	Y	Er	Si	O	Ca	Al	Mg
Point 1	19.21	—	—-	11.70	60.65	8.44	—	—
Point 2	1.16	—	—	13.06	59.37	13.78	10.18	2.45
Point 3	—	15.29	—	16.00	61.82	6.89	—	—
Point 4	—	7.18	—	15.50	50.17	9.58	12.14	5.43
Point 5	—	0.96	—	13.56	59.62	13.03	10.40	2.42
Point 6	—	—	20.27	12.11	61.12	6.50	—	—
Point 7	—	—	8.70	10.95	59.15	8.09	10.95	4.65
Point 8	—	—	0.92	3.29	58.74	19.61	3.29	2.07

图5 X1-Gd2SiO5与X2-RE2SiO5(RE=Y, Er)涂层腐蚀25 h后的截面形貌

Fig. 5 Cross-sectional microstructures of the X1-Gd2SiO5 coating after corrosion for 25 h (a) X1-Gd2SiO5; (b) X2-Y2SiO5; (c) X2-Er2SiO5

表5 图5中标记区域的EDS元素组成

Table 5 EDS elemental compositions of the marked regions in Fig. 5

EDS/ (%, in atom)	Gd	Y	Er	Si	O	Ca	Al	Mg
Point 1	24.48	—	—	16.22	51.61	7.68	—	—
Point 2	1.05	—	—	12.62	59.63	14.25	9.78	2.66
Point 3	—	26.70	—	15.78	50.12	7.40	—	—
Point 4	—	17.10	—	8.23	51.25	2.92	16.41	4.09
Point 5	—	0.94	—	14.23	57.36	13.94	11.98	1.54
Point 6	—	—	28.80	12.77	52.22	6.22	—	—
Point 7	—	—	7.12	13.05	49.26	7.08	18.26	5.24

图6 不同涂层在1400 ℃下CMAS熔盐腐蚀的示意图

Fig. 6 Schematic diagrams of different coatings under CMAS molten salt corrosion at 1400 ℃ (a) Reaction process; (b) X1-Gd2SiO5; (c) X2-Y2SiO5; (d) X2-Er2SiO5

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富铝CMAS对稀土硅酸盐环境障涂层的腐蚀行为与机制研究

Corrosion Behavior and Mechanism of Aluminum-rich CMAS on Rare-earth Silicate Environmental Barrier Coatings:

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