硅酸镱环境障涂层抗熔盐腐蚀行为与机制研究

doi:10.15541/jim20220265

无机材料学报 ›› 2022, Vol. 37 ›› Issue (12): 1267-1274.DOI: 10.15541/jim20220265

硅酸镱环境障涂层抗熔盐腐蚀行为与机制研究

刘平平¹^,²(), 钟鑫¹(), 张乐³, 李红²(), 牛亚然¹, 张翔宇¹, 李其连³, 郑学斌¹

1.中国科学院上海硅酸盐研究所, 上海 200050
2.上海大学复合材料研究中心, 上海 200072
3.中国航空制造技术研究院, 北京 100024

收稿日期:2022-05-06 修回日期:2022-05-29 出版日期:2022-12-20 网络出版日期:2022-06-16
通讯作者: 钟鑫, 助理研究员. E-mail: zhongxin@mail.sic.ac.cn;
李红, 研究员. E-mail: lihong2007@shu.edu.cn
作者简介:刘平平(1995-), 女, 硕士研究生. E-mail: ppliu1234@163.com
基金资助:
国家科技重大专项(2017-VI-0020-0092);上海市青年科技英才扬帆计划(19YF1453900);上海市自然科学基金(20ZR1465700)

Molten Salt Corrosion Behaviors and Mechanisms of Ytterbium Silicate Environmental Barrier Coating

LIU Pingping¹^,²(), ZHONG Xin¹(), ZHANG Le³, LI Hong²(), NIU Yaran¹, ZHANG Xiangyu¹, LI Qilian³, ZHENG Xuebin¹

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Research Center of Composite Materials, Shanghai University, Shanghai 200072, China
3. Avic Manufacturing Technology Institute, Beijing 100024, China

Received:2022-05-06 Revised:2022-05-29 Published:2022-12-20 Online:2022-06-16
Contact: ZHONG Xin, assistant professor. E-mail: zhongxin@mail.sic.ac.cn;
LI Hong, professor. E-mail: lihong2007@shu.edu.cn
About author:LIU Pingping (1995-), female, Master candidate. E-mail: ppliu1234@163.com
Supported by:
National Science and Technology Major Project(2017-VI-0020-0092);Shanghai Sailing Program(19YF1453900);Natural Science Foundation of Shanghai(20ZR1465700)

摘要/Abstract

摘要：

稀土硅酸盐环境障涂层(EBC)是应用于新一代高推重比航空发动机热端部件的重要材料, 但其在高温熔盐环境的腐蚀行为与机制尚不明晰。本工作采用真空等离子喷涂技术(VPS)制备了Yb₂SiO₅/Yb₂Si₂O₇/Si环境障涂层, 并研究了该涂层体系在900 ℃、Na₂SO₄+25% NaCl(质量分数)熔盐环境中的腐蚀行为与机制。研究发现, 所制备的Yb₂SiO₅/Yb₂Si₂O₇/Si涂层体系结构致密, 各层之间结合良好; 涂层体系腐蚀240 h, 熔盐组分渗透Yb₂SiO₅涂层, 在Yb₂Si₂O₇中间层发生富集。涂层中Yb₂SiO₅相具有良好的稳定性, Yb₂O₃第二相与熔盐发生反应, 且随腐蚀时间延长, Yb₂O₃含量减少。中间层Yb₂Si₂O₇相与熔盐反应生成磷灰石相NaYb₉Si₆O₂₆和钠硅酸盐, 并产生Cl₂和SO₂等挥发性物质, 从而影响服役寿命。硅黏结层中未发现熔盐渗透现象, 保持完整。该涂层体系具有良好的抗熔盐腐蚀性能。

关键词: 环境障涂层, 硅酸镱, Na₂SO₄+25% NaCl熔盐, 腐蚀机制

Abstract:

Environmental barrier coating (EBC) is essential for protection of ceramic matrix composite hot-sections in future gas turbine engines with high thrust-to-weight ratio. Rare-earth silicates, such as Yb₂SiO₅ and Yb₂Si₂O₇, have been developed for potential application as EBC. However, the corrosion behaviors and mechanisms of EBC in molten salt environment such as Na₂SO₄ at high temperature are not clear. In this work, the Yb₂SiO₅/Yb₂Si₂O₇/Si coating was prepared by vacuum plasma spraying (VPS). The molten salt (Na₂SO₄+25% NaCl, in mass) corrosion behaviors and mechanisms of the coating at 900 ℃ for 60-240 h were investigated. Results showed that the Yb₂SiO₅/Yb₂Si₂O₇/Si coating exhibited dense structure with good bonding between the triple ceramic layers. The molten salt of Na₂SO₄+25% NaCl penetrated the Yb₂SiO₅ top layer and enriched in the Yb₂Si₂O₇ interlayer, while the interfacial bonding between the coating and substrate still remained good after corrosion for 240 h. The Yb₂SiO₅ phase in the top layer exhibited good stability, while the second phase of the Yb₂O₃ reacted with molten salt. The content of the Yb₂O₃ decreased with the increase of corrosion time. The Yb₂Si₂O₇ phase in the interlayer reacted with molten salt to form apatite phase of NaYb₉Si₆O₂₆ and sodium silicate as well as volatile species such as Cl₂ and SO₂, which might shorten the service life of the coating. Moreover, there was almost no molten salt in the silicon bond layer, which remained intact. The Yb₂SiO₅/Yb₂Si₂O₇/Si coating exhibited good resistance to molten salt corrosion.

Key words: environmental barrier coating, ytterbium silicate, Na₂SO₄+25% NaCl molten salt, corrosion mechanism

中图分类号:

TQ174

刘平平, 钟鑫, 张乐, 李红, 牛亚然, 张翔宇, 李其连, 郑学斌. 硅酸镱环境障涂层抗熔盐腐蚀行为与机制研究[J]. 无机材料学报, 2022, 37(12): 1267-1274.

LIU Pingping, ZHONG Xin, ZHANG Le, LI Hong, NIU Yaran, ZHANG Xiangyu, LI Qilian, ZHENG Xuebin. Molten Salt Corrosion Behaviors and Mechanisms of Ytterbium Silicate Environmental Barrier Coating[J]. Journal of Inorganic Materials, 2022, 37(12): 1267-1274.

图/表 11

表1 真空等离子喷涂参数

Table 1 Operating parameters used for vacuum plasma spraying

	Yb₂SiO₅	Yb₂Si₂O₇	Si
Primary Ar/(L·min^-1)	46	53	52
Secondary H₂/(L·min^-1)	14	10	13
Carrier Ar/(L·min^-1)	2.3	2.3	2.0
Spray distance/mm	220	220	290

图1 喷涂态Yb2SiO5/Yb2Si2O7/Si涂层的XRD图谱和显微结构

Fig. 1 XRD patterns and SEM morphologies of as-sprayed Yb2SiO5/Yb2Si2O7/Si coating (a) XRD patterns; (b) Surface morphology; (c-e) Cross-sectional morphologies

图2 Yb2SiO5/Yb2Si2O7/Si涂层熔盐腐蚀不同时间的宏观形貌

Fig. 2 Macro-photographs of Yb2SiO5/Yb2Si2O7/Si coating after molten salt corrosion for different time (a) As-sprayed; (b) 60 h; (c)100 h; (d) 240 h

图3 Yb2SiO5/Yb2Si2O7/Si涂层经熔盐腐蚀不同时间的XRD图谱

Fig. 3 XRD patterns of Yb2SiO5/Yb2Si2O7/Si coating after molten salt corrosion for different time

图4 Yb2SiO5/Yb2Si2O7/Si涂层经熔盐腐蚀不同时间的低倍和高倍形貌及其不同位置元素分析

Fig. 4 Surface morphologies of Yb2SiO5/Yb2Si2O7/Si coating after molten salt corrosion for different time and correponding EDS analyses of different areas (a-c) Low magnification; (d-f) High magnification

图5 Yb2SiO5 面层经熔盐腐蚀不同时间的截面形貌及其元素面分析

Fig. 5 Cross-sectional morphologies and corresponding element analyses of Yb2SiO5 top layer after molten salt corrosion for different time

图6 Yb2SiO5/Yb2Si2O7/Si涂层经熔盐腐蚀不同时间的截面形貌及其EDS元素面分析

Fig. 6 Cross-sectional morphologies and corresponding EDS element mappings of Yb2SiO5/Yb2Si2O7/Si EBCs after molten salt corrosion for different time Colorful figures are available on website

图7 经Na2SO4+25% NaCl熔盐腐蚀不同时间的涂层体系Yb2Si2O7中间层渗透区高倍截面形貌及EDS元素面分析

Fig. 7 High-magnification cross-sectional morphologies and corresponding EDS mappings of infiltration zone in Yb2Si2O7 interlayer after molten salt corrosion for different time Colorful figures are available on website

表2 图7中标记区域的EDS元素组成/%(原子分数)

Table 2 EDS elemental compositions of the marked regions in Fig. 7/%(in atom)

Position	Yb	Si	Na	O
1	21.69	14.27	1.98	62.06
2	24.91	12.57	-	62.52
3	18.29	18.09	-	63.62
4	10.15	18.67	2.41	58.77
5	22.50	13.75	1.67	62.08
6	24.92	12.57	-	62.51
7	18.03	18.31	-	63.66
8	8.95	19.25	13.25	58.55
9	22.93	13.20	2.04	61.82
10	24.45	12.96	-	62.59
11	17.82	18.04	-	63.25
12	8.91	19.21	13.39	58.49

图8 Yb2SiO5/Yb2Si2O7/Si涂层经900 ℃、Na2SO4+25% NaCl熔盐腐蚀示意图

Fig. 8 Schematic diagrams of Yb2SiO5/Yb2Si2O7/Si coating under Na2SO4+25% NaCl molten salt corrosion at 900 ℃

图9 Yb2SiO5和Yb2Si2O7涂层的EPR图谱

Fig. 9 EPR spectra of Yb2SiO5 and Yb2Si2O7 coating

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硅酸镱环境障涂层抗熔盐腐蚀行为与机制研究

Molten Salt Corrosion Behaviors and Mechanisms of Ytterbium Silicate Environmental Barrier Coating

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