Ti掺杂Hf(Zr)B2-SiC抗烧蚀涂层的制备及其抗烧蚀机理

doi:10.15541/jim20240249

无机材料学报 ›› 2024, Vol. 39 ›› Issue (12): 1357-1366.DOI: 10.15541/jim20240249 CSTR: 32189.14.10.15541/jim20240249

所属专题：【结构材料】热障与环境障涂层(202412)

Ti掺杂Hf(Zr)B₂-SiC抗烧蚀涂层的制备及其抗烧蚀机理

郭晓阳¹(), 张小琳¹, 姜岩¹(), 田原¹, 耿志²

1.沈阳化工大学辽宁省特种功能材料合成与制备重点实验室, 沈阳 110142
2.沈阳新瑞特机电设备有限公司, 沈阳 110015

收稿日期:2024-05-17 修回日期:2024-07-13 出版日期:2024-07-16 网络出版日期:2024-07-16
通讯作者: 姜岩, 讲师. E-mail: na_jiangyan@sina.com
作者简介:郭晓阳(1999-), 男, 硕士研究生. E-mail: guoxiaoyang707722@163.com
基金资助:
辽宁省教育厅青年项目(JYTQN2023371)

Ti-doped Hf(Zr)B₂-SiC Anti-ablation Coatings: Preparation and Ablation Resistance Mechanism

GUO Xiaoyang¹(), ZHANG Xiaolin¹, JIANG Yan¹(), TIAN Yuan¹, GENG Zhi²

1. Key Laboratory of Special Functional Materials Synthesis and Preparation in Liaoning Province, Shenyang University of Chemical Technology, Shenyang 110142, China
2. Shenyang Xinruite Electromechanical Equipment Co. Ltd., Shenyang 110015, China

Received:2024-05-17 Revised:2024-07-13 Published:2024-07-16 Online:2024-07-16
Contact: JIANG Yan, lecturer. E-mail: na_jiangyan@sina.com
About author:GUO Xiaoyang (1999-), male, Master candidate. E-mail: guoxiaoyang707722@163.com
Supported by:
Liaoning Provincial Department of Education Youth Project(JYTQN2023371)

摘要/Abstract

摘要：

为了提高碳基材料在高温含氧环境下的抗烧蚀性能, 以石墨为基体, 采用浆料法和反应熔渗相结合的方式在其表面制备了Ti掺杂HfB₂-SiC、ZrB₂-SiC复合涂层。研究了涂层的物相组成、微观形貌和元素分布, 考察了涂层在2300 ℃的抗烧蚀能力。结果表明：渗硅后的Ti掺杂Hf(Zr)B₂-SiC复合涂层结构十分致密, HfTiB₂、ZrTiB₂陶瓷相镶嵌于涂层中, 残余硅连续分布在Hf(Zr)B₂、SiC颗粒周围, 涂层与基体结合良好且无缺陷; 在2300 ℃烧蚀480 s后, HfTiB₂-SiC、ZrTiB₂-SiC复合涂层试样的质量烧蚀率分别为-2.71×10^-3和-4.20×10^-1 mg/s(略微增重), 线烧蚀率分别为1.88×10^-4和3.70×10^-4 μm/s。HfTiB₂-SiC复合涂层烧蚀后表面形成了以HfTiO₄-HfO₂为骨架、TiO₂和SiO₂为填充相的Hf-Ti-Si-O复相氧化层, 而ZrTiB₂-SiC复合涂层烧蚀后表面形成了以ZrTiO₄和ZrO₂为镶嵌相、SiO₂玻璃为半连续相, 且带有微孔的Zr-Ti-Si-O复相氧化层。其中, HfTiO₄、HfO₂、ZrTiO₄、ZrO₂等高熔点相可以有效抵抗高温火焰的冲刷, 高温下具有流动性的TiO₂、SiO₂可以填充烧蚀产生的孔隙缺陷并阻塞氧扩散通道, 防止氧向涂层内部和基体扩散, 二者共同作用实现了陶瓷涂层优异的抗烧蚀防护效果。

关键词: 陶瓷涂层, 抗烧蚀性能, 浆料法, 反应熔渗, 复相玻璃层

Abstract:

In order to improve the ablation resistance of carbon-based materials in elevated-temperature and oxygenated environments, Ti-doped HfB₂-SiC and ZrB₂-SiC composite coatings were prepared on the surface of graphite via a hybrid method involving slurry dipping and reactive infiltration. Phase compositions, microstructures, and element distributions of the composite coatings were studied, and anti-ablation ability of the coating was evaluated at 2300 ℃. Results show that structures of Ti-doped Hf(Zr)B₂-SiC composite coatings are very dense after silicon infiltration. Both HfTiB₂ and ZrTiB₂ ceramic phases are embedded in the coatings, which exhibit no defects and establish robust bonds with the graphite substrates. Residual silicon continuously distributes around Hf(Zr)B₂ and SiC particles. After undergoing ablation at 2300 ℃ for 480 s, the mass ablation rates of HfTiB₂-SiC and ZrTiB₂-SiC composite coating samples are -2.71×10^-3 and -4.20×10^-1 mg/s, respectively, indicating a slight weight gain. The corresponding line ablation rates are 1.88×10^-4 and 3.70×10^-4 μm/s, respectively. Following ablation, a Hf-Ti-Si-O multiphase oxide layer composed of HfTiO₄-HfO₂ as the skeleton and TiO₂-SiO₂ as the filling phase forms on the surface of HfTiB₂-SiC coating. In contrast, a Zr-Ti-Si-O multiphase oxide layer with some micropores, comprising embedded ZrTiO₄ and ZrO₂ phases and a semi-continuous SiO₂ glass phase, develops on the ablative surface of ZrTiB₂-SiC coating. High-melting-point phases, such as HfTiO₄, HfO₂, ZrTiO₄, and ZrO₂, effectively counteract high-temperature flame erosion. Meanwhile, TiO₂ and SiO₂, possessing high-temperature fluidity, can seal the pore defects generated by erosion and thereby preventing oxygen from diffusing into the coatings and substrates. Therefore, the synergy between high-temperature skeletons and filling phases significantly enhances the anti-ablation protection of coatings.

Key words: ceramic coating, ablation resistance, slurry dipping, reaction infiltration, multiphase glass layer

中图分类号:

TQ174

郭晓阳, 张小琳, 姜岩, 田原, 耿志. Ti掺杂Hf(Zr)B₂-SiC抗烧蚀涂层的制备及其抗烧蚀机理[J]. 无机材料学报, 2024, 39(12): 1357-1366.

GUO Xiaoyang, ZHANG Xiaolin, JIANG Yan, TIAN Yuan, GENG Zhi. Ti-doped Hf(Zr)B₂-SiC Anti-ablation Coatings: Preparation and Ablation Resistance Mechanism[J]. Journal of Inorganic Materials, 2024, 39(12): 1357-1366.

图/表 14

图1 涂层样品制备流程

Fig. 1 Preparation process of the coating sample

图2 HfTiB2-SiC涂层XRD图谱, 表面、截面微观结构及EDS元素分析

Fig. 2 XRD pattern, surface and cross-sectional microstructures, and EDS element analysis of HfTiB2-SiC coating (a) XRD pattern; (b) Surface morphology; (c) Enlarged view of Fig. (b); (d) EDS element mappings of Fig. (c); (e) EDS element point-analysis of Fig. (c); (f) Cross-sectional morphology; (g) Enlarged view of Fig. (f); (h) EDS element mappings of Fig. (g); (i) EDS element point-analysis of Fig. (g)

图3 ZrTiB2-SiC涂层XRD图谱, 表面、截面微观结构及EDS元素分析

Fig. 3 XRD pattern, surface and cross-sectional microstructures, and EDS element analysis of ZrTiB2-SiC coating (a) XRD pattern; (b) Surface morphology; (c) Enlarged view of Fig. (b); (d) EDS element mappings of Fig. (c); (e) EDS element point-analysis of Fig. (c); (f) Cross-sectional morphology; (g) Enlarged view of Fig. (f); (h) EDS element mappings of Fig. (g); (i) EDS element point-analysis of Fig. (g)

图4 HfTiB2-SiC涂层试样烧蚀480 s后表面XRD图谱、表面和截面微观形貌及元素分布

Fig. 4 XRD pattern, surface and cross-sectional microstructures, and element distribution of HfTiB2-SiC coating sample after ablation for 480 s (a) XRD pattern; (b) Surface microscopic morphology of the ablation center; (c) Enlarged view of Fig. (b); (d) EDS element mappings of Fig. (c); (e) Microscopic morphology of the transition zone; (f) Surface element analysis of Fig. (e); (g) Cross-sectional morphology of the ablation center; (h) EDS element mappings of Fig. (g); (i) EDS element point-analysis of Fig. (c, g)

图5 ZrTiB2-SiC涂层试样烧蚀480 s后表面XRD图谱、烧蚀中心表面和截面微观形貌及元素分布

Fig. 5 XRD pattern, microstructures and element distributions of the ablation center surface and cross-sectional of ZrTiB2-SiC coating sample after ablation for 480 s (a) XRD pattern; (b) Surface microstructure; (c) Enlarged view of Fig. (b); (d) Enlarged view of Fig. (c); (e) EDS element mappings of Fig. (d); (f) Cross-sectional microscopic morphology; (g) Enlarged view of Fig. (f); (h) EDS element mappings of Fig. (g); (i) EDS element point-analysis of Fig. (d, g)

图6 涂层烧蚀过程中发生反应的吉布斯自由能随温度的变化曲线

Fig. 6 Gibbs free energy variation curves with temperature for the reaction occurring during coating ablation process

图7 涂层烧蚀过程中氧化产物蒸气压(a)和分解压(b)随温度的变化曲线

Fig. 7 Temperature dependent curves of vapor pressure (a) and decomposition pressure (b) for the oxidation products during coating ablation process

图8 复合涂层烧蚀过程示意图

Fig. 8 Schematic diagram of composite coating ablation process (a) Before ablation; (b) During ablation; (c) After ablation

图S1 等离子火焰烧蚀150 s后HfTiB2-SiC涂层表面XRD图谱, 表面、截面微观形貌及EDS元素分析

Fig. S1 XRD pattern, surface and cross-sectional microstructures and EDS element analysis of HfTiB2-SiC coating after plasma flame ablation for 150 s (a) XRD pattern; (b) Surface microstructure; (c) Enlarged view of Fig. (b); (d) Enlarged view of the ablation center; (e) Surface element analysis of Fig. (d); (f) Cross-sectional morphology; (g) Enlarged view of Fig. (f); (h) Surface element analysis of Fig. (g); (i) Element point analysis of Fig. (d, g)

表S1 图2(c)中点1元素原子分数

Table S1 Element atomic fraction of Spot 1 in Fig. 2(c)

Element	Spot 1/%
B	30.42
C	59.20
Si	0.66
Ti	2.00
Hf	7.72

表S2 图3(c)中点1元素原子分数

Table S2 Element atomic fraction of Spot 1 in Fig. 3(c)

Element	Spot 1/%
B	57.66
C	30.13
Si	0
Ti	2.87
Zr	9.35

表S3 图4(c)中点1-3元素原子分数

Table S3 Eelement atomic fraction of Spots 1-3 in Fig. 4(c)

Element	Spot 1/%	Spot 2/%	Spot 3/%
O	64.15	64.42	60.46
Si	3.70	33.04	16.30
Ti	0.24	0.55	0.37
Hf	31.91	1.99	22.87

表S4 图5(d)中点1-3元素原子分数

Table S4 Element atomic fraction of Spots 1-3 in Fig. 5(d)

Element	Spot 1/%	Spot 2/%	Spot 3/%
O	64.20	72.86	57.10
Si	1.75	13.14	29.01
Ti	2.69	2.56	5.31
Zr	31.36	11.44	8.58

表S5 图5(g)中点4和点6元素原子分数

Table S5 Element atomic fraction of Spots 4 and 6 in Fig. 5(g)

Element	Spot 4/%	Spot 6/%
C	17.38	12.51
O	42.38	59.93
Si	0.59	20.94
Ti	2.38	4.75
Zr	37.27	1.86

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Ti掺杂Hf(Zr)B₂-SiC抗烧蚀涂层的制备及其抗烧蚀机理

Ti-doped Hf(Zr)B₂-SiC Anti-ablation Coatings: Preparation and Ablation Resistance Mechanism

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