流延成型结合反应熔渗制备ZrB2-SiC陶瓷及其微观结构与氧化行为研究

doi:10.15541/jim20240035

无机材料学报 ›› 2024, Vol. 39 ›› Issue (8): 955-964.DOI: 10.15541/jim20240035

• 研究快报 • 上一篇

流延成型结合反应熔渗制备ZrB₂-SiC陶瓷及其微观结构与氧化行为研究

谭敏¹^,²(), 陈小武¹^,²(), 杨金山¹^,², 张翔宇¹^,², 阚艳梅¹^,², 周海军¹^,², 薛玉冬¹^,², 董绍明¹^,²()

1.中国科学院上海硅酸盐研究所, 高性能陶瓷和超精密微结构国家重点实验室, 上海 200050
2.中国科学院大学材料与光电研究中心, 北京 100049

收稿日期:2024-01-16 修回日期:2024-03-04 出版日期:2024-08-20 网络出版日期:2024-03-30
通讯作者: 陈小武, 副研究员. E-mail: xwchen@mail.sic.ac.cn;
董绍明, 研究员. E-mail: smdong@mail.sic.ac.cn
作者简介:谭敏(1998-), 男, 硕士研究生. E-mail: tanmin21@mails.ucas.ac.cn

Microstructure and Oxidation Behavior of ZrB₂-SiC Ceramics Fabricated by Tape Casting and Reactive Melt Infiltration

TAN Min¹^,²(), CHEN Xiaowu¹^,²(), YANG Jinshan¹^,², ZHANG Xiangyu¹^,², KAN Yanmei¹^,², ZHOU Haijun¹^,², XUE Yudong¹^,², DONG Shaoming¹^,²()

1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-01-16 Revised:2024-03-04 Published:2024-08-20 Online:2024-03-30
Contact: CHEN Xiaowu, associate professor. E-mail: xwchen@mail.sic.ac.cn;
DONG Shaoming, professor. E-mail: smdong@mail.sic.ac.cn
About author:TAN Min (1998-), male, Master candidate. E-mail: tanmin21@mails.ucas.ac.cn
Supported by:
National Key R&D Program of China(2022YFB3707700);Shanghai Science and Technology Innovation Action Plan(21511104800);National Natural Science Foundation of China(52172111);National Science and Technology Major Project(2017-IV-0005-0042);Key Research Program of the Chinese Academy of Sciences(ZDRW-CN-2021-2-2);Science Center for Gas Turbine Project(P2022-B-IV-001-001)

摘要/Abstract

摘要：

ZrB₂基陶瓷通常需要在高温高压条件下才能烧结致密, 而利用反应熔渗Si的方式可在1500 ℃制得ZrB₂-SiC致密陶瓷。相较于常规制备方法, 反应制备法更容易获得晶粒细小、成分均匀的超高温陶瓷相。本研究以ZrSi₂、B₄C和C为原料, 通过流延成型结合反应熔渗制备ZrB₂-SiC陶瓷(简称ZBC陶瓷)。此外, 还以ZrB₂和SiC为原料, 通过相同的工艺制备了一组ZrB₂-SiC陶瓷(简称ZS陶瓷)作为对比样品。对两组陶瓷的微观形貌进行表征, 发现ZBC陶瓷中ZrB₂相的颗粒尺寸较小且弥散分布在陶瓷中, 而ZS陶瓷中ZrB₂相的颗粒尺寸较大。在1600 ℃空气环境中对两组陶瓷进行循环氧化测试, 总共循环氧化5次, 每次2 h。分析两者的氧化行为, 发现ZBC陶瓷与ZS陶瓷在氧化过程中表面都会形成玻璃态SiO₂-ZrO₂氧化层, 起到阻隔氧气的作用。不同点在于ZBC陶瓷中ZrO₂弥散分布在SiO₂中, 而ZS陶瓷是大尺寸的ZrO₂与玻璃态SiO₂共存。在降温过程中, 弥散分布的ZrO₂能够提高玻璃态SiO₂的黏度, 抑制其结晶, 所以ZBC陶瓷的表面氧化层能够保持致密的结构; 而ZS陶瓷氧化层中SiO₂大量结晶并与ZrO₂共晶反应产生ZrSiO₄, 由于热应力导致氧化层开裂, 使其阻隔氧气的作用大大减弱。分析两者的抗氧化性能, 发现ZBC陶瓷的氧化层厚度变化与质量增加均小于ZS陶瓷, 表明ZBC陶瓷的抗氧化性能优于ZS陶瓷。

关键词: 超高温陶瓷, ZrB₂-SiC, 氧化行为, 反应熔渗

Abstract:

ZrB₂-based ceramics typically necessitate high temperature and pressure for sintering, whereas ZrB₂-SiC ceramics can be fabricated at 1500 ℃ using the process of reactive melt infiltration with Si. In comparison to the conventional preparation method, reactive synthesis allows for the more facile production of ultra-high temperature ceramics with fine particle size and homogeneous composition. In this work, ZrSi₂, B₄C, and C were used as raw materials to prepare ZrB₂-SiC via combination of tape casting and reactive melt infiltration herein referred to as ZBC ceramics. Control sample of ZrB₂-SiC was also prepared using ZrB₂ and SiC as raw materials through an identical process designated as ZS ceramics. Microscopic analysis of both ceramic groups revealed smaller and more uniformly distributed particles of the ZrB₂ phase in ZBC ceramics compared to the larger particles in ZS ceramics. Both sets of ceramics underwent cyclic oxidation testing in the air at 1600 ℃ for a cumulative duration of 5 cycles, each cycle lasting 2 h. Analysis of the oxidation behavior showed that both ZBC ceramics and ZS ceramics developed a glassy SiO₂-ZrO₂ oxide layer on their surfaces during the oxidation. This layer severed as a barrier against oxygen. In ZBC ceramics, ZrO₂ is finely distributed in SiO₂, whereas in ZS ceramics, larger ZrO₂ particles coexist with glassy SiO₂. The surface oxide layer of ZBC ceramics maintains a dense structure because the well-dispersed ZrO₂ increases the viscosity of glassy SiO₂, preventing its crystallization during the cooling. Conversely, some SiO₂ in the oxide layer of ZS ceramics may crystallize and form a eutectic with ZrO₂, leading to the formation of ZrSiO₄. This leads to cracking of the oxide layer due to differences in thermal expansion coefficients, weakening its barrier effect. An analysis of the oxidation resistance shows that ZBC ceramics exhibit less increase in oxide layer thickness and mass compared to ZS ceramics, suggesting superior oxidation resistance of ZBC ceramics.

Key words: ultra-high temperature ceramic, ZrB₂-SiC, oxidation behavior, reactive melt infiltration

中图分类号:

TQ174

谭敏, 陈小武, 杨金山, 张翔宇, 阚艳梅, 周海军, 薛玉冬, 董绍明. 流延成型结合反应熔渗制备ZrB₂-SiC陶瓷及其微观结构与氧化行为研究[J]. 无机材料学报, 2024, 39(8): 955-964.

TAN Min, CHEN Xiaowu, YANG Jinshan, ZHANG Xiangyu, KAN Yanmei, ZHOU Haijun, XUE Yudong, DONG Shaoming. Microstructure and Oxidation Behavior of ZrB₂-SiC Ceramics Fabricated by Tape Casting and Reactive Melt Infiltration[J]. Journal of Inorganic Materials, 2024, 39(8): 955-964.

图/表 12

Fig. 1 Flow chart for the processing of ceramics

Table 1 Raw materials and their molar ratios for ceramics preparation

	ZBC			ZS
Raw materials	ZrSi₂	B₄C	C	ZrB₂	SiC
Molar ratio	2	1	3	1	2

Fig. 2 Microstructure and morphology of ZBC samples (a) XRD patterns of ZBC porous preforms before and after heat treatment; (b) Cross-sectional morphology of ZBC porous preforms after heat treatment; (c) XRD patterns of ceramics after reactive melt infiltration

Fig. 3 Morphologies and corresponding EDS analyses of ZBC ceramics (a-c) Surface; (d-f) Cross section

Fig. 4 Morphologies and corresponding EDS analyses of ZS ceramics (a-c) Surface; (d-f) Cross section

Fig. 5 XRD patterns of ceramics oxidized at 1600 ℃ in the air for different periods (a) ZBC; (b) ZS

Fig. 6 ZrO2-SiO2 binary phase diagram[28]

Fig. 7 Surface morphologies of ZBC ceramics oxidized at 1600 ℃ for different periods (a-c) 2 h; (d-f) 6 h; (g-i) 10 h

Fig. 8 Surface morphologies of ZS ceramics oxidized at 1600 ℃ for different periods (a-c) 2 h; (d-f) 6 h; (g-i) 10 h

Fig. 9 Cross-sectional SEM morphologies of ceramics oxidized at 1600 ℃ for different periods (a, d, g) 2 h; (b, e, h) 6 h; (c, f, i) 10 h

Fig. 10 Thickness of the oxide layer of ceramics oxidized at 1600 ℃ for different periods

Fig. 11 Weight change curves of ZBC and ZS ceramics oxidized at 1600 ℃ for different periods

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流延成型结合反应熔渗制备ZrB₂-SiC陶瓷及其微观结构与氧化行为研究

Microstructure and Oxidation Behavior of ZrB₂-SiC Ceramics Fabricated by Tape Casting and Reactive Melt Infiltration

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