前驱体转化陶瓷法制备Ti3SiC2陶瓷及其热稳定性研究

doi:10.15541/jim20240013

无机材料学报 ›› 2024, Vol. 39 ›› Issue (6): 733-740.DOI: 10.15541/jim20240013

• 研究论文 • 上一篇

前驱体转化陶瓷法制备Ti₃SiC₂陶瓷及其热稳定性研究

郑斌¹(), 康凯¹, 张青², 叶昉², 解静¹, 贾研¹, 孙国栋¹(), 成来飞²()

1.长安大学材料科学与工程学院, 西安710064
2.西北工业大学超高温结构复合材料重点实验室, 西安 710072

收稿日期:2024-01-08 修回日期:2024-03-07 出版日期:2024-06-20 网络出版日期:2024-03-08
通讯作者: 孙国栋, 教授. E-mail: sunguodong@chd.edu.cn;
成来飞, 教授. E-mail: chenglf@nwpu.edu.cn
作者简介:郑斌(2000-), 男, 硕士研究生. E-mail: 1522186275@qq.com
基金资助:
国家自然科学基金(52272034);陕西省重点研发计划(2023JBGS-15);陕西省自然科学基础研究计划(2020JQ-372);长安大学中央高校基本科研业务费专项资金(300102313202)

Preparation and Thermal Stability of Ti₃SiC₂ Ceramics by Polymer Derived Ceramics Method

ZHENG Bin¹(), KANG Kai¹, ZHANG Qing², YE Fang², XIE Jing¹, JIA Yan¹, SUN Guodong¹(), CHENG Laifei²()

1. School of Materials Science and Engineering, Chang'an University, Xi'an 710064, China
2. Science and Technology on Thermostructural Composite Materials Laboratory, Northwestern Polytechnical University, Xi'an 710072, China

Received:2024-01-08 Revised:2024-03-07 Published:2024-06-20 Online:2024-03-08
Contact: SUN Guodong, professor. E-mail: sunguodong@chd.edu.cn;
CHENG Laifei, professor. E-mail: chenglf@nwpu.edu.cn
About author:ZHENG Bin (2000-), male, Master candidate. E-mail: 1522186275@qq.com
Supported by:
National Natural Science Foundation of China(52272034);Shaanxi Province Key R&D Program of China(2023JBGS-15);Natural Science Basic Research Program of Shaanxi Province(2020JQ-372);Special Funding for Basic Scientific Research Business Expenses in Central Universities of Chang'an University(300102313202)

摘要/Abstract

摘要：

Ti₃SiC₂具有良好的高温稳定性, 可作为改性材料来提高C/C复合材料的抗氧化性能, 应用潜力巨大。本工作以钛粉和液态聚碳硅烷(Liquid Polycarbosilane, LPCS)作为原料, 采用前驱体转化陶瓷(Polymer Derived Ceramics, PDC)法在1200、1300、1400、1500 ℃下制备了四种相含量的Ti₃SiC₂陶瓷, 研究了烧结温度对其物相组成及形貌的影响, 以及不同Ti₃SiC₂相含量对陶瓷材料的抗氧化和抗热震性能的影响。结果表明, 在Ti : Si物质的量比为3 : 1.5, 烧结温度为1300、1400、1500 ℃条件下, 均有层状结构的Ti₃SiC₂生成。当烧结温度为1400 ℃时, 陶瓷产物中Ti₃SiC₂质量分数达到92.10%, 抗弯强度达172.68 MPa。在1300 ℃静态空气环境下氧化7 h, 陶瓷氧化增重随Ti₃SiC₂相含量增大而逐渐降低, 这是由于氧化过程中材料表面生成了以TiO₂为主相的保护膜, 有效延缓了氧气向内部扩散。对试样进行1300 ℃空气热震和抗弯强度测试发现, 随着热震次数的增加, 所有材料的残余强度均有所下降; 但随着Ti₃SiC₂相含量增大, 试样的抗热震性能和残余强度均提高。Ti₃SiC₂相质量分数为92.10%的试样经过30次热震后失重30.66%, 残余强度为120.18 MPa, 这主要归因于层状结构的Ti₃SiC₂大幅增加了裂纹扩展路径及其良好的抗氧化性能。

关键词: Ti₃SiC₂, 无压烧结, 抗氧化性能, 抗热震性能

Abstract:

Ti₃SiC₂ compound can enhance the oxidation resistance of C/C composites as a modifying material, thanks for its superior high-temperature stability, indicating significant potential for applications. In this work, titanium powder and liquid polycarbosilane (LPCS) were served as starting materials for producing Ti₃SiC₂ ceramics with four different phase contents by polymer derived ceramics (PDC) method at temperatures of 1200, 1300, 1400, and 1500 ℃, respectively. Effects of sintering temperature on the phase compositions and morphology of the ceramics were studied. Additionally, the impact of varying Ti₃SiC₂ phase contents on oxidation resistance and thermal shock resistance were also explored. The results showed that layered Ti₃SiC₂ formed at Ti : Si molar ratio of 3 : 1.5 when sintered at 1300, 1400, and 1500 ℃, respectively. After sintered at 1400 ℃, the mass fraction of Ti₃SiC₂ in the ceramic product reached 92.10% with the bending strength of 172.68 MPa. When subjected to a static air environment of 1300 ℃ for 7 h, the oxidation weight of the ceramics obtained progressively reduction with the increase of Ti₃SiC₂ phase content. During the oxidation process, a protective film primarily consisted of TiO₂ was formed on the surface, which effectively slowed down the oxygen diffusion into the interior. Air thermal shock tests at 1300 ℃ and flexural strength assessments demonstrated that the residual strength of all materials decreased with the increase of thermal shock times. Nevertheless, the thermal shock resistance and residual strength of the samples were enhanced with the increase of Ti₃SiC₂ phase content. After 30 times thermal shock, the sample with the mass fraction of Ti₃SiC₂ phase of 92.10% experienced 30.66% weight loss and retained residual strength of 120.18 MPa, primarily due to the layered structure of Ti₃SiC₂ which is significantly extends the crack propagation path and its superior oxidation resistance.

Key words: Ti₃SiC₂, pressureless sintering, oxidation resistance, thermal shock resistance

中图分类号:

TB34

郑斌, 康凯, 张青, 叶昉, 解静, 贾研, 孙国栋, 成来飞. 前驱体转化陶瓷法制备Ti₃SiC₂陶瓷及其热稳定性研究[J]. 无机材料学报, 2024, 39(6): 733-740.

ZHENG Bin, KANG Kai, ZHANG Qing, YE Fang, XIE Jing, JIA Yan, SUN Guodong, CHENG Laifei. Preparation and Thermal Stability of Ti₃SiC₂ Ceramics by Polymer Derived Ceramics Method[J]. Journal of Inorganic Materials, 2024, 39(6): 733-740.

图/表 17

图1 不同温度烧结的Ti3SiC2的XRD图谱

Fig.1 XRD patterns of Ti3SiC2 sintered at different temperatures

表1 不同温度烧结试样物相的质量分数

Table 1 Mass percentages of phases in samples sintered at different temperatures

Group	TiC/%	Ti₅Si₃/%	Ti₃SiC₂/%
A	45.58	54.42	0
B	37.16	45.52	17.32
C	7.90	0	92.10
D	47.97	0	52.03

图2 不同温度烧结的试样SEM照片

Fig. 2 SEM images of samples sintered at different temperatures (a) Group A; (b) Group B; (c) Group C; (d) Group D

表2 不同温度烧结的试样密度及孔隙率

Table 2 Density and porosity of samples sintered at different temperatures

Group	Density/(g·cm^-3)	Porosity/%
A	1.77	27.52
B	1.62	22.25
C	1.82	18.47
D	1.69	18.53

图3 三组试样的热重曲线

Fig. 3 Thermogravimetric curves of samples from three groups (a) Group B; (b) Group C; (c) Group D

图4 三组试样1300 ℃空气氧化后(a)单位表面积增重和(b)单位表面积增重平方与时间的关系

Fig. 4 Relationships of (a) weight gain per unit surface area and (b) weight gain per unit surface area square with time of three groups after oxidation in air at 1300 ℃

表3 B~D组1300 ℃空气氧化速率常数

Table 3 Air oxidation rate constants of group B-D at 1300 ℃

Group	K_p/(kg²·m^-4·h^-1)
B	0.8485
C	0.1636
D	0.4399

图5 三组试样表面的SEM照片及EDS图谱

Fig. 5 SEM images and EDS mappings of the surfaces of three groups (a) Group B; (b) Group C; (c) Group D

图6 三组试样氧化后表面的XRD图谱

Fig. 6 XRD patterns of the oxidized surface of three groups

图7 氧化过程吉布斯自由能的变化

Fig. 7 Changes of Gibbs free energy in oxidation process

图8 三组试样截面SEM照片及EDS分析

Fig. 8 SEM images and EDS analyses of cross-sections of three groups (a) Group B; (b) Group C; (c) Group D

表4 不同次数热震后材料的质量变化率

Table 4 Material mass change rates after different thermal shocks

Group	Mass change rate/%
Group	15 times	30 times
B	37.95	39.34
C	30.09	30.66
D	35.81	36.91

图9 三组试样热震30次后的XRD图谱

Fig. 9 XRD patterns three groups of samples after 30 thermal shocks

图10 不同次数热震后三组试样的三点弯曲载荷-位移曲线

Fig. 10 Three-point flexural load-displacement curves of samples of three groups after different thermal shock times (a) Group B; (b) Group C; (c) Group D

图11 不同次数热震后三组试样的抗弯强度

Fig. 11 Bending strengths of samples from three groups after different thermal shock times Colorful figure is available on website

图12 不同次数热震后三组试样的宏观照片

Fig. 12 Macro photos of samples of three groups after different thermal shock times (a) 0 times; (b) 15 times; (c) 30 times

图13 热震15次后C组试样的SEM照片

Fig.13 SEM images of a sample from group C after 15 thermal shocks (a) Delamination; (b) Crack deflection

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前驱体转化陶瓷法制备Ti₃SiC₂陶瓷及其热稳定性研究

Preparation and Thermal Stability of Ti₃SiC₂ Ceramics by Polymer Derived Ceramics Method

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