硅酸盐学报

纳米复相陶瓷SiC/（Hf_xTa_1-_x）C/C的制备、微结构演变及力学性能

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汪震越 ¹ , 卢丽 ² , 文青波 ² , 余兆菊 ¹^,³

硅酸盐学报 | 聚合物先驱体陶瓷专题—研究论文 2024,52(9): 2757-2766

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硅酸盐学报 |聚合物先驱体陶瓷专题—研究论文 2024 , 52 (9) : 2757 -2766

纳米复相陶瓷SiC/（Hf_xTa_1-_x）C/C的制备、微结构演变及力学性能

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汪震越¹, 卢丽², 文青波², 余兆菊¹^,³

作者信息

^1．厦门大学材料学院，高性能陶瓷纤维教育部重点实验室，福建厦门 361005

^2．中南大学，粉末冶金国家重点实验室，长沙 410083

^3．厦门大学材料学院，厦门市电子陶瓷材料与元器件重点实验室，福建厦门 361005

通讯作者:

余兆菊（1976—），女，博士，教授；

文青波（1987—），男，博士，教授。

作者简介:

汪震越（1999—），男，硕士研究生。

Preparation, Microstructure Evolution and Mechanical Properties of SiC/(Hf_xTa₁_-_x)C/C Nanocomposites

Zhenyue WANG¹, Li LU², Qingbo WEN², Zhaoju YU¹^,³

Affiliations

^1.Key Laboratory of High Performance Ceramic Fibers, Xiamen University, Xiamen 361005, Fujian, China

^2.State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China

^3.Key Laboratory of Electronic Ceramic Materials and Devices, Xiamen University, Xiamen 361005, Fujian, China

Corresponding Author:

YU Zhaoju (1976-), female, Ph.D., Professor; E-mail: zhaojuyu@xmu.edu.cn;

WEN Qingbo (1987-), male, Ph.D., Professor. wentsingbo@csu.edu.cn

WANG Zhenyue (1999-), male, Master candidate. E-mail: 1278615062@qq.com

出版时间: 2024-09-20 doi: 10.14062/j.issn.0454-5648.20240090

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摘要

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采用聚合物先驱体转化法结合放电等离子烧结技术，制备出近致密的SiC/（Hf_xTa_1-_x）C/C纳米复相材料。通过X射线衍射仪、透射电子显微镜、扫描电子显微镜，纳米压痕仪对SiC/（Hf_xTa_1-_x）C/C纳米复相陶瓷的微结构演变及其力学性能进行了表征。结果表明，通过对单源聚合物先驱体进行分子设计，改变SSP中的Hf/Ta比例，可以控制最终固溶（Hf_xTa_1-_x）C的组成。最终块体SiC/（Hf_0.2Ta_0.8）C/C纳米复相陶瓷的开孔率为4.87%，其纳米压痕硬度为（7.72±1.36）GPa，弹性模量为（76.71±7.89）GPa，展现出良好的力学性能。

关键词

单源先驱体 / 聚合物先驱体转化法 / 放电等离子烧结 / 碳化硅基复相陶瓷

Abstract

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Introduction

HfC and TaC are typical ultra-high temperature ceramics (UHTCs), which are important candidate materials for thermal protection components in high-speed aircraft. However, their oxidation resistance at medium and low temperatures is relatively poor. Due to the similar crystal structures of HfC and TaC, and the close atomic radii of Hf and Ta (r_Hf = 1.585 Å, r_Ta=1.457 Å, Δr < 0.15), theoretically, they can form an infinitely miscible substitutional solid solution (Hf_xTa_1-_x)C (0 < x < 1). Among them, Hf_0.2Ta_0.8C has a melting point as high as 4 300 K, which is recognized as the highest melting point carbide. Compared with single-component HfC and TaC, (Hf_xTa_1-_x)C exhibits higher initial oxidation temperature and lower oxidation rate, indicating significantly improved oxidation resistance. In this work, a series of processable liquid single-source precursors (SSPs) were successfully prepared by introducing HfCl₄ and TaCl₅ into allylhydridopolycarbosilane (AHPCS). Through the polymer-derived ceramic (PDC) method, SiC/(Hf_xTa_1-_x)C/C nanocomposites with core-shell structured SiC@C and (Hf_xTa_1-_x)C@C nanoparticles were obtained, and the evolution of phase composition and microstructure during the ceramic transformation process was investigated. Combining PDC and spark plasma sintering (SPS) technology, nearly dense SiC/(Hf_xTa_1-_x)C/C bulk materials were prepared, and the mechanical properties of the resulting bulk ceramic were investigated.

Methods

Chemically stoichiometric amounts of HfCl₄ and TaCl₅ were weighed and reacted with AHPCS in CHCl₃ solvent at 60 ℃ to prepare a series of SSPs. The molecular structure of the synthesized SSPs was characterized using Fourier-transform infrared spectroscopy (FT-IR, Nicolet iS10, Thermo Fisher Scientific). Thermal behavior analysis of the SSPs was conducted using a thermogravimetric analyzer (TGA, STA 449 F5 Jupiter, NETZSCH). The SSPs were heat-treated at temperatures ranging from 900 ℃ to 1 600 ℃ to obtain SiC/(Hf_xTa_1-_x)C/C nanocomposite powders. The phase composition of the ceramic powders was analyzed using X-ray diffraction (XRD, SmartLab-SE, Rigaku Corporation) with Cu Kα1 radiation (λ=1.540 6 Å). The microstructure and phase composition of the samples were analyzed using transmission electron microscopy (TEM, Talos F200S, Thermo Fisher Scientific) and selected area electron diffraction (SAED). The powders were sintered using a spark plasma sintering (SPS, CXSPS-40A, Chenxin Corporation) at 50 MPa and 2 200 ℃ to prepare SiC/(Hf_0.2Ta_0.8)C/C bulk materials, named as LAH2T8-bulk. The surface morphology of LAH2T8-bulk was observed using scanning electron microscopy (SEM, CLARA, TESCAN). The hardness and elastic modulus of the bulk materials were measured using a nano-indenter (iNano, Nanomechanics, Inc.) with a Berkovich tip under a maximum load of 20 mN. The volume density and porosity of LAH2T8-bulk were measured using the water immersion method.

Results and discussion

During the synthesis of liquid SSPs, the main reactions are dehydrochlorination between metal chlorides and AHPCS. The crosslinking of liquid SSPs is achieved through further consumption of Si-H via dehydrochlorination reactions. The ceramic yield of the obtained SSPs at 900 ℃ exceeds 90%. By combining the PDC method with SPS, nearly dense SiC/(Hf_0.2Ta_0.8)C/C ceramic bulk with an open porosity of 4.87% were successfully prepared. In the crystalline phases, the mass fractions of β-SiC and (Hf_0.2Ta_0.8)C are 60.7% and 39.3%, respectively, with average grain sizes of both phases being less than 90 nm. The measured nanoindentation hardness is (7.72±1.36) GPa, and the elastic modulus is (76.71±7.89) GPa.

Conclusions

By altering the feed ratio of HfCl₄/TaCl₅ during the synthesis process of the SSPs and designing their molecular structure, the composition of the transition metal carbide solid solution products in the final SiC/(Hf_xTa_1-_x)C/C nanocomposites can be effectively controlled. After heat treatment at 1 600 ℃, core-shell structured (Hf_0.2Ta_0.8)C@C and SiC@C nanoparticles were in-situ formed in the ceramic matrix. The combination of the PDC approach with SPS technology results in the bulk SiC/(Hf_0.2Ta_0.8)C/C ceramic nanocomposites with good mechanical properties.

Key words

single-source-precursor / polymer derived ceramic / spark plasma sintering / silicon carbide-based nanocomposite

引用本文

汪震越, 卢丽, 文青波, 余兆菊. 纳米复相陶瓷SiC/（Hf_xTa_1-_x）C/C的制备、微结构演变及力学性能. 硅酸盐学报, 2024 , 52 (9) : 2757 -2766 . DOI: 10.14062/j.issn.0454-5648.20240090

Zhenyue WANG, Li LU, Qingbo WEN, Zhaoju YU. Preparation, Microstructure Evolution and Mechanical Properties of SiC/(Hf_xTa₁_-_x)C/C Nanocomposites[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (9) : 2757 -2766 . DOI: 10.14062/j.issn.0454-5648.20240090

基金

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国家自然科学基金(51872246; 52061135102)

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2024年第52卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240090

接收时间：2024-01-30
首发时间：2026-10-22
出版时间：2024-09-20

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收稿日期：2024-01-30
修回日期：2024-03-27

基金

国家自然科学基金(51872246; 52061135102)

作者信息

^1．厦门大学材料学院，高性能陶瓷纤维教育部重点实验室，福建厦门 361005

^2．中南大学，粉末冶金国家重点实验室，长沙 410083

^3．厦门大学材料学院，厦门市电子陶瓷材料与元器件重点实验室，福建厦门 361005

通讯作者:

余兆菊（1976—），女，博士，教授；

文青波（1987—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240090

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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