硅酸盐学报

先驱体转化含铪超高温陶瓷研究进展

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郭效扩 ¹^,² , 王小宙 ² , 毛卫国 ¹

硅酸盐学报 | 综合评述 2025,53(9): 2739-2752

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硅酸盐学报 |综合评述 2025 , 53 (9) : 2739 -2752

先驱体转化含铪超高温陶瓷研究进展

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郭效扩¹^,², 王小宙², 毛卫国¹

作者信息

^1．长沙理工大学材料科学与工程学院，长沙 410114

^2．国防科技大学空天科学学院，新型陶瓷纤维及其复合材料重点实验室，长沙 410073

通讯作者:

王小宙（1984—），男，博士，副研究员；

毛卫国（1979—），男，博士，教授。

作者简介:

郭效扩（1999—），男，硕士研究生。

Research Progress on Polymer-Derived Hafnium-Containing Ultra-High Temperature Ceramics

Xiaokuo GUO¹^,², Xiaozhou WANG², Weiguo MAO¹

Affiliations

^1.College of Materials Science and Engineering, Changsha University of Science & Technology, Changsha 410114, China

^2.Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China

Corresponding Author:

WANG Xiaozhou (1984-), male, Ph.D., Associate researcher. E-mail: wangler2002@163.com;

MAO Weiguo (1979-), male, Ph.D., Professor. ssamao@126.com

GUO Xiaokuo (1999-), male, Master candidate. E-mail: 3337142190@qq.com

出版时间: 2025-09-20 doi: 10.14062/j.issn.0454-5648.20240676

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摘要

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含铪超高温陶瓷具有优异的耐超高温、抗氧化、抗烧蚀及良好的力学性能，在高速飞行器等领域有着广泛的应用前景。先驱体转化法因先驱体分子结构可设计、成型性能好、制备温度低、陶瓷产物性能可控等特点而受到广泛关注。本文综述了先驱体转化含铪超高温陶瓷的研究进展，包括有机铪聚合物的分类及其制备方法、交联和热解及其转化陶瓷的组成、结构、性能与应用；最后对先驱体转化含铪超高温陶瓷的发展趋势进行了展望。

关键词

先驱体转化法 / 超高温陶瓷 / 有机铪聚合物 / 合成 / 组成与结构

Abstract

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Hafnium-containing ultra-high temperature ceramics refer to hafnium carbide, hafnium boride, hafnium nitride, and their multiphase ceramics, which have extremely high melting point, high hardness, high stability, excellent mechanical properties, oxidation resistance, and ablation resistance. They are ideal candidate materials for high-temperature applications such as an aerodynamic surface of high-speed aircraft, propulsion system components, plasma arc electrodes, high-temperature furnace heating elements, and high-temperature shielding. It is difficult to prepare high-purity hafnium-containing ceramic powder. The self-diffusion coefficient of ceramics is low, and conventional powder sintering has some bottlenecks in preparing large-size and complex-shaped ultra-high temperature ceramic materials. Polymer-derived ceramic is an efficient method for preparing high-performance hafnium-containing ultra-high temperature ceramic fibers and composites because of the advantages of design-able composition and structure, diversity of molding shapes, low preparation temperature, and uniform distribution of the prepared ceramics.

According to the bonding method, organic hafnium polymers can be divided into a single source and polymer-modified precursor containing Hf-O, Hf-C, and Hf-N bonds, which can be used to prepare ultra-high temperature ceramic powders, coatings, fibers, and composites. Polymers containing Hf-O bonds can be obtained via de-HCl condensation of hafnium-containing chlorides (such as HfCl₄, etc.) and hydroxyl compounds (such as sucrose, etc.) with di(multi)functionality or modification of organosilicon polymers with organic hafnium compounds (such as Hf(OC₄H₉)₄, etc.), which have the advantages of cheap and easy to obtain raw materials, simple synthesis process conditions, easy industrial production, and good stability of the prepared ceramics. However, the low densification ability restricts its applications. Polymers containing Hf-C bonds are mainly obtained via de-chlorination condensation of hafnium-containing chlorides (such as Cp₂HfCl₂, etc.) and organometallic reagents, which have high ceramic yield, good ultra-high temperature performance of the pyrolytic ceramics and high hafnium content that can be introduced by a single-source precursor route. However, cyclopentadiene rigid structures limit their melting and dissolution performance, and there is still a need to improve their formability. There are also some problems, such as the synthesis process is complex. The complex network structure and large molecular weight also limit the precursor's melting and dissolution properties synthesized by a polymer modified precursor route. The type of precursor and heat treatment process affect the composition, structure, and properties of organic hafnium polymers solidified by thermal cross-linking, gas-phase reaction cross-linking, catalytic cross-linking, and irradiation cross-linking, as well as polymer-derived HfC, HfN or HfB₂-based ceramics. Compared with the conventional inorganic powder sintering method, the hafnium-containing ultra-high temperature ceramics derived from organic hafnium polymer precursors (especially non-oxygen precursors) have the advantages of smaller grain size, more uniform distribution, lower oxygen content, and lower synthesis temperature, as well as more superior ultra-high temperature resistance, oxidation resistance, and ablation resistance.

Summary and Prospects

Synthesis of organic hafnium polymers gradually tends to be non-oxidation, simplification, low cost, high conversion rate, and high performance. The pyrolysis of polymers containing Hf-O bonds needs to undergo the carbon-thermal reduction process at high temperatures, and the prepared ceramics have more pores and cracks and insufficient performance, so non-oxygen hafnium-containing polymers are an important direction for future research. The molding performance of solid precursors limits their application in preparing ultra-high temperature ceramic composites via the PIP method, and liquid precursors with a high ceramic yield becomes a hot direction for future development. In addition, polymer-derived continuous ultra-high temperature ceramic fibers and their composites is a research hotspot, and exploring a new paradigm of artificial intelligence to accelerate the research of ultra-high temperature ceramic materials is also an important direction for development.

Key words

polymer-derived ceramics / ultra-high temperature ceramics / organic hafnium polymers / synthesis / composition and structure

引用本文

郭效扩, 王小宙, 毛卫国. 先驱体转化含铪超高温陶瓷研究进展. 硅酸盐学报, 2025 , 53 (9) : 2739 -2752 . DOI: 10.14062/j.issn.0454-5648.20240676

Xiaokuo GUO, Xiaozhou WANG, Weiguo MAO. Research Progress on Polymer-Derived Hafnium-Containing Ultra-High Temperature Ceramics[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (9) : 2739 -2752 . DOI: 10.14062/j.issn.0454-5648.20240676

基金

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国家自然科学基金(51872329)

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2025年第53卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240676

接收时间：2024-10-26
首发时间：2026-10-21
出版时间：2025-09-20

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收稿日期：2024-10-26
修回日期：2024-11-14

基金

国家自然科学基金(51872329)

作者信息

^1．长沙理工大学材料科学与工程学院，长沙 410114

^2．国防科技大学空天科学学院，新型陶瓷纤维及其复合材料重点实验室，长沙 410073

通讯作者:

王小宙（1984—），男，博士，副研究员；

毛卫国（1979—），男，博士，教授。

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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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