硅酸盐学报

（TiZrNbTaMe）C （Me=V, Cr, Mo, W）高熵陶瓷的显微结构演变及元素分布

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孔庆易 ¹^,³ , 王恺 ²^,³ , 陈磊 ²^,³ , 苏文韬 ²^,³ , 霍思嘉 ¹^,³ , 王玉金 ¹^,³

硅酸盐学报 | 研究论文 2025,53(2): 241-248

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硅酸盐学报 |研究论文 2025 , 53 (2) : 241 -248

（TiZrNbTaMe）C （Me=V, Cr, Mo, W）高熵陶瓷的显微结构演变及元素分布

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孔庆易¹^,³, 王恺²^,³, 陈磊²^,³, 苏文韬²^,³, 霍思嘉¹^,³, 王玉金¹^,³

作者信息

^1．哈尔滨工业大学，材料结构精密焊接与连接全国重点实验室，哈尔滨 150001

^2．哈尔滨工业大学，金属精密热加工国家级重点实验室，哈尔滨 150001

^3．哈尔滨工业大学材料科学与工程学院，特种陶瓷研究所，哈尔滨 150001

通讯作者:

王玉金（1974—），男，博士，教授。

作者简介:

孔庆易（1998—），男，博士研究生。

Microstructural Evolution and Elemental Distribution of (TiZrNbTaMe)C (Me=V, Cr, Mo, W) High-Entropy Ceramics

Qingyi KONG¹^,³, Kai WANG²^,³, Lei CHEN²^,³, Wentao SU²^,³, Sijia HUO¹^,³, Yujin WANG¹^,³

Affiliations

^1.National Key Laboratory of Precision Welding & Joining of Materials and Structures, Harbin Institute of Technology, Harbin 150001, China

^2.National Key Laboratory of Precision Hot Processing of Metals, Harbin Institute of Technology, Harbin 150001, China

^3.Institute for Advanced Ceramics, School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China

Corresponding Author:

WANG Yujin (1974-), male, Ph.D., Professor. E-mail: wangyuj@hit.edu.cn

KONG Qingyi (1998-), male, Doctoral candidate. E-mail: kongqy_iachit@163.com

出版时间: 2025-02-20 doi: 10.14062/j.issn.0454-5648.20240577

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摘要

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随着航空航天、核能和特种冶炼行业的快速发展，对新型超高温、抗辐照、耐腐蚀等极端环境使役性能需求不断提升，亟需新材料创制和性能调控。过渡金属碳化物具有高熔点、抗辐照、耐腐蚀和理化性能稳定等优异性能，是极端环境用特种陶瓷重要的组成部分。现今，碳化物陶瓷更是逐渐从单一组元发展到多组元碳化物固溶体体系，乃至高熵陶瓷体系。本工作采用热压烧结，制备4种高熵碳化物陶瓷（TiZrNbTaMe）C（Me=V, Cr, Mo, W），比较Me元素对陶瓷组织结构和力学性能的影响。结果表明：4种高熵碳化物陶瓷均呈现面心立方结构，其中V、Cr和Mo元素有助于烧结促进致密化，致密度均超过98%。除（TiZrNbTaCr）C外，其他高熵陶瓷体系的金属元素分布均匀，而Cr元素在（TiZrNbTaCr）C陶瓷中出现晶界偏聚现象，导致碳化物晶粒中的Cr含量较低。Cr元素在碳化物高熵陶瓷中的固溶度与金属元素的种类和含量密切相关。（TiZrNbTaCr）C陶瓷具有最佳的综合力学性能，其维氏硬度为29.8 GPa，断裂韧性为3.71 MPa·m^1/2。

关键词

过渡金属碳化物 / 高熵陶瓷 / 组织演变 / 力学性能

Abstract

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Introduction

Ultra-high temperature ceramics include a series of high melting point materials, such as transition metal carbides, nitrides and borides, especially transition metal carbides with excellent high-temperature mechanical properties, stable physico-chemical properties, corrosion resistance and radiation resistance, showing broad prospects for application in the hypersonic aircraft, rocket engines, fourth-generation nuclear reactor, and other extreme environments. However, the traditional single-component transition metal carbide ceramics have been unable to meet the emerging requirements under extreme environments, there is an urgent need to develop a new high-performance material under ultra-high temperature. In recent years, the concept of multi-component "high entropy" has greatly expanded the scope of material composition design and property optimization. Compared with single-component carbides, multi-component ceramics perform better in terms of overall properties, including hardness, creep resistance, oxidation resistance and radiation resistance. These improvements mainly result from their complex component composition, electronic structure and lattice distortion. At present, the influence of elemental species on the microstructure evolution and mechanical properties of carbide high-entropy ceramics is not reported. In this paper, (TiZrNbTaMe)C (Me=V, Cr, Mo, W) high-entropy ceramics are prepared by hot press sintering, and the effects of Me elemental species on the physical phase, microstructure evolution, and mechanical properties of (TiZrNbTaMe) high-entropy ceramics are investigated.

Methods

In this work, (TiZrNbTaMe)C (Me=V, Cr, Mo, W) high-entropy ceramics with equimolar ratio were prepared by carbothermal reduction-assisted hot pressing using transition metal oxides and carbon black as raw materials. The oxides and carbon black were mixed using a planetary ball mill (Fritsch, model P4, Germany). Carbide powders were obtained by carbothermal reduction under vacuum using a pressureless sintering furnace (WS0404, Ningxia Sincere Co. Ltd., China) with a process of 1500 ℃/1 h. The synthesized carbide powders were loaded into graphite molds, and the ceramic samples were prepared by a two-step hot pressing method (AVS, model 1540, USA). The samples were held at 1850 ℃ for 1 h, and then at 2100 ℃ for 0.5 h under pressure of 30 MPa or 10 Pa. Phase analysis was carried out by X-ray diffractometry (XRD; D/max-B, Rigaku, Japan) using Cu-K_α rays. Scanning electron microscopy (SEM; Quanta 200FEG, USA) was used to analyze the microstructure and elemental content and distribution. Transmission electron microscopy (TEM; Talos F200X, USA) was used to analyze the microstructure, elemental content and distribution, and grain boundary characteristics of the materials. The relative densities of the samples were measured using image analysis software (Photoshop, Adobe, USA) based on the pores in the SEM photographs. Vickers hardness was measured using a Vickers hardness tester (HVS-30) at a load of 9.8 N with a holding time of 15 s. Fracture toughness was also measured using the indentation method. The interaction parameters between the metal elements were also calculated using DFT calculation.

Results and discussion

The high-entropy ceramics are all characterized by an FCC crystal structure. Except for the (TiZrNbTaW)C sample, the porosity of the other three high entropy ceramics is low, and their density exceeds 98% and the element distribution is relatively uniform. Compared with the (TiZrNbTaMo)C sample, the grain sizes of the (TiZrNbTaV)C and (TiZrNbTaCr)C samples are significantly reduced, which are 2.69 μm and 5.39 μm, respectively. This shows that the addition of V and Cr elements helps to improve the sintering properties of the (TiZrNbTaMe)C system and inhibit grain growth. The element content analysis results of (TiZrNbTaCr)C show that the Cr element segregates significantly at the grain boundaries, while the other four metal elements are distributed more evenly. The segregation of Cr at the grain boundaries may be related to chromium carbides with low melting points. For example, the melting point of Cr₃C₂ is about 1810 ℃, while the sintering temperature is as high as 2100 ℃, suggesting that chromium carbides may form a liquid phase and aggregate at the grain boundaries during sintering. In addition, the complex composition of high-entropy ceramics may also affect the solid solubility of Cr. The interaction coefficients between Cr and each metal element in transition metal carbides show that the interaction parameter values of Cr and other metal elements are high. It is difficult for Cr to form a solid solution with other metal elements, thus tending to be enriched at the grain boundaries. Therefore, (Ti_xZr_0.4-_xNb_0.2Ta_0.2Cr_0.2)C ceramics with different Ti and Zr contents (x=0, 0.2, 0.3 and 0.4) were designed and prepared. The effect of Ti content on the solid solubility of Cr in the (TiZrNbTaCr)C sample was investigated. As the x value increases from 0 to 0.4, the solid solubility of Cr in the grains increases from 3.18% to 8.68%. It shows that the increase of Ti content is beneficial to improve the solid solubility of Cr. In addition, for the (TiZrNbTaCr)C sample, the high lattice distortion leads to solid solution strengthening in the grains and the high density of the system increases its hardness, which has the best mechanical properties. Its Vickers hardness and fracture toughness reach 29.8 GPa and 3.71 MPa·m^1/2, respectively.

Conclusions

The four (TiZrNbTaMe)C (Me=V, Cr, Mo, W) high-entropy ceramics are all face-centered cubic structures, and the elements are uniformly distributed in the high-entropy ceramic systems except for the (TiZrNbTaCr)C sample. The (TiZrNbTaCr)C sample is also characterized by the presence of a significant Cr segregation at grain boundaries, resulting in a low Cr content inside the grains. The (TiZrNbTaCr)C sample has the best overall mechanical properties, with the Vickers hardness and fracture toughness reaching 29.8 GPa and 3.71 MPa·m^1/2, respectively. In-depth studies show that the solid solubility of Cr element in high-entropy carbide ceramics is closely related to the species and content of metal elements. Enhancing the content of Ti element helps to improve the solid solubility of Cr element in high-entropy carbide ceramics, in which the solid solubility of Cr element in the grain of (Ti_0.4Nb_0.2Ta_0.2Cr_0.2)C system reaches the maximum value of about 8.68%.

Key words

transition metal carbides / high-entropy ceramics / microstructure evolution / mechanical properties

引用本文

孔庆易, 王恺, 陈磊, 苏文韬, 霍思嘉, 王玉金. （TiZrNbTaMe）C （Me=V, Cr, Mo, W）高熵陶瓷的显微结构演变及元素分布. 硅酸盐学报, 2025 , 53 (2) : 241 -248 . DOI: 10.14062/j.issn.0454-5648.20240577

Qingyi KONG, Kai WANG, Lei CHEN, Wentao SU, Sijia HUO, Yujin WANG. Microstructural Evolution and Elemental Distribution of (TiZrNbTaMe)C (Me=V, Cr, Mo, W) High-Entropy Ceramics[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (2) : 241 -248 . DOI: 10.14062/j.issn.0454-5648.20240577

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国家自然科学基金(52032002)

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2025年第53卷第2期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240577

接收时间：2024-09-02
首发时间：2026-10-22
出版时间：2025-02-20

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收稿日期：2024-09-02
修回日期：2024-09-22

基金

国家自然科学基金(52032002)

作者信息

^1．哈尔滨工业大学，材料结构精密焊接与连接全国重点实验室，哈尔滨 150001

^2．哈尔滨工业大学，金属精密热加工国家级重点实验室，哈尔滨 150001

^3．哈尔滨工业大学材料科学与工程学院，特种陶瓷研究所，哈尔滨 150001

通讯作者:

王玉金（1974—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240577

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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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