(TiVNbMoW)Cx高熵陶瓷的单相形成过程与碳空位调控

doi:10.15541/jim20240477

无机材料学报 ›› 2025, Vol. 40 ›› Issue (5): 511-520.DOI: 10.15541/jim20240477

(TiVNbMoW)C_x高熵陶瓷的单相形成过程与碳空位调控

崔宁¹(), 张玉新¹^,³, 王鲁杰²^,³^,⁴(), 李彤阳²^,³^,⁴, 于源², 汤华国²^,³, 乔竹辉²^,³^,⁴()

1.青岛理工大学机械与汽车工程学院, 青岛 266525
2.中国科学院兰州化学物理研究所, 兰州 730000
3.烟台先进材料与绿色制造山东省实验室, 烟台 264006
4.烟台中科先进材料与绿色化工产业技术研究院, 烟台 264006

收稿日期:2024-11-12 修回日期:2024-12-22 出版日期:2025-05-20 网络出版日期:2025-01-09
通讯作者: 王鲁杰, 副研究员. E-mail: ljwang@licp.cas.cn;
乔竹辉, 研究员. E-mail: zhqiao@licp.cas.cn
作者简介:崔宁(1987-), 男, 副教授. E-mail: cuining@qut.edu.cn
基金资助:
国家自然科学基金(252102080);国家自然科学基金(52375217);山东省实验室(SYS202204);甘肃省青年科学基金(23JRRA598)

Single-phase Formation Process and Carbon Vacancy Regulation of (TiVNbMoW)C_x High-entropy Ceramics

CUI Ning¹(), ZHANG Yuxin¹^,³, WANG Lujie²^,³^,⁴(), LI Tongyang²^,³^,⁴, YU Yuan², TANG Huaguo²^,³, QIAO Zhuhui²^,³^,⁴()

1. School of Mechanical and Automotive Engineering, Qingdao University of Technology, Qingdao 266525, China
2. Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
3. Shandong Laboratory of Advanced Materials and Green Manufacturing at Yantai, Yantai 264006, China
4. Yantai Zhongke Research Institute of Advanced Materials and Green Chemical Engineering, Yantai 264006, China

Received:2024-11-12 Revised:2024-12-22 Published:2025-05-20 Online:2025-01-09
Contact: WANG Lujie, associate professor. E-mail: ljwang@licp.cas.cn;
QIAO Zhuhui, professor. E-mail: zhqiao@licp.cas.cn
About author:CUI Ning (1987-), male, associate professor. E-mail: cuining@qut.edu.cn
Supported by:
National Natural Science Foundation of China(252102080);National Natural Science Foundation of China(52375217);Shandong Provincial Laboratory(SYS202204);Gansu Youth Science Foundation(23JRRA598)

摘要/Abstract

摘要：

高熵过渡金属碳化物(HETMCs)因其卓越的物化特性, 逐渐成为先进结构材料领域的研究热点, 尤其是(TiVNbMoW)C以其出色的力学性能与耐磨性而备受关注。然而, 关于(TiVNbMoW)C的单相形成过程及碳空位浓度对其力学性能影响的研究尚存在不足。本研究创新性地选用TiC、VC、NbC、Mo₂C、WC、单质W粉及石墨粉为原料, 采用放电等离子热压烧结技术, 成功制备出具有不同碳空位浓度的(TiVNbMoW)C_x, 并系统研究了碳空位对材料的相组成及演变、显微形貌及力学性能的影响, 结果如下。1) Ti-V-Nb-Mo-W-C体系在1500 ℃下Mo、Ti、Nb和V元素对应的碳化物已经开始相互固溶, 形成(MoTiNbV)C相; 随着温度升高, W元素参与固溶, 1700 ℃时材料实现致密化, 1800 ℃时形成(TiVNbMoW)C高熵单相。2) C与过渡金属质量比(C/TM)对试样的相结构和显微组织影响显著。当C/TM为0.7时, W元素无法固溶, 试样由(MoTiNbV)C和W₂C两相组成; 当C/TM为0.8时, 试样为单相(TiVNbMoW)C且存在大量的碳空位; 当C/TM为0.9时, 碳空位达到饱和; 当C/TM为1.0时, 碳在试样内部富集, 并导致致密化程度下降。3) 合适的碳空位浓度有益于细化晶粒并提升材料的力学性能, C/TM为0.8的试样展现出最高的硬度、弹性模量和断裂韧性, 综合力学性能最佳。本研究为深入理解(TiVNbMoW)C_x高熵碳化物提供了重要基础, 未来可通过引入其他元素优化材料性能, 拓展其在高端制造等领域的应用。

关键词: 高熵过渡金属碳化物, 致密化, 碳空位浓度, 力学性能

Abstract:

High-entropy transition metal carbides (HETMCs) have emerged as promising candidate materials in advanced structural application due to their superior physical and chemical properties compared to traditional carbides. Among these materials, (TiVNbMoW)C has garnered attention due to its outstanding mechanical properties and wear resistance. However, previous studies on the single-phase formation process of (TiVNbMoW)C and the effect of carbon vacancy concentration on its mechanical properties remain inadequate. In this study, TiC, VC, NbC, Mo₂C, WC, elemental W powder, and graphite powder were innovatively selected as raw materials, and (TiVNbMoW)C_x with different carbon vacancy concentrations was successfully prepared by spark plasma hot pressing sintering technology. Effects of carbon vacancies on phase composition, phase evolution, microstructure, and mechanical property of the material were systematically studied. The results show that in the Ti-V-Nb-Mo-W-C system, the carbides corresponding to Mo, Ti, Nb and V elements began to dissolve into each other at 1500 ℃, forming (MoTiNbV)C phase. With increase of temperature, W element gradually participates in solid solution, resulting in densification of the material at 1700 ℃, and formation of (TiVNbMoW)C as a high entropy single phase occurs at 1800 ℃. The mass ratio of carbon to transition metals (C/TM) has a great influence on phase structure and microstructure of the material. When the C/TM is 0.7, the W element cannot dissolve sufficiently to form a single-phase structure, resulting in a composition consisting of (MoTiNbV)C and W₂C phases. At a C/TM of 0.8, the sample exhibits a single-phase (TiVNbMoW)C structure characterized by a large number of carbon vacancies. At a C/TM of 0.9, carbon vacancies reach saturation. At a C/TM of 1.0, excessive carbon enrichment within the material results in a decreased degree of densification. An optimal concentration of carbon vacancies is beneficial for grain refinement and enhancement of the mechanical properties of materials. The sintered sample with a C/TM of 0.8 exhibits the highest hardness, elastic modulus and fracture toughness, demonstrating the most favorable integral mechanical properties. Therefore, this study provides an important basis for a comprehensive understanding of (TiVNbMoW)C_x high-entropy carbides. Future research may introduce additional elements to optimize material properties and broaden its application in high-end manufacturing and related fields.

Key words: high-entropy transition metal carbide, densification, carbon vacancy concentration, mechanical property

中图分类号:

TQ174

崔宁, 张玉新, 王鲁杰, 李彤阳, 于源, 汤华国, 乔竹辉. (TiVNbMoW)C_x高熵陶瓷的单相形成过程与碳空位调控[J]. 无机材料学报, 2025, 40(5): 511-520.

CUI Ning, ZHANG Yuxin, WANG Lujie, LI Tongyang, YU Yuan, TANG Huaguo, QIAO Zhuhui. Single-phase Formation Process and Carbon Vacancy Regulation of (TiVNbMoW)C_x High-entropy Ceramics[J]. Journal of Inorganic Materials, 2025, 40(5): 511-520.

图/表 12

表1 原料粉末的基本参数

Table 1 Basic parameters of raw material powders

Raw powder	Average particle size/µm	Purity/%	Crystal structure	Lattice constant/Å
TiC	1	99.9	fcc	4.33
VC	1	99.9	fcc	4.18
NbC	1	99.9	fcc	4.47
Mo₂C	1	99.9	hcp	a=3.01, c=4.74
WC	1	99.9	hcp	a=2.91, c=2.83
W	1	99.9	bcc	a=3.165
Graphite	0.05	99.9

表2 具有不同C/TM试样的原料组成

Table 2 Raw material composition of samples with different C/TM

C/TM	Mass fraction/%
C/TM	TiC	VC	NbC	Mo₂C	WC	W	Graphite
1.0	11.26	11.84	19.74	19.18	36.85	0	1.13
0.9	11.39	11.98	19.96	19.40	37.27	0	0
0.8	11.53	12.12	20.19	19.62	18.85	17.69	0
0.7	11.66	12.26	20.43	19.85	0	35.80	0

图1 C/TM为0.9的混合粉末的SE-SEM照片及其能谱分析

Fig. 1 SE-SEM image and EDS analyses of mixed powders with C/TM of 0.9

图2 混合粉末和不同温度烧结试样的XRD图谱(a)及其局部放大图(b)

Fig. 2 XRD patterns (a) and enlarged patterns (b) of mixed powders and samples sintered at different temperatures

图3 不同温度烧结试样的相对密度

Fig. 3 Relative densities of samples sintered at different temperatures

图4 不同温度烧结C/TM为0.9试样的SE-SEM照片及其能谱分析

Fig. 4 SE-SEM images and EDS analyses of samples with C/TM of 0.9 sintered at different temperatures (a) 1500 ℃; (b) 1600 ℃; (c) 1700 ℃; (d) 1800 ℃; (e) EDS analyses of spots in Fig. (a-d). Colorful figures are available on website

图5 1800 ℃下烧结不同C/TM试样的BE-SEM照片及其能谱分析

Fig. 5 BE-SEM images and EDS analyses of different C/TM samples sintered at 1800 ℃ (a) C/TM=1.0; (b) C/TM=0.9; (c) C/TM=0.8; (d) C/TM=0.7; (e) EDS analyses of spots in Fig. (d). Colorful figures are available on website

图6 1800 ℃下烧结不同C/TM试样的XRD图谱(a)及其局部放大图(b)

Fig. 6 XRD patterns (a) and enlarged patterns (b) of different C/TM samples sintered at 1800 ℃

图7 1800 ℃下烧结不同C/TM试样的相对密度

Fig 7 Relative densities of different C/TM samples sintered at 1800 ℃

图8 1800 ℃下烧结不同C/TM试样的EBSD图及其对应的晶粒分布

Fig. 8 EBSD mappings and corresponding grain size distributions of different C/TM samples sintered at 1800 ℃ (a) C/TM=1.0; (b) C/TM=0.9; (c) C/TM=0.8; (d) C/TM=0.7

表3 1800 ℃下烧结不同C/TM试样的硬度、弹性模量和断裂韧性

Table 3 Hardness, elastic modulus and fracture toughness of different C/TM samples sintered at 1800 ℃

Sample	Hardness/GPa	Elastic modulus/GPa	Fracture toughness/(MPa·m^1/2)
1800-1.0	20.60±1.42	421.34±7.88	3.32±0.09
1800-0.9	26.98±1.51	452.86±9.33	2.87±0.10
1800-0.8	30.64±0.93	502.37±8.85	3.94±0.09
1800-0.7	28.01±1.10	490.53±5.79	3.00±0.10

图9 1800 ℃下烧结不同C/TM试样的裂纹扩展SE-SEM照片

Fig. 9 SE-SEM images of crack propagation of different C/TM samples sintered at 1800 ℃ (a) C/TM=1.0; (b) C/TM=0.9; (c) C/TM=0.8; (d) C/TM=0.7

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(TiVNbMoW)C_x高熵陶瓷的单相形成过程与碳空位调控

Single-phase Formation Process and Carbon Vacancy Regulation of (TiVNbMoW)C_x High-entropy Ceramics

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(TiVNbMoW)Cx高熵陶瓷的单相形成过程与碳空位调控

Single-phase Formation Process and Carbon Vacancy Regulation of (TiVNbMoW)Cx High-entropy Ceramics

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(TiVNbMoW)C_x高熵陶瓷的单相形成过程与碳空位调控

Single-phase Formation Process and Carbon Vacancy Regulation of (TiVNbMoW)C_x High-entropy Ceramics