液相聚合物前驱体法制备高熵碳化物纳米粉体

doi:10.15541/jim20200391

无机材料学报 ›› 2021, Vol. 36 ›› Issue (4): 393-398.DOI: 10.15541/jim20200391 CSTR: 32189.14.10.15541/jim20200391

液相聚合物前驱体法制备高熵碳化物纳米粉体

孙娅楠¹(), 叶丽¹, 赵文英¹, 陈凤华¹, 邱文丰², 韩伟健¹, 刘伟³, 赵彤¹()

1.中国科学院化学研究所, 极端环境高分子材料重点实验室, 北京 100190
2.华南理工大学华南软物质科学与技术高等研究院, 广州 510641; 航天特种材料及工艺技术研究所, 北京 100074

收稿日期:2020-07-13 修回日期:2020-10-27 出版日期:2021-04-20 网络出版日期:2020-11-05
通讯作者: 赵彤, 研究员. E-mail: tzhao@iccas.ac.cn
作者简介:孙娅楠(1989-), 女, 博士研究生. E-mail: sunyanan@iccas.ac.cn
基金资助:
国家自然科学基金(21803062)

Synthesis of High Entropy Carbide Nano Powders via Liquid Polymer Precursor Route

SUN Yanan¹(), YE Li¹, ZHAO Wenying¹, CHEN Fenghua¹, QIU Wenfeng², HAN Weijian¹, LIU Wei³, ZHAO Tong¹()

1. Key Laboratory of Science and Technology on High-tech Polymer Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
2. South China Advanced Institute for Soft Matter Science and Technology, South China University of Technology, Guangzhou 510641, China

Received:2020-07-13 Revised:2020-10-27 Published:2021-04-20 Online:2020-11-05
Contact: ZHAO Tong, professor. E-mail: tzhao@iccas.ac.cn
About author:SUN Yanan(1989-), female, PhD candidate. E-mail: sunyanan@iccas.ac.cn
Supported by:
Natural Science Foundation of China(21803062)

摘要/Abstract

摘要：

高熵碳化物陶瓷是近年来发展的新型材料, 由于具有高硬度、高模量和低热导率等优异性能而备受关注。液相聚合物前驱体法在陶瓷化过程中可以实现多元素的均匀分散, 制备高熵陶瓷具有独特的优势, 但是相关报道较少。本研究以金属醇盐为原料, 通过可控水解缩合反应制备了金属醇盐共聚物溶液, 加入碳源烯丙基酚醛(AN)后得到了澄清的粘稠液相高熵碳化物前驱体(PHEC), 在真空下1800 ℃裂解2 h获得了(Ti, Zr, Hf, Ta)C高熵碳化物陶瓷纳米粉末。通过不同手段对前驱体和陶瓷粉体进行表征, 结果表明: 裂解温度低于800 ℃所获得的样品主要为t-ZrO₂及氧化物固溶体, 1000 ℃开始发生碳热还原反应形成碳化物固溶体, 温度升高至1800 ℃后转化为高熵碳化物陶瓷; 所得陶瓷粉末纯度高, 元素分布均匀, 颗粒尺寸一致, 粒径~100 nm。制备的液相陶瓷前驱体具有高陶瓷产率(28.6 wt%)和低黏度(150 mPa?s)的特点, 在极性溶剂中溶解性良好。所开发的液相前驱体法在制备高熵陶瓷纳米粉体、陶瓷纤维和陶瓷基复合材料领域具有重要应用价值。

关键词: 高熵陶瓷, 碳化物, 固溶体, 纳米粉体, 液相前驱体法

Abstract:

High entropy carbide ceramics have been proposed in recent years for their promising properties as high hardness, high modulus and low thermal conductivity. Liquid polymer precursor method, of which multiple elements distribute homogeneously during the pyrolysis process, is considered to be favorable in fabricating high entropy ceramics. However, few reports have studied the synthesis of liquid precursor. In this work, liquid polymer precursor of (Ti, Zr, Hf, Ta)C were synthesized by co-hydrolysis and polycondensation of equiatomic metal containing monomers, and adding allyl-functional novolac resin (AN) as carbon source. The obtained polymer precursors of high entropy carbide ceramics (PHECs) were soluble in propyl alcohol and stable for months. The corresponding high entropy carbide ceramic nano powders were obtained by pyrolyzing PHEC at 1800 ℃ for 2 h in vacuum. The precursors and ceramic powders were characterized by different methods. Results reveal that the ceramic sample pyrolyzed at 800 ℃ are composed of t-ZrO₂ and oxide solid solutions, and carbothermal reduction reaction began after pyrolyzed at 1000 ℃, with carbide solid solutions being generated. After being pyrolyzed at 1800 ℃, the samples convert to target high entropy carbide ceramics. As-obtained ceramics are characterized to be high purity with uniform distribution of nanosized particles (~100 nm). The synthesized precursor has high ceramic yield (28.6wt%), low viscosity (150 mPa·s), and good solubility in polar solvents. Therefore, the proposed liquid polymer precursor method is reliable in preparation of high entropy ceramic nano powders, ceramic fibers and ceramic matrix composites.

Key words: high entropy ceramic, carbide, solid solution, nano powder, liquid precursor

中图分类号:

TB383

孙娅楠, 叶丽, 赵文英, 陈凤华, 邱文丰, 韩伟健, 刘伟, 赵彤. 液相聚合物前驱体法制备高熵碳化物纳米粉体[J]. 无机材料学报, 2021, 36(4): 393-398.

SUN Yanan, YE Li, ZHAO Wenying, CHEN Fenghua, QIU Wenfeng, HAN Weijian, LIU Wei, ZHAO Tong. Synthesis of High Entropy Carbide Nano Powders via Liquid Polymer Precursor Route[J]. Journal of Inorganic Materials, 2021, 36(4): 393-398.

图/表 9

图1 PHEC的外观图片

Fig. 1 Photograph of PHEC

表1 PHEC的金属含量及陶瓷产率及粘度

Table 1 Metal content, yield and viscosity of PHEC

Item	Metal content/wt%	Yield/ wt%	Viscosity/(mPa∙s)
Item	Metal content/wt%	Yield/ wt%	1	2
(Ti, Zr, Hf, Ta)C	28	28.6	150	162

图2 PHEC的红外结构图谱

Fig. 2 FT-IR spectrum of PHEC

图3 PHEC的1H NMR图谱

Fig. 3 1H NMR spectra of PHEC

图4 PHEC固化样品的热失重曲线

Fig. 4 TGA curves of cured PHEC

图5 PHEC裂解过程的XRD表征

Fig. 5 Characterization of pyrolysis process for PHEC (A) XRD patterns of products pyrolyzed at different temperatures; (B) Enlarged images of XRD patterns of products pyrolyzed at 1400~ 1800 ℃; (C) Lattice parameter and crystallite size of samples pyrolyzed at 1400-1800 ℃

图6 PHEC的裂解过程原理示意图及可能发生的化学反应

Fig. 6 Schematic diagram of pyrolysis process for PHEC and possible reactions

图7 1800 ℃裂解PHEC陶瓷粉末的SEM表征

Fig. 7 SEM analyses of PHEC ceramic powders pyrolyzed at 1800 ℃ (A) SEM image; (B) EDS mapping of selected pattern marked with rectangle

图8 PHEC1800 ℃裂解陶瓷粉末的TEM分析

Fig. 8 TEM analyses of PHEC ceramic powders pyrolyzed at 1800 ℃ (A) TEM image; (B) HR-TEM image; (C) EDS mapping of Ti, Zr, Hf and Ta

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液相聚合物前驱体法制备高熵碳化物纳米粉体

Synthesis of High Entropy Carbide Nano Powders via Liquid Polymer Precursor Route

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