HfC前驱体的合成及其裂解行为研究

doi:10.15541/jim20160692

无机材料学报 ›› 2017, Vol. 32 ›› Issue (10): 1095-1101.DOI: 10.15541/jim20160692 CSTR: 32189.14.10.15541/jim20160692

HfC前驱体的合成及其裂解行为研究

张程^{1, 2}, 龚俊捷², 董志军^{1, 2}, 孟剑^{1, 2}, 周思成², 袁观明^{1, 2}, 李轩科^{1, 2, 3}

(1. 武汉科技大学, 省部共建耐火材料与冶金国家重点实验室, 武汉 430081; 武汉科技大学, 湖北省煤转化与新型炭材料重点实验室, 武汉 430081; 3. 湖南大学材料科学与工程学院, 长沙 410082)

收稿日期:2016-12-22 修回日期:2017-02-06 出版日期:2017-10-20 网络出版日期:2017-09-21
作者简介:张程(1991–), 男, 硕士研究生. E-mail: 13026122724@sina.cn
基金资助:
国家自然科学基金(51352001, 91016003, 51372177)

HfC Precursor: Synthesis and Pyrolysis Behavior

ZHANG Cheng^{1, 2}, GONG Jun-Jie², DONG Zhi-Jun^{1, 2}, MENG Jian^{1, 2}, ZHOU Si-Cheng², YUAN Guan-Ming^{1, 2}, LI Xuan-Ke^{1, 2, 3}

(1. The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China; 2. The Hubei Province Key Laboratory of Coal Conversion & New Carbon Materials, Wuhan University of Science and Technology, Wuhan 430081, China; 3. Hunan University, College of Materials Science and Engineering, Changsha 410082, China)

Received:2016-12-22 Revised:2017-02-06 Published:2017-10-20 Online:2017-09-21
About author:ZHANG Cheng. E-mail: 13026122724@sina.cn
Supported by:
National Natural Science Foundation of China(51352001, 91016003, 51372177)

摘要/Abstract

摘要：

以HfCl₄、乙酰丙酮、无水甲醇、对苯二酚为原料, 采用一锅法合成了HfC陶瓷前驱体, 通过前驱体裂解制备得到了HfC陶瓷粉体。采用XRD、FTIR、SEM/EDS、TEM、SAED等分析手段对裂解产物的组成、形貌和微观结构进行了分析和表征, 利用TG-DSC和TG-MS对前驱体的裂解行为进行了研究。结果表明: HfC前驱体在600℃左右开始陶瓷化, 在1300℃左右开始形成HfC陶瓷相, 在1500℃及以上完全转化为HfC陶瓷及自由碳。HfC陶瓷相具有单晶结构, 颗粒粒径在50~100 nm之间。HfC陶瓷相的形成基于前驱体在低温段裂解形成的HfO₂的碳热还原反应, 裂解过程中形成的自由碳抑制了HfC晶体的生长。

关键词: HfC, 前驱体, 裂解行为, 碳热还原反应

Abstract:

Hafnium carbide ceramic powders were prepared by pyrolysis of a novel precursor, which was synthesized via one pot method using hafnium tetrachloride, acetylacetone, methanol, and hydroquinone as raw materials. The composition, morphology and microstructure of the pyrolysis products were characterized by XRD, FTIR, SEM/EDS, TEM, and SAED. The pyrolysis behavior of the obtained HfC precursor was investigated by TG-DSC and TG-MS. The results show that the ceramization of the HfC precursor starts at about 600℃, and the formation of HfC ceramics is initiated at about 1300℃. At temperature above 1500℃, the precursor completely transforms into HfC ceramics and free carbon. The as-obtained HfC phase has a single crystal structure and the size of the HfC particles ranges from 50 to 100 nm. Formation of the HfC ceramics can be attributed to the carbothermal reduction reaction of the HfO₂, which is produced by pyrolysis of the precursor at a relative low temperature. The growth of the HfC crystals is retarded by free carbon formed during pyrolysis of the precursor.

Key words: Hafnium carbide, precursor, pyrolysis behavior, carbothermal reduction reaction

中图分类号:

TB332

张程, 龚俊捷, 董志军, 孟剑, 周思成, 袁观明, 李轩科. HfC前驱体的合成及其裂解行为研究[J]. 无机材料学报, 2017, 32(10): 1095-1101.

ZHANG Cheng, GONG Jun-Jie, DONG Zhi-Jun, MENG Jian, ZHOU Si-Cheng, YUAN Guan-Ming, LI Xuan-Ke. HfC Precursor: Synthesis and Pyrolysis Behavior[J]. Journal of Inorganic Materials, 2017, 32(10): 1095-1101.

图/表 7

图1 HfC前驱体的合成路线

Fig. 1 Synthesis route of HfC precursor

图2 前驱体及其不同温度裂解产物的FTIR谱图

Fig. 2 FTIR spectra of the HfC precursor and products pyrolyzed at different temperatures(a) 400-800℃; (b) 1000-1500℃

图3 HfC前驱体在不同温度段裂解产物的XRD谱图

Fig. 3 XRD patterns of the products from HfC precursor pyrolyzed at different temperatures(a) 400-1000℃; (b) 1200-1600℃

图4 HfC前驱体的TG-DSC曲线

Fig. 4 TG-DSC curves of the HfC precursor

图5 HfC前驱体裂解过程中释放的气体产物的TG-MS分析

Fig. 5 TG-MS analysis of the released gaseous products during the pyrolysis of HfC precursor

图6 前驱体在不同温度裂解1 h所得产物的SEM照片、EDS图谱及EDS面扫描元素分布图

Fig. 6 SEM images, EDS patterns and EDS mapping of the pyrolysis products from HfC precursor at different temperatures for 1 h(a, e) 1200℃; (b, f) 1300℃; (c)1400℃; (d, g)1500℃; (h, i, j)1600℃

图7 HfC前驱体1600℃裂解所得产物的(a~b)TEM、(c) HRTEM照片及选区电子衍射谱(d)

Fig.7 TEM (a-b) and HRTEM (c) images as well as SAED pattern (d) of the pyrolysis products from HfC precursor at 1600℃ for 1 h

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HfC前驱体的合成及其裂解行为研究

HfC Precursor: Synthesis and Pyrolysis Behavior

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