钛、钨氧化物碳热还原-碳化的热力学和热分析

摘要
图/表
参考文献
相关文章 (1)

全文: PDF (513 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要为了研究采用TiO₂、WO_2.72和炭黑粉末为原料,在惰性气氛下通过碳热还原-碳化制备(Ti,W)C固溶体的过程机理,采用HSC Chemistry热力学分析软件、热重和差示扫描量热分析方法,对物相的演变过程进行分析。结果表明,因球磨导致原料反应活性升高、气-固反应共存等,实际的反应起始温度低于热力学计算值。随温度升高,TiO₂和WO_2.72分别按TiO₂→Ti₄O₇→Ti₃O₅→Ti₂O₃→TiO→TiC和WO_2.72→WO₂→W→W₂C→WC的转变顺序被还原并碳化。为了加速反应的动力学进程,通过碳热还原-碳化制备(Ti,W)C固溶体的最终温度应在1 400 ℃以上。

	服务

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	梁艳
	张立
	李霞
	余鹏
	刘涛
	凌群

关键词 ： (Ti, W)C, WO_2.72, 碳热还原-碳化, 热力学分析, 热分析, 粉末制备

Abstract：HSC Chemistry thermodynamic analysis software, thermo-gravimetric and differential scanning calorimetric methods were used to analyze the evolution process of the reduction and carbonization of TiO₂ and WO_2.72by carbon under the condition of an inert atmosphere. The results show that due to the increased reaction activity of the raw materials by ball-milling and the existence of gas-solid synergetic reaction, the actual reaction temperature is lower than the one of the thermodynamic calculation result. As the temperature increases, TiO₂ and WO_2.72are gradually reduced and carbonized in the order of TiO₂→Ti₄O₇→Ti₃O₅→Ti₂O₃→TiO→TiC and WO_2.72→WO₂→W→W₂C→WC, respectively. The final reaction temperature is suggested to be above 1400 °C to speed up the kinetic process of the reaction.

Key words： (Ti W)C WO_2.72 carbothermal reduction-carbonization thermodynamic analysis thermal analysis powder preparation

收稿日期: 2021-01-08 出版日期: 2021-05-07

ZTFLH:

TG178

基金资助:湖南省自然科学基金资助项目(2019JJ40373); 中南大学中央高校基本科研业务费专项资金资助项目(1053320191447); 国家自然科学基金资助项目(51574292)

引用本文:

梁艳, 张立, 李霞, 余鹏, 刘涛, 凌群. 钛、钨氧化物碳热还原-碳化的热力学和热分析[J]. 粉末冶金材料科学与工程, 2021, 26(2): 91-98.
LIANG Yan, ZHANG Li, LI Xia, YU Peng, LIU Tao, LING Qun. Thermodynamic and thermal analysis on carbothermal reduction-carbonization of titanium and tungsten oxides. Materials Science and Engineering of Powder Metallurgy, 2021, 26(2): 91-98.

链接本文:

http://pmbjb.csu.edu.cn/CN/ 或 http://pmbjb.csu.edu.cn/CN/Y2021/V26/I2/91

[1] 龚涤凡, 李詠侠, 杨海林, 等. 纳米SiC对Ti(C,N)基金属陶瓷微观组织与性能的影响[J]. 粉末冶金材料科学与工程, 2020, 25(4): 321-329.
GONG Difan, LI Yongxia, YANG Hailin, et al.Nano-SiC addition on microstructure, mechanical properties and high temperature oxidation resistance of Ti(C,N)-based cermets[J]. Materials Science and Engineering of Powder Metallurgy, 2020, 25(4): 321-329.
[2] 蔺绍江, 陈肖, 熊惟皓. Ti(C_0.7N_0.3)对(Ti,W,Ta)C-Mo-Ni系金属陶瓷组织与性能的影响[J]. 粉末冶金材料科学与工程, 2020, 25(1): 11-15.
LIN Shaojiang, CHEN Xiao, XIONG Weihao.Effects of Ti(C_0.7N_0.3) addition on the microstructure and properties of (Ti,W,Ta)C-Mo-Ni cermets[J]. Materials Science and Engineering of Powder Metallurgy, 2020, 25(1): 11-15.
[3] 崔焱茗, 张立, 黄龙, 等. 原料中C/N原子比对TiCN基金属陶瓷组织结构和性能的影响[J]. 粉末冶金材料科学与工程, 2020, 25(1): 58-64.
CUI Yanming, ZHANG Li, HUANG Long, et al.Effects of C/N atomic ratio in raw materials on the microstructure and properties of Ti(C,N)-based cermets[J]. Materials Science and Engineering of Powder Metallurgy, 2020, 25(1): 58-64.
[4] 肖桥平, 张立, 罗国凯, 等. 无金属粘结相 TiCN 基金属陶瓷在 NaOH 溶液中的电化学腐蚀行为[J]. 粉末冶金材料科学与工程, 2019, 24(2): 120-128.
XIAO Qiaoping, ZHANG Li, LUO Guokai, et al.Electrochemical corrosion behavior of binderless TiCN-based cermets in NaOH solution[J]. Materials Science and Engineering of Powder Metallurgy, 2019, 24(2): 120-128.
[5] HUI Y, YING D, YONG YS, et al.Ti(C,N)-based cermets with two kinds of core-rim structures constructed by β-Co microspheres[J]. Advances in Materials Science and Engineering, 2020(2): 1-11.
[6] LI P, YE J, LIU Y, et al.Study on the formation of core/rim structure in Ti(CN)-based cermets[J]. International Journal of Refractory Metals and Hard Materials, 2012, 35(11): 27-31.
[7] PARK C, NAM S, KANG S, et al.Carbide/binder interfaces in Ti(CN)-(Ti,W)C/(Ti,W)(CN)-based cermets[J]. Journal of Alloys and Compounds, 2016, 657: 671-677.
[8] 张国鹏. (Ti,M)C基金属陶瓷的制备、组织与性能研究[D]. 武汉: 华中科技大学, 2014.
ZHANG Guopeng.The Research on the preparation, microstructure and mechanical properties of (Ti,M)C-based cermets[D]. Wuhan: Huazhong University of Science and Technology, 2014.
[9] 庞立娟, 邓刚, 张雪峰, 等. (Ti,M)C复式碳化物制备方法的研究进展[J]. 粉末冶金工业, 2017, 27(3): 57-62.
PANG Lijuan, DENG Gang, ZHANG Xuefeng, et al.Research progress on preparation of (Ti,M)C composite carbides[J]. Powder Metallurgy Industry, 2017, 27(3): 57-62.
[10] KWON H, JUNG S A, SUH C Y, et al.Mechanical properties of (Ti_xW₁-_x)C-Co cermet prepared by carbothermal reduction of high energy ball milled TiO₂-WO₃-C[J]. Ceramics International, 2016, 43(2): 1943-1947.
[11] 郑启文, 杨天恩, 熊计. (Ti,W)C固溶体基金属陶瓷的研究进展[J]. 硬质合金, 2017, 34(1): 61-74.
ZHENG Qiwen, YANG Tianen, XIONG Ji.Research and development of (Ti,W)C-based cermets[J]. Cemented Carbide, 2017, 34(1): 61-74.
[12] 方民宪, 陈厚生. 碳热还原法制取Ti(C,N)的热力学原理[J]. 粉末冶金材料科学与工程, 2006, 11(6): 329-329.
FANG Minxian, CHEN Housheng.Thermodynamic principle of preparing Ti(C,N) by carbon-heat reducing[J]. Materials Science and Engineering of Powder Metallurgy, 2006, 11(6): 329-329.
[13] PAN F, DU Z, LI S F, et al.Preparation of nano-sized tungsten carbide via fluidized bed[J]. Chinese Journal of Chemical Engineering, 2020, 28(3): 306-315.
[14] WU K H, JIANG Y, JIAO S Q, et al.Preparations of titanium nitride, titanium carbonitride and titanium carbide via a two-step carbothermic reduction method[J]. Journal of Solid State Chemistry, 2019, 277: 793-803.
[15] 丁伟民, 郑勇, 王守文, 等. 原位碳热还原法制备Ti(C,N)基金属陶瓷的烧结技术研究[J]. 硬质合金, 2018, 35(4): 227-234.
DING Weimin, ZHENG Yong, WANG Shouwen, et al.Research on sintering process of Ti(C,N)-based cermets prepared by in situ carbothermal reduction method[J]. Cemented Carbide, 2018, 35(4): 227-234.
[16] SEN W, XU B Q, YANG B, et al.Preparation of TiC powders by carbothermal reduction method in vacuum[J]. Transactions of Nonferrous Metals Society of China, 2011, 21(1): 185-190.
[17] 杨高玲. Co诱导可控制备超细WC粉体及其调控机理研究[D].赣州: 江西理工大学, 2019.
YANG Gaoling.Controllable preparation of ultrafine WC powder induced by Co and its regulation mechanism[D]. Ganzhou: Jiangxi University of Science and Technology, 2019.
[18] WANG K F, TANG X L, JIAO S Q, et al.A short and facile process to synthesize WC-Co cemented carbides[J]. International Journal of Refractory Metals and Hard Materials, 2020, 92: 105288.
[19] PAN F, DU Z, LI S F, et al.Preparation of nano-sized tungsten carbide via fluidized bed[J]. Chinese Journal of Chemical Engineering, 2019, 28(3): 306-315.
[20] 吴爱华, 唐建成, 叶楠, 等. 微波碳化法制备纳米WC粉末及其机理[J]. 粉末冶金材料科学与工程, 2014,19(6): 862-866.
WU Aihua, TANG Jiancheng, YE Nan, et al.Fabrication and mechanism of WC nano-powders prepared by microwave carbonization[J]. Materials Science and Engineering of Powder Metallurgy, 2014, 19(6): 862-866.
[21] KWON H, KIM W, KIM J.Stability domains of (Ti,W)C and (Ti,W)(CN) during carbothermal reduction of TiO₂/WO₃ mixture at 1 500 K[J]. Journal of the European Ceramic Society, 2017, 37: 1355-1371.
[22] 王耀奇, 任学平, 侯红亮, 等. 氢化钛氧化处理及其热分解行为[J]. 粉末冶金材料科学与工程, 2015, 20(1): 1-6.
WANG Yaoqi, REN Xueping, HOU Hongliang, et al.Oxidation treatment and hot decomposition behavior of titanium hydride[J]. Materials Science and Engineering of Powder Metallurgy, 2015, 20(1): 1-6.
[23] 张立, 吴冲浒, 王振波, 等. 硬质合金常用模压成形剂的热分解特性[J]. 粉末冶金材料科学与工程, 2010, 15(6): 674-678.
ZHANG Li, WU Chonghu, WANG Zhenbo, et al.Thermal dissociation characteristics of the binders for compression molding of cemented carbides[J]. Materials Science and Engineering of Powder Metallurgy, 2010, 15(6): 674-678.
[24] REZAN S A, ZHANG G Q, OSTROVSKI O.Effect of gas atmosphere on carbothermal reduction and nitridation of titanium dioxide[J]. Metallurgical and Materials Transactions B, 2011, 43(1): 73-81.