燃烧合成法制备NdB6超细粉体及反应机理

doi:10.3724/SP.J.1077.2014.13516

无机材料学报 ›› 2014, Vol. 29 ›› Issue (7): 711-716.DOI: 10.3724/SP.J.1077.2014.13516 CSTR: 32189.14.SP.J.1077.2014.13516

燃烧合成法制备NdB₆超细粉体及反应机理

豆志河, 张廷安, 文明, 史冠勇, 赫冀成

(东北大学材料与冶金学院, 多金属共生矿生态化冶金教育部重点实验室, 沈阳 110819)

收稿日期:2013-10-09 修回日期:2014-01-23 出版日期:2014-07-20 网络出版日期:2014-06-20
作者简介:豆志河(1978-), 男, 博士, 副教授. E-mail:douzh@smm.neu.edu.cn
基金资助:
国家自然科学基金(51002025) National Natural Science Foundation of China (51002025)

Preparation of Ultra-fine NdB₆ Powders by Combustion Synthesis and Its Reaction Mechanism

DOU Zhi-He, ZHANG Ting-An, WEN Ming, SHI Guan-Yong, HE Ji-Cheng

(Key Laboratory for Ecological Metallurgy of Multimetallic Mineral (Ministry of Education), School of Materials and Metallurgy, Northeastern University, Shenyang 110819 China)

Received:2013-10-09 Revised:2014-01-23 Published:2014-07-20 Online:2014-06-20
About author:DOU Zhi-He. E-mail:douzh@smm.neu.edu.cn

摘要/Abstract

摘要：

以B₂O₃、Nd₂O₃和Mg为原料, 采用燃烧合成法制备出NdB₆超细粉体。考察了反应气氛、制样压力和物料配比对反应产物微观形貌和物相的影响。采用XRD、SEM对产物进行了表征, 结果表明: 燃烧产物由NdB₆、MgO以及少量Mg₃B₂O₆和Nd₂B₂O₆组成, 稀硫酸处理去除可溶性成分后, 产物为单一的NdB₆相, 纯度为99.1%。随着制样压力的增大, NdB₆颗粒尺寸逐渐变小。制样压力为20 MPa时, 制备的NdB₆粉末平均粒度小于500 nm。Mg-B₂O₃-Nd₂O₃三相反应历程: 首先Mg还原Nd₂O₃生成单质Nd和MgO, 然后引发Mg还原B₂O₃生成单质B和MgO, 同时生成的Nd和B反应得到NdB₆, 反应的表观活化能为691.59 kJ/mol, 反应级数为3.2。

关键词: 燃烧合成, 六硼化钕, 超细粉体, 反应机理

Abstract:

Ultrafine powders NdB₆ were prepared by combustion synthesis with B₂O₃, Nd₂O₃ and Mg as raw materials. The effects of reaction atmosphere, sample pressure and raw materials ratio on the reaction product morphology and phases were studied. Characterizations by XRD and SEM show that the products consist of NdB₆, MgO and a little amount of Mg₃B₂O₆ and Nd₂B₂O₆. After reaction with sulphuric acid at low concentration to eliminate the latter three components, the pure NdB₆ is obtained (purity 99.1%). As the preparation pressure increases, the NdB₆ particle sizes become small. When the sample pressure is 20 MPa, the average particle size is less than 500 nm. The preparation reaction process is as follows: firstly, Mg reduces Nd₂O₃ to generate Nd and MgO; and then, the reaction between Mg and B₂O₃ are ignited to generate B and MgO; at the same time, the generated Nd and B are reacted to produce NdB₆. The apparent activation energy of the reaction is 691.59 kJ/mol and the reaction order is 3.2.

Key words: combustion synthesis, neodymium hexaboride, ultrafine powder, reaction mechanism

中图分类号:

TQ174

豆志河, 张廷安, 文明, 史冠勇, 赫冀成. 燃烧合成法制备NdB₆超细粉体及反应机理[J]. 无机材料学报, 2014, 29(7): 711-716.

DOU Zhi-He, ZHANG Ting-An, WEN Ming, SHI Guan-Yong, HE Ji-Cheng. Preparation of Ultra-fine NdB₆ Powders by Combustion Synthesis and Its Reaction Mechanism[J]. Journal of Inorganic Materials, 2014, 29(7): 711-716.

图/表 6

图1 燃烧产物的XRD图谱

Fig. 1 XRD patterns of combustion products (a) excessive 5% of Mg in contrast to the theoretical mass ratio of reaction (1) and preparing sample pressure at 20 MPa in air; (b) excessive 10% of Mg in contrast to the theoretical mass ratio of reaction (1) and preparing sample pressure at 20 MPa in vacuum

图2 浸出产物的XRD图谱

Fig. 2 XRD patterns of leaching products

图3 燃烧产物的SEM照片及能谱分析结果

Fig. 3 SEM images of burning products and EDS results (a) theoretical mass ratio of reaction (1); (b)~(d) excessive 5%, 10% and 20% amount of Mg, respectively, more than theoretical mass ratio of reaction (1); (e) and (f) excessive 10% amount of Mg more than theoretical mass ratio of reaction (1) and reaction pressure at 10 MPa and 20 MPa, respectively; (g) and (h) EDS results of region1 and region 2 in sample (c), respectively

图4 NdB6粉末的SEM照片及能谱分析结果

Fig. 4 SEM images of NdB6 powders and EDS result The preparing pressures for samples (a)-(c) are 5, 10 and 20 MPa in atmosphere, respectively, and samples (d)-(f) are 5, 10 and 20 MPa in vacuum, respectively; (g) EDS result of region 1 in (f)

图5 不同反应体系的DSC曲线

Fig. 5 DSC curves of different reaction systems (a) Mg~B2O3 system; (b) Mg~Nd2O3 system; (c) Mg~B2O3~Nd2O3 system

图6 Mg-Nd2O3-B2O3体系的反应机理

Fig. 6 Reaction mechanism of Mg-Nd2O3-B2O3 system

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燃烧合成法制备NdB₆超细粉体及反应机理

Preparation of Ultra-fine NdB₆ Powders by Combustion Synthesis and Its Reaction Mechanism

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