碱式氯化镁晶须制备纳米氧化镁热分解动力学研究

doi:10.15541/jim20180508

无机材料学报 ›› 2019, Vol. 34 ›› Issue (7): 781-785.DOI: 10.15541/jim20180508 CSTR: 32189.14.10.15541/jim20180508

碱式氯化镁晶须制备纳米氧化镁热分解动力学研究

苟生莲^1,^2,³,乃学瑛¹,肖剑飞¹,叶俊伟⁴,董亚萍¹,李武^1,²()

^1. 中国科学院青海盐湖研究所中国科学院盐湖资源综合高效利用重点实验室, 西宁 810008
^2. 青海省盐湖资源化学重点实验室, 西宁 810008
^3. 中国科学院大学, 北京 100049
^4. 大连理工大学化工学院, 大连 116024

收稿日期:2018-10-26 修回日期:2019-01-08 出版日期:2019-07-20 网络出版日期:2019-06-26
作者简介:苟生莲(1992-), 女, 硕士研究生. E-mail:goushenglian@163.com
基金资助:
国家自然科学基金柴达木盐湖化工科学研究联合基金(U1607101);青海省科技厅项目(2019-ZJ-7029)

Preparation and Thermal Decomposition of Basic Magnesium Chloride Whiskers

GOU Sheng-Lian^1,^2,³,NAI Xue-Ying¹,XIAO Jian-Fei¹,YE Jun-Wei⁴,DONG Ya-Ping¹,LI Wu^1,²()

^1. Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, China
^2. Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province, Xining 810008, China
^3. University of Chinese Academy of Sciences, Beijing 100049, China
^4. School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

Received:2018-10-26 Revised:2019-01-08 Published:2019-07-20 Online:2019-06-26
Supported by:
NSFC-Qaidam Salt Lake Chemical Science Research Joint Fund(U1607101);Qinghai Provincial Science and Technology Department Project(2019-ZJ-7029)

摘要/Abstract

摘要：

采用水热法以氯化镁和氢氧化钙为原料制备了碱式氯化镁(BMC)晶须, 然后热解得到了纳米氧化镁。经透射电镜(TEM)和选区电子衍射(SAED)分析其粒径在20~40 nm之间, 暴露晶面族为{111}和{110}。通过热重差热分析(TG-DTA)、扫描电镜(SEM)、X射线衍射(XRD)以及红外光谱(FT-IR)分析确定了碱式氯化镁晶须热分解过程分四步进行, 前两步分别脱去两个结晶水, 第三步脱氯化氢, 最后脱羟基水。采用Satava法和微分法对BMC晶须的热分解机理和动力学进行了研究, 得出第一步反应热分解机理为随机成核与随后生长、第二步为二维扩散、第三步为相边界反应、第四步为一维相边界反应。

关键词: 碱式氯化镁, 纳米氧化镁, 热分解, 晶须, 水热法

Abstract:

Basic magnesium chloride (BMC) whiskers were prepared by hydrothermal method using magnesium chloride and calcium hydroxide as raw materials. Subsequently, nano-MgO was obtained by pyrolysis of the resulting whisker. Transmission electron microscopy (TEM) images showed that the diameter of nano-MgO was between 20 and 40 nm. The corresponding selected-area electron diffraction (SAED) pattern demonstrated the single-crystalline nature with the exposed plane of {111} and {110}. TG-DTG, SEM, XRD, and FT-IR analysis confirmed the four-step pyrolysis processes of BMC whisker. Results showed two molecules of crystal water lost during the first and second steps, respectively. Subsequently, two hydrogen chloride molecules were released in the third step. Finally, hydroxy water was dehydrated. The thermal decomposition kinetics of BMC whisker was studied by means of Satava and differential method. It indicates that the first step of the thermal decomposition of BMC whiskers is random nucleation and subsequent growth mechanism. The second step is two-dimensional diffusion. The third and the final steps are phase boundary reaction and one-dimensional phase boundary reaction mechanism, respectively.

Key words: basic magnesium chloride, nano magnesium oxide, thermal decomposition, whiskers, hydrothermal method

中图分类号:

TQ132

苟生莲, 乃学瑛, 肖剑飞, 叶俊伟, 董亚萍, 李武. 碱式氯化镁晶须制备纳米氧化镁热分解动力学研究[J]. 无机材料学报, 2019, 34(7): 781-785.

GOU Sheng-Lian, NAI Xue-Ying, XIAO Jian-Fei, YE Jun-Wei, DONG Ya-Ping, LI Wu. Preparation and Thermal Decomposition of Basic Magnesium Chloride Whiskers[J]. Journal of Inorganic Materials, 2019, 34(7): 781-785.

图/表 9

图1 样品的XRD图谱(a)和SEM照片(b)

Fig. 1 XRD patten (a) and SEM image (b) of the sample

图2 样品的TG-DTA分析结果

Fig. 2 TG-DTA curves of the sample

图3 样品经不同温度灼烧后产物的XRD图谱

Fig. 3 XRD patterns of the products burned at different temperatures

图4 样品经不同温度灼烧后产物的SEM 照片

Fig. 4 SEM images of the products burned at different temperatures (a) 220 ℃; (b) 300 ℃; (c) 340 ℃; (d) 500 ℃

图5 经500 ℃灼烧后产物的TEM照片及电子衍射分析结果

Fig. 5 TEM images and SAED patterns of the product burned at 500 ℃

图6 经不同温度灼烧后产物的FT-IR谱图

Fig. 6 FT-IR spectra of the products burned at different temperatures (a) BMC; (b) 220 ℃; (c) 300 ℃; (d) 340 ℃; (e) 500 ℃

表1 G(α)函数表达式和四步反应相关系数

Table 1 Algebraic expressions of G(α) and the correlation coefficients for the four decomposition steps

Function name	Mechanism	G(α)	R²
Function name	Mechanism	G(α)	Ⅰ	Ⅱ	Ⅲ	Ⅳ
Avrami-Erofeev equation	Random nucleation and its subsequent growth	[-ln(1-α)]^3/4	0.9991	0.9521	0.9129	0.9829
Jander equation	Two-dimensional diffusion	[1-(1-α)^1/2]^1/2	0.9716	0.9978	0.9919	0.9957
Mampel power low	Phase boundary reaction	α^1/2	0.9598	0.9929	0.9970	0.9817
Mampel power low	Phase boundary reaction(One-dimensional)	α	0.9988	0.9932	0.9916	0.9996

图7 a和b的关系图

Fig. 7 Diagram of a and b

表2 BMC晶须热分解动力学计算结果

Table 2 Dynamic calculation results of the thermal decomposition of BMC whiskers

Parameter	Ⅰ	Ⅱ	Ⅲ	Ⅳ
n	0.6	0.6	0.5	1.1
E/(kJ?mol^-1)	38.16	152.35	125.38	85.52
A/min^-1	1.01×10⁵	4.87×10¹⁴	3.65×10¹⁰	1.90×10⁶

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碱式氯化镁晶须制备纳米氧化镁热分解动力学研究

Preparation and Thermal Decomposition of Basic Magnesium Chloride Whiskers

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