凝胶陈化对ZrB2粉末制备的影响

doi:10.3724/SP.J.1077.2014.13564

无机材料学报 ›› 2014, Vol. 29 ›› Issue (7): 717-721.DOI: 10.3724/SP.J.1077.2014.13564 CSTR: 32189.14.SP.J.1077.2014.13564

凝胶陈化对ZrB₂粉末制备的影响

杨碧云¹, 李军平², 汪庭语¹, 李锐星¹, 冯志海², 才鸿年³

(1. 北京航空航天大学材料科学与工程学院, 北京100191; 2. 航天材料及工艺研究所, 北京100076; 3. 中国兵器装备集团公司, 北京100089)

收稿日期:2013-10-30 修回日期:2013-12-03 出版日期:2014-07-20 网络出版日期:2014-06-20
作者简介:杨碧云(1989–), 女, 硕士研究生. E-mail: yangbiyun08@163.com
基金资助:
国家自然科学基金(51372006);国家人力资源和社会保障部2010年度高层次留学人才回国工作资助(人社厅函2010, No.411)

Effects of Gel Aging on Synthesis of ZrB₂ Powders

YANG Bi-Yun¹, LI Jun-Ping², WANG Ting-Yu¹, LI Rui-Xing¹, FENG Zhi-Hai², CAI Hong-Nian³

(1. School of Materials Science and Engineering, Beihang University, Beijing 100191, China; 2. Aerospace Research Institute of Materials & Processing Technology, Beijing 100076, China; 3. China South Industries Group Corporation, Beijing 100089, China)

Received:2013-10-30 Revised:2013-12-03 Published:2014-07-20 Online:2014-06-20
About author:YANG Bi-Yun. E-mail: yangbiyun08@163.com
Supported by:
National Natural Science Foundation of China (51372006);Scientific Research Starting Foundation for Returned Overseas Chinese Scholars, Ministry of Education, Start-Up Fund for High-End Returned Overseas Talents (Renshetinghan 2010, No;411)

摘要/Abstract

摘要：

以正丙醇锆、硼酸、醋酸和D-果糖为原料, 采用溶胶-凝胶法, 结合高温碳热还原反应制备得到了长柱状单相ZrB₂粉末。反应体系中, D-果糖不仅提供碳热还原反应的碳源, 同时作为化学修饰剂, 起到抑制正丙醇锆快速水解的作用。通过对比未陈化和陈化的凝胶制备得到的产物, 探讨了陈化过程对于ZrB₂粉末制备的影响。结果表明, 凝胶陈化有利于ZrO₂向ZrB₂的完全转化。当起始原料满足n(B)/n(Zr) = 3.5~4, n(C)/n(Zr)= 7时, 采用室温陈化7 d的凝胶在1550℃保温2 h可获得长度为4~7 μm, 横截面等效直径约为1 μm, 长径比约为4~7, 比表面积为2.53 m²/g, D₅₀ = 6.46 μm的单相长柱状ZrB₂粉末。

关键词: 陈化, 溶胶-凝胶, 合成, ZrB2

Abstract:

ZrB₂ particles were synthesized by a Sol-Gel method using zirconium n-propoxide, boric acid, acetic acid and D-fructose. D-Fructose acts as both a modifier and a carbon source for carbothermal reduction reaction. For comparison, both nascent state gel and aged gel were used to clarify the aging-time-dependent mechanism for ZrB₂ synthesis. As a result, a single phase ZrB₂ powder with a uniform size and shape distribution can be obtained from the aged gel with a boron and carbon to zirconium molar ratio of 3.5-4 and 7, respectively, after reduced at 1550 ℃ for 2 h. Besides, the synthesized ZrB₂ particles exhibit prism-like morphology with average particle size of ca. 4-7 μm in length, 1 μm in diameter of excircle of the cross-section and 4-7 in aspect ratio, when initial raw materials ratio n(B)/n(Zr) is 3.5-4 and n(C)/n(Zr) is 7. The median diameter D₅₀ is 6.46 μm and specific surface area is about 2.53 m²/g. Furthermore, a complete carbothermal reduction of ZrO₂ can be achieved using the aged gel.

Key words: aging, Sol-Gel, synthesis, ZrB2

中图分类号:

TQ174

杨碧云, 李军平, 汪庭语, 李锐星, 冯志海, 才鸿年. 凝胶陈化对ZrB₂粉末制备的影响[J]. 无机材料学报, 2014, 29(7): 717-721.

YANG Bi-Yun, LI Jun-Ping, WANG Ting-Yu, LI Rui-Xing, FENG Zhi-Hai, CAI Hong-Nian. Effects of Gel Aging on Synthesis of ZrB₂ Powders[J]. Journal of Inorganic Materials, 2014, 29(7): 717-721.

图/表 8

图1 制备ZrB2粉末的工艺流程图

Fig. 1 Flow chart for the synthesis of ZrB2 powder

图2 采用未陈化凝胶制备的试样在1550 ℃保温2 h后的XRD图谱

Fig. 2 XRD patterns of ZrB2 powders calcined at 1550 ℃ for 2 h using nascent state gels Molar ratios of (a) B/Zr = 3.5, C/Zr = 5; (b) B/Zr = 3.5, C/Zr = 7; (c) B/Zr = 4, C/Zr = 7

图3 n(C)/n(Zr) = 8, n(B)/n(Zr)= 3.5(a)和 4(b)采用未陈化凝胶制备的试样在1550 ℃保温2 h后的XRD图谱

Fig. 3 XRD patterns of ZrB2 powders calcined at 1550 ℃ for 2 h using nascent state gels with n(C)/n(Zr)= 8 and different B/Zr molar ratios of (a) 3.5 and (b) 4

图4 n(C)/n(Zr) = 7, n(B)/n(Zr) = 3.5(a)和 4(b)采用陈化凝胶制备的试样在1550 ℃保温2 h后的XRD图谱

Fig. 4 XRD patterns of ZrB2 powders calcined at 1550 ℃ for 2 h using aged gels with n(C)/n(Zr) = 7 and different B/Zr molar ratios of 3.5 (a) and 4 (b)

图5 n(B)/n(Zr) = 3.5, n(C)/n(Zr)= 7采用陈化凝胶制备的试样在(a)1300 ℃和(b)1550 ℃保温2 h后的XRD图谱

Fig. 5 XRD patterns of ZrB2 powders calcined at (a) 1300 ℃ and (b) 1550 ℃ for 2 h using aged gels with molar ratios of B/Zr = 3.5 and C/Zr = 7

图6 n(B)/n(Zr)= 3.5, n(C)/n(Zr)= 7采用陈化凝胶在1550 ℃保温2 h制备的ZrB2粉末的SEM照片

Fig. 6 SEM image of ZrB2 powders calcined at 1550 ℃ for 2 h using the aged gel with molar ratios of B/Zr = 3.5 and C/Zr = 7

图7 n(B)/n(Zr) = 3.5, n(C)/n(Zr) = 7采用陈化凝胶在1550 ℃保温2 h得到的ZrB2粉末的粒度分布图

Fig. 7 Particle size distribution of ZrB2 powders calcined at 1550 ℃ for 2 h using the aged gel with molar ratios of B/Zr = 3.5 and C/Zr = 7

表1 起始原料n(B)/n(Zr) = 3.5, n(C)/n(Zr) = 7, 采用未陈化和陈化凝胶在1550 ℃保温2 h得到的ZrB2粉末的比表面积(BET)

Table1 Specific surface areas (BET) of ZrB2 powders calcined at 1550 ℃for 2 h using nascent state gels and aged gels with molar ratios of B/Zr = 3.5 and C/Zr = 7

Sample	Gel	BET/(m²·g^-1)
1	Nascent state	15.29
2	Aged	2.53

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凝胶陈化对ZrB₂粉末制备的影响

Effects of Gel Aging on Synthesis of ZrB₂ Powders

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