TiO2-ZrO2聚合溶胶形成过程的小角X射线散射研究

doi:10.11949/j.issn.0438-1157.20170730

化工学报 ›› 2018, Vol. 69 ›› Issue (4): 1731-1740.DOI: 10.11949/j.issn.0438-1157.20170730

• 材料化学工程与纳米技术 • 上一篇下一篇

TiO₂-ZrO₂聚合溶胶形成过程的小角X射线散射研究

杜倩倩¹, 谷景华¹, 默广², 魏彦茹², 殷文杰¹, 李甲¹

1. 北京航空航天大学材料科学与工程学院, 北京 100191;
2. 中国科学院高能物理研究所, 北京 100039

收稿日期:2017-06-05 修回日期:2017-10-09 出版日期:2018-04-05 发布日期:2018-04-05
通讯作者: 谷景华
基金资助:
国家自然科学基金项目（51178017）。

Study on formation of polymeric TiO₂-ZrO₂ sols by small angle X-ray scattering

DU Qianqian¹, GU Jinghua¹, MO Guang², WEI Yanru², YIN Wenjie¹, LI Jia¹

1. School of Materials Science and Engineering, Beihang University, Beijing 100191, China;
2. Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100039, China

Received:2017-06-05 Revised:2017-10-09 Online:2018-04-05 Published:2018-04-05
Supported by:
supported by the National Natural Science Foundation of China (51178017).

摘要/Abstract

摘要：

由金属醇盐（M（OR）₄）水解制备溶胶的方法已广泛应用于溶胶-凝胶法制备纳米孔无机膜。通过控制异丙醇钛[Ti（i-OC₃H₇）₄]和正丙醇锆[Zr（n-OC₃H₇）₄]的混合物在异丙醇（i-C₃H₇OH）中水解制备聚合型TiO₂-ZrO₂溶胶，利用小角X射线散射方法（SAXS）研究了初始反应混合物Ti（i-OC₃H₇）₄：Zr（n-OC₃H₇）₄：H₂O：i-C₃H₇OH=0.9：0.1：m：30（摩尔比，m=1.8，2.0，2.2）形成TiO₂-ZrO₂溶胶的过程，探讨了水与醇盐摩尔比H₂O/M（OR）₄（M=Ti+Zr）、反应温度和正丙醇锆对TiO₂-ZrO₂溶胶形成的影响。研究结果表明，H₂O/M（OR）₄=1.8时，只有少量胶粒形成；H₂O/M（OR）₄=2.0～2.2时，TiO₂-ZrO₂溶胶中胶粒具有质量分形结构，分形维数1.2 ≤ D_m < 1.4；随着H₂O/M（OR）₄增加，胶粒的形成时间缩短，胶粒大小和分形维数均增大，溶胶的稳定性显著下降。升高反应温度有利于胶粒形成。[Ti（i-OC₃H₇）₄+Zr（n-OC₃H₇）₄]混合物比Ti（i-OC₃H₇）₄水解快，H₂O/M（OR）₄相同时，TiO₂-ZrO₂溶胶比TiO₂溶胶稳定性差。

关键词: 金属醇盐水解, SAXS, 聚合溶胶, TiO₂-ZrO₂溶胶, 胶粒分形

Abstract:

Metal oxide sols can be prepared from metal alkoxides M(OR)₄ by hydrolyzation, which has been widely used in synthesis of nano-porous ceramic membranes by sol-gel method. Polymeric TiO₂-ZrO₂ sols were prepared by controlled hydrolyzation of the mixture of titanium isopropoxide and zirconium n-propoxide in isopropanol. The formation of TiO₂-ZrO₂ sols from the initial reactant mixtures with a molar ratio of Ti(i-OC₃H₇)₄:Zr(n-OC₃H₇)₄:H₂O:i-C₃H₇OH=0.9:0.1:m:30 (m=1.8, 2.0, 2.2) was investigated by small angle X-ray scattering (SAXS). The effects of the molar ratio of water to metal alkoxides H₂O/M(OR)₄ (M=Ti+Zr) in the initial reactant mixture, reaction temperature and Zr(n-OC₃H₇)₄ on formation of TiO₂-ZrO₂ sols were discussed. When the molar ratio of H₂O/M(OR)₄=1.8, a few colloidal particles form. When the molar ratio of H₂O/M(OR)₄ is in the range of 2.0-2.2, the colloidal particles in TiO₂-ZrO₂ sols have a mass fractal structure with a fractal dimension of 1.2 ≤ D_m < 1.4. As the molar ratio of H₂O/M(OR)₄ increases from 2.0 to 2.2, the duration of colloidal particle formation becomes shorter, the size and fractal dimension of colloidal particles increase, and the stability of TiO₂-ZrO₂ sol decreases. Furthermore, the mixture of[Ti(i-OC₃H₇)₄+Zr(n-OC₃H₇)₄] hydrolyzes faster than Ti(i-OC₃H₇)₄. TiO₂-ZrO₂ sol has lower stability than TiO₂ sol from the initial reactant mixtures with the same molar ratio of H₂O/M(OR)₄.

Key words: hydrolysis of metal alkoxides, SAXS, polymeric sol, TiO₂-ZrO₂sol, fractal dimension of colloidal particle

中图分类号:

O648.1

杜倩倩, 谷景华, 默广, 魏彦茹, 殷文杰, 李甲. TiO₂-ZrO₂聚合溶胶形成过程的小角X射线散射研究[J]. 化工学报, 2018, 69(4): 1731-1740.

DU Qianqian, GU Jinghua, MO Guang, WEI Yanru, YIN Wenjie, LI Jia. Study on formation of polymeric TiO₂-ZrO₂ sols by small angle X-ray scattering[J]. CIESC Journal, 2018, 69(4): 1731-1740.

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TiO₂-ZrO₂聚合溶胶形成过程的小角X射线散射研究

Study on formation of polymeric TiO₂-ZrO₂ sols by small angle X-ray scattering

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