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

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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. 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).

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. 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
  • 通讯作者: 谷景华
  • 基金资助:

    国家自然科学基金项目(51178017)。

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 ≤ Dm < 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

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-OC3H74]和正丙醇锆[Zr(n-OC3H74]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-OC3H74:Zr(n-OC3H74: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 ≤ Dm < 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-OC3H74+Zr(n-OC3H74]混合物比Ti(i-OC3H74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

CLC Number: