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Study on the sol-gel-synthesis of glasses with novel structure

新型结构玻璃的溶胶-凝胶法合成研究

基本信息

批准号：
07455349
负责人：
KAMIYA Kanichi
金额：
$ 3.65万
依托单位：
Mie University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

The sol-gel method using metal alkoxides as raw materials was appliedto the preparation of glasses with unique compositions and structure which can not be achieved by the conventional melting technique. Following results were obtained.(1) Germanate glasses : The Na_20-Ge0_2 and Pb0-Ge0_2 glasses were obtainable by the sol-gel method. The structure, especially coordination state of Ge in those glasses was examined by several tchniques such as X-ray radial distribution function analyzes, EXAFS,IR and Raman spectroscopy. It was found that the amount of 6-fold coordinated Ge ions in the sol-gel-derived glasses was almost twice as large as the corresponding melt-derived glasses.(2) Titanate glasses : The Na_20-Ti0_2, Ba0-Ti0_2, PbO-TiO_2, Nb_20_5-Ti0_2, and Bi_20_3-Ti0_2 glasses with very high content of Ti0_2 were also prepared by the sol-gel method. The coordination state of Ti in the former two glasses was 5- and 6-fold, respectively, and the Ti0_n polyhedra were highly distorted, making … More these glasses usable in the nonlinear optics. The latter three glasses, really, exhibited third-order optical nonlinear susceptibility as high as 10^<-12> esu.(3) Li and K-glicolato complex of 5-fold coordinated Si was thermally decomposed to obtain Li_20- or K_20-Si0_2 glasses with unique structure. While Li-Si complex gave glasses with the structure similar to corresponding melt-derived glasses, it was considered that K-Si complex produced glasses containing a small amount of 5-fold coordinated Si.(4) Alumina gels which transformed partly to alpha-alumina around 500ﾟC was prepared from aluminum alkoxide under carefully controlled hydrolysis condition. Also, carefully designed hydrolysis reaction of Zr-and Si-alkoxides was found to lead to the Zr0_2-Si0_2 gel which produced ZrSi0_4 around 800ﾟC,when a lithium compound was added as a mineralizer.All above results have confirmed that the sol-gel method can really make glasses and gels with unique or novel structure and compositions at relatively low elevated temperatures. Less

以金属醇盐为原料的溶胶-凝胶法可以制备出传统熔融法无法制备的具有独特组成和结构的玻璃。获得了以下结果。(1)锗酸盐玻璃：采用溶胶-凝胶法制备了Na_（20）-Ge_（0_2）和Pb_（0_2）-Ge_（0_2）玻璃。用X射线径向分布函数分析、EXAFS、IR和拉曼光谱等技术对玻璃的结构，特别是Ge的配位状态进行了研究。结果发现，在溶胶-凝胶衍生的玻璃中的6倍配位的Ge离子的量几乎是相应的熔融衍生的玻璃的两倍大。(2)滴定镜：采用溶胶-凝胶法制备了高TiO_2含量的Na_（20）-TiO_2、Ba_（0）-TiO_2、PbO-TiO_2、Nb_（20）_5-TiO_2和Bi_（20）_3-TiO_2玻璃。前两种玻璃中Ti的配位状态分别为5倍和6倍，Ti_（0_n）多面体高度扭曲， ...更多信息这些玻璃可用于非线性光学。实际上，后三种玻璃的三阶光学非线性极化率高达10^<-12>esu。(3)Li和K-五配位的Glicolato络合物热分解得到了具有独特结构的Li_（20）-SiO_2或K_（20）-SiO_2玻璃。虽然Li-Si络合物得到的玻璃具有与相应的熔体衍生玻璃类似的结构，但认为K-Si络合物产生的玻璃含有少量的5次配位的Si。(4)在严格控制的水解条件下，由铝醇盐制备了在500 ℃左右部分转化为α-氧化铝的氧化铝凝胶。另外，当锂化合物作为矿化剂加入时，Zr和Si的醇盐在800 ℃左右发生水解反应生成ZrO_2-SiO_2凝胶，证实了溶胶-凝胶法确实可以在较低的高温下制备出具有独特或新颖结构和组成的玻璃和凝胶。少