Studies on Synthesis, Structure and Properties of Oxide-Based new Functional Non-Silicate Glasses

用X射线和中子径向分布函数分析、高分辨固态多核MAS核磁共振、红外和拉曼光谱等手段，对完全不含“成玻璃剂”的铜酸铋、没食子酸盐、铝酸盐、钛酸盐、碲酸盐、钒酸盐二元或三元玻璃以及氮氧化物玻璃的结构进行了全面的研究。研究发现，最重要的阳离子，如Ga^&lt；3+&gt；，Al^&lt；3+&gt；，Ti^&lt；4+&gt；和Te^&lt；4+&gt；在玻璃中以四配位的形式存在。另一方面，V^&lt；5+&gt；不仅以VO_5三角双锥的形式存在，而且以VO_4四面体的形式存在。高铅玻璃中的Pb2+以PbO_3和PbO_4的形式存在，与硅酸盐、硼酸盐和没食子酸盐等玻璃体系无关。这意味着Pb^&lt；2+&gt；，Bi^&lt；3+&gt；处于BiO_5和BiO_6的配位状态，这表明与Pb^&lt；2+&gt；相比，没食子酸盐玻璃中的Bi^&lt；3+&gt；具有更强的离子性质。氮氧化物玻璃中氮的配位状态研究表明，二重Ni-…研究了Na_2O-K_2O-Ga_2O_3-TiO_2非硅酸盐非常规玻璃的电学性质。利用THG方法研究了TeO^2玻璃的三阶非线性光学性质。其X_(3)为1.4×10~(-12)esu，约为石英玻璃的50倍，是目前已知的最大的单组分玻璃。这一结果确实表明TeO_2玻璃可能是最有前途的非线性光学材料主体玻璃之一。此外，系统地研究了含过渡金属氧化物、碱金属氧化物和碱土金属氧化物等的TeO2基二元玻璃的非线性光学性质，找出了影响CHI(3)值的最重要参数。在此基础上，有可能设计出具有理想性能的铜酸铋、没食子酸酯、铝酸盐、钛酸盐、碲酸盐和钒酸盐二元或三元玻璃，以及氮氧化物玻璃。较少

The structure of bismuth cuprate, gallate, aluminate, titanate, tellurite and vanadate binary or ternary glasses, which all do not contain "so-called" glass-former at all, and oxynitride glasses has been fully investigated by means of X-ray and neutron radial distribution function analysis, high resolution solid-state multinuclear MAS NMR, and IR and Raman spectroscopy. It has found that the most significant cations, such as Ga^<3+>, Al^<3+>, Ti^<4+>, and Te^<4+>, take a four-fold coordination in glasses. On the other hand, V^<5+> is present not only as VO_5 trigonal bipyramid but also as VO_4 tetrahedra. Pb^<2+> in high-lead glasses is in the forms of PbO_3 and PbO_4 irrespective of glass systems such as silicate, borate and gallate. This means that Pb^<2+>, Bi^<3+> is in the coordination states of BiO_5 and BiO_6, indicating that Bi^<3+> in gallate glasses is rather ionic compared to Pb^<2+>. Search of the coordination state of nitrogen in oxynitride glasses revealed that two-fold ni … More trogen with one non bridging bond as well as three-fold nitrogen is present.The electrical properties of Na_2O-K_2O-Ga_2O_3-TiO_2 non-silicate non-silicate non-conventional glasses have been studied. It has been recognized that the glass system shows a "mixed alkali effect" although it does not contain any glass formers.The third order nonlinear optical properties of TeO^2 glasses have been investigated by the THG method. The chi(3) for it was 1.4x10^<-12> esu, which is about 50 times larger than that of silica glass and found to be the largest among the single component glasses to far known. This result really shows that TeO_2 glasses may be one of the most promising candidates as host glasses for nonlinear optical materials. In addition, the nonlinear optical properties of TeO_2-based binary glasses containing transition metal oxides, alkali oxides and alkaline earth metal oxides and so on, have been systematically investigated in order to find out the most important parameters to govern the chi(3) value.Based on the present results, it becomes possible to design the glasses with desirable properties of bismuth cuprate, gallate, aluminate, titanate, tellurite and vanadate binary or ternary glasses, and oxynitride glasses. Less