若干钠锗酸盐晶体和熔体的温致结构变化及其锗配位数的拉曼光谱研究  

Temperature Dependent Structure Evolutions of Crystals and Their Melts of Sodium Germantes and Germanium Coordinationstudy by Raman Spectroscopy

作　　者：王媛媛[1] 尤静林[1,2,3] 西蒙·派特里克 郑少波[1] 

机构地区：[1]上海大学材料科学与工程学院,上海200072 [2]法国国家科学研究中心高温和辐射研究所,45071 [3]奥尔良大学,奥尔良法国45067

出　　处：《光散射学报》2012年第4期325-332,共8页The Journal of Light Scattering

基　　金：国家自然科学基金重点(50932005);面上项目(20973107;40973046);法国LE STUDIUM机构资助

摘　　要：本文测定了Na4GeO4、Na2GeO3、Na2Ge4O9和Na4Ge9O20等晶体从273K到1413K升温及熔体的拉曼光谱,结合分析金红石型GeO2的相关结构和光谱,研究了其微结构单元在升温过程中的变化、熔体中的形态和锗的氧配位数及其温致变化。Na4GeO4和Na2GeO3晶体结构单元为GeO4四面体,在升温过程及其熔体中锗维持四配位。Na2Ge4O9和Na4Ge9O20晶体结构单元为GeO4四面体和GeO6八面体共存,升温过程中,GeO6八面体将发生结构转变,在熔融状态全部转变为GeO4四面体,并产生与钠离子等摩尔分数的非桥氧,在熔体中锗的氧配位数为4。研究还表明,桥氧的对称弯曲振动模可以反映不同微结构单元间的连接,并且随着温致结构的变化而产生特征性的变化。Temperature dependent structure evolutions of Na4 GeO4, Na2 GeO3, Na2 Ge4O9 and Na4 Ge9O20 crystals from 27 3 to 1413 K and their melts and germanium coordination are studied by high temperature Raman spectroscopy combining with the microstructure and spectrum study of rutile type GeO2. The results indicate that there are only tetrahedral GeO4 units in Na4 GeO4 and Na2GeO3 crystals, remaining unchanged with the increasing temperature. The coordination number of germanium for both Na4 GeO4 and Na2 GeO3 melts is four. In both Na2 Ge4 09 and Na4 Ge9 020 crystals, octahedral GeO6 units coexist with tetrahedral GeO4 units. With the increasing temperature, GeO6 units transform into GeO4 units and non-bridging oxygen is formed while the coordination number of germani-um is four bridge-oxy different u in both melts of Na2 Ge4 O9 and Na4 Ge9 gen symmetric bending vibration modes nits and changed dramatically with 020. The results also demonstrate that could reflect the linkage types between temperature dependent structure evolution.

关 键 词：锗酸盐 熔体 配位数 高温拉曼光谱 

分 类 号：O614.431[理学—无机化学]