In some oxide glasses the cations may exist in different coordination states. Thispaper advances an EXAFS analysis method to study the near neighbour structure andthe content of atoms having different coordination num...In some oxide glasses the cations may exist in different coordination states. Thispaper advances an EXAFS analysis method to study the near neighbour structure andthe content of atoms having different coordination numbers. Taking the glasses ofLi_?-O-ZnO-GeO_2 system as example, we have studied the ratio of 4-fold to 6-foldoxygen coordinations of Ge atoms, which varies with the composition of glasses. Thenear neighbour structural parameters of Ge atoms have also been determined.展开更多
Raman, IR spectra, RDF and visible spectrum were used to study the glass structure and the valence states of niobium ions in P_2O_5-Nb_2O_5-Li_2O noncrystalling system. The colour-changing mechanism was studied. For 1...Raman, IR spectra, RDF and visible spectrum were used to study the glass structure and the valence states of niobium ions in P_2O_5-Nb_2O_5-Li_2O noncrystalling system. The colour-changing mechanism was studied. For 10Nb_2O_5xP_2O_5(90-x)Li_2O (x=40,45,50,55) system glasses, it was known that the glass colout changing from light gold-yellow to blue with increasing is aroused by the Nb^(3+) ion increasing, not by the change of niobium ion coordination.展开更多
磷酸盐玻璃在光学领域有广泛的应用,然而因为简单的磷酸盐玻璃的化学稳定性和热机械性能较差,已经难以满足日益发展的激光装置的高性能要求。在磷酸盐玻璃中加入少量的硅可以形成六配位的硅网络体并且极大的改善这些性能。因此研究这种...磷酸盐玻璃在光学领域有广泛的应用,然而因为简单的磷酸盐玻璃的化学稳定性和热机械性能较差,已经难以满足日益发展的激光装置的高性能要求。在磷酸盐玻璃中加入少量的硅可以形成六配位的硅网络体并且极大的改善这些性能。因此研究这种磷硅酸盐玻璃的结构细节有重要的意义。但是由于玻璃结构缺乏长程有序,其结构研究比较复杂。现代固体核磁共振(NMR)技术能够从原子尺度对无序状态的物质局域结构进行解析,是一种强大的用来研究玻璃结构的技术手段。本文的目的是探究碱土金属对磷硅酸盐玻璃中六配位硅结构的影响。我们采用传统的熔融-冷却法制备了(2MO-3P2O5)(1−x)·(SiO2)x(M=Ca,Sr,Ba)体系的磷硅酸盐玻璃。并且运用先进的固体核磁共振技术和拉曼光谱对此磷硅酸盐玻璃结构进行了表征。31P和29Si MAS NMR表明其网络结构由磷氧四面体P(2)和P(3)与四配位和六配位的硅氧多面体相互连接构成,随着二氧化硅含量的增加六配位硅的比例呈现减少的趋势。类似地,在拉曼光谱的结构中和六配位硅相连的磷基团的峰也随着硅含量的增加而减弱。基于双量子相干和P-P同核间J耦合作用的重聚INADEQUATE实验证明了不同的磷氧四面体之间的连接情况,P(2)和P(3)两种结构单元在玻璃中是相对分离的,他们大多数都是与自身相连接。和之前报道的有关Na2OP2O5-SiO2体系的玻璃相比较,不同的是,在Na2O-P2O5-SiO2玻璃中一个P(3)结构单元最多有一个Si(6)-O-P(3)键,而对于本文的碱土金属磷硅酸盐玻璃一个P(3)结构单元最多有0.4–0.7个Si(6)-O-P(3)键。说明碱土金属比碱金属对六配位硅的稳定作用更弱一些。这种结构与组成之间的关系对设计玻璃组成和性质能提供重要的依据,尤其在大型的激光装置中对磷酸盐玻璃基质的化学和热稳定性有着很高的要求,详细的结构信息能为通过改变组成来提高善玻璃性能搭建桥梁。展开更多
基金Project supported by National Natural Science Foundation of China.
文摘In some oxide glasses the cations may exist in different coordination states. Thispaper advances an EXAFS analysis method to study the near neighbour structure andthe content of atoms having different coordination numbers. Taking the glasses ofLi_?-O-ZnO-GeO_2 system as example, we have studied the ratio of 4-fold to 6-foldoxygen coordinations of Ge atoms, which varies with the composition of glasses. Thenear neighbour structural parameters of Ge atoms have also been determined.
文摘Raman, IR spectra, RDF and visible spectrum were used to study the glass structure and the valence states of niobium ions in P_2O_5-Nb_2O_5-Li_2O noncrystalling system. The colour-changing mechanism was studied. For 10Nb_2O_5xP_2O_5(90-x)Li_2O (x=40,45,50,55) system glasses, it was known that the glass colout changing from light gold-yellow to blue with increasing is aroused by the Nb^(3+) ion increasing, not by the change of niobium ion coordination.
文摘磷酸盐玻璃在光学领域有广泛的应用,然而因为简单的磷酸盐玻璃的化学稳定性和热机械性能较差,已经难以满足日益发展的激光装置的高性能要求。在磷酸盐玻璃中加入少量的硅可以形成六配位的硅网络体并且极大的改善这些性能。因此研究这种磷硅酸盐玻璃的结构细节有重要的意义。但是由于玻璃结构缺乏长程有序,其结构研究比较复杂。现代固体核磁共振(NMR)技术能够从原子尺度对无序状态的物质局域结构进行解析,是一种强大的用来研究玻璃结构的技术手段。本文的目的是探究碱土金属对磷硅酸盐玻璃中六配位硅结构的影响。我们采用传统的熔融-冷却法制备了(2MO-3P2O5)(1−x)·(SiO2)x(M=Ca,Sr,Ba)体系的磷硅酸盐玻璃。并且运用先进的固体核磁共振技术和拉曼光谱对此磷硅酸盐玻璃结构进行了表征。31P和29Si MAS NMR表明其网络结构由磷氧四面体P(2)和P(3)与四配位和六配位的硅氧多面体相互连接构成,随着二氧化硅含量的增加六配位硅的比例呈现减少的趋势。类似地,在拉曼光谱的结构中和六配位硅相连的磷基团的峰也随着硅含量的增加而减弱。基于双量子相干和P-P同核间J耦合作用的重聚INADEQUATE实验证明了不同的磷氧四面体之间的连接情况,P(2)和P(3)两种结构单元在玻璃中是相对分离的,他们大多数都是与自身相连接。和之前报道的有关Na2OP2O5-SiO2体系的玻璃相比较,不同的是,在Na2O-P2O5-SiO2玻璃中一个P(3)结构单元最多有一个Si(6)-O-P(3)键,而对于本文的碱土金属磷硅酸盐玻璃一个P(3)结构单元最多有0.4–0.7个Si(6)-O-P(3)键。说明碱土金属比碱金属对六配位硅的稳定作用更弱一些。这种结构与组成之间的关系对设计玻璃组成和性质能提供重要的依据,尤其在大型的激光装置中对磷酸盐玻璃基质的化学和热稳定性有着很高的要求,详细的结构信息能为通过改变组成来提高善玻璃性能搭建桥梁。
