Wang Weimin, Christensen Randilynn, Curtis Brittany, Hynek David, Keizer Sydney, Wang James, Feller Steve, Martin Steve W, Kieffer John
Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan, USA.
Phys Chem Chem Phys. 2017 Jun 21;19(24):15942-15952. doi: 10.1039/c6cp08939a.
Elastic properties of alkali containing glasses are of great interest not only because they provide information about overall structural integrity but also they are related to other properties such as thermal conductivity and ion mobility. In this study, we investigate two mixed-network former glass systems, sodium borosilicate 0.2NaO + 0.8[xBO + (1 - x)SiO] and sodium borogermanate 0.2NaO + 0.8[xBO + (1 - x)GeO] glasses. By mixing network formers, the network topology can be changed while keeping the network modifier concentration constant, which allows for the effect of network structure on elastic properties to be analyzed over a wide parametric range. In addition to non-linear, non-additive mixed-glass former effects, maxima are observed in longitudinal, shear and Young's moduli with increasing atomic number density. By combining results from NMR spectroscopy and Brillouin light scattering with a newly developed statistical thermodynamic reaction equilibrium model, it is possible to determine the relative proportions of all network structural units. This new analysis reveals that the structural characteristic predominantly responsible for effective mechanical load transmission in these glasses is a high density of network cations coordinated by four or more bridging oxygens, as it provides for establishing a network of covalent bonds among these cations with connectivity in three dimensions.
含碱玻璃的弹性性质备受关注,不仅因为它们能提供有关整体结构完整性的信息,还因为它们与其他性质相关,如热导率和离子迁移率。在本研究中,我们研究了两种混合网络形成体玻璃体系,即0.2NaO + 0.8[xBO + (1 - x)SiO]的硼硅酸钠玻璃和0.2NaO + 0.8[xBO + (1 - x)GeO]的硼锗酸钠玻璃。通过混合网络形成体,可以在保持网络改性剂浓度不变的情况下改变网络拓扑结构,从而能够在较宽的参数范围内分析网络结构对弹性性质的影响。除了非线性、非加和性的混合玻璃形成体效应外,随着原子数密度的增加,纵向模量、剪切模量和杨氏模量均出现最大值。通过将核磁共振光谱和布里渊光散射的结果与新开发的统计热力学反应平衡模型相结合,可以确定所有网络结构单元的相对比例。这种新的分析表明,在这些玻璃中主要负责有效机械载荷传递的结构特征是由四个或更多桥氧配位的网络阳离子的高密度,因为它能在这些阳离子之间建立三维连通的共价键网络。