The electrical characteristics of lithium silicate glasses
The electrical behaviour of a series of lithium silicate glasses has been characterised by the versatile a.c. impedance technique. The advantage of using a combination of complex plane and spectroscopic plots in the data analysis is shown. The compositional dependence of the conductivities of the phase separated glasses, which exhibit complex two-phase spinodal decomposition or nucleation and growth textures, is related to the volume fraction of the phases present in the conduction pathway and the tortuosity of the effective medium. The compositional dependence of the conductivities of homogeneous lithium silicate glasses is accounted for by postulating a glass structure composed of silicate anion clusters which are surrounded by a lithia-rich phase which constitutes the preferred conduction pathway. Annealing effects are also reported. The effect of surface roughness on the response of the electrode/electrolyte interface, a phenomenon originally reported by de Levie, and contact problems between the metal electrode and the glass electrolyte are discussed. Novel results regarding the effect of gold electrode recrystallisation on the a.c. response of glass electrolytes are reported. The a.c. impedance technique is shown to be a very useful, surface sensitive tool for monitoring interfacial phenomena such as atmospheric corrosion and surface ion-exchange. The technique is also successfully applied to studies of the mechanism of glass-ceramic formation, where the identification of surface crystallisation products and residual glass, by electrical measurement, is possible. Conclusive evidence for the presence of an effective medium conduction mechanism (percolation theory) in the inhomogeneous glass-ceramic, is given. The electrical data are corroborated by electron microscopy, x-ray diffractometry, energy dispersive x-ray analysis and Fourier Transform Infrared Spectroscopy.