Preparation and humidity sensitive impedance of spinel ceramic nickel germanate

Abstract

This thesis concerns the formation, sintering and humidity dependent electrical behaviour of the spinel ceramic material nickel germanate, Ni(_2)Ge0(_4).Ni(_2)Ge0(_4) has been prepared via the solid state reaction between NiO and GeO(_2) over a range of temperatures, and characterised using a number of techniques. The sintering behaviour of pressed pellets of Ni(_2)Ge0(_4) has also been investigated, together with a characterisation of the microstructure of the sintered bodies. Substitutional doping of Ni(_2)GeO(_4) with Li as a replacement for Ni is found to promote a high degree of shrinkage in the sintering process, probably due to the formation of a liquid phase. XRD revealed that even when 10 % of the Ni atoms were replaced with Li, no change in the crystal structure could be detected. A C. impedance spectroscopy of Ni(_2)Ge0(_4) samples was used to investigate the humidity sensitivity of this material. Equivalent circuit analysis, based on a network of resistors and constant phase elements, shows that the humidity sensitivity is due to conduction in a surface layer of water, in agreement with the models currently popular in the Uterature. Measurement of the water adsorption isotherm of Ni(_2)Ge0(_4) in pellet form indicates that a single monolayer of water is formed at around 20 %R(_H), with an approximately linear increase in water layer thickness up to around 80 %R(_H), after which capillary condensation causes a large increase in the volume of adsorbed water. The information gained on the thickness of this layer of water has been correlated with the resistance of the layer measured by impedance spectroscopy, and subsequently used to provide evidence for a model of the humidity sensitive conduction. The conduction in the surface layer is thought to be due to dissociation of the water, where the amount of dissociation is exponentially dependent on the humidity.