Papers by Author: Stephen Skinner

Abstract: K2NiF4 type oxides have received considerable attention in recent years as possible mixed conducting membranes for technologically important applications such as solid oxide fuel cells and oxygen generators. Much of this interest has focused on the oxygen interstitial containing oxides such as La2NiO4+δ. This contribution will review some of the recent work on these and related materials and will present new data on the La2MO4+δ (M= Ni, Co or Mn) systems. In particular data on the oxide ion diffusivity of these systems, as determined by oxygen isotopic exchange and SIMS analysis highlighting the fast oxide ion diffusion (1 x 10-7 cm2s-1 at 750oC) present, will be discussed and the significance of these data evaluated in relation to solid oxide fuel cell systems. A further section of the presentation will consider the oxygen defect species present and discuss the nature of the mobile oxygen ions. Finally some preliminary data on the application of these materials as cathodes will be presented and the performance of the cathodes on intermediate temperature electrolytes discussed.

Abstract: Strontium is one of the most common substituents in apatite crystals. The presence and behavior of Sr in apatite-group phases are of considerable significance in biology. The present paper investigates the substitution of strontium for calcium in a glass-ceramic of the following composition 4.5SiO23Al2O31.5P2O54CaO1CaF2. The glasses were characterized using Differential Thermal Analysis (DTA), X-ray powder diffraction (XRD), neutron diffraction (ND) and 19F Resonance Magic Angle Spinning Nuclear Magnetic Resonance (MAS-NMR). The all calcium glass crystallized to calcium fluorapatite (Ca5(PO4)3F). Substituting strontium partially for calcium resulted in the formation of a mixed strontium/calcium fluorapatites. In contrast complete substitution resulted in the formation of strontium fluorapatite. MAS-NMR showed the the F to be present as F-Ca(3) representing a fluoride ion surrounded by three Ca2+ ions in the all calcium glass and was present as F-Sr(3) in the all strontium glass. In the mixed glasses fluorine was present as FCa( 3), F-Ca(2)Sr, F-CaSr(2) and F-Sr(3). Ca had a higher tendency to occupy the F-M(3) sites than Sr which may reflect the higher charge to size ratio of Ca2+ relative to Sr2+ and its greater affinity for F- ions.