The submicroscopic structure of reaction fronts in solid-solid reactions and its correlation with reaction mechanism and kinetics

Abstract

Experimental investigations of the atomic structure of topotaxial solid-solid reaction fronts were performed. XRD, TEM, SAED, EDS, RBS and specifically cross-sectional high-resolution electron microscopy (HRTEM) were applied to solidsolid reaction interfaces of a number of topotaxial model systems. The reaction kinetics of a suicide-forming reaction was shown to depend on the orientation of the silicide NiSi 2. HRTEM revealed a corresponding difference in the atomic structure of the reaction front. The reaction mechanism of spinel-forming reactions was found to be determined by the spinel/oxide lattice misfit which at the moving reaction front has to be steadily accommodated. Sign and degree of the lattice misfit at the reaction front were systematically varied in the experiments by studying a series of different spinels, viz. Mg 2TiO 4, MgFe 2O 4, MgAl 2O 4, MgCr 2O 4 and MgIn 2O 4, revealing interfacial dislocations of different types. Respective results are discussed in terms of a model featuring the interplay between kinetic reaction barriers, the atomic mechanism of the solid state reaction and the properties of the interfacial defects (ledges, dislocations) persisting at the moving reaction front.