Radiation-Induced Topological Disorder in Irradiated Network Structures

Abstract

This report summarizes results of a research program investigating the fundamental principles underlying the phenomenon of topological disordering in a radiation environment. This phenomenon is known popularly as amorphization, but is more formally described as a process of radiation-induced structural arrangement that leads in crystals to loss of long-range translational and orientational correlations and in glasses to analogous alteration of connectivity topologies. The program focus has been on a set compound ceramic solids with directed bonding exhibiting structures that can be described as networks. Such solids include SiO2, Si3N4, SiC, which are of interest to applications in fusion energy production, nuclear waste storage, and device manufacture involving ion implantation or use in radiation fields. The principal investigative tools comprise a combination of experimental diffraction-based techniques, topological modeling, and molecular-dynamics simulations that have proven a rich source of information in the preceding support period. The results from the present support period fall into three task areas. The first comprises enumeration of the rigidity constraints applying to (1) more complex ceramic structures (such as rutile, corundum, spinel and olivine structures) that exhibit multiply polytopic coordination units or multiple modes of connecting such units, (2) elemental solids (such as graphite, silicon and diamond) for which a correct choice of polytope is necessary to achieve correct representation of the constraints, and (3) compounds (such as spinel and silicon carbide) that exhibit chemical disorder on one or several sublattices. With correct identification of the topological constraints, a unique correlation is shown to exist between constraint and amorphizability which demonstrates that amorphization occurs at a critical constraint loss. The second task involves the application of molecular dynamics (MD) methods to topologically-generated models of amorphized network silicas. These methods are shown to generate fully connected topologically-disordered networks, equilibrated to achieve accurately-specified atomic coordinates that can be compared to correlation data derived from diffraction experiments. The MD equilibrations demonstrate the insensitivity of diffraction methods to substantial differences in intermediate-range topology, with the exception of the first diffraction peak which is shown to be uniquely sensitive to topological differences. The third task concerns application of MD simulations to amorphization of silicon carbide, which exhibits anomalous amorphizability. Amorphization of this compound is shown to derive from its facility for tolerating chemical disorder, and a critical homonuclear bond density threshold is established as a criterion for its amorphization.