David Keen

Abstract:

We adopt a reverse Monte Carlo refinement approach, using experimental X-ray total scattering data, to develop a structure model for synthetic, hydrated amorphous calcium carbonate (ACC). The ACC is revealed to consist of a porous calcium-rich framework that supports interconnected channels containing water and carbonate molecules. The existence of a previously unrecognized nanometer-scale channel network suggests mechanisms of how additives can be accommodated within the structure and provide temporary stabilization, as well as influence the crystallization process. Moreover, while lacking long-range order, the calcium-rich framework in the ACC contains similar Ca packing density to that present in calcite, aragonite, and vaterite, yielding clues of how the amorphous material converts into the different crystalline forms. Our results provide a new starting point for advancing our understanding of biomineralization as well as the development of biomimetic approaches to next-generation materials synthesis. © 2010 American Chemical Society.

Abstract:

We describe neutron-scattering experiments performed to investigate the magnetic order and dynamics of half-doped La1.5Sr0.5CoO4. This layered perovskite exhibits a near-ideal checkerboard pattern of Co2+/Co3+ charge order at temperatures below ~800 K. Magnetic correlations are observed at temperatures below ~60 K but the magnetic order only becomes established at 31 K, a temperature at which a kink is observed in the susceptibility. On warming above 31 K we observed a change in the magnetic correlations which we attribute either to a spin canting or to a change in the proportion of inequivalent magnetic domains. The magnetic excitation spectrum is dominated by an intense band extending above a gap of approximately 3 meV up to a maximum energy of 16 meV. A weaker band exists in the energy range of 20–30 meV. We show that the excitation spectrum is in excellent quantitative agreement with the predictions of a spin-wave theory generalized to include the full magnetic degrees of freedom of high-spin Co2+ ions in an axially distorted crystal field, coupled by Heisenberg exchange interactions. The magnetic order is found to be stabilized by dominant antiferromagnetic Co2+–Co2+ interactions acting in a straight line through Co3+. No evidence is found for magnetic scattering from the Co3+ ions, supporting the view that Co3+ is in the S=0 state in this material.