High pressure polymorphs of LiCoPO4 and LiCoAsO4

Olivine-LiCoXO₄ (X = P, As) compounds might transform to the denser spinel-type and Na₂CrO₄-type structures under pressure. In this work, the relative energetic stability of the three polymorphs and the pressure of the possible polymorphic transformations are investigated combining experiments and first principles calculations. Olivine-LiCoAsO₄ is predicted to transform to the Na₂CrO₄-like structure at 0.4 GPa and to the spinel structure at 5.8 GPa (0 K). Quenching HP/HT experiments show that olivine-LiCoAsO₄ treated at 6 GPa/1173 K transforms to the spinel-like structure. Computational results indicate that olivine-LiCoPO₄ transforms to the Na₂CrO₄-like form at around 4 GPa (0 K), the latter being the stable form till very high pressures (21.6 GPa). In good agreement with this, olivine-LiCoPO₄ when subjected to 6 GPa/1173 K and 15 GPa/1173 K is converted to the Na₂CrO₄-type polymorph. Crystallographic data of the new compound LiCoPO₄ within the Na₂CrO₄ structural type are provided.     

An experimental study on the flow behavior of micellar solutions

At higher concentration levels, the inner structure of micellar solutions cannot be detected directly by optical means. Nevertheless, the flow behavior of the micellar solutions reflects their micellar structures. Hence, in this study the material behavior of micellar surfactant solutions was investigated by rheometrical means in steady and oscillatory shear flows. The flow behavior of the solutions was found to be strongly dependent on the concentration of the surfactants. At very low concentrations, the surfactant solution shows Newtonian behavior. With increasing concentration, a transition to shear thinning behavior and increasing viscoelasticity was found. The complex material structure is modeled according to the flow behavior by discrete and continuous relaxation time spectra, depending on the concentration. Received: 3 May 2000/Accepted: 18 September 2000