Thermal stability and thermoelectric properties of p-type Ba_8Ga_(16)Ge_(30) clathrates

The thermal stability of p-type Ba_8Ga_(16)Ge_(30) clathrates grown from gallium flux has been tested by heat treatment in low pressure Ar atmosphere at 400, 600, and 800 °C. Significant gallium loss was observed for all samples during heat treatment. The treatment at 400 °C does not significantly change the sample properties, and the samples remain p-type and comparable to the untreated, as-prepared, sample. At 600 °C the sample switches from extrinsic p-type to extrinsic n-type, presumably due to significant loss of Ga, and shows a high thermopower but a reduced electrical conductivity compared to as-made n-type samples. Surprisingly, after a thermal treatment at 800 °C, the crystal structure seemingly loses less Ga, only reducing the hole concentration to near intrinsic levels and thus has a negative impact on ZT. Regardless of the heat treatment temperature of the p-type samples the thermal conductivity remained exceptionally low, for some samples 0.9 W/m K. Heat treatment can thus greatly affect the thermoelectric properties of p-type Ba_8Ga_(16)Ge_(30), but the crystal structure remains intact

Strong-Coupling Theory of Rattling-Induced Superconductivity

In order to clarify the mechanism of the enhancement of superconducting transition temperature $T_{\rm c}$ due to anharmonic local oscillation of a guest ion in a cage composed of host atoms, i.e., {\it rattling}, we analyze the anharmonic Holstein model by applying the Migdal-Eliashberg theory. From the evaluation of the normal-state electron-phonon coupling constant, it is found that the strong coupling state is developed, when the bottom of a potential for the guest ion becomes wide and flat. Then, $T_{\rm c}$ is enhanced with the increase of the anharmonicity in the potential, although $T_{\rm c}$ is rather decreased when the potential becomes a double-well type due to very strong anharmonicity. From these results, we propose a scenario of anharmonicity-controlled strong-coupling tendency for superconductivity induced by rattling. We briefly discuss possible relevance of the present scenario with superconductivity in $\beta$-pyrochlore oxides.Comment: 8 pages, 6 figure

Differences in catalytic properties between mesoporous and nanoparticulate platinum

Conventional Pt/Al2O3 catalysts prepared by wet-impregnation are composed of Pt nanoparticles exposing convex and facetted surfaces deposited on high-surface area ?-Al2O3 supports. A hexagonal phase mesoporous Pt material (denoted H1-Pt) prepared by chemical reduction in the aqueous domains of a lyotropic liquid crystalline template exposes however mainly a concave surface with expected different catalytic properties. A series of Pt/Al2O3 catalysts were prepared using H1-Pt, Pt-black or wet-impregnated Pt, and the samples were characterized by SEM-EDX and TEM, and finally evaluated for CO oxidation. The H1-Pt/Al2O3 catalyst showed an ignition profile for CO oxidation at lower temperatures and thus appeared less sensitive to CO poisoning than the two other types of samples. This difference may be related to the differences in surface curvature

Thermal stability and thermoelectric properties of p-type Ba8Ga16Ge30 clathrates

The thermal stability of p-type Ba(8)Ga(16)Ge(3)0 clathrates grown from gallium flux has been tested by heat treatment in low pressure Ar atmosphere at 400, 600, and 800 degrees C. Significant gallium loss was observed for all samples during heat treatment. The treatment at 400 degrees C does not significantly change the sample properties, and the samples remain p-type and comparable to the untreated, as-prepared, sample. At 600 degrees C the sample switches from extrinsic p-type to extrinsic n-type, presumably due to significant loss of Ga, and shows a high thermopower but a reduced electrical conductivity compared to as-made n-type samples. Surprisingly, after a thermal treatment at 800 degrees C, the crystal structure seemingly loses less Ga, only reducing the hole concentration to near intrinsic levels and thus has a negative impact on ZT. Regardless of the heat treatment temperature of the p-type samples the thermal conductivity remained exceptionally low, for some samples 0.9 W/m K. Heat treatment can thus greatly affect the thermoelectric properties of p-type Ba(8)Ga(16)Ge(3)0, but the crystal structure remains intact. (C) 2009 American Institute of Physics. [doi: 10.1063/1.3236635