A. Prokofiev, X. Yan, M. Ikeda, S. Löffler, S. Paschen:
"Crystal growth of intermetallic clathrates: Floating zone process and ultra rapid crystallization";
Journal of Crystal Growth,
We studied the crystal growth process of type-I transition metal clathrates in two different regimes: a regime of moderate cooling rate, realized with the floating zone technique, and a regime of ultra rapid cooling, realized by the melt spinning technique. In the former regime, bulk Ba8AuxSi46−xBa8AuxSi46−x and Ba8Cu4.8GaxGe41.2−xBa8Cu4.8GaxGe41.2−x single crystals were grown. We investigated segregation effects of the constituting elements by measurements of the composition profiles along the growth direction. The compositional non-uniformity results in a spatial variation of the electrical resistivity which is discussed as well. Structural features of clathrates and their extremely low thermal conductivities imply specifics in growth behavior which manifest themselves most pronouncedly in a rapid crystallization process. Our melt spinning experiments on Ba8Au5Si41Ba8Au5Si41 and Ba8Ni3.5Si42.5Ba8Ni3.5Si42.5 (and earlier on some other clathrates) have revealed surprisingly large grains of at least 1 μm. Because of the anomalously high growth rate of the clathrate phase the formation of impurity phases is considerably kinetically suppressed. We present our scanning and transmission electron microscopy investigations of melt spun samples and discuss structural, thermodynamic and kinetic aspects of the unusual clathrate nucleation and crystallization.
A1. Segregation; A1. Crystallites; A2. Floating zone technique; B1. Nanomaterials
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