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Abstract  

The phase transition and the crystal structures of CuITe were investigated by differential thermal analysis and X-ray powder diffraction measurements in the temperature range between 300 and 683 K. The new phase transition in CuITe was observed at 592 K. The enthalpy of transition is ΔH=0.125 kJ mol-1. The new phase above 592 K belongs to tetragonal system with the space group I41 /amd.

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Journal of Thermal Analysis and Calorimetry
Authors:
Y. Akishige
,
H. Shigematsu
,
T. Tojo
,
H. Kawaji
, and
T. Atake

Summary Specific heats on the single crystals of Sr2Nb2O7, Sr2Ta2O7 and (Sr1-xBax)2Nb2O7 were measured in a wide temperature range of 2-600 K. Heat anomalies of a λ-type were observed at the incommensurate phase transition of T INC (=495 K) on Sr2Nb2O7 and at the super-lattice phase transition of T SL (=443 K) on Sr2Ta2O7; the transition enthalpies and the transition entropies were estimated. Furthermore, a small heat anomaly was observed at the low temperature ferroelectric phase transition of T LOW (=95 K) on Sr2Nb2O7. The transition temperature T LOW decreases with increasing Ba content x and it vanishes for samples of x>2%.

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Summary The size effect on the crystal structure including the chemical bonding nature has been investigated for several kinds of BaTiO3 nanopowder with the particle sizes down to 50 nm in diameter, by means of powder diffraction using high-energy synchrotron radiation. The Rietveld refinement reveals that the BaTiO3 nanopowder consists of tetragonal and cubic structure components at 300 K. The feature of coexistence can be illustrated by the core/shell model for the particle, in which the shell with a cubic structure covers the core with a tetragonal structure. The thickness of the cubic shell is almost constant irrespective of the particle sizes, and is estimated as approximately 8 nm. Hence, the critical particle-size, where the entire particle is covered with the cubic shell, is suggested as 16 nm. The charge density distributions of the BaTiO3 nanopowder in the cubic phase at 410 K are revealed by the maximum entropy method. Changes in the bonding electron density and the ionic valence expected are not observed clearly even in the 50 nm crystal compared with the bulk crystal.

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Abstract  

The phase transitions of α,α-trehalose dihydrate (T h) were investigated by either differential thermal analysis (DTA) with an in-house apparatus of variable-pressure type equipped with an open sample holder or commercially available TG (thermal gravimetry)-DTA apparatus for comparison under the same experimental conditions as to the heating rate (2°C min−1), the type of pan (open), and the particle size of T h (63 μm). The former DTA measurements were carried out under five different total pressures, 101, 75, 61, 48 and 35 kPa, which provided quite helpful information necessary for confirmative assignments of the endothermic peaks due to either melting or dehydration of T h. The usage of largely different amount of T h, 126 and 14 mg for the DTA and TG-DTA measurements respectively, led to their different DTA traces, showing that there were largely different extents of the influence by the measured sample surface exposed to the surrounding atmosphere on its dehydration behavior. In addition the high thermal sensitivity achieved with such mass of T h gave rise to an interesting discovery of an unidentified thermal event at 92°C prior to either melting or dehydration of T h.

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Abstract  

In this study, GdBaSr(Cu3−x M x)O7−δ bulk samples (M=Zn and Ni; 0≤x≤0.1) were prepared via solid-state reaction. Specific heat measurement (measured with thermal relaxation technique using PPMS) shows an obvious specific heat jump around the T c for GdBaSrCu3O7−δ sample as observed in most of the high temperature superconductors. It shifts towards lower temperature with increasing of both Zn and Ni doping contents, whose tendency is similar to the decreasing of T c. Debye temperature, ΘD (derived from specific heat measurements) calculated at around 10 K is found to be directly proportional to the T c.

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Abstract  

We have developed a multi-channel measurement system for combinatorial investigation of thermoelectric materials. The measurement apparatus has ten series of pin-probe array which enables us to measure the Seebeck coefficient and electric conductivity of 10 samples simultaneously. A successful measurement on a composition-spread thin films library indicated that this measurement system is highly useful for the high-speed exploration of thermoelectric materials by combinatorial approach.

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Journal of Thermal Analysis and Calorimetry
Authors:
H. Shigematsu
,
Y. Akishige
,
T. Matsui
,
T. Tojo
,
H. Kawaji
, and
T. Atake

Summary The phase diagram of the mixed crystal (K1-xRbx)2SeO4 was determined by means of thermal analysis and neutron scattering experiments. The hexagonal to orthorhombic phase transition line exists for any x. The normal-incommensurate phase transition temperature decreases continuously with increasing Rb content. However, the incommensurate-commensurate phase transition was not observed except for K2SeO4. According to the clear softening of the Σ2- Σ 3 phonon branches and the finite frequency at 0 K for x>0.34, an existence of the hypothetical phase transition was confirmed.

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Summary Thermodynamic properties of a layered perovskite oxide Gd2SrCo2O7 have been studied. Powder X-ray diffraction, electric resistivity, magnetic susceptibility and heat capacity measurements were carried out. The crystal structure was determined as I4/mmm. The temperature dependence of the magnetic susceptibility was fitted to the Curie-Weiss behavior with antiferromagnetic interaction. Spin state of Co3+ ion was derived to be intermediate spin state configuration (t2g 5eg 1). The spin ordering was observed as a broad anomaly in the heat capacity curve with a peak at 2 K. The measured entropy was 35.47 J K-1mol-1, which was 65% of expected value. Thus the spin ordering should not be completed at the lowest temperature 0.2 K covered in the present experiments and/or some short range ordering remains at higher temperatures.

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Journal of Thermal Analysis and Calorimetry
Authors:
M. Tachibana
,
T. Tojo
,
H. Kawaji
,
T. Atake
,
N. Morita
,
H. Ikuta
,
Y. Uchimoto
, and
M. Wakihara

Abstract  

Heat capacity of spinel LiCr1/6Mn11/6O4-d (d=0, 0.0184)was measured between 5 and 300 K. Both compounds showed no anomaly in the measured temperature range, especially around the room temperature where a structural phase transition is reported for the parent compound LiMn2O4. The non-stoichiometric compound LiCr1/6Mn11/6O3.9816 has greater heat capacity than that of the stoichiometric LiCr1/6Mn11/6O4. Molecular dynamics study on the vibrational property of LiMn2O4-d revealed that the lattice defects in the non-stoichiometric compound increase the low frequency phonons compared with the stoichiometric compound. It should be related to the greater heat capacity of the non-stoichiometric compound LiCr1/6Mn11/6O3.9816.

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Abstract  

The heat capacity of PbMO3 (M=Ti, Zr and Hf) at constant pressure was measured using a differential scanning calorimeter (DSC) from room temperature up to 870 K. Large anomalies were found in the heat capacity curves, corresponding to the ferroelectricparaelectric phase transition in PbTiO3 (PT), the antiferroelectric-paraelectric phase transitions in PbZrO3 (PZ) and PbHfO3 (PH). The transition entropies were estimated as 7.3 J K−1 mol−1 (PT), 9.9 J K−1 mol−1 (PZ) and 9.3 J K−1 mol−1 (PH). These values of transition entropies are much larger than that of a typical displacive-type phase transition.

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