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Abstract  

The heat capacity of 9.70 and 11.35 mol% yttria stabilized zirconia ((ZrO2)1–x(Y2O3)x; x=0.0970, 0.1135) was measured by adiabatic calorimetry between 13 and 300 K, and some thermodynamic functions were calculated and given in a table. A large excess heat capacity extending from the lowest temperature to room temperature with a broad maximum at about 75 K was found in comparison with the heat capacity calculated from those of pure zirconia and yttria on the basis of simple additivity rule. The shape of the excess heat capacity is very similar to the Schottky anomaly, which may be attributed to a softening of lattice vibration. The amount of the excess heat capacity decreased with increasing yttria doping, while the maximum temperature did not vary. The relationships among the excess heat capacity, defect structure and interatomic force constants, and also the role of oxygen vacancy were discussed.

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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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Abstract  

The complex phase transitions involving dielectricity and magnetism on distorted triangular lattice antiferromagnets, "KNiCl3-family" crystals, which have the crystal structures derived from the prototype CsNiCl3, were studied through the heat capacity measurements. These crystals are classified into characteristic three groups from the viewpoint of magnetic and structural properties clarified so far. The results of the dielectric constant measurement as a function of temperature are also presented in detail. The present calorimetric study reveaed that the structural successive phase transitions rather than the magnetic transitions in these crystals are recognized more distinctly as the presence of specific heat anomalies at the respective phase transition points.

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Abstract  

Heat capacity measurements were carried out on Pb1-xLaxWO4+x/2 (x=0.2) and Pb1-xLa2x/3WO4 (x=0.2, 0.5) solid solutions prepared by sintering and mechanical alloying (MA) methods. For all the solid solutions, sintered samples showed slightly larger heat capacity around 100 K in comparison with MA samples, which was presumably caused by the excitation of mobile oxide ion motion. For sintered scheelite-type structured PbWO4s, high-temperature synthesis introduced oxide ion interstitials even for the Pb1-xLa2x/3WO4 system, which resulted in the excess heat capacity at low temperature for excitation. On the other hand, for the samples prepared by room-temperature MA technique, oxide ion seemed to occupy the regular sites rather than interstitial ones and excess heat capacities were not observed.

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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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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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Abstract  

A new phase transition (III–IV) was found at 311 K in CsCoPO4 by DSC measurements. The crystal structure of all the phases, I–IV, in CsCoPO4 was studied by synchrotron-radiation X-ray powder diffraction. The diffractometry revealed that CsCoPO4 had the same crystal structure as that of corresponding phases in CsZnPO4. An extremely large particle size effect was found on III–IV phase transition in CsCoPO4; the phase transition enthalpy decreases with decreasing the particle size around 0.1 mm. Such large particle size effects had been also observed in CsZnPO4. However, no III–IV phase transition was observed in the particle smaller than 0.1 mm of CsZnPO4, while such a critical size was not found in CsCoPO4.

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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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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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Abstract  

The sample of LiCoO2 was synthesized, and the heat capacity was measured by adiabatic calorimetry between 13 and 300 K. The smoothed values of the heat capacity were calculated from the data. The thermodynamic functions, standard enthalpy, entropy and Gibbs energy, of LiCoO2 were calculated from the heat capacity and the numerical values are tabulated at selected temperatures from 15 to 300 K. The heat capacity, enthalpy, entropy, and Gibbs energy at T=298.15 K are 71.57 J K–1mol–1, 9.853 kJ mol–1, 52.45 J K–1 mol–1, –5.786 kJ mol–1, respectively.

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