Heat capacities of U1–yLayO2 were measured by means of direct heating pulse calorimetry in the temperature range from 300 to 1500 K. An anomalous increase in the heat capacity curve of each sample was observed similarly to the case of U1–yGdyO2, found recently in our laboratory. As the lanthanum content of U1–yLayO2 increased, the onset temperature of an anomalous increase in the heat capacity decreased and the excess heat capacity increased. The enthalpy of activation (Hf) and the entropy of activation (Sf) of the thermally excited process, which cause the excess heat capacity were obtained to be 2.14, 1.63 and 1.50 eV and 39.4, 34.2 and 31.8 J·K–1·mol–1 for U0.956La0.044O2, U0.910La0.090O2 and U0.858La0.142O2, respectively. The values at zero La content extrapolated by using the data of Hf and Sf for U1–yLayO2 were in good agreement with the experimental values of undoped UO2 so far reported, similarly to the case of Gddoped UO2. The electrical conductivities of U1–yLayO2 (y=0.044 and 0.142) were also measured as a function temperature. No anomaly was seen in the electrical conductivity curve. It may be concluded that the excess heat capacity originates from the predominant contribution of the formation of oxygen clusters and from the small contribution of the formation of electron-hole pairs.
Authors:S. Yamashita, A. Naito, Y. Nakazawa, K. Saito, H. Taniguchi, K. Kanoda, and M. Oguni
Summary Using a thermal relaxation calorimetry technique, we have measured heat capacities of κ-(BEDT-TTF)4Hg2.89Br8 system under magnetic fields between 0 and 6 T. With the increase of cooling rate from room temperature to liquid helium temperature, we have observed a remarkable but systematic tendency that the thermal anomaly associated with the superconductive transition shifts to the lower temperatures. The course of this phenomenon is attributable to the degree of disorder in the mercury chains which give an incommensurate potential to the superconducting planes.