Authors:M. Mansori, C. Favotto, K. Jardet, M. Roubin, A. Sebaoun, and P. Satre
The oxygen exchange between the condensed phase(s) and the gas phase was studied as a function of temperature for superconducting
phases of the system (Bi,Pb)-Sr-Ca-Cu-O.
An oxygen probe apparatus allowed confirmation that the variation in oxygen composition in the Pb2212 and Pb2223 superconducting
phases is a reversible phenomenon on heating and cooling. It was demonstrated that the mass loss of both phases, for the 905
and 980°C isotherms, was due to the oxygen composition variation and to PbO loss (this latter phenomenon begin irreversible).
Thermochemical and thermodynamical properties of HTSC phases are reviewed for the Y-Ba-Cu-O system and also presented for the newly calculated Bi-Sr-Cu-O system stressing out stoichiometric and phenomenological viewpoints. Simulated data are listed for (H298o-Hoo, phase transformation temperatures, standard entropies, standard enthalpies of formation, heat capacities in crystalline phase, etc. Pseudobinary phase diagrams are treated showing the effect of oxygen partial pressure particularly illustrated on the (Sr, Bi, Ba)-Cu-O system.
Uranium oxides are known as nonstoichiometric compounds whose composition changes according to external conditions such as temperature and oxygen partial pressure. The change of composition caused by the formation of defect structure results in a change of their properties. In this paper, the compositional changes of UO2 and doped UO2 [(U, M)O2; M=La, Ti, Pu, Th, Nb, Cr, etc.] and also those of other uranium oxides (U4O9, U3O8) are shown against oxygen partial pressure. From the results of doped UO2, it is concluded that the valence control rule holds to a first approximation. The defect structures are estimated both from log x vs. log Po2 (x: deviation from the stoichiometric composition and Po2: oxygen partial pressure) and log vs. log Po2 (: electrical conductivity) relations. The defect structures of UO2 and doped UO2 are derived based on the Willis model for UO2+x. The detect structure of U4O9 phase is similar to that of UO2+x, but the defect structures of U3O8 phase are complicated due to the existence of many higher-order phase transitions. The thermodynamic data such as the partial molar enthalpy and entropy and the heat capacity are important to characterize the defect structure. The high temperature heat capacities of UO2 doped with Gd show pronounced increases at high temperatures the onset temperature decreases as the dopant content increases. The increase of heat capacity is interpreted to be due to the formation of lattice defects. The heat capacity measurements on U4O9 and U3O8 clucidate the presence of the phase transition. The mechanisms of these phase transitions are discussed.
Authors:H. Yang, Y. Cho, H. Eun, E. Kim, and I. Kim
Kinetics of a thermal dechlorination and oxidation of gadolinium oxychloride (GdOCl) originating from a molten salt process
was investigated under various oxygen partial pressures by using a non-isothermal thermogravimetric (TG) analysis. The results
of isoconversional analysis of the TG data suggests that the dechlorination and oxidation of GdOCl follows a single step reaction
and the observed activation energy was determined as 137.7�4.1 kJ mol−1. The kinetic rate equation was derived for a conversion of the GdOCl with a linear-contacting boundary reaction model. The
power dependency for oxygen and the pre-exponential factor was determined as 0.306 and 1.012 s−1 Pa−0.306, respectively.
Authors:A. Sebaoun, P. Satre, M. Mansori, and A. L'Honore
TG-DTA and X-ray diffraction measurements at different temperatures and under different oxygen partial pressures were carried out on the species Bi1.6Pb0.4Sr2CuO6±x, Bi1.6Pb0.4Sr2CaCu2O8±y and Bi1.6Pb0.4Sr2Ca2Cu3O10±z to analyse the influence of the oxygen chemical potential on the phase transformations. A new phase was found at isobaric invariant equilibrium for 0.5≤
/PTot≤1 at 884°C. This new phase presents a buffer effect towards oxygen exchange between superconducting oxides and the gas phase.
Authors:P. H. Larsen, P. V. Hendriksen, and M. Mogensen
Acceptor doped lanthanum chromites are potential interconnect materials to be used in high temperature Solid Oxide Fuel Cells (SOFC). However, instability of these materials when exposed to low oxygen partial pressure causes a volume expansion that can be detrimental to the SOFC performance. The stability of La0.8Sr0.2Cr0.97V0.03O3 is determined as function ofpO2 and temperature by isothermal thermogravimetry and dilatometry. The experimental data are analysed using a simple model for the defect chemistry. The relation between expansion behaviour and change in defect chemistry is discussed using a simple structural model.
Thermogravimetric measurements of the equilibrium oxygen partial pressure (
) as a function of the oxygen contenty were performed on Nd1.85Ce0.15Cu1+δOy samples with controlled Cu contents (1+δ=1.00, 1.01 and 1.02) at 1173 and 1237 K. The data obtained showed a dependence of the oxygen non-stoichiometry on the nominal Cu content. These measurements are discussed in terms of the presence of Cu defects in the T′ structure. The superconducting response of this material in samples with controlled oxygen and Cu contents was also studied. The superconducting response was found to be very sensitive to the presence of small amounts of cationic and anionic defects.
The objects for the studies of this paper are iron sulfates where the iron has second or third valences and where coordination
between iron, sulfur and oxygen is different. DSC technique is used to investigate thermal stability and enthalpy changes
when iron compounds are treated in different gas medium. The main objective is to compare thermal stability and enthalpy of
iron oxy-sulphate, often detected as an intermediate, with commonly known iron sulphates.
DSC curves of samples with equal mass under different gas medium, determining different partial pressure of oxygen in the
gas phase, are the base for comparative study of the sample’s thermal properties. Obtained different values of the enthalpy
and mass losses and kinetic parameters demonstrate that the stability of oxy-sulphate strongly depended on the value of oxygen
partial pressure in the gas phase.
The new evidences from the experimental study help to propose the mechanism of the decomposition and to compare some of the
iron sulphates properties.
Authors:K. Kakinuma, H. Yamamura, H. Haneda, and T. Atake
The structural characterization, thermogravimetric analysis and electrical properties for solid solution system, (Ba1–xLax)2In2O5+x with perovskite-type structure were investigated. X-ray diffraction showed that the orthorhombic phase was in the range of 0.0<x
0.3, the tetragonal phase 0.3<x
0.5, and the cubic phase 0.5<x. The sharp transition of electrical conductivity shifted to a lower temperature with increasing x and disappeared at the phase boundary between the orthorhombic and tetragonal phases. This perovskite-related oxide exhibited a pure oxide-ion conduction over the oxygen partial pressure range of 1 atm to 10–3.5 atm, and the electrical conductivity reached the value of 1.610–1 (S cm–1) at 1073 K, which was nearly equal to that of the yttria stabilized zirconia. These properties were successfully explained in terms of disordered oxygen ions.