Phase relations and thermodynamic properties of condensed phases in the system calcium-copper-oxygen

The isothermal sections of the phase diagram for the system Ca-Cu-0 at 1073 and 1223 K have been determined. Several compositions in the ternary system were quenched after equilibration, and the phases present were identified by optical microscopy, X-ray diffraction, and electron probe microanalysis. Two ternary compounds Ca2CuO3 and Cao.8&uO1.9s were identified at 1073 K. However, only Ca2CuO3 was found to be stable at 1223 K. The thermodynamic properties of the two ternary compounds were determined using solid-state cells incorporating either an oxide or a fluoride solid electrolyte. The results for both types of cells were internally consistent. The compound C ~ O . ~ & U Ow~h.i~ch~ c, a n also be represented as Ca15Cu18035h, as been identified in an earlier investigation as Cao.828CuOz. Using a novel variation of the galvanic cell technique, in which the emf of a cell incorporating a fluoride electrolyte is measured as a function of the oxygen potential of the gas phase in equilibrium with the condensed phase electrodes, it has been confirmed that the compound Cao.828CuO1.93 (Ca15Cu18035d) oes not have significant oxygen nonstoichiometry. Phase relations have been deduced from the thermodynamic data as a function of the partial pressure of oxygen for the system Ca-Cu-0 at 873, 1073, and 1223 K.

Phase Relations in the System Cu-Gd-O and Gibbs Energy of Formation of CuGd204

The phase relations in the system Cu-Gd-O have been determined at 1273 K by X-ray diffrac- tion, optical microscopy, and electron microprobe analysis of samples equilibrated in quartz ampules and in pure oxygen. Only one ternary compound, CuGd2O4, was found to be stable. The Gibbs free energy of formation of this compound has been measured using the solid-state cell Pt, Cu2O + CuGd2O4 + Gd2O3 // (Y2O3) ZrO2 // CuO + Cu2O, Pt in the temperature range of 900 to 1350 K. For the formation of CuGd2O4 from its binary component oxides, CuO (s) + Gd2O3 (s) → CuGd2O4 (s) ΔG° = 8230 - 11.2T (±50) J mol-1 Since the formation is endothermic, CuGd2O4 becomes thermodynamically unstable with respect to CuO and Gd2O3 below 735 K. When the oxygen partial pressure over CuGd2O4 is lowered, it decomposes according to the reaction 4CuGd2O4 (s) → 4Gd2O3 (s) + 2Cu2O (s) + O2 (g) for which the equilibrium oxygen potential is given by Δμo 2 = −227,970 + 143.2T (±500) J mol−1 An oxygen potential diagram for the system Cu-Gd-O at 1273 K is presented.

Phase relations in the systems Cu–O–R2O3(R = Tm, Lu) and Gibbs energies of formation of Cu2R2O5 compounds

The phase relations in the systems Cu–O–R2O3(R = Tm, Lu) have been determined at 1273 K by X-ray diffraction, optical microscopy and electron probe microanalysis of samples equilibrated in evacuated quartz ampules and in pure oxygen. Only ternary compounds of the type Cu2R2O5 were found to be stable. The standard Gibbs energies of formation of the compounds have been measured using solid-state galvanic cells of the type, Pt|Cu2O + Cu2R2O5+ R2O3‖(Y2O3)ZrO2‖CuO + Cu2O‖Pt in the temperature range 950–1325 K. The standard Gibbs energy changes associated with the formation of Cu2R2O5 compounds from their binary component oxides are: 2CuO(s)+ Tm2O3(s)→Cu2Tm2O5(s), ΔG°=(10400 – 14.0 T/K)± 100 J mol–1, 2CuO(s)+ Lu2O3(s)→Cu2Lu2O5(s), ΔG°=(10210 – 14.4 T/K)± 100 J mol–1 Since the formation is endothermic, the compounds become thermodynamically unstable with respect to component oxides at low temperatures, Cu2Tm2O5 below 743 K and Cu2Lu2O5 below 709 K. When the chemical potential of oxygen over the Cu2R2O5 compounds is lowered, they decompose according to the reaction, 2Cu2R2O5(s)→2R2O3(s)+ 2Cu2O(s)+ O2(g) The equilibrium oxygen potential corresponding to this reaction is obtained from the emf. Oxygen potential diagrams for the Cu–O–R2O3 systems at 1273 K are presented.

Phase Transformation Introduced by Mechanical and Chemical Surface Preparations of Tetragonal Zirconia Polycrystals

Cutting of Y2O3-doped TZP rods by a low-speed diamond saw introduces an unidentified, metastable phase X (x-ZrO2) coexisting with the tetragonal (t-ZrO2) and the monoclinic (m-ZrO2) phases initially present in the sample. Further mechanical deformation of the cut surface by indentation or polishing sustains the x-ZrO2. Chemical etching removes the x-ZrO2 and increases the m-ZrO2content.

Pressure-induced phase transitions in LiRbSO4: a Raman spectroscopic study

Room-temperature Raman spectra of LiRbSO4 were studied as a function of pressure up to 170 kbar for two different orientations of the crystal. Four pressure-induced phase transitions at about 2, 17, 32 and 57 kbar were observed. The transitions at 17 and 57 kbar have slow kinetics, taking about 4 h for their completion. These phase transitions are associated with the orientations of the SO4 ions in the unit cell.

Pulsed NMR study of molecular motions and phase transitions in [N(CH3)4]PbX3 (X=Cl, Br, I)

Proton spin—lattice relaxation time (T1) is measured in [N(CH3)4]PbX3 (X=Cl, Br, I) from 300-77 K at 9.75 MHz. All the compounds show discontinuous changes in T1 values (at 256, 270 and 277 K, respectively), indicating phase transitions. Single T1 minimum is observed in all the cases and the T1 variation is explained in terms of [N(CH3)4] and CH3 group dynamics. The activation energy Eα decreases from chloride to iodide (from 4 to 2 kcal/mol). In bromide and iodide, T1 is found to decrease with increase in temperature at higher temperatures, indicating the presence of spin—rotation interaction.

Spectroscopic investigations of phase transitions in complex solids

Spectroscopic methods have provided information of seminal importance in understanding phase transitions in solids. After briefly examining some fundamental concept related to phase transitions, we shall discuss several case studies particularly involving the use of vibrational (IR and Raman) spectroscopy. Examples will include both order-disorder and displacive transitions. Under the former are included transitions in nitrates, ammonium halides, alkylammonium salts, plastic state of C60 and superionic conductors (specially CsHSO4). In addition, we shall discuss some aspects of incommensurate phase transitions, the glass transition and electronic phase transitions. Transitions of phosphonitrilic halide tetramers and alkane dicarboxylic acids are also examined

Dense granular flow down an inclined plane A comparison between the hard particle model and soft particle simulations

The granular flow down an inclined plane is simulated using the discrete element (DE) technique to examine the extent to which the dynamics of an unconfined dense granular flow can be well described by a hard particle model First, we examine the average coordination number for the particles in the flow down an inclined plane using the DE technique using the linear contact model with and without friction, and the Hertzian contact model with friction The simulations show that the average coordination number decreases below 1 for values of the spring stiffness corresponding to real materials, such as sand and glass, even when the angle of inclination is only 10 larger than the angle of repose Additional measures of correlations in the system, such as the fraction of particles with multibody contact, the force ratio (average ratio of the magnitudes of the largest and the second largest force on a particle), and the angle between the two largest forces on the particle, show no evidence of force chains or other correlated motions in the system An analysis of the bond-orientational order parameter indicates that the flow is in the random state, as in event-driven (ED) simulations V Kumaran, J Fluid Mech 632, 107 (2009), J Fluid Mech 632, 145 (2009)] The results of the two simulation techniques for the Bagnold coefficients (ratio of stress and square of the strain rate) and the granular temperature (mean square of the fluctuating velocity) are compared with the theory V Kumaran, J Fluid Mech 632, 107 (2009), J Fluid Mech 632, 145 (2009)] and are found to be in quantitative agreement In addition, we also conduct a comparison of the collision frequency and the distribution of the precollisional relative velocities of particles in contact The strong correlation effects exhibited by these two quantities in event-driven simulations V Kumaran, J Fluid Mech 632, 145 (2009)] are also found in the DE simulations (C) 2010 American Institute of Physics doi 10 1063/1 3504660]

The effect of progesterone replacement on gene expression in the corpus luteum during induced regression and late luteal phase in the bonnet monkey (Macaca radiata)

Background: In higher primates, although LH/CG play a critical role in the control of corpus luteum (CL) function, the direct effects of progesterone (P4) in the maintenance of CL structure and function are unclear. Several experiments were conducted in the bonnet monkey to examine direct effects of P4 on gene expression changes in the CL, during induced luteolysis and the late luteal phase of natural cycles. Methods: To identify differentially expressed genes encoding PR, PR binding factors, cofactors and PR downstream signaling target genes, the genome-wide analysis data generated in CL of monkeys after LH/P-4 depletion and LH replacement were mined and validated by real-time RT-PCR analysis. Initially, expression of these P4 related genes were determined in CL during different stages of luteal phase. The recently reported model system of induced luteolysis, yet capable of responsive to tropic support, afforded an ideal situation to examine direct effects of P4 on structure and function of CL. For this purpose, P4 was infused via ALZET pumps into monkeys 24 h after LH/P4 depletion to maintain mid luteal phase circulating P4 concentration (P4 replacement). In another experiment, exogenous P4 was supplemented during late luteal phase to mimic early pregnancy. Results: Based on the published microarray data, 45 genes were identified to be commonly regulated by LH and P4. From these 19 genes belonging to PR signaling were selected to determine their expression in LH/P-4 depletion and P4 replacement experiments. These 19 genes when analyzed revealed 8 genes to be directly responsive to P4, whereas the other genes to be regulated by both LH and P4. Progesterone supplementation for 24 h during the late luteal phase also showed changes in expression of 17 out of 19 genes examined. Conclusion: These results taken together suggest that P4 regulates, directly or indirectly, expression of a number of genes involved in the CL structure and function.

Growth temperature induced effects in non-polar a-plane GaN on r-plane sapphire substrate by RF-MBE

Non-polar a-plane GaN films were grown on an r-plane sapphire substrate by plasma assisted molecular beam epitaxy (PAMBE). The effect of growth temperature on structural, morphological and optical properties has been studied. The growth of non-polar a-plane (1 1 - 2 0) orientation of the GaN epilayers were confirmed by high resolution X-ray diffraction (HRXRD) study. The X-ray rocking curve (XRC) full width at half maximum of the (1 1 - 2 0) reflection shows in-plane anisotropic behavior and found to decrease with increase in growth temperature. The atomic force micrograph (AFM) shows island-like growth for the film grown at a lower temperature. Surface roughness has been decreased with increase in growth temperature. Room temperature photoluminescence shows near band edge emission at 3.434-3.442 eV. The film grown at 800 degrees C shows emission at 2.2 eV, which is attributed to yellow luminescence along with near band edge emission. (C) 2010 Elsevier B.V. All rights reserved.

Thermodynamics and phase equilibria in the Ga---Sb system

The optimum values of the solution parameters of a multiparameter integral free-energy function have been determined using experimental data from the Ga-Sb system. The equation is represented as DELTAG(xs) = x(1 - x)[(1 - x)(a1 + a2T + a3T ln T) + x(a4 + a5T + a6T ln T) + x(1 - x)(a7 + a8T + a9xT)].The integral and the corresponding partial form of the free energy function have been found to be of use when interpreting the high temperature thermodynamic data, atomic interactions and phase equilibria in the Ga-Sb system.

Thermodynamics and phase equilibria in the system Ga---In using multi-parameter functions

A four and a five-parameter functions are used to analyse and interpret the high and low temperature thermodynamic data and phase equilibria in the Ga-In system.

Grain size effect on the phase transformation temperature of nanostructured CuFe2O4

We report a large decrease in tetragonal to cubic phase transformation temperature when grain size of bulk CuFe2O4 is reduced by mechanical ball milling. The change in phase transformation temperature was inferred from in situ high temperature conductivity and x-ray diffraction measurements. The decrease in conductivity with grain size suggests that ball milling has not induced any oxygen vacancy while the role of cation distribution in the observed decrease in phase transformation temperature is ruled out from in-field Fe-57 Mossbauer and extended x-ray absorption fine structure measurements. The reduction in the phase transformation temperature is attributed to the stability of structures with higher crystal symmetry at lower grain sizes due to negative pressure effect. (C) 2011 American Institute of Physics. doi: 10.1063/1.3493244]

Parallel Tempering Simulations of Liquid-Phase Adsorption of n-Alkane Mixtures in Zeolite LTA-5A

Adsorption of n-alkane mixtures in the zeolite LTA-5A under liquid-phase conditions has been studied using grand canonical Monte Carlo (GCMC) simulations combined with parallel tempering. Normal GCMC techniques fail for some of these systems due to the preference of linear molecules to coil within a single cage in the zeolite. The narrow zeolite windows severerly restrict interactions of the molecules, making it difficult to simulate cooperative rearrangements necessary to explore configuration space. Because of these reasons, normal GCMC simulations results show poor reproducibility in some cases. These problems were overcome with parallel tempering techniques. Even with parallel tempering, these are very challenging systems for molecular simulation. Similar problems may arise for other zeolites such as CHA, AFX, ERI, KFI, and RHO having cages connected by narrow windows. The simulations capture the complex selectivity behavior observed in experiments such as selectivity inversion and azeotrope formation.

Interdiffusion study on Co(W) solid solution and topological close-packed mu phase in Co-W system

An interdiffusion study is conducted on the Co-W system by a diffusion couple technique. The interdiffusion coefficient of the Co(W) solid solution and the Co7W6 mu phase is determined. The activation energy is found to increase with the W content of the Co(W) solid solution. (C) 2010 Elsevier Ltd. All rights reserved.