Potentiometric determination of the gibbs energies of formation of SrZrO3 and BaZrO3

The Gibbs free energies of formation of strontium and barium zirconates have been determined in the temperature range 960 to 1210 K using electrochemical cells incorporating the respective alkaline-earth fluoride single crystals as solid electrolytes. Pure strontium and barium monoxides were used in the reference electrodes. During measurements on barium zirconate, the oxygen partial pressure in the gas phase over the electrodes was maintained at a low value of 18.7 Pa to minimize the solubility of barium peroxide in the monoxide phase. Strontium zirconate was found to undergo a phase transition from orthorhombic perovskite to) with space group Cmcm; D-2h(17) to tetragonal perovskite (t) having the space group 14/mcm; D-4h(18) at 1123 (+/- 10) K. Barium zirconate does not appear to undergo a phase transition in the temperature range of measurement. It has the cubic perovskite (c) structure. The standard free energies of formation of the zirconates from their component binary oxides AO (A = Sr, Ba) with rock salt (rs) and ZrO2 with monoclinic (m) structures can be expressed by the following relations:SrO (rs) + ZrO2 (m) --> SrZrO3 (o) Delta G degrees = -74,880 - 14.2T (+/-200) J mol(-1) SrO (rs) + ZrO2 (m) --> SrZrO3 (t) Delta G degrees = -73,645 - 15.3T (+/-200) J mol(-1) BaO (rs) + ZrO2 (m) --> BaZrO4 (c) Delta G degrees = -127,760 - 1.79T (+/-250) J mol(-1) The results of this study are in reasonable agreement with calorimetric measurements reported in the literature. Systematic trends in the stability of alkaline-earth zirconates having the stoichiometry AZrO(3) are discussed.

Probing the structural changes in the phase transitions of a Bi2MoO6 catalyst: the nature of the intermediate-temperature phase

The nature of the phase transitions of Bi2MoO6 has been investigated by the combined use of X-ray diffraction and Xray absorption spectroscopy. The distorted MoO6 octahedra in the low-temperature form are shown to undergo further distortion in the intermediate-temperature form before transforming to MoO4 tetrahedra in the high-temperature phase. (C) 1995 Academic Press, Inc.

Al2O3---ZrO2 composite coatings for thermal-barrier applications

Graded alternate layers of Al2O3 and 8% Y2O3-ZrO2 and their admixtures were plasma sprayed onto bond-coated mild steel. They were evaluated for thermal-shock resistance, thermal-barrier characteristics, hot corrosion resistance (molten NaCl corrodant) and depth of attack, adhesion strength and the presence of phases. Although front-back temperature drops of 423-623 K were observed, some of the coatings showed good adherence even after 100 thermal shack cycles. In the sequence of the graded layers, the oxide which is directly in contact with the bond coat appears to influence the properties especially in coatings of 150 and 300 mu m thickness. Molten NaCl readily attacks the films at high hot-face temperatures (1273 K for 1 h) and the adhesive strength falls significantly by 50-60%. Diffusion of alkaline elements is also found to depend on the chemical composition of the outer coating directly facing the molten corrodant. (C) 1997 Elsevier Science Limited.

Interplay of spin and lattice degrees of freedom in the frustrated antiferromagnet CdCr2O4: High-field and temperature-induced anomalies of the elastic constants

Temperature and magnetic field studies of the elastic constants of the chromium spinel CdCr2O4 show pronounced anomalies related to strong spin-phonon coupling in this frustrated antiferromagnet. A detailed comparison of the longitudinal acoustic mode propagating along the 111] direction with a theory based on an exchange-striction mechanism leads to an estimate of the strength of the magnetoelastic interaction. The derived spin-phonon coupling constant is in good agreement with previous determinations based on infrared absorption. Further insight is gained from intermediate and high magnetic field experiments in the field regime of the magnetization plateau. The role of the antisymmetric Dzyaloshinskii-Moriya interaction is discussed.

Critical buckling temperature of single-walled carbon nanotubes embedded in a one-parameter elastic medium based on nonlocal continuum mechanics

In this paper, the critical budding temperature of single-walled carbon nanotubes (SWCNTs), which are embedded in one-parameter elastic medium (Winkler foundation) is estimated under the umbrella of continuum mechanics theory. Nonlocal continuum theory is incorporated into Timoshenko beam model and the governing differential equations of motion are derived. An explicit expression for the non-dimensional critical buckling temperature is also derived in this work. The effect of the nonlocal small scale coefficient, the Winkler foundation parameter and the ratio of the length to the diameter on the critical buckling temperature is investigated in detail. It can be observed that the effects of nonlocal small scale parameter and the Winkler foundation parameter are significant and should be considered for thermal analysis of SWCNTs. The results presented in this paper can provide useful guidance for the study and design of the next generation of nanodevices that make use of the thermal buckling properties of embedded single-walled carbon nanotubes. (C) 2011 Elsevier B.V. All rights reserved.

Universal Stability and Temperature Dependent Phase Transformation in Group VIIIB-IB Transition Metal FCC Nanowires

Atomistic simulation of Ag, Al, Au, Cu, Ni, Pd, and Pt FCC metallic nanowires show a universal FCC -> HCP phase transformation below a critical cross-sectional size, which is reported for the first time in this paper. The newly observed HCP structure is also confirmed from previous experimental results. Above the critical cross-sectional size, initial < 100 >/{100} FCC metallic nanowires are found to be metastable. External thermal heating shows the transformation of metastable < 100 >/{100} FCC nanowires into < 110 >/{111} stable configuration. Size dependent metastability/instability is also correlated with initial residual stresses of the nanowire by use of molecular static simulation using the conjugant gradient method at a temperature of 0 K. It is found that a smaller cross-sectional dimension of an initial FCC nanowire shows instability due to higher initial residual stresses, and the nanowire is transformed into the novel HCP structure. The initial residual stress shows reduction with an increase in the cross-sectional size of the nanowires. A size dependent critical temperature is also reported for metastable FCC nanowires using molecular dynamic, to capture the < 110 >/{111} to < 100 >/{100} shape memory and pseudoelasticity.

Limiting ionic conductance of symmetrical, rigid ions in aqueous solutions: Temperature dependence and solvent isotope effects

Limiting ionic conductance (Lambda(0)) of rigid symmetrical unipositive ions in aqueous solution shows a strong temperature dependence. For example, Lambda(0) more than doubles when the temperature is increased from 283 to 318 K. A marked variation also occurs when the solvent is changed from ordinary water (H2O) to heavy water (D2O). In addition, Lambda(0) shows a nonmonotonic size dependence with a skewed maximum near Cs+. Although these important results have been known for a long time, no satisfactory theoretical explanation exists for these results. In this article we present a simple molecular theory which provides a nearly quantitative explanation in terms of microscopic structure and dynamics of the solvent. A notable feature of this theory is that it does not invoke any nonquantifiable models involving solvent-berg or clatherates. We find the strong temperature dependence of Lambda(0) to arise from a rather large number of microscopic factors, each providing a small but nontrivial contribution, but all acting surprisingly in the same direction. This work, we believe, provides, for the first time, a satisfactory explanation of both the anomalous size and temperature dependencies of Lambda(0) of unipositive ions in molecular terms. The marked change in Lambda(0) as the solvent is changed from H2O to D2O is found to arise partly from a change in the dielectric relaxation and partly from a change in the effective interaction of the ion with the solvent.

Strontium and calcium zirconyl citrates as precursors for the low-temperature synthesis of SrZrO3 and CaZrO3 fine powders

Synthesis and the thermal decomposition behavior of new molecular precursors, strontium, and calcium zirconyl citrates are presented. The pathway to the metazirconate formation has been found to proceed through a multistep process. The precursors yield SrZrO3 and CaZrO3 fine powders at temperatures as low as 650 degrees C. Physico-chemical, spectroscopic, thermoanalytical, and microscopic techniques have enabled the identification of the sequence of events leading to the perovskite formation and proposition of a thermolysis scheme. Retention of the molecular level mixing of the metal ions during the course of the precursor decomposition is supported by these techniques. Prior to the formation of MZrO3 (M = Sr and Ca) an ionic oxycarbonate, M2Zr2O5CO3 (M = SI. and Ca), intermediate is produced by the thermal decomposition of the citrate precursors.

Temperature dependence of non-Debye disorder in doped manganites

Ca-doped manganite La1-xCaxMnO3 samples with x=0.2 and 0.4 were investigated by extended x-ray absorption fine structure (EXAFS) as a function of temperature and preparation method. The samples exhibit characteristic resistivity change across the metal-insulator (MI) transition temperature whose shape and position depend on Ca-doping concentration and sample thermal treatment. EXAFS results evidenced an increase of nonthermal disorder at the MI transition temperature which is significantly correlated with the resistivity behavior.

Temperature dependence of the levitation effect - Implications for separation of multicomponent mixtures

Sufficiently long molecular dynamics simulations have been carried out on spherical monatomic sorbates in NaY zeolite, interacting via simple Lennard-Jones potentials, to investigate the dependence of the levitation effect on the temperature. Simulations carried out in the range 100-300 K suggest that the anomalous peak in the diffusion coefficient (observed when the levitation parameter, gamma, is near unity) decreases in intensity with increase in temperature. The rate of cage-to-cage migrations also exhibits a similar trend. The activation energy obtained from Arrhenius plots is found to exhibit a minimum when the diffusion coefficient is a maximum, corresponding to the gamma approximate to 1 sorbate diameter. In the linear or normal regime, the activation energy increases with increase in sorbate diameter until it shows a sharp decrease in the anomalous regime. Locations and energies of the adsorption sites and their dependence on the sorbate size gives interesting insight into the nature of the underlying potential-energy surface and further explain the observed trend in the activation energy with sorbate size. Cage residence times, tau(c), show little or no change with temperature for the sorbate with diameter corresponding to gamma approximate to 1, whereas there is a significant decrease in tau(c) with increase in temperature for sorbates in the linear regime. The implications of the present study for the separation of mixtures of sorbates are discussed.

Temperature-dependent valence-band photoemission spectra of La1-xSrxMnO3

We have studied the temperature dependence of the photoemission spectra of La1-xSrxMnO3 (x=0.0, 0.2, and 0.4) and found that the spectral line shape dramatically changes in the entire valence-band region, particularly for x=0.2 and 0.4. By contrast, the spectra of La0.6Sr0.4CoO3 show no significant temperature dependence. From comparison between the temperature-and composition-(x) dependent spectral changes and the temperature-composition phase diagram of La1-xSrxMnO3, we suggest that the changes are related to the degree of hole localization on oxygen p orbitals, which is influenced by electron-lattice coupling and magnetic correlations.

The effect of temperature on the surface tension and adsorption functions of the Fe-S-O melts - an analysis based on interaction parameters

The present investigation analyses the thermodynamic behaviour of the surfaces and adsorption as a function of temperature and composition in the Fe-S-O melts based on the Butler's equations. The calculated-values of the surface tensions exhibit an elevation or depression depending on the type of the added solute at a concentration which coincides with that already present in the system. Generally, the desorption of the solutes as a function of temperature results in an initial increase followed by a decrease in the values of the surface tension. The observations are analyzed based on the surface interaction parameters which are derived in the present research.

The two-step positive temperature coefficient in resistance characteristics of n-(Ba,Pb)TiO3 ceramics created through inclusion of grain boundary modifier additives

Donor-doped n-(Ba,Pb)TiO3 polycrystalline ceramics exhibit distinctly two-step positive temperature coefficient of resistance (PTCR) characteristics when formulated with suitable combinations of B2O3 and Al2O3 as grain boundary modifiers by heterogeneous addition. B2O3 or Al2O3 when added singularly resulted in either steep or broad PTCR jumps respectively across the phase transition. The two-step PTCR is attributed to the activation of the acceptor states, created through B2O3 and Al2O3, for various temperature regimes above the Curie point (T-c). The changing pattern of trap states is evident from the presence of Ti4+-O--Al3+ type hole centres in the grain boundary layer regions, identified in the electron paramagnetic resonance (EPR) spectra. That charge redistribution occurs among the inter-band gap defect states on crossing the Curie temperature is substantiated by the temperature coefficient in the EPR results. Capacitance-voltage results clearly show that there is an increase in the density of trap states with the addition of B2O3 and Al2O3. The spread in energy values of these trap states is evident from the large change in barrier height (phi similar or equal to 0.25-0.6 eV) between 500 and 650 K.

Ising pyrochlore magnets: Low-temperature properties, "ice rules," and beyond

Pyrochlore magnets are candidates for what Harris et al. [Phys. Rev. Lett. 79, 2554 (1997)] call "spin-ice" behavior. We present theoretical simulations of relevance for the pyrochlore family R2Ti2O7 (R = rare earth) supported by magnetothermal measurements on selected systems. Ey considering long-ranged dipole-dipole as well as short-ranged superexchange interactions, we get three distinct behaviors: (i) an ordered doubly degenerate state, (ii) a highly disordered state with a broad transition to paramagnetism, and (iii) a partially ordered state with a sharp transition to paramagnetism. Closely corresponding behavior is seen in the real compounds.