186 resultados para Phase rule and equilibrium.
Resumo:
In this paper the results of a detailed investigation on the metastable phase relations in undercooled as well as rapidly solidified Al---Ge alloys containing 2–50 at.% Ge are reported. Data obtained on the structure and morphology of phases enable us to arrive at the phase relations and transformation processes occurring in undercooled and rapidly quenched melts of this system. These results are explained with the help of a metastable phase diagram consisting of a peritectic and eutectic reaction involving metastable phases.
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Investigations on the phase relations and dielectric properties of (1 -x)BaTiO3 + xNd2/3TiO 3 (BNT) ceramics sintered in air below 1650 K have been carried out. X-ray powder diffraction studies indicate apparent phase singularity for compositions with x < 0.3. Nd2Ti207 is detected at higher neodymium concentrations. The unit cell parameter changes continuously with neodymium content, and BaTiO3 is completely cubic at room temperature with x -- 0.0525, whereas electron diffraction studies indicate that the air-sintered BNT ceramics with x > 0.08 contain additional phases that are partly amorphous even to an electron beam. SEM observations reveal that BaTiO3 grains are mostly covered by a molten intergranular phase, and show the presence of randomly distributed Nd2Ti207 grains. Energy dispersive X-ray analysis shows the Ba-Nd-Ti ternary composition of the intergranular phase. Differential thermal analysis studies support the formation of a partial melt involving dissolution-precipitation of boundary layers of BaTiO3 grains. These complex phase relations are accounted for in terms of the phase instability of BaTiO3 with large cation-vacancy concentration as a result of heavy Nd 3+ substitution. The absence of structural intergrowth in (1 - x)BaTiO3 + xNd2/3TiO3 under oxidative conditions leads to a separation of phases wherein the new phases undergo melting and remain X-ray amorphous. BNT ceramics with 0.1 < x < 0.3 have ~eff >~ 104 with tan 6 < 0.1 and nearly flat temperature capacitance characteristics. The grain-size dependence of ee,, variations of ~eff and tan 6 with the measuring frequency, the non-ohmic resistivities, and the non-linear leakage currents at higher field-strengths which are accompanied by the decrease in eeff and rise in tan 3, are explained on the basis of an intergranular (internal boundary layer) dielectric characteristic of these ceramics.
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We focus on athermal phase transitions where in discrete and dissipative avalanches are observed in physical observables as the system jumps from one metastable state to another, when driven by an external field. Using higher order statistics of time dependent avalanches, or noise, in electrical resistivity during temperature-driven martensite transformation in thin nickel-titanium films, we demonstrate evidence suggesting the existence of a singular `global instability' or divergence of the correlation length as a function of temperature at the transition. These results not only establish a mapping of non-equilibrium first order phase transition and equilibrium critical phenomena, but perhaps also call for a re-evaluation of many existing experimental claims of self-organized criticality.
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Extensive molecular dynamics (MD) simulations have been performed in a B2-NiAl nanowire using an embedded atom method (EAM) potential. We show a stress induced B2 -> body-centered-tetragonal (BCT) phase transformation and a novel temperature and cross-section dependent pseudo-elastic/pseudo-plastic recovery from such an unstable BCT phase with a recoverable strain of similar to 30% as compared to 5-8% in polycrystalline materials. Such a temperature and cross-section dependent pseudo-elastic/pseudo-plastic strain recovery can be useful in various interesting applications of shape memory and strain sensing in nanoscale devices. Effects of size, temperature, and strain rate on the structural and mechanical properties have also been analyzed in detail. For a given size of the nanowire the yield stress of both the B2 and the BCT phases is found to decrease with increasing temperature, whereas for a given temperature and strain rate the yield stress of both the B2 and the BCT phase is found to increase with increase in the cross-sectional dimensions of the nanowire. A constant elastic modulus of similar to 80 GPa of the B2 phase is observed in the temperature range of 200-500 K for nanowires of cross-sectional dimensions in the range of 17.22-28.712 angstrom, whereas the elastic modulus of the BCT phase shows a decreasing trend with an increase in the temperature.
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An indigenous electron energy loss spectrometer has been designed and fabricated for the study of free molecules. The spectrometer enables the recording of low-resolution electronic spectra of molecules inthe vapour phase with ready access to the vacuum ultraviolet region. Electron energy loss spectra of aliphatic alcohols and carbonyl compounds as wellas of benzene derivatives have been recorded with the indigenous spectrometer and the electronic transitions in these molecules discussed.
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Abstract is not available.
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The study on the formation and growth of topological close packed (TCP) compounds is important to understand the performance of turbine blades in jet engine applications. These deleterious phases grow mainly by diffusion process in the superalloy substrate. Significant volume change was found because of growth of the p phase in Co-Mo system. Growth kinetics of this phase and different diffusion parameters, like interdiffusion, intrinsic and tracer diffusion coefficients are calculated. Further the activation energy, which provides an idea about the mechanism, is determined. Moreover, the interdiffusion coefficient in Co(Mo) solid solution and impurity diffusion coefficient of Mo in Co are determined.
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Tlie sclxuntion and clraractcrization of vitamins Al and An nnd related compoundsby reversed-pllasc paper cliromatogrnpl~y as well as ly thin-lqxr chromategraphy have hen rcportccl carlicrl * $. Thin-lnycr chromatography has also been used for the separatinn and charncterizatio11 of carotenoids from natural sourccs3~ ‘1. I-Iowcver, 130tr.rc,1~1~ofib scrvccl that carotenoid misturcs cannot be separated on a sin& aclsorhnt with ;1 sin& solvent. The scparntion and clctermi1wtion of carotenoid alclclydes from plants, microorganisms and animnl tissues have lxxn carriecl out by nicans of thin-layer clirf.~li~ato~apI~~U. Apocarotcnals awl apocarotcnoic acid have been detected in ornnges by the same technique’*
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Thermotropic liquid crystals are known to display rich phase behavior on temperature variation. Although the nematic phase is orientationally ordered but translationally disordered, a smectic phase is characterized by the appearance of a partial translational order in addition to a further increase in orientational order. In an attempt to understand the interplay between orientational and translational order in the mesophases that thermotropic liquid crystals typically exhibit upon cooling from the high-temperature isotropic phase, we investigate the potential energy landscapes of a family of model liquid crystalline systems. The configurations of the system corresponding to the local potential energy minima, known as the inherent structures, are determined from computer simulations across the mesophases. We find that the depth of the potential energy minima explored by the system along an isochor grows through the nematic phase as temperature drops in contrast to its insensitivity to temperature in the isotropic and smectic phases. The onset of the growth of the orientational order in the parent phase is found to induce a translational order, resulting in a smectic-like layer in the underlying inherent structures; the inherent structures, surprisingly, never seem to sustain orientational order alone if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. The Arrhenius temperature dependence of the orientational relaxation time breaks down near the isotropic-nematic transition. We find that this breakdown occurs at a temperature below which the system explores increasingly deeper potential energy minima.
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The coexisting phases in the pseudobinary system BaO-Y2O3 have been identified by equilibrating samples containing different amounts of component oxides at 1173, 1273 and 1373 K. Only two ternary oxides, BaY2O4 and Ba3Y4O9, have been found to be stable in the temperature range of investigation. Solid state galvanic cells: Pt, O2+BaO+BaF2double vertical barBaF2+2mol%Al2O3double vertical barBaF2+BaY2O4+Y2O3+O2, Pt and Pt, O2+BaO+BaF2double vertical barBaF2+2mol% Al2O3double vertical barBaF2+BaY2O4+Ba3Y4O9+O2, Pt have been employed for determining the Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from the component oxides in the range 850 to 1250 K. A composite solid electrolyte incorporating Al2O3-dispersed BaF2 was used in the cells. To prevent interaction between the Al2O3 powder and electrode materials, the solid electrolyte was coated with pure BaF2. The Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from component oxides are given by: Δf0 (BaY2O4, s)=−128,310+5.211T (±580) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K) and ΔGfo(Ba3Y4O9, s)= −317,490 −24.704T (±1100) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K).
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Infrared spectra of atmospherically important dimethylquinolines (DMQs), namely 2,4-DMQ, 2,6-DMQ, 2,7-DMQ, and 2,8-DMQ in the gas phase at 80 degrees C were recorded using a long variable path-length cell. DFT calculations were carried out to assign the bands in the experimentally observed spectra at the B3LYP/6-31G* level of theory. The spectral assignments particularly for the C-H stretching modes could not be made unambiguously using calculated anharmonic or scaled harmonic frequencies. To resolve this problem, a scaled force field method of assignment was used. Assignment of fundamental modes was confirmed by potential energy distributions (PEDs) of the normal modes derived by the scaled force fields using a modified version of the UMAT program in the QCPE package. We demonstrate that for large molecules such as the DMQs, the scaling of the force field is more effective in arriving at the correct assignment of the fundamentals for a quantitative vibrational analysis. An error analysis of the mean deviation of the calculated harmonic, anharmonic, and force field fitted frequencies from the observed frequency provides strong evidence for the correctness of the assignment.
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When the size (L) of a one-dimensional metallic conductor is less than the correlation length λ-1 of the Gaussian random potential, one expects transport properties to show ballistic behaviour. Using an invariant imbedding method, we study the exact distribution of the resistance, of the phase θ of the reflection amplitude of an incident electron of wave number k0, and of dθ/dk0, for λL ll 1. The resistance is non-self-averaging and the n-th resistance moment varies periodically as (1 - cos 2k0L)n. The charge fluctuation noise, determined by the distribution of dθ/dk0, is constant at low frequencies.
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The existing models describing electrochemical phase formation involving both adsorption and a nucleation/growth process are modified. The limiting cases leading to the existing models are discussed. The characteristic features of the potentiostatic transients are presented. A generalization of the Avrami ansatz is given for two or more competitive irreversibly growing phases.
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The pressure dependence of critical parameters xc, Tc, and β have been analysed in four systems namely cyclohexane + acetic anhydride, n-heptane + acetic anhydride, methanol + n-heptane, and carbon disulphide + acetonitrile. The separation temperature was found to increase linearly with pressure the value of dTc/dP being 28 mK, 11 mK, 22 mK, and 25 mK respectively. These are in fair agreement with earlier measurements available for two systems. For the methanol + n-heptane system dTc/dP is apparently not consistent with the value predicted from the specific heat and thermal expansion data.Die Druckabhängigkeit der kritischen Parameter xc, Tc und β ist in den vier Systemen Cyclohexan + Essigsäureanhydrid, n-Heptan + Essigsäureanhydrid, Methanol + n-Heptan und Schwefelkohlenstoff + Acetonitril analysiert worden. Es wurde gefunden, daß die kritische Temperatur linear mit dem Druck ansteigt. Die Werte für dTc/dP betragen 28 mK, 11 mK, 22 mK und 25 mK. Sie sind in guter überein-stimmung mit früheren Messungen an zweien dieser Systeme. Für Methanol + n-Heptan stimmt der Wert für dT/dP offensichtlich nicht mit Werten, die mit Hilfe von Daten für die spezifische Wärme und die thermische Ausdehnung vorhergesagt wurden, überein.