901 resultados para Energy|Materials science
Resumo:
Critical exponent of the electrical conductivity in the paracoherence region (gamma) of the high temperature superconductor YBa2Cu3O7-x (YBCO) has been estimated for high quality thin film on ZrO2 substrate prepared by high pressure oxygen sputtering. High energy ion irradiation was carried out using 100 MeV O-16(7+) ions at liquid nitrogen to see the effects of disorder on the value of the exponent. The critical exponent from a value of about 2 to 1.62 upon irradiation. Studies were also carried film to see the effect of ageing and annealing.
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Sparingly soluble neodymium copper oxalate (NCO) single crystals were grown by gel method, by the diffusion of a mixture of neodymium nitrate and cupric nitrate into the set gel containing oxalic acid. Tabular crystal, revealing well-defined dissolution figures has been recorded. X-ray diffraction studies of the powdered sample reveal that NCO is crystalline. Infrared absorption spectrum confirmed the formation of oxalato complex with water of crystallization, while energy dispersive X-ray analysis established the presence of neodymium dominant over copper in the sample. X-ray photoelectron spectroscopic studies established the presence of Nd and Cu in oxide states besides (C2O4)(2-) oxalate group. The intensities of Nd (3d(5/2)) and Cu (2p(3/2)) peaks measured in terms of maximum photoelectron count rates also revealed the presence of Nd in predominance. The inductively coupled plasma analysis supports the EDAX and XPS data by the estimation of neodymium percentage by weight to that of copper present in the NCO sample. On the basis of these findings, an empirical structure for NCO has been proposed. The implications are discussed.
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Blocks of 3Y-TZP were indented with conical diamond indenters. indentation caused tetragonal to monoclinic phase transformation in a subsurface. Of the cracks generated in the subsurface, radial and lateral cracks can be accounted for by a continuum model of the indented subsurface, built using a combination of the Boussinesq and blister stress fields. Additional ring, median and cone cracks were also observed. It is hypothesized that the latter are motivated by the reduction in blister strength or residual energy brought about by the material damage caused by the phase transformation. This damage reduces the load bearing capacity of the material progressively with increasing normal load.
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Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.
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Drop tube provides a low-cost alternative to study the influence of microgravity in materials processing. In the present paper, the current status of the drop tubes and associated experiments on materials processing are reviewed. Emphasis is placed on the advantages and limitations of these studies. It is pointed out that despite size limitation, large opportunities exist to study the fundamental aspects of the influence of gravity in materials processing.
Resumo:
Amorphous conducting carbon films are prepared by plasma assisted chemical vapour deposition and their d.c. conductivity (similar to 100 Scm(-1)) is studied from 300K down to 4.2K. The films were irradiated by high energy ion beam(I+13, 170 MeV) with a dose of 10(13) ions/cm(2). As a result a marked decrease in conductivity by two to three orders in magnitude was observed. The structural changes and the defects in the films caused by ion irradiation are studied using photoluminescence, persistent photoconductivity, and ESR spectroscopy.
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Laser processing of structure sensitive hypereutectic ductile iron, a cast alloy employed for dynamically loaded automative components, was experimentally investigated over a wide range of process parameters: from power (0.5-2.5 kW) and scan rate (7.5-25 mm s(-1)) leading to solid state transformation, all the way through to melting followed by rapid quenching. Superfine dendritic (at 10(5) degrees C s(-1)) or feathery (at 10(4) degrees C s(-1)) ledeburite of 0.2-0.25 mu m lamellar space, gamma-austenite and carbide in the laser melted and martensite in the transformed zone or heat-affected zone were observed, depending on the process parameters. Depth of geometric profiles of laser transformed or melt zone structures, parameters such as dendrile arm spacing, volume fraction of carbide and surface hardness bear a direct relationship with the energy intensity P/UDb2, (10-100 J mm(-3)). There is a minimum energy intensity threshold for solid state transformation hardening (0.2 J mm(-3)) and similarly for the initiation of superficial melting (9 J mm(-3)) and full melting (15 J mm(-3)) in the case of ductile iron. Simulation, modeling and thermal analysis of laser processing as a three-dimensional quasi-steady moving heat source problem by a finite difference method, considering temperature dependent energy absorptivity of the material to laser radiation, thermal and physical properties (kappa, rho, c(p)) and freezing under non-equilibrium conditions employing Scheil's equation to compute the proportion of the solid enabled determination of the thermal history of the laser treated zone. This includes assessment of the peak temperature attained at the surface, temperature gradients, the freezing time and rates as well as the geometric profile of the melted, transformed or heat-affected zone. Computed geometric profiles or depth are in close agreement with the experimental data, validating the numerical scheme.
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Chalcogenide glasses with compositions Ge7.5AsyTe92.5-y (y = 20, 40, 45, 47.5, 50, 52.5, 55) and Ge10AsyTe90-y (y = 15, 20, 22.5, 35, 40, 45, 50) have been prepared by the melt-quenching technique. The amorphous nature of these glasses has been confirmed by X-ray powder diffractometry. The thermal stability of these glasses has been studied using differential scanning calorimetry (DSC). The compositional dependence of the glass transition temperature, T(g), the crystallization temperatures, T(c1) and T(c2), and the melting temperature, T(m), are reported. The glass-forming tendency, K(gl), and the activation energy of crystallization, E, are calculated. The activation energy decreases with increasing tellurium content for both sets of glasses.
Resumo:
The standard Gibbs energies of formation of lanthanum orthoferrite (LaFeO3-delta) and hexaferrite (LaFe12O19)were determined using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte and pure oxygen gas at ambient pressure as the reference electrode. From emf of the solid-state cell, the Gibbs energy of formation of nonstoichiometric orthoferrite (LaFeO3-delta) is obtained. To derive values for the stoichiometric phase, variation of the oxygen nonstoichiometric parameter with oxygen partial pressure was measured using thermogravimetry under controlled gas mixtures. The results obtained for LaFeO3 and LaFe12O19 can be summarized by the following equations, which represent the formation of ternary oxides from their component binary oxides: 1/2 La2O3 + 1/2 Fe2O3 -> LaFeO3: Delta G degrees (LaFeO3) (+/- 450) (J mol(-1)) = -62920 - 2.12T (K), and 1/2 La2O3 + 9/2Fe(2)O(3) + Fe3O4 -> LaFe12O19; Delta G degrees (LaFe12O19) (+/- 200) (J mol(-1)) = -103900 + 21.25T (K). These data are discussed critically in comparison with thermodynamic values reported in the literature from a variety of measurements. The values obtained in this study are consistent with calorimetric entropy and enthalpy of formation of the perovskite phase and with some of the Gibbs energy measurements reported in the literature. For the lanthanum hexaferrite (LaFe12O19) there are no prior thermodynamic measurements for comparison. (c) 2011 Elsevier B.V. All rights reserved.
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Geometry and energy of argon clusters confined in zeolite NaCaA are compared with those of free clusters. Results indicate the possible existence of magic numbers among the confined clusters. Spectra obtained from instantaneous normal mode analysis of free and confined clusters give a larger percentage of imaginary frequencies for the latter indicating that the confined cluster atoms populate the saddle points of the potential energy surface significantly. The variation of the percentage of imaginary frequencies with temperature during melting is akin to the variation of other properties. It is shown that confined clusters might exhibit inverse surface melting, unlike medium-to-large-sized free clusters that exhibit surface melting. Configurational-bias Monte Carte (CBMC) simulations of n-alkanes in zeolites Y and A are reported. CBMC method gives reliable estimates of the properties relating to the conformation of molecules. Changes in the conformational properties of n-butane and other longer n-alkanes such as n-hexane and n-heptane when they are confined in different zeolites are presented. The changes in the conformational properties of n-butane and n-hexane with temperature and concentration is discussed. In general, in zeolite Y as well as A, there is significant enhancement of the gauche population as compared to the pure unconfined fluid.
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Nanometric granular materials represent a new class of materials with significant promise. We shall discuss in this paper two phase granular materials where one of the phases having nanometric dimension is embedded in a matrix of larger dimension. These materials show many interesting properties which include structural, magnetic and transport properties, The phase transformation of the embedded particles shows distinctive behavior and yields new insight. We shall first highlight the strategy of synthesis of these materials through rapid solidification. This will be followed by three examples where the nanoscale dimension of the embedded particles play a unique role. These are melting and solidification of the nanodispersed embedded particles and the superconducting transition. (C) 1997 Elsevier Science S.A.
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The effect of aluminosilicate (Al2SiO5) on the upturn characteristics of ZnO varistor ceramics has been investigated. Addition of Al2SiO5 shifts the point of upturn above 10(4) A cm(-2). The extended nonlinearity in the high current density region is better correlatable to the presence of higher density of trap stales and changing pattern of trap depths at the grain boundary interface as much as the grain interior conductivity. Microstructure studies show the formation and involvement of a liquid phase during sintering. The secondary phases, predominantly are antimony spinel, Zn7Sb2O12, zinc silicate, Zn2SiO4 and magnesium aluminium silicate. MgAl2Si3O10. Energy dispersive X-ray analyses (EDAX) show that Al and Si are distributed more in the grain boundaries and within the secondary phases than in the grain interiors. Capacitance-voltage analyses and dielectric dispersion studies indicate the presence of negative capacitance and associated resonance, indicative of the oscillatory charge redistribution involving increased trapping at the interface states. The admittance spectroscopy data show that the type of trap slates remains unaltered whereas the addition of Al2SiO5 increases the density of low energy traps. (C) 1997 Published by Elsevier Science S.A.
Resumo:
Silane (SiH4) was used as an n-type dopant in GaAs grown by low pressure metalorganic vapor phase epitaxy using trimethylgallium (TMGa) and arsine (AsH3) as source materials. The electron carrier concentrations and silicon (Si) incorporation efficiency are studied by using Hall effect, electrochemical capacitance voltage profiler and low temperature photoluminescence (LTPL) spectroscopy. The influence of growth parameters, such as SiH4 mole fraction, growth temperature, TMGa and AsH3 mole fractions on the Si incorporation efficiency have been studied. The electron concentration increases with increasing SIH4 mole fraction, growth temperature, and decreases with increasing TMGa and AsH3 mole fractions. The decrease in electron concentration with increasing TMGa can be explained by vacancy control model. The PL experiments were carried out as a function of electron concentration (10(17) - 1.5 x 10(18) cm(-3)). The PL main peak shifts to higher energy and the full width at half maximum (FWHM) increases with increasing electron concentrations. We have obtained an empirical relation for FWHM of PL, Delta E(n) (eV) = 1.4 x 10(-8) n(1/3). We also obtained an empirical relation for the band gap shrinkage, Delta E-g in Si-doped GaAs as a function of electron concentration. The value of Delta E-g (eV) = -2.75 x 10(-8) n(1/3), indicates a significant band gap shrinkage at high doping levels. These relations are considered to provide a useful tool to determine the electron concentration in Si-doped GaAs by low temperature PL measurement. The electron concentration decreases with increasing TMGa and AsH3 mole fractions and the main peak shifts to the lower energy side. The peak shifts towards the lower energy side with increasing TMGa variation can also be explained by vacancy control model. (C) 1999 Elsevier Science S.A. All rights reserved.
Resumo:
The present research describes the modeling of the thermodynamic properties of the liquid Al-Ga-In-As alloys at 1073 and 1173 K, and investigates the solid-liquid equilibria in the systems. The isothermal molar excess free energy function for the liquid alloys is represented in terms of 37 parameters pertaining to six of the constituent binaries, four ternaries and the quaternary interactions in the system. The corresponding solid alloys which consist of AlAs, GaAs and InAs are assumed to be quasi-regular ternary solutions. The solidus and liquidus compositions are calculated at 1073 and 1173 K using the derived values of the partial components for the solid and liquid alloys at equilibrium. They are in good agreement with those of the experimentally determined values available in the literature. (C) 1999 Elsevier Science S.A. All rights reserved.