Electrochemical phase formation involving multicomponents: hemispherical overlap models for varied nucleation and growth conditions

The phenomenological theory of hemispherical growth in the context of phase formation with more than one component is presented. The model discusses in a unified manner both instantaneous and progressive nucleation (at the substrate) as well as arbitrary growth rates (e.g. constant and diffusion controlled growth rates). A generalized version of Avrami ansatz (a mean field description) is used to tackle the ''overlap'' aspects arising from the growing multicentres of the many components involved, observing that the nucleation is confined to the substrate plane only. The time evolution of the total extent of macrogrowth as well as those of the individual components are discussed explicitly for the case of two phases. The asymptotic expressions for macrogrowth are derived. Such analysis depicts a saturation limit (i.e. the maximum extent of growth possible) for the slower growing component and its dependence on the kinetic parameters which, in the electrochemical context, can be controlled through potential. The significance of this model in the context of multicomponent alloy deposition and possible future directions for further development are pointed out.

Metastable extension of the fluorite phase field in Y2O3---ZrO2 and its effect on grain growth

Pure Y2O3 and Y2O3---ZrO2 solid solutions have been prepared by melt atomization and by pyrolysis of nitrate solutions. Extended solubility is readily achieved in both techniques for the entire composition range investigated: melts with 0–30% ZrO2 and precursors with 0–50% ZrO2. However, solidification of under cooled droplets yields almost exclusively single phase powders with the structure of cubic yttria (D53). In contrast, the pyrolysis route leads to a sequence of metastable microstructures beginning with a nanocrystalline disordered fluorite-based (C1) solid solution. Further heating leads to the evolution of much larger (micron size) flake crystals with a {001} texture, concurrent with partial ordering of the oxygen ions to the sites occupied in the D53 structure. The driving force for ordering and the rate of grain growth decrease with increasing ZrO2 addition. Abrupt heating to high temperatures or electron irradiation can induce ordering without substantial grain growth. There is no significant reduction in porosity during the recrystallization, which with the other observations suggests that grain growth is driven by the free energy available for the ordering transformation from fluorite to the yttria structure. This route offers opportunities for single crystal thin film development at relatively low processing temperatures.

Electrical switching studies on Ge-Te-Tl chalcogenide glasses: Effect of thallium on the composition dependence of switching voltages

Bulk Ge(17)Te83_,JI glasses (05x.5_13), have been found to exhibit memory type electrical switching. The switching voltages (also known as threshold voltage V-th) of Ge17Te83-xTlx glasses are found to decrease with increasing thallium content. The rate of decrease of Vtry is greater at lower concentrations and \textbackslashid, falls at a slower rate for higher thallium concentrations (x 6). The addition of thallium to the Ge-Te network fragments the covalent network and introduces ionic nature to it; the reduction in network connectivity leads to the decrease in switching voltages with thallium content. The decrease in the glass transition temperatures of Ge17Te83-xTlx glasses with increasing thallium concentration supports the idea of decrease in network connectivity with TI addition. The more metallic nature of TI also contributes to the observed reduction in the switching voltages of Ge17Te83-xTlx glasses with TI content. Further, there is an interesting correlation seen between the threshold voltage V-th and the average bond energy, as a function of TI content. In addition, the switching voltages of Ge17Te83-xTlx glasses have been found to decrease with sample thickness almost linearly. The set-reset studies indicate that the Ge17Te83-xTl2 sample can be switched for more than 10 cycles, whereas other glasses could not be reset beyond two switching cycles. (C) 2010 Elsevier B.V. All rights reserved.

Metastable extension of the fluorite phase field in Y2O3---ZrO2 and its effect on grain growth

Pure Y2O3 and Y2O3-ZrO2 solid solutions have been prepared by melt atomization and by pyrolysis of nitrate solutions. Extended solubility is readily achieved in both techniques for the entire composition range investigated: melts with 0-30% ZrO2 and precursors with 0-50% ZrO2. However, solidification of under cooled droplets yields almost exclusively single phase powders with the structure of cubic yttria (D5(3)). In contrast, the pyrolysis route leads to a sequence of metastable microstructures beginning with a nanocrystalline disordered fluorite-based (C1) solid solution. Further heating leads to the evolution of much larger (micron size) flake crystals with a {001} texture, concurrent with partial ordering of the oxygen ions to the sites occupied in the D5(3) structure. The driving force for ordering and the rate of grain growth decrease with increasing ZrO2 addition. Abrupt heating to high temperatures or electron irradiation can induce ordering without substantial grain growth. There is no significant reduction in porosity during the recrystallization, which with the other observations suggests that grain growth is driven by the free energy available for the ordering transformation from fluorite to the yttria structure. This route offers opportunities for single crystal thin film development at relatively low processing temperatures.

Non-Linear effects of membrane fluctuations in the dilute lamellar phase

The static structure factor of the dilute sterically stabilised lamellar phase is calculated and found to have an Ornstein-Zernike form with a correlation length that diverges at infinite dilution. The relaxation time for concentration fluctuations at large wave number q is shown to go as q-3 with a coefficient independent of the membrane bending rigidity. The membrane fluctuations also give rise to strongly frequency-dependent viscosities at high frequencies.

Orientational ordering in C70. Evidence for three distinct phase transitions

Variable-temperature X-ray diffraction studies of C70 suggest the occurrence of two phase transitions around 350 and 280 K where the high-temperature phase is fcc and the low-temperature phase is monoclinic, best described as a distorted hcp structure with a doubled unit cell; two like-phases (possibly hcp) seem to coexist in the 280-350 K range. Application of pressure gives rise to three distinct transitions associated with characteristic pressure coefficients, the extrapolated values of the transition temperatures at ambient pressure being around 340, 325 and 270 K. Pressure delineates closely related phases Of C70 just as in the case Of C60 which exhibits two orientational phase transitions at high pressures.

Phase relations and gibbs energies in the system Mn-Rh-O

Phase relations in the system Mn-Rh-O are established at 1273 K by equilibrating different compositions either in evacuated quartz ampules or in pure oxygen at a pressure of 1.01 x 10(5) Pa. The quenched samples are examined by optical microscopy, X-ray diffraction, and energy-dispersive X-ray analysis (EDAX). The alloys and intermetallics in the binary Mn-Rh system are found to be in equilibrium with MnO. There is only one ternary compound, MnRh2O4, with normal spinel structure in the system. The compound Mn3O4 has a tetragonal structure at 1273 K. A solid solution is formed between MnRh2O4 and Mn3O4. The solid solution has the cubic structure over a large range of composition and coexists with metallic rhodium. The partial pressure of oxygen corresponding to this two-phase equilibrium is measured as a function of the composition of the spinel solid solution and temperature. A new solid-state cell, with three separate electrode compartments, is designed to measure accurately the chemical potential of oxygen in the two-phase mixture, Rh + Mn3-2xRh2xO4, which has 1 degree of freedom at constant temperature. From the electromotive force (emf), thermodynamic mixing properties of the Mn3O4-MnRh2O4 solid solution and Gibbs energy of formation of MnRh2O4 are deduced. The activities exhibit negative deviations from Raoult's law for most of the composition range, except near Mn3O4, where a two-phase region exists. In the cubic phase, the entropy of mixing of the two Rh3+ and Mn3+ ions on the octahedral site of the spinel is ideal, and the enthalpy of mixing is positive and symmetric with respect to composition. For the formation of the spinel (sp) from component oxides with rock salt (rs) and orthorhombic (orth) structures according to the reaction, MnO (rs) + Rh2O3 (orth) --> MnRh2O4 (sp), DELTAG-degrees = -49,680 + 1.56T (+/-500) J mol-1. The oxygen potentials corresponding to MnO + Mn3O4 and Rh + Rh2O3 equilibria are also obtained from potentiometric measurements on galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte. From these results, an oxygen potential diagram for the ternary system is developed.

Phase-relations in the system CAO-SIO2-ZRO2 AT 1573-K

Zirconia-based solid electrolytes with zircon (ZrSiO4) as the auxiliary electrode have been suggested of sensing silicon concentrations in iron and steel melts. A knowledge of phase relations in the ternary system MO-SiO2-ZrO2 (M = Ca, Mg) is useful for selecting an appropriate auxiliary electrode. In this investigation, an isothermal section for the phase diagram of the system CaO-SiO2ZrO2 at 1573 K has been established by equilibrating mixtures of component oxides in air, followed by quenching and phase identification by optical miroscopy, energy disperse analysis of X-rays (EDAX) and X-ray diffraction analysis (XRD). The equilibrium phase relations have also been confirmed by computation using the available thermodynamic data on condensed phases in the system. The results indicate that zircon is not in thermodynamic equilibrium with calcia-stabilized zirconia or calcium zirconate. The silica containing phase in equilibrium with stabilized zirconia is Ca3ZrSi2O9. Calcium zirconate can coexist with Ca3ZrSi2O9 and Ca2SiO4.

Phase relations in the system Cu─Ho─O and stability of Cu2Ho2O5

The phase relations in the system Cu-Ho-O have been determined at 1300 K using X-ray diffraction, optical microscopy, and electron microprobe analysis of samples equilibrated in evacuated quartz ampules and in pure oxygen. Only one ternary compound, Cu2Ho2O5, was found to be stable. The Gibbs free energy of formation of this compound has been measured using the solid-state cell Pt,Cu2O + Cu2Ho2O5 + Ho2O3/(Y2O3)ZrO2/CuO + Cu2O,Pt in the temperature range of 973 to 1350 K. For the formation of Cu2Ho2O5 from its binary component oxides, 2CuO(s) + Ho2O3(S) --> Cu2Ho2O5(s) DELTAG-degrees = 11190 - 13.8T(+/- 120) J-mol-1 Since the formation is endothermic, CU2Ho2O5 becomes thermodynamically unstable with respect to CuO and Ho2O3 below 810 K. When the oxygen partial pressure over Cu2Ho2O5 is lowered, it decomposes according to the reaction 2Cu2Ho2O5(s) --> 2Ho2O3(s) + 2Cu2O(S) + O2(g) for which the equilibrium oxygen potential is given by DELTAmu(O2) = - 238510 + 160.2T(+/- 450) J.mol-1 The decomposition temperature at an oxygen partial pressure of 1.52 x 10(4) Pa was measured using a combined DTA-TGA apparatus. Based on these results, an oxygen potential diagram for the system Cu-Ho-O at 1300 K is presented.

Phase separation in critical and off-critical fluids: specific experimental behaviours at criticality

The phase separation in fluids close to a critical point can be observed in the form of either an interconnected pattern (critical case) or a disconnected pattern (off-critical case). These two regimes have been investigated in different ways. First, a sharp change in pattern is shown to occur very close to the critical point when the composition is varied. No crossover has been observed between the t1 behaviour (interconnected) and a t1/3 behaviour (disconnected), where t is time. This latter growth law, which occurs in the case of compact droplets, will be discussed. Second, it has been observed that a growing interconnected pattern leaves a signature in the form of small droplets. The origin of such a distribution will be discussed in terms of coalescence of domains. No distribution of this kind is observed in the off-critical case.

Raman phase conjugator

We have developed a multipurpose high pressure gas cell which can be used to generate phase conjugate beams using various stimulated scattering processes. This high pressure cell can also be used as a tunable laser source using the process of stimulated Raman scattering. The phase conjugate nature of backward scattered Raman signals was investigated through distortion correction studies.

Synthesis of Cuprates of Perovskite Structure in the Ba-Pb-Cu-O, Ba-Bi-Cu-O, and Ba-Pb-Tl-Cu-O Systems: Possible High Tc Superconductivity in a Perovskite-like Phase in the Ba-Pb-Tl-Cu-O System

Cubic cuprates (a not, vert, similar 18.6 Å) with a BaCuO2-type structure were obtained in the Ba-Pb-Cu-O and Ba-Bi-Cu-O systems by the reaction of the component oxides at a high temperature (1370-1420 K), followed by quenching. By annealing these phases in oxygen at 1070-1120 K, perovskite-like phase (a not, vert, similar 4.3 Å) of the formulae BaPb1-xCuxO3-y and BaBi1-xCuxO3-y (0 < x ? 0.5) were obtained. A perovskite of nominal composition BaPb0.25Tl0.25 Cu0.5O3-y, prepared by a similar procedure, was found to be superconducting with a Tc of not, vert, similar 70 K.

Inherent structures of phase-separating binary mixtures: Nucleation, spinodal decomposition, and pattern formation

An energy landscape view of phase separation and nonideality in binary mixtures is developed by exploring their potential energy landscape (PEL) as functions of temperature and composition. We employ molecular dynamics simulations to study a model that promotes structure breaking in the solute-solvent parent binary liquid, at low temperatures. The PEL of the system captures the potential energy distribution of the inherent structures (IS) of the system and is obtained by removing the kinetic energy (including that of intermolecular vibrations). The broader distribution of the inherent structure energy for structure breaking liquid than that of the structure making liquid demonstrates the larger role of entropy in stabilizing the parent liquid of the structure breaking type of binary mixtures. At high temperature, although the parent structure of the structure breaking binary mixture is homogenous, the corresponding inherent structure is found to be always phase separated, with a density pattern that exhibits marked correlation with the energy of its inherent structure. Over a broad range of intermediate inherent structure energy, bicontinuous phase separation prevails with interpenetrating stripes as signatures of spinodal decomposition. At low inherent structure energy, the structure is largely phase separated with one interface where as at high inherent structure energy we find nucleation type growth. Interestingly, at low temperature, the average inherent structure energy (< EIS >) exhibits a drop with temperature which signals the onset of crystallization in one of the phases while the other remains in the liquid state. The nonideal composition dependence of viscosity is anticorrelated with average inherent structure energy.

Supersolid Phase in One-Dimensional Bose-Hubbard Model With Extended Range Interactions: DMRG And Field Theoretic Study at Different Densities

We use the Density Matrix Renormalization Group and the Abelian bosonization method to study the effect of density on quantum phases of one-dimensional extended Bose-Hubbard model. We predict the existence of supersolid phase and also other quantum phases for this system. We have analyzed the role of extended range interaction parameters on solitonic phase near half-filling. We discuss the effects of dimerization in nearest neighbor hopping and interaction as well as next nearest neighbor interaction on the plateau phase at half-filling.