High temperature stability of oxysulfides containing Ce3+ and Y3+ ions

Standard Gibbs energies of formation of oxysulfides of cerium and yttrium from their respective oxedes were determined using solid oxide galvanic cells incorporating calcia-stabilized zirconia as the electrolyte in the temperature range 870–1120 K. The sulfur potential over the electrode containing the oxide and oxysulfide was fixed by a buffer mixture of Ag + Ag2S. A small amount of CaH2 was added to the buffer to generate an equilibrium ratio of H2S and H2 species in a closed system containing the buffer and the electrode. The sulfur potential is transmitted to the electrode via the gas phase. The results can be summarized by the equations 2left angle bracketCeO2right-pointing angle bracket+1/2(S2)→left angle bracketCe2O2Sright-pointing angle bracket+(O2) ΔG°=430600−109·7T(±400)J mol−1 left angle bracketY2O3right-pointing angle bracket+1/2(S2)→left angle bracketY2O2Sright-pointing angle bracket+1/2(O2) ΔG°=114780−1·45T(±200)J mol−1 The values are compared with data reported in the literature. The stability field diagram for the Ce---O---S system has been developed using the results of this study for Ce2O2S and data for other phases from the literature.

Axisymmetric melting of a long cylinder due to an infinite flux

By employing a new embedding technique, a short-time analytical solution for the axisymmetric melting of a long cylinder due to an infinite flux is presented in this paper. The sufficient condition for starting the instantaneous melting of the cylinder has been derived. The melt is removed as soon as it is formed. The method of solution is simple and straightforward and consists of assuming fictitious initial temperature for some fictitious extension of the actual region.

Thermal studies on melting and crystallization of polyamide fibres

Effect of heating rate on melting and crystallization of polyamide fibres has been examined using differential scanning calorimetric (DSC) technique. Peak temperature for melting (T m) and crystallization (T k) get suppressed with the increase in the heating rate which has been explained on the basis of chain orientation. Heat of melting (DeltaH m) and crystallization (DeltaH k) have been measured.DeltaH m vs. T m shows a nonlinear dependence which has been explained on the basis of entropy change. Quantitative difference inDeltaH m andDeltaH k values has been explained on the basis of orientation and degradation of the polymer.

Non-equilibrium trapping in Al---In system

The comparative trapping efficiency of indium in aluminium solid solution during vapour deposition and rapid solidification at room temperature was evaluated by studying the nature of the decomposition of the metastable solid solution. A spinodal decomposition was observed in the case of rapid solidification while vapour deposited foils decompose by a nucleation and growth type of process. From this we conclude that rapid solidification effects a more efficient non-equilibrium trapping of indium in aluminium solid solution compared to vapour deposition at room temperature.

CFD analysis of high frequency miniature pulse tube refrigerators for space applications with thermal non-equilibrium model

High frequency, miniature, pulse tube cryocoolers are extensively used in space applications because of their simplicity. Parametric studies of inertance type pulse tube cooler are performed with different length-to-diameter ratios of the pulse tube with the help of the FLUENT (R) package. The local thermal non-equilibrium of the gas and the matrix is taken into account for the modeling of porous zones, in addition to the wall thickness of the components. Dynamic characteristics and the actual mechanism of energy transfer in pulse are examined with the help of the pulse tube wall time constant. The heat interaction between pulse tube wall and the oscillating gas, leading to surface heat pumping, is quantified. The axial heat conduction is found to reduce the performance of the pulse tube refrigerator. The thermal non-equilibrium predicts a higher cold heat exchanger temperature compared to thermal equilibrium. The pressure drop through the porous medium has a strong non-linear effect due to the dominating influence of Forchheimer term over that of the linear Darcy term at high operating frequencies. The phase angle relationships among the pressure, temperature and the mass flow rate in the porous zones are also important in determining the performance of pulse tuberefrigerator.

Melting of an Anchored Bilayer: Phase Transitions in the Organic-Inorganic Hybrid Pervoskite (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 (n=11, 13, 15, 17)

The conformation, organization, and phase transitions of alkyl chains in organic-inorganic hybrids based on the double pervoskite-slab lead iodides, (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 (n = 11, 13, 15, 17) have been investigated by X-ray diffraction, calorimetry, and infrared vibrational spectroscopy. In these hybrid solids, double pervoskite (CH3NH3)Pb2I7 slabs are interleaved with alkyl ammonium chains with the anchored alkyl chains arranged as tilted bilayers and adopting a planar all-trans conformation at room temperature. The (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 compounds exhibit a single reversible phase transition above room temperature with the associated enthalpy change varying linearly with alkyl chain length. This transition corresponds to the melting in two-dimensions of the alkyl chains of the anchored bilayer and is characterized by increased conformational disorder of the methylene units of the chain and loss of tilt angle coherence leading to an increase in the interslab spacing. By monitoring features in the infrared spectra that are characteristic of the global conformation of the alkyl chains, a quantitative relation between conformational disorder and melting of the anchored bilayer is established. It is found that, irrespective of the alkyl chain length, melting occurs when at least 60% of the chains in the anchored bilayer of (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 have one or more gauche defects. This concentration is determined by the underlying lattice to which the alkyl chains are anchored.

Turbulence-induced melting of a nonequilibrium vortex crystal in a forced thin fluid film

To gain a better understanding of recent experiments on the turbulence-induced melting of a periodic array of vortices in a thin fluid film, we perform a direct numerical simulation of the two-dimensional Navier-Stokes equations forced such that, at low Reynolds numbers, the steady state of the film is a square lattice of vortices. We find that as we increase the Reynolds number, this lattice undergoes a series of nonequilibrium phase transitions, first to a crystal with a different reciprocal lattice and then to a sequence of crystals that oscillate in time. Initially, the temporal oscillations are periodic; this periodic behaviour becoming more and more complicated with increasing Reynolds number until the film enters a spatially disordered nonequilibrium statistical steady state that is turbulent. We study this sequence of transitions using fluid-dynamics measures, such as the Okubo-Weiss parameter that distinguishes between vortical and extensional regions in the flow, ideas from nonlinear dynamics, e.g. Poincare maps, and theoretical methods that have been developed to study the melting of an equilibrium crystal or the freezing of a liquid and that lead to a natural set of order parameters for the crystalline phases and spatial autocorrelation functions that characterize short- and long-range order in the turbulent and crystalline phases, respectively.

Low-Temperature Processing of ZrB2-ZrC Composites by Reactive Hot Pressing

Dense ZrB2-ZrC and ZrB2-ZrC x∼0.67 composites have been produced by reactive hot pressing (RHP) of stoichiometric and nonstoichiometric mixtures of Zr and B4C powders at 40 MPa and temperatures up to 1600 °C for 30 minutes. The role of Ni addition on reaction kinetics and densification of the composites has been studied. Composites of ∼97 pct relative density (RD) have been produced with the stoichiometric mixture at 1600 °C, while the composite with ∼99 pct RD has been obtained with excess Zr at 1200 °C, suggesting the formation of carbon deficient ZrC x that significantly aids densification by plastic flow and vacancy diffusion mechanism. Stoichiometric and nonstoichiometric composites have a hardness of ∼20 GPa. The grain sizes of ZrB2 and ZrC x∼0.67 are ∼0.6 and 0.4 μm, respectively, which are finer than those reported in the literature.

Melting of an Anchored Bilayer: Molecular Dynamics Simulations of the Structural Transition in (CnH2n+1NH3)(2)PbI4 (n=12, 14, 16, 18)

The thermally driven Structural phase transition in the organic-inorganic hybrid perovskite (CnH2n+1NH3)(2)PbI4 has been investigated using molecular dynamics (MD) simulations. This system consists of positively charged alkyl-amine chains anchored to a rigid negatively charged PbI4 sheet with the chains organized as bilayers with a herringbone arrangement. Atomistic simulations were performed using ail isothermal-isobaric ensemble over a wide temperature range from 65 to 665 K for different alkyl chain lengths, n = 12, 14, 16, and 18. The simulations are able to reproduce the essential Features of the experimental observations of this system, including the existence of a transition, the linear variation of the transition temperature with alkyl chain length, and the expansion of the bilayer thickness at the transition. By use of the distance fluctuation Criteria, it is Shown that the transition is associated With a Melting of the alkyl chains of the anchored bilayer. Ail analysis of the conformation of the alkyl chains shows increased disorder in the form of gauche defects above due melting transition. Simulations also show that the melting transition is characterized by the complete disappearance of all-trans alkyl chains in the anchored bilayer, in agreement with experimental observations. A conformationally disordered chain has a larger effective cross-sectional area, and above due transition a uniformly tilted arrangement of the anchored chains call no longer be Sustained. At the melt the angular distribution of the orientation of the chains are 110 longer uniform; the chains are splayed allowing for increased space for individual chains of the anchored bilayer. This is reflected in a sharp rise in the ratio of the mean head-to-head to tail-to-tail distance of the chains of the bilayer at the transition resulting in in expansion of the bilayer thickness. The present MD simulations provide a simple explanation as to how changes in conformation of individual alkyl-chains gives rise to the observed increase in the interlayer lattice spacing of (CnH2n+1NH3)(2)PbI4 at the melting transition.

Novel fluorescence detection technique for non-contact temperature sensing in microchip PCR

DNA amplification using Polymerase Chain Reaction (PCR) in a small volume is used in Lab-on-a-chip systems involving DNA manipulation. For few microliters of volume of liquid, it becomes difficult to measure and monitor the thermal profile accurately and reproducibly, which is an essential requirement for successful amplification. Conventional temperature sensors are either not biocompatible or too large and hence positioned away from the liquid leading to calibration errors. In this work we present a fluorescence based detection technique that is completely biocompatible and measures directly the liquid temperature. PCR is demonstrated in a 3 ILL silicon-glass microfabricated device using non-contact induction heating whose temperature is controlled using fluorescence feedback from SYBR green I dye molecules intercalated within sensor DNA. The performance is compared with temperature feedback using a thermocouple sensor. Melting curve followed by gel electrophoresis is used to confirm product specificity after the PCR cycles. (c) 2007 Elsevier B.V. All rights reserved.

Phase-Field Simulation of Fusion Interface Events during Solidification of Dissimilar Welds: Effect of Composition Inhomogeneity

We investigate the events near the fusion interfaces of dissimilar welds using a phase-field model developed for single-phase solidification of binary alloys. The parameters used here correspond to the dissimilar welding of a Ni/Cu couple. The events at the Ni and the Cu interface are very different, which illustrate the importance of the phase diagram through the slope of the liquidus curves. In the Ni side, where the liquidus temperature decreases with increasing alloying, solutal melting of the base metal takes place; the resolidification, with continuously increasing solid composition, is very sluggish until the interface encounters a homogeneous melt composition. The growth difficulty of the base metal increases with increasing initial melt composition, which is equivalent to a steeper slope of the liquidus curve. In the Cu side, the initial conditions result in a deeply undercooled melt and contributions from both constrained and unconstrained modes of growth are observed. The simulations bring out the possibility of nucleation of a concentrated solid phase from the melt, and a secondary melting of the substrate due to the associated recalescence event. The results for the Ni and Cu interfaces can be used to understand more complex dissimilar weld interfaces involving multiphase solidification.

Orientational melting and reorientational motion in a cubane molecular crystal: A molecular simulation study

Detailed molecular simulations are carried out to investigate the effect of temperature on orientational order in cubane molecular crystal. We report a transition from an orientationally ordered to an orientationally disordered plastic crystalline phase in the temperature range 425-450 K. This is similar to the experimentally reported transition at 395 K. The nature of this transition is first order and is associated with a 4.8% increase in unit Cell volume that is comparable to the experimentally reported unit cell volume change of 5.4% (Phys. Rev. Lett. 1997, 78, 4938). An orientational order parameter, eta(T), has been defined in terms of average angle of libration of a molecular 3-fold axis and the orientational melting has been characterized by using eta(T). The orientational melting is associated with an anomaly in specific heat at constant pressure (C-p) and compressibility (kappa). The enthalpy of transition and entropy of transition associated with this orientational melting are 20.8 J mol(-1) and 0.046 J mol(-1) K-1, respectively. The structure of crystalline as well as plastic crystalline phases is characterized by using various radial distribution functions and orientational distribution functions. The coefficient of thermal expansion of the plastic crystalline phase is more than twice that of the crystalline phase.

Electron temperature distribution across a shock wave in a partially ionized gas

The electron temperature structure in a weakly ionized plasma is studied allowing the degree of ionization to vary across the shock wave. The values of the electron temperature and the downstream equilibrium temperature obtained with variable ionization are less than those for frozen ionization. The electron temperature rises sharply behind the shock for variable ionization while a gradual increase is predicted by frozen ionization.

Investigations on the melting and bending modulus of polymer grafted bilayers using dissipative particle dynamics

Understanding the influence of polymer grafted bilayers on the physicomechanical properties of lipid membranes is important while developing liposomal based drug delivery systems. The melting characteristics and bending moduli of polymer grafted bilayers are investigated using dissipative particle dynamics simulations as a function of the amount of grafted polymer and lipid tail length. Simulations are carried out using a modified Andersen barostat, whereby the membrane is maintained in a tensionless state. For lipids made up of four to six tail beads, the transition from the low temperature L-beta phase to the L-alpha phase is lowered only above a grafting fraction of G(f)=0.12 for polymers made up of 20 beads. Below G(f)=0.12 small changes are observed only for the HT4 bilayer. The bending modulus of the bilayers is obtained as a function of G(f) from a Fourier analysis of the height fluctuations. Using the theory developed by Marsh Biochim. Biophys. Acta 1615, 33 (2003)] for polymer grafted membranes, the contributions to the bending modulus due to changes arising from the grafted polymer and bilayer thinning are partitioned. The contributions to the changes in kappa from bilayer thinning were found to lie within 11% for the lipids with four to six tail beads, increasing to 15% for the lipids containing nine tail beads. The changes in the area stretch modulus were also assessed and were found to have a small influence on the overall contribution from membrane thinning. The increase in the area per head group of the lipids was found to be consistent with the scalings predicted by self-consistent mean field results. (C) 2010 American Institute of Physics.

Heterogeneous nucleation of solidification of cadmium particles embedded in an aluminium matrix

A hypomonotectic alloy of Al-4.5wt%Cd has been manufactured by melt spinning and the resulting microstructure examined by transmission electron microscopy. As-melt spun hypomonotectic Al-4.5wt%Cd consists of a homogeneous distribution of faceted 5 to 120 nm diameter cadmium particles embedded in a matrix of aluminium, formed during the monotectic solidification reaction. The cadmium particles exhibit an orientation relationship with the aluminium matrix of {111}Al//{0001}Cd and lang110rangAlAl//lang11¯20> Cd, with four cadmium particle variants depending upon which of the four {111}Al planes is parallel to {0001}Cd. The cadmium particles exibit a distorted cuboctahedral shape, bounded by six curved {100}Al//{20¯23}Cd facets, six curved {111}Al/{40¯43}Cd facets and two flat {111}Al//{0001}Cd facets. The as-melt spun cadmium particle shape is metastable and the cadmium particles equilibrate during heat treatment below the cadmium melting point, becoming elongated to increase the surface area and decrease the separation of the {111}Al//{0001}Cd facets. The equilibrium cadmium particle shape and, therefore, the anisotropy of solid aluminium-solid cadmium and solid aluminium -liquid cadmium surface energies have been monitored by in situ heating in the transmission electron microscope over the temperature range between room temperature and 420 °C. The anisotropy of solid aluminium-solid cadmium surface energy is constant between room temperature and the cadmium melting point, with the {100}Al//{20¯23}Cd surface energy on average 40% greater than the {111}Al//{0001}Cd surface energy, and 10% greater than the {111}Al//{40¯43Cd surface energy. When the cadmium particles melt at temperatures above 321 °C, the {100}Al//{20¯23}Cd facets disappear and the {111}Al//{40¯43}Cd and {111}A1//{0001}Cd surface energies become equal. The {111}Al facets do not disappear when the cadmium particles melt, and the anisotropy of solid aluminium-liquid cadmium surface energy decreases gradually with increasing temperature above the cadmium melting point. The kinetics of cadmium solidification have been examined by heating and cooling experiments in a differential scanning calorimeter over a range of heating and cooling rates. Cadmium particle solidification is nucleated catalytically by the surrounding aluminium matrix on the {111}Al faceted surfaces, with an undercooling of 56 K and a contact angle of 42 °. The nucleation kinetics of cadmium particle solidification are in good agreement with the hemispherical cap model of heterogeneous nucleation.