Phase transitions of adsorbed fluids computed from multiple-histogram reweighting

This paper demonstrates the effectiveness of using multiple-histogram reweighting (MHR) to study phase transitions in confined fluids by examining capillary condensation, prewetting, and layering transitions for different systems. A comparison is made with previously published simulations, where available, to establish the accuracy of MHR as applied to inhomogeneous systems. Overlap between adjacent state points is assessed through single-histogram reweighting. Capillary condensation for methane adsorption in slit-like graphite pores exhibits 2D behaviour. Crossover of the effective exponent for the width of the coexistence curve from 2D Ising-like (1/8) further away from the critical point to mean-field (1/2) near the critical point is observed. The reduced critical temperature, the density and the effective value of the exponent for the model system are 0.77, 0.482, and 0.119, respectively, based on a fit to the simulation data. Prewetting transitions are observed for adsorption of Ar on solid CO₂ using model potentials. The wetting temperature is estimated based on the intersection of the pre-wetting and bulk vapour-liquid lines, and also by extrapolation to zero of the difference between the saturation and prewetting chemical potentials. The reduced wetting temperature is estimated to be around 0.69. The reduced prewetting critical temperature, calculated from the disappearance of the two peaks in the density probability distribution, is estimated to be 0.92. The monolayer to bilayer (1-2) transition for propane on graphite is computed over a range of temperatures. Results for the 1–2 layering transition computed from MHR from a small system are in good agreement with grand canonical Monte Carlo simulations for a much larger system.     

Quasi-2D and prewetting transitions of square-well fluids on a square-well substrate

Molecular simulation methodologies are employed to study the first-order transition of variable square-well (SW) fluids on a wide range of weak attractive surfaces. Surface phase diagram of SW fluids of attractive well diameter λ _ff = 1.5, 1.75, 2.0 on a smooth, structureless surface modelled by a SW potential is reported via grand-canonical transition-matrix Monte Carlo (GC-TMMC) and histogram reweighting techniques. Fluids with λ _ff = 1.5 and 1.75 show quasi-2D vapour–liquid phase transition; on the other hand, prewetting transition is visible for a SW fluid with larger well-extent λ _ff = 2.0. The prewetting line, its length, and closeness to the bulk saturation curve are found to depend strongly on the nature of the fluid–fluid and fluid–wall interaction potentials. Boundary tension of surface coexistence films is calculated by two methods. First, the finite size scaling approach of Binder is used to evaluate the boundary tension via GC-TMMC. Second, the results of the boundary tension are verified by virtue of its relation to the pressure tensor components, which are calculated using a NVT-Monte Carlo approach. The results from the two methods are in good agreement. Boundary tension is found to increase with the increase in the wall–fluid interaction range for the quasi-2D system; conversely, boundary tension for thin–thick film, at prewetting transition, decreases with the increase in the wall–fluid interaction range.     

Particle size dependence of the superconductivity and ferromagnetism in YBCO nanoparticles

Magnetic properties of superconducting yttrium barium copper oxide (YBa₂Cu₃O_7-δ) nanoparticles (31–43 nm) prepared by a chemical route have been studied. These nanoparticles have been found to clearly exhibit ferromagnetism at room temperature while superconducting transition is observed at lower temperatures. The low temperature hysteresis loops show evidence suggesting the presence of a large paramagnetic contribution in addition to the superconducting contributions from the particles. Bulk YBCO obtained by pelletizing and heating the same nanoparticles at a high temperature, displays the usual superconducting characteristics and gives no trace of ferromagnetism down to 10 K. The superconducting transition temperature of the nanoparticles is lower than for the bulk YBCO and there is a trend of decreasing T _c with smaller size of the particles. In contrast the ferromagnetic moment increases with decreasing particle size. The development of ferromagnetism is attributed to the presence of surface oxygen vacancies that lead to electron redistribution on the different ions at the surface. The simultaneous decrease of superconducting T _c and the increase of ferromagnetism with decreasing size considered as being reflective of the increased role of finite size and surface defects that weaken the superconductivity and enhance the ferromagnetism. Possible coexistence of surface ferromagnetism and bulk superconductivity at lower temperatures is discussed.     

Coexistence of glass and ferroelectric order in deuterated betaine phosphate0.05 betaine phosphite0.95 crystals

The dielectric spectra of ferroelectric hydrogen bonded betaine phosphate_0.05 betaine phosphite_0.95 (DBP_0.05DBPI_0.95) was investigated in the very wide temperature (300–20 K) and frequency (20–35 GHz) regions. The dielectric dispersion was analyzed in terms of distribution of relaxation times, using Tichonov regularization method. Strongly asymmetric and broad distribution of relaxation times below ferroelectric phase transition temperature T _c?≈?253 K clearly differs from the one that is usually observed in ferroelectrics. The observed disorder in deuterons system close to ferroelectric phase transition temperature is an embryo of coexistence ferroelectric order and dipolar glass disorder observed at low temperatures.     

Pulverization of the flux line lattice, the phase coexistence and the spinodal temperature of the order—disorder transition in a weakly pinned crystal of Yb3Rh4Sn13

We have studied metastability effects pertaining to the peak effect (PE) in critical current density (J _c) via isofield scans in AC susceptibility measurements in a weakly pinned single crystal of Yb₃Rh₄Sn₁₃ (T _c(0) ≈ 7.6 K). The order-disorder transition in this specimen proceeds in a multi-step manner. The phase coexistence regime between the onset temperature of the PE and the spinodal temperature (where metastability effects cease) seems to comprise two parts, where ordered and disordered regions dominate the bulk behavior, respectively. The PE line in the vortex phase diagram is argued to terminate at the low field end at a critical point in the elastic (Bragg) glass phase.     

Measuring surface and bulk relaxation in glassy polymers

We present a comprehensive study of gold nanoparticle embedding into polystyrene (PS) surfaces at temperatures ranging from T _g + 8 K to T _g − 83 K and times as long as 10⁵ minutes. This range in times and temperatures allows the first concurrent observation of and differentiation between surface and bulk behavior in the 20nm region nearest the free surface of the polymer film. Of particular importance is the temperature region near the bulk glass transition temperature where both surface and bulk processes can be measured. The results indicate that for the case of PS, enhanced surface mobility only exists at temperatures near or below the bulk T _g value. The surface relaxation times are only weakly temperature dependent and near T _g , the enhanced mobility extends less than 10nm into the bulk of the film. The results suggest that both the concept of a “surface glass transition” and the use of glass transition temperatures to measure local mobility near interfaces may not universally apply to all polymers. The results can also be used to make a quantitative connection to molecular dynamics simulations of polymer films and surfaces.     

Grain Boundary Grooving as an Indicator of Grain Boundary Phase Transformations

The atomic force microscopy (AFM) was used to study the grain boundary (GB) groove profiles far away from the melting temperature T _m. It is shown that AFM allows one to measure the temperature dependence of the GB energy in a rather broad temperature interval (from 0.85 T _m to T _m). The GB energy and GB segregation of Bi were measured at 1123 K in the interval of the Bi bulk concentration x ^v _Bi from 5 to 140 ppm Bi. The transition from monolayer to multilayer adsorption is observed for the 19a GB at 1123 K and x ^v _Bi = 60 at. ppm Bi. At the same point (1123 K and x ^v _Bi = 60 at. ppm Bi) a discontinuity of the first derivative of the GB energy is observed. These features were explained using the model of GB prewetting phase transformation developed previously.     

Critical magnetic field of surface superconductivity in lead

The critical superconductivity field H _c3 is measured on lead single crystals. It is shown that the temperature dependence of H _c3/H _c in the vicinity of superconducting transition temperature T _c is essentially nonlinear. Relative changes in the value of H _c3/H _c reach approximately 30%, which cannot be described by the Ginzburg-Landau theory. The experimental temperature dependences lead to the conclusion that the surface superconducting transition temperature noticeably exceeds the superconducting transition temperature in the bulk of the semiconductor. The differences in the critical temperatures and in the Ginzburg-Landau parameters for lead are estimated.     

高温退火对蓝宝石基片的表面形貌和对CeO2缓冲层以及Tl-2212超导薄膜生长的影响

研究了蓝宝石(1102)基片在不同温度和时间下退火时表面形貌和表面相结构的变化,以及它对CeO₂缓冲层和Tl-2212超导薄膜生长的影响.原子力显微镜(AFM)研究表明,在流动氧环境中1000℃温度下退火,蓝宝石(1102)的表面首先局部区域形成台阶结构,然后表面形成叠层台阶结构,随着退火时间的延长,表面发生了台阶合并现象,表面形貌最终演化为稳定的具有光滑平台的宽台阶结构.XRD测试表明,通过高温热处理可以大幅度提高蓝宝石基片表面结构的完整性.在1000℃温度下热处理20 h的蓝宝石 关键词： Tl-2212超导薄膜 蓝宝石 缓冲层     

Magneto-optical Faraday and Kerr effect of orthoferrite thin films at high temperatures

Orthoferrites present, as bulk materials, reorientation transitions of their magnetic moment alignment at temperatures depending on the rare-earth (RE) ion. In particular, orthoferrites (REFeO₃) with RE = Sm, Dy, present this transition at T _SRT = 443 K and 36 K, respectively. The spectra of the complex Kerr and Faraday angle have been measured on orthoferrite thin films (RE = Sm, Dy, Y), which were prepared by pulsed laser deposition on amorphous quartz substrates. The obtained spectra exhibit contributions of both surfaces and interfaces. Propagation effects of the polarized light in the magneto-optical medium which is interpreted in terms of a simplified theoretical formalism, is also observed. For selected photon energies, temperature dependent Faraday rotation measurements, , on orthoferrite thin films (RE = Sm, Dy, Y) have been performed. A quite different thermal variation compared to the bulk magnetization has been observed. Curie temperatures are found to be close to the bulk values or slightly larger by 10 K to 20 K as in the case of DyFeO₃ and YFeO₃. For RE = Sm and Dy, increases with increasing temperature contrary to the saturation magnetization, passes through a maximum at about 460 K and vanishes with a T _C of 647±18 K, 695 K for RE = Sm and Dy respectively. Received 28 July 2000     

Experimental gravity induced coexistence curve of methyl fluoride near the critical point

Abstract

The top part of the coexistence curve of methyl fluoride in the critical region has been determined first by direct observation of the disappearance of the meniscus of the fluid situated in a high-pressure light scattering cell and subsequently from the measured maximum depolarization ratio of an appreciable number of isochores close to the critical point. The experimental data obtained from direct observations yield a coexistence curve which nearly coincides with that found recently from pVT measurements. However, the data obtained from light scattering experiments describe a gravity induced coexistence curve which lies above the previous one and which shows a minimum at the critical point. The complete experimental data have been used to evaluate the critical parameters p_c, ρ_c and T_c and the critical exponent β.     

Magnetostructural phase transitions in manganese arsenide single crystals

The effect of an external magnetic field with a strength up to 140 kOe on the phase transitions in manganese arsenide single crystals has been investigated. The existence of unstable magnetic and crystal structures at temperatures above the Curie temperature T _C = 308 K has been established. The displacements of manganese and arsenic atoms during the magnetostructural phase transition and the shift in the temperature of the first-order magnetostructural phase transition in a magnetic field have been determined. It has been shown that the magnetocaloric effect in a magnetic field of 140 kOe near the Curie temperature T _C is equal to ??T ?? 13 K. A model of the superparamagnetic state in MnAs above the temperature T _C has been proposed using the data on the magnetic properties and structural transformation in the region of the first-order magnetostructural phase transition. It has been demonstrated that, at temperatures close to T _C, apart from the contribution to the change in the entropy from the change in the magnetization there is a significant contribution from the transformation of the crystal lattice due to the magnetostructural phase transition.     

Cross-Over Between First-Order and Critical Wetting at the Liquid-Vapour Interface of n-Alkane/Methanol Mixtures: Tricritical Wetting and Critical Prewetting

A simple mean-field theory is presented which describes the basic observations of recent experiments revealing rich wetting behaviour of n-alkane/methanol mixtures at the liquid-vapour interface. The theory, qualitative and in part heuristic, is based on a microscopic lattice-gas model from which a Cahn–Landau approach is distilled. Besides the physics associated with the short-range components of the intermolecular interactions, effects of the long-range tails of the net van der Waals forces between interfaces are also taken into account. Further, gravitational thinning of the wetting phase is incorporated. The calculation of the spreading coefficient S is extended to the experimentally relevant situation in which the bulk adsorbate is slightly away from two-phase coexistence due to gravity. Analysis of this novel approximation to S for systems with short-range forces leads to the conclusion that the surface specific heat exponents _s =1,1/2, and 0, for first-order wetting, tricritical wetting and critical wetting, respectively, are robust with respect to (weak) gravitational thinning, consistently with experiment. For three different systems the adsorption is calculated as a function of temperature and compared with the experimentally measured ellipticity. Including weak long-range forces which favour wetting in the theory does not visibly alter the critical wetting transition for the nonane/methanol mixture, in contrast with the generic expectation of first-order wetting for such systems, but in good agreement with experiment. For decane/methanol weak long-range forces bring the transition very close to the prewetting critical point, leading to an adsorption behaviour closely reminiscent of short-range tricritical wetting, observed experimentally for alkane chain length between 9.6 and 10. Finally, for undecane/methanol the transition is clearly of first order. First-order wetting is also seen in the experiment.     

The tricritical point in an ethanediol-nitroethane-cyclohexane-methanol solution

Applying the polythermal method the coexistence region of three liquid phases in an ethanediol-nitroethane-cyclohexane-methanol system has been found for several temperatures. From this the temperature and composition of the tricritical point has been determined as T _TCP = 37.5 ± 1°C and mass fraction :x _ethanediol = 0.09 ± 0.01, x _nitroelhane = 0.45 ± 0.01 x _{cycelohcexane} = 0.40 ± 0.02, x _methanol = 0.060 ± 0.005. The point at which, for a given polytherm, the transition from a two-phase to a three-phase region takes place at the highest temperature is identified as the critical end-point.

Functions of temperature versus heights of menisci separating the individual phases have been determined for selected values of concentration.     

GINZBURG-LANDAU THEORY AND VORTEX LATTICE OF HIGH-TEMPERATURE SUPERCONDUCTORS

The thermodynamics of the vortex lattice of high-temperature superconductors has been studied by solving the generalized Ginzburg-Landau equations derived microscopically. Our numerical simulation indicates that the structure of the vortex lattice is oblique at the temperature far away from the transition temperature T_c, where the mixed s-d_x²-y² state is expected to have the lowest energy. Whereas, very close to T_c, the d_x²-y² wave is slightly lower energetically, and a triangular vortex lattice recovers. The coexistence and the coupling between the s and d waves would account for the unusual dynamic behaviours such as the upward curvature of the upper critical field curve H_C2(T), as observed in dc magnetization measurements on single-crystal YBa₂Cu₃O₇ samples.     

Electrical resistivity of liquid Bi–Sb alloys

The electrical resistivities of liquid Bi–Sb alloys have been measured by DC four-probe method within Bi-rich composition through a wide temperature range. The distinct anomaly of a hump shape was observed on resistivity–temperature (ρndash;T) curves for liquid Bi–Sb alloys on heating at the relatively high temperatures. These anomalies have revealed the temperature-induced liquid–liquid phase transition in Bi–Sb melts. The DSC results for BiSb20wt% alloy further prove the existence of liquid–liquid transition. Measuring the ρ–T curves first on heating and then on cooling we have found that on cooling the ρ–T curve remained linear. It means that the postulated liquid–liquid transition may be irreversible.     

Magnetic field and temperature-induced first-order transition in Gd5(Si1.5Ge2.5): a study of the electrical resistance behavior

Magnetic field (0–4 T) and temperature dependencies (4.2–320 K) of the electrical resistance of Gd₅(Si_1.5Ge_2.5), which undergoes a reversible first-order ferromagnetic↔paramagnetic phase transition, have been measured. The electrical resistance of Gd₅(Si_1.5Ge_2.5) indicates that the magnetic phase transition can be induced by both temperature and magnetic field. The temperature dependence of the electrical resistance, R(T), for heating at low temperatures in the zero magnetic field has the usual metallic character, but at a critical temperature of T_cr=216 K the resistance shows a 20% negative discontinuity due to the transition from the low-temperature high-resistance state to the high-temperature low-resistance state. The R(T) dependence for cooling shows a similar but positive 25% discontinuity at 198 K. The isothermal magnetic field dependence of the electrical resistance from 212T224 K indicates the presence of temperature-dependent critical magnetic fields which can reversibly transform the paramagnetic phase into the ferromagnetic phase and vice versa. The critical magnetic fields diagram determined from the isothermal magnetic field dependencies of the electrical resistance of Gd₅(Si_1.5Ge_2.5) shows that the FM↔PM transition in zero magnetic field on cooling and heating occurs at 206 and 213 K, respectively. The full isothermal magnetic filed hysteresis for the FM↔PM transition is 2 T, and the isofield temperature gap between critical magnetic fields is 7 K.     

Vortex Excitations Above Tc in the Cuprate Superconductor Bi2Sr2Ca2Cu3O10 as Revealed by ESR

Using electron spin resonance (ESR) technique we have obtained data evidencing the existence of magnetic vortices in high-temperature superconductors at temperatures above the critical one T _c. We have studied magnetic excitations in Bi₂Sr₂Ca₂Cu₃O₁₀ single crystals above T _c with the method of surface spin decoration. The surface layer of diphenylpicrylhydrazyl was used as a sensitive probe of magnetic field distortions. The temperature dependence of the ESR signal parameters has indicated that far above T _c the magnetic flux of a sample is affected by the superconducting order parameter fluctuations while close to T _c its changes are due to vortex-type excitations.     

Critical Exponents of Kappa Carrageenan in the Coil-Helix and Helix-Coil Hysteresis Loops

The steady-state fluorescence technique was used to study coil-helix (sol-gel) and helix-coil (gel-sol) transitions of the kappa carrageenan-water system with various carrageenan contents. Fluorescence (I) and scattered light (I_sc ) intensities were measured against temperature to determine critical phase transition temperatures and exponents. It was observed that the coil-helix transition temperatures, T_ch were much lower than the helix-coil (T_hc ) transition temperatures due to the hysteresis of the phase transition loops. The gel fraction exponent (β) was measured and found to be in accord with the classical Flory-Stockmayer model.