A high pressure raman study of ThO2 to 40 GPa and pressure-induced phase transition from fluorite structure

The pressure dependence of the first-order Raman peak and two second-order Raman features of ThO₂ crystallizing in the fluorite-type structure is investigated using a diamond anvil cell, up to 40GPa. A phase transition from the fluorite phase is observed near 30 GPa as evidenced by the appearance of seven new Raman peaks. The high pressure phases of ThO₂ and CeO₂ exhibit similar Raman features and from this it is believed that the two structures are the same, and have the PbCl₂-type structure. The pressure dependence dω/dP of the observed phonons and their mode Grüneisen parameters are similar to the isostructural CeO₂. The observed second-order Raman features are also identified from the calculated phonon dispersion curves for ThO₂.     

Pressure induced phase transformation of semiconductor clathrates

Pressure induced phase transformation and amorphization for Ge-based type-I clathrates have been investigated by means of synchrotron XRD and Raman experiments under high pressure. The XRD results of Sr₈Ga₁₆Ge₃₀, Ba₈Ga₁₆Ge₃₀, and I₈Sb₈Ge₃₈ demonstrated volume collapse phase transitions at 18, 33, and 42 GPa, respectively. Reitveld analyses performed for I₈Sb₈Ge₃₈ reveal a deformation of six-member rings of 14-hedron cages with increasing pressure.     

纳米晶粒在高压下的相变

文章报道了纳米晶粒的晶粒尺寸对压力诱导相变的影响的最新研究进展．采用热力学理论揭示了纳米晶体材料的相变压力与同种大块材料不同的主要因素是体积变化率、表面能差和内能差．通过估算这3个因素的具体大小，可解释文献中报道的实验结果，并且可以确定同种大块材料和纳米晶体材料之间的相变压力发生差异的控制因素．在纳米晶体材料中，晶粒尺寸对结构稳定性和相变压力的影响与体系本身有关．     

Kinetics of a first-order phase transition: computer simulations and theory

We make a quantitative comparison between the predictions of the Becker-Döring equations and computer simulations on a model of a quenched binary A-B alloy. The atoms are confined to the vertices of a simple cubic lattice, interact through attractive nearest neighbor interactions, and move by interchanges of nearest neighbor pairs (Kawasaki dynamics). We study in particular the time evolution of the number of clusters of A atoms of each size, at four different concentrations: _A=0.035, 0.05, 0.075, and 0.1 atoms per lattice site. The temperature is 0.59 times the critical temperature. At this temperature the equilibrium concentration of A atoms in the B-rich phase is _A ^eq =0.0145 atoms/lattice site. The coefficients entering the Becker-Döring equations are obtained by extrapolation from previously published low-density calculations, leaving the time scale as the only adjustable parameter. We find good agreement at the three lower densities. At 10% density the agreement is, as might be expected, less satisfactory but still fairly good-indicating a quite wide range of utility for the Becker-Döring equations.Supported in part by NSF Grant DMR81-14726 and DOE Contract DE-AC02-76ERO3077.     

Kinetics and systematics of structural phase transitions in the regular lanthanide metals under pressure

Abstract

Techniques and results of studies on the kinetics and hysteresis of the structural phase transitions in lanthanides under pressures up to 58 GPa and temperatures between 200 K and 520 K are presented. The transformation rates show the same time dependence as for diffusion controlled transitions, however, other interpretations of this time dependence are also possible. Estimates of the 0 K equilibrium transition pressures are derived from the pressure and temperature dependence of the activation free energies A, G. A comparison of critical radius ratios, R_ux/R_5p for all the regular lanthanides at the various phase transitions shows simple systematics in the high pressure behaviour of the lanthanides.     

A high pressure Raman study of TeO2 to 30 GPa and pressure-induced phase changes

The effect of pressure on the Raman modes in TeO₂ (paratellurite) has been investigated to 30GPa, using the diamond cell and argon as pressure medium. The pressure dependence of the Raman modes indicates four pressure-induced phase transitions near 1 GPa, 4.5 GPa, 11 GPa and 22 GPa. Of these the first is the well studied second-order transition fromD ₄ ⁴ symmetry toD ₂ ⁴ symmetry, driven by a soft acoustic shear mode instability. The remarkable similarity in the Raman spectra of phases I to IV suggest that only subtle changes in the structure are involved in these phase transitions. The totally different Raman spectral features of phase V indicate major structural changes at the 22GPa transition. It is suggested that this high pressure-phase is similar to PbCl₂-type, from high pressure crystal chemical considerations. The need for a high pressure X-ray diffraction study on TeO₂ is emphasized, to unravel the structure of the various high pressure phases in the system.     

Pressure-induced phase transition and stability of EuO and EuS with NaCl structure

We have predicted the phase transition pressures and corresponding relative volume changes of EuO and EuS having NaCl-type structure under high pressure using three-body interaction potential (TBIP) approach. In addition, the conditions for relative stability in terms of modified Born criterion has been checked. Our calculated results of phase transitions, volume collapses and elastic behaviour of these compounds are found to be close to the experimental results. This shows that the inclusion of three-body interaction effects makes the present model suitable for high pressure studies.      

First-principles study of A7 to simple cubic phase transformation in As

First-principles plane-wave pseudopotential approaches were used to investigate the structural phase transition of As from the rhombohedral structure to the simple cubic (sc) one under high pressure at the transition pressure of 22 GPa, which is also found to be accompanied by a volume reduction of 0.8%. The detailed structural changes during the phase transition were analyzed.     

Kinetics of the initial stage in a first-order phase transformation in thin films

The nucleation and growth of islands of a new phase on the surface of solids has been studied both experimentally and theoretically for the particular case of the transition from the pyrochlore to perovskite phase in a thin film of a lead zirconate-titanate ferroelectric. This transformation was chosen because the new-phase islands have a stable circular shape in this case, a relatively large size (10⁻⁵–10⁻⁴ m) permitting their observation with an optical microscope, and a low growth rate (10⁻⁸–10⁻⁹ m/s). A theoretical analysis of the process, based on the kinetic theory of first-order phase transitions proposed earlier, has been carried out and the behavior in time of all main characteristics of a phase transformation, namely, nucleation rate, concentration of the new-phase islands, their size distribution, and relative overheating, has been calculated. The same characteristics have been measured experimentally, thus permitting one for the first time to make a thorough comparison of the theoretical with experimental data on the kinetics of first-order phase transitions. They have been found to be in a good agreement. Fiz. Tverd. Tela (St. Petersburg) 39, 121–126 (January 1997)     

A characterization of first-order phase transitions for superstable interactions in classical statistical mechanics

We give bounds on finite-volume expectations for a set of boundary conditions containing the support of any tempered Gibbs state and prove a theorem connecting the behavior of Gibbs states to the differentiability of the pressure for continuum statistical mechanical systems with long-range superstable potentials. Convergence of grand canonical Gibbs states is also studied.     

Absence of first-order phase transitions for antiferromagnetic systems

We consider a spin system with nearest-neighbor antiferromagnetic pair interactions in a two-dimensional lattice. We prove that the free energy of this system is differentiable with respect to the uniform external fieldh, for all temperatures and allh. This implies the absence of a first-order phase transition in this system.     

Electric permittivity and dielectric loss of castor oil during its transformation to the high pressure phase

Abstract

The changes of permittivity and dielectric loss of commercially pure castor oil observed during its transition to the high pressure phase are described. Discussion about physical properties of this phase is shortly presented too.     

A first-order level-2 phase transition in thermodynamic formalism

We show the existence of a phase transition at the level of measures for the generalized dimension of the maximal entropy measure in a model that was considered by F. Hofbauer and which is related to a model of M. Fisher. The model presented here is related to the one-dimensional Ising model in which a wall effect is assumed. In this situation, the problem has to be considered in the one-dimensional lattice . In general there is no first-order transition for the Ising model in the lattice , but under our assumptions such transitions can occur. The Ising model has the purpose of explaining the magnetization of ferromagnetic systems at low temperatures. The main difference of our result from a previous result of F. Hofbauer is that the transition is analyzed in the setting of the generalized dimension. This setting is more closely related to the observables. The main purpose of this paper is to explain another mathematical model for phase transition using the mathematical results obtained by F. Hofbauer. We also use results of the thermodynamic formalism in an essential way.     

Finite-size scaling study of a first-order temperature-driven symmetry-breaking structural phase transition

We present a study of finite-size effects in a model exhibiting a first-order temperature-driven symmetry-breaking structural phase transition in theL × cylindrical geometry in theL limit. Exact studies demonstrate the applicability of our scaling ansatz even in the one-dimensional limit, making this model ideal for studying finite-size effects. The scaling ansatz, similar to the previously developed ansatz for field-driven transitions, demonstrates that latent heat is crucial in driving these transitions. This ansatz is supported by a 2×2 phenomenological transfer matrix based upon the symmetries of the system; this produces an analytic free energy which has the scaling form. Order parameter probability distributions show that the high- and low-temperature phases coexist only in a small finite-size-affected regime near the bulk transition temperature; this regime vanishes exponentially fast asL diverges.     

First principles study of pressure-induced magnetic transition in CrN

First principles calculation was performed using tight-binding LMTO method with local density approximation (LDA) and atomic sphere approximation (ASA) to understand the electronic properties of chromium nitride. The equilibrium geometries, the magnetic moment, the electronic band structure, the total and partial DOS are obtained under various pressures and are analyzed in comparison with the available experimental data. The most stable structure of CrN is NaCl structure in the FM state. A pressure-induced second order magnetic phase transition from ferromagnetic (FM) to non-magnetic (NM) at very high pressure of 0.5549 Mbar is predicted. Our results indicate that CrN can be used as a hydrogen storage material.     

Pressure induced phase transition behaviour in f-electron based dialuminides

The rare-earth and actinide based compounds are endowed with several exotic physical and chemical properties due to the presence of f-electrons. These properties exhibit interesting changes under the action of various thermodynamic fields and hence continues to be a subject of extensive research. For instance, under pressure, the nature of f-electrons can be changed from localized to itinerant, leading to a variety of changes in their structural, physical and chemical properties. The present review on the high pressure phase transition behaviour of dialuminides of rare earths and actinides is an outcome of research in our laboratory during the last five years using a unique combination of a Guinier diffractometer and a diamond anvil cell built in-house. To bring out the correlations between the compressibility and structural behaviour with the electronic structure, we have also carried out electronic structure calculation. Further, the usefulness of Villars’ three parameter structure maps in predicting pressure induced structural transitions has been explored and this has been illustrated with the available phase transition data.     

Some recent investigations of materials under high pressures

By subjecting materials to high pressures one can significantly reduce interatomic and intermolecular distances. This causes drastic changes in the nature of electronic and vibrational states and also in bonding, bringing about several unusual structural, electronic and magnetic phase transitions. In addition, these studies provide a very useful data about the equation of state of the materials of interest. Several examples from our work are presented which elucidate the richness of physics under these conditions.     

Kinetics of first-order phase transitions in the asymptotic stage

We construct an asymptotic theory that describes the kinetics of first-order phase transitions. The theory is a considerable refinement of the well-known Lifshits-Slezov theory. The main difference between the two is that the Lifshits—Slezov theory uses for the first integral of the kinetic equation an approximate solution of the characteristic equation, which is valid in the entire range of sizes except for the blocking point, i.e., it uses a nonuniformly applicable approximation. At the same time, the behavior of the characteristic solution near the blocking point determines the asymptotic behavior of the size distribution function of the nuclei for the new phase. Our theory uses a uniformly applicable solution of the characteristic equation, a solution valid at long times over the entire range of sizes. This solution is used to find the asymptotic behavior of all basic properties of first-order phase transitions: the size distribution function, the average nucleus size, and the nucleus density. Zh. éksp. Teor. Fiz. 113, 2193–2208 (June 1998)     

Volume changes of castor oil during its transformation to the high pressure phase

Abstract

Time dependencies p(t)_V,T, nd V(t),_P,T, at room temperature as castor oil phase transition indicators were investigated. The time after which the transition takes place, within the pressure range from 0.36 up to 1.05 GPa, strongly depends on pressure. Its minimum, at about 0.6 GPa is equal to 15 hours. Under the same conditions of experiment the largest change in volume (about ?2%) was detected. The relative changes of volume on pressure for the normal state of castor oil and for its new high pressure state have been found to be approximately the same. A large hysteresis of volume changes after the phase transition has also been observed.