钙钛矿铁电体在超高压下的相变研究进展

钙钛矿型铁电材料的晶体结构与压力有很大的关系.本文综述了三种最常见最简单的钙钛矿型铁电体BaTiO3、PbTiO3、KNbO3、稍微复杂的PZT(Pb(Zr1-xTix)O3)和弛豫铁电体PMN(Pb(Mg1/3Nb2/3)O3在超高压下晶胞参数和晶体结构与压力的变化.对于上述五种钙钛矿型铁电体,随着压力的增加,晶胞参数都变小,发生从铁电相到顺电相的转变.此外,随着压力的增加,还会发生铁电相到铁电相的转变和铁电相的重新出现.     

AgAlSe2晶体高压相变的第一性原理研究

基于密度泛函理论,采用广义梯度近似法,研究了黄铜矿结构AgAlSe₂在高压下的晶体结构、晶格动力学稳定性与电子结构.结果显示:在0 GPa时AgAlSe₂的晶格参数与实验值吻合,在13.9 GPa附近,质量密度、Se-Ag键长、Se-Al键长、晶格常数a突然增大,相对晶胞体积V/V₀、晶格常数c突然减小,声子谱出现虚频,结构变得不稳定,带隙发生突变,数值呈减小趋势.表明AgAlSe₂晶体在13.9 GPa附近发生结构相变.该研究为AgAlSe₂晶体在理论上所能承受的高压提供信息支撑.     

基于冲击光谱测量的氧化铝晶体高压相变诊断技术

氧化铝晶体是一种优良的光学透明窗口材料,更是地球内部的重要组成物质.利用气炮加载结合冲击光谱测量,不仅能够获得其发光特征,并且根据光谱分布特征得到高压结构相变信息.在自主搭建的冲击光谱动态测试平台上,结合多通道辐射高温计以及ICCD瞬态光谱测试技术在40~120 GPa的压力区间,研究了c切向氧化铝晶体的辐射发光效应.在可见光波段400~700 nm区间获得了氧化铝晶体的发光光谱和辐射温度结果,证实了光谱的结构特征和表观温度值与该压力下氧化铝的结构相变存在明显的关联性.     

Temperature Dependence of Critical Sample Thickness for Spontaneous Cholesteric-Nematic Phase Transition Between Surfaces with Homeotropic Anchoring

Temperature dependence of the critical sample thickness at which a cholesteric structure unwinds spontaneously between surfaces with homeotropic anchoring are presented for some dielectrically negative chiral nematic mixtures. The results obtained are pertinent to the application of the nematic-cholesteric phase change-effect in liquid crystal devices.     

高压下Pca21相TiO2直接相变的第一性原理研究

利用第一性原理的GGA+U方法对TiO2的金红石相(P42/mnm)、铌铁矿相(Pbcn)和Pca21相(Pca21)进行了计算.首先,优化了这几个相的晶体结构及相关参数,分析了焓曲线图,发现在减压至8.4 GPa时,Pca21相直接相变为铌铁矿相.其次,通过拟合分析了三阶Birch-Murnaghan状态方程得到Pca21相的体弹模量B0与类萤石结构实验值(202 GPa)非常符合.最后,通过讨论Pca21相的相变压强和体弹模量,进一步证明Pca21相结构更符合类萤石实验结果.     

Pressure Dependence of the Metal-Insulator and Superconducting Phase Transitions in (TMTSF)2 Reo4

Measurements of the pressure and temperature dependence of the a-axis resistivity of (TMTSF) ₂ReO₄, are presented. The metal-insulator transition seen in this material at the remarkably high temperature of ～180 K at ambient pressure and which is associated with an ordering of the ReO₄, anions is suppressed under pressure. For pressures above ～9.5 kbar we observe a superconducting transition near 1.3 K. There is a narrow intermediate pressure regime about 2.5 kbar in width in which both superconductivity and effects of anion ordering are observed. In this regime (i) a superconducting transition is seen near 1.3 K even though ρ just above the transition can be up to 10-100 times greater than ρ(300 K), and (ii) there is an extraordinarily large hysteresis in p below ～ 100 K with the possibility of varying the resistance of the low temperature state by several orders of magnitude by appropriate temperature cycling. These results establish the first order character of the transition. We suggest that at high pressures the anions remain frozen in a metastable disordered state to low temperatures.     

Phase Transition of 1,16-Hexadecanediol

It was found that 1,16-hexadecanediol exhibited a solid-solid phase transition. X-ray diffraction experiments and dielectric constant measurements were carried out in order to investigate the structure of the high-temperature phase. A model of molecular arrangement in the high-temperature phase was presented. The high-dielectric constant values were observed in the high-temperature phase. It is considered that the high-temperature phase of 1,16-hexadecanediol is a rotator phase in analogy with n-higher alcohols.     

High Pressure Studies of the Phase Transition Enthalpies of the Liquid Crystal EBBA up to 2.5 kbar

The liquid crystal p-Ethoxy-benzylidee-p-n-butylaniline(EBBA) exhibits one nematic-liquid isotropic and two solid-nematic coexistence lines.

With a high pressure micro calorimeter based on differential scanning calorimetry (DSC) previously described the phase transition enthalpies of these three phase transitions have been measured in the pressure range 1 bar to 2.5 kbar. Numerical data are presented for the transition temperatures, the enthalpy changes, the entropy changes, and the volume changes for both solid-nematic transitions as well as for the nematic-liquid isotropic transition.

Additionally the effect of impurities on the nematic-liquid isotropic transition enthalpy at normal pressure is discussed.     

Effect of Pressure on Antiferromagnetic Transition in Alkali-Electro-Sodalite

Abstract

Pressure (0–19 kbar) and temperature (4–300 K) dependent EPR study of Sodium-Electro-Sodalite (SES) is presented. SES, which consists of a bcc sub-lattice of F-centers supported by a zeolite-like framework, is known to be a Mott insulator at room temperature. On cooling, SES undergoes an AF transition at 48±2 K providing the first example of an s-electron antiferromagnet. We find that the width of the EPR resonance above T _N is influenced not only by a strong exchange interaction, but also by a fast spin-lattice relaxation. Also, with increasing pressure, T _N decreases linearly and extrapolates to 0 K at about 65 kbar. The reason for this seemingly unexpected behavior is briefly discussed.     

ENDOR Study of the Phase Transition in Benzil

ENDOR spectroscopy was used to elucidate the domain structure of benzil accompanying its phase transition at 84°K. Spectral twinning was observed on a single-crystalline sample as a result of multidomain formation below the phase transition temperature. This twinning was explained by applying the Landau theory of phase transitions. With knowledge of the anisotropy of the proton hyperfine interaction, we extracted the angle between the domains and the morphologic two-fold axis to be 1.55° at 2°K.     

Pressure Dependence of the Electromechanical and Vibrational Properties of Pentaerythritol

The elastic, piezoelectric and dielectric constants of pentaerythritol, C (CH₂OH)₄, (PET) have been computed as a function of pressure employing the structural data of KATRUSIAK and the lattice dynamical model of RAMAMOORTHY and KRISHNAMURTHY. Using these electromechanical constants, the Young's modulus, the linear compressibility, the bulk modulus and the acoustic wave velocities are computed for various high pressures. The pressure dependence of the vibration spectrum of PET using rigid and non‐rigid lattice models is also obtained. The anomalous variation of these electromechanical and other physical quantities predict the most probable pressure for phase transition in PET to be around 280 MPa. The mechanism of the transition and the variation in the physical behaviour accompanying the transition are discussed.     

Crystal Structure and Phase Transition of Diglycine Perchlorate

Abstract  

Diglycine perchlorate (DGPCl), a new 2:1 adduct formed between glycine and perchloric acid has been obtained and studied using differential scanning calorimetry and single crystal X-ray diffraction. DGPCl undergoes a reversible first-order phase transition at 261.5 K. The crystal structures at 150 and 293 K have been determined to be triclinic, space group P‐1, Z = 2, suggesting the first-order phase transition to be an isostructural phase transition. The DGPCl crystal consists of five glycinium-monoprotonated glycinium dimers and five perchlorate anions in an asymmetric unit. The glycine moieties in the glycinium-monoprotonated glycinium dimers are non-planar. Two types of hydrogen bonds are present in the crystal, strong O–H···O hydrogen bonds and a weak N–H···O hydrogen bonds. The short, strong O–H···O hydrogen bond connects the glycinium ion and mono protonated glycinium ion. In four of the dimers, the O–H and H···O bond lengths are different, indicating the hydrogen atom to be located more close to the monoprotonated glycinium ion. However, in one of the glycinium-monoprotonated glycinium dimer the O··H and H··O bond lengths are nearly equal, suggesting the hydrogen atom (O···H···O) to be attached to the oxygen atoms of both glycine moieties. On thermal transition some of these hydrogen bonds are weakened and in all dimers the hydrogen atom seems to be located more close to the mono protonated glycinium ion.     

C12H9SN晶体铁弹相变的研究

采用慢度曲面法研究C12H9SN晶体的铁弹相变.在现有实验数据的基础上,模拟计算C 12 H9 SN晶体高温正交相的弹性劲度系数对慢度曲面的影响.结果表明,非对角元c12,c13,c23的变化对慢度曲面最大值的取向没有影响,同时也确定出与该相变直接相关的弹性劲度系数为c55.该晶体相变的对称性变化是由高温正交相mmm点群变成低温单斜相2/m点群.     

高低温偏硼酸钡晶体的相变和生长

本文探讨了BBO晶体α相和β相之间的相变问题,同时简要地介绍了国内外α-BBO晶体和β-BBO晶体的生长方法,并展望了α-BBO晶体和β-BBO晶体研究的发展趋势×-β相变的深入研究;α-BBO和β-BBO亚稳态生长条件的研究;生长工艺的优化以及新的生长工艺的发展;β-BBO薄膜的研究.     

Kinetics of Overall Phase Transition in Changing Size System

Kinetics of phase transition is studied for the more general case when the size of the system is assumed time dependent. In the three dimensional case typical examples in this respect could be connected with the solution of cosmological problems. In the two dimensional case could be the spreading and crystallization of undercooled water on oil or the experiments concerning phase transition in monolayers in a Lengmuir balance. The time dependence of the degree of overall transformation α(t) is formulated in a generalized form corresponding to above assumption. Explicit solutions are given for a constant rate of expanding (or shrinking) and for a constant acceleration of the size change of the system under the assumption that both nucleation rate I and linear growth rate G are constants. It is demonstrated that the process of phase transition proceeds much faster in a shrinking systems and is impeded in expanding ones. The reason for this effect is that parts of the new phase, formed in the initial parts of the system, are transferred into the diminishing volume (or surface). Thus the concentration of the new phase is mechanically increased.     

Phase Transition Studies of the Liquid Crystal Pentyloxybenzylidene Phenylazoaniline

Phase transition studies of the liquid crystal pentyloxybenzylidene phenylazoaniline are investigated with density and ultrasonic velocity measurements. The density variation with temperature confirms that the isotropic liquid-nematic, nematic-smectic A and smectic A-smectic B transitions are of first order. The temperature variation of ultrasonic velocity confirms all the phase transitions. The adiabatic compressibility (β_ad), Rao number (R_n) and Molar compressibility (B) are estimated from density and ultrasonic velocity.     

Phase Transition of Magnesium Sulphite Hydrates in Aqueous Suspension

Solution mediated phase transitions in aqueous suspension (pH 9.5) of MgSO₃ hydrates were studied at 50, 60, 65, and 70 °C for hexa- to trihydrate and 25, 30, and 35 °C for tri- to hexahydrate conversion. The former conversion is controlled by the diffusion growth of the new phase crystals whereas the latter process is controlled by both the initial phase dissolution and the new phase growth.     

Effect of In and Sb Vacancies on Temperature Dependence of InSb Lattice Parameter at High Temperatures

The temperature dependence of the thermal expansion coefficient for InSb has been determined in the range 25–515 °C by precision measurements of the lattice parameter of InSb single crystals. It is shown that beginning from 460 °C the temperature dependence of the lattice parameter for InSb single crystals grown from melts of different compositions is essentially affected by vacancies in the indium and antimony sublattices. The vacancy concentration and possible deviation of InSb from the stoichiometric composition are estimated from a relative decrease in the lattice parameter.     

Thermal Expansion of Thiourea in the Range of Phase Transition

By means of a quartz dilatometer three principal expansion coefficients have been determined in the temperature range 100–273°K, and their anisotropy within (100) plane. The appearance of singular points, corresponding to phase transformations, depends on direction of measurements but most drastic changes are observed along the crystallographic c-axis, in agreement with the direction of the weakest intermolecular interactions. The calculated pressure necessary to shift the phase equilibrium I/II to room temperature is in good agreement with the value observed in a direct experiment.¹¹     

Nonlinear Optics of Nematic and Blue Phase Liquid Crystals

We present a critical reexamination of individual electronic and collective optical nonlinearities of nematic liquid crystals (NLC) in the context of all-optical transmission switching of femtoseconds – CW lasers, and report recent observations of similar optical nonlinearities in Blue-phase liquid crystals (BPLC) and their utilization in feasibility demonstrations of polarization-free nonlinear grating diffraction and transmission switching of CW as well as pulsed lasers.