Phase Transitions of Urea Adducts with n-Paraffins under High Pressure

The temperatures of the phase transition between orthorhombic and hexagonal structures of the urea adducts with n-paraffins, n-C_nH_2n+2 (n = 14–44), have been measured by differential thermal analysis for the pressure range up to 250MPa. The transition temperatures increase both with pressure and with the number of carbon atoms of the guest paraffins. The increasing rate of the transition temperatures with pressure is about half of that of pure paraffin crystals. The pressure dependences of the lattice constants have also been measured by X-ray diffraction. The specific volume changes discontinuously at the transition pressure; the result suggests that the phase transition of the urea adducts with n-paraffins is a first-order one. Furthermore, the specific volume change at the transition pressure decreases with the number of carbon atoms of the guest paraffins; 3.4 × 10-⁶ m³/Kg for n = 16 and 2.1 × 10-⁶ m³/Kg for n = 44.     

High Pressure Investigations of the Phase Transitions in Cholesteryl Pentanoate and Cholesteryl Hexanoate

At high pressures too cholesteryl n-penta-noate (CH-5) and cholesteryl n-hexanoate (CH-6) exhibit only a cholesteric liquid crystalline phase. Our light reflection measurements up t o 2600 bars yield no indication of a pressure induced smectic phase which was suggested by Tikhomirova and Ginzberg' for CH-5 at about 850 bars and 120°C. The Obtained pressure (P_t)-temperature (T_t) phase diagrams show the expected widening of the cholesteric range with P_t and T_t. In the case of CH-5 the marked crystallization curve besides a melting curve could be explained by the transformation of the cholesteric into a metastable crystalline solid phase.     

DCS Study of Smectic Phase Transitions

A previously described technique for measuring the order of phase transitions^l-3 using DSC has been applied to the liquid crystalline transitions found in TBBA. All of the values obtained were in agreement with those that have been measured by other techniques, and also with what would be anticipated from the nature of the transition. This study has shown that the technique is applicable to smectic-smectic transitions in liquid crystals.     

High Pressure Studies on Mesomorphic and Polymesomorphic Transitions

The paper presents the following results: (1) pressure induced mesomorphism in p-p'-n-butylazobenzene and biphenyl p-ethyl benzoate. (2) the monotropic nematic-isotropic transition in trans-p-n-propoxy-x-methyl cyanophenyl cinnamate becoming enantiotropic under pressure, (3) suppression of the cholesteric mesophase in cholesteryl nonanoate and the location of a solid-cholesteric-isotropic triple point at ～ 2.85 kbar. confirming an earlier observation of Keyes. Weston and Daniels on the same compound, (4) a measurement of dT/dp for the solid-smectic A, smectic A-cholesteric and cholesteric-isotropic transitions in cholesteryl myristate and a comparison with the values evaluated from the Clausius-Clapeyron equation using the known latent heat and volumetric data.     

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.     

Successive Phase Transitions in Lipid Membranes

On the basis of a statistical model previously proposed by the present authors, a new sort of phase transition recently observed in the fluid-like phase of DPL bilayer and mono-layer above the main transition temperature is investigated as successive orientational transitions accompanied with conformational changes. The effects of lateral pressure on the transition temperatures and latent entropies observed in DPL monolayer are also explained consistently. This type of phase transition is expected to occur in DML, DSL and DBL as well, although it has not been observed yet in the case of these molecules.     

Phase Evolution in Solidification Process of Germanium at High Pressure

In this paper the phase evolution in the solidification process of germanium under high pressure is investigated. Data obtained on electrical resistance changes, and in situ differential thermal measurements as well as X-ray diffraction enable us to arrive at the phase relations and transformation processes occurred during solidification under high pressure. At high pressure above 4 GPa, the metallic germanium phase is first solidified from the melt and then transformed into GeI phase and/or GeIII phase. The kinetics of the nonequilibrium transitions is briefly discussed.     

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.     

A Study on the First Order Phase Transitions in Hydrocarbon Crystals

A polarization hot stage microscopy study was made on the phase transitions in n-octacosane and n-hexatriacontane hydrocarbon crystals. Advancement rates of transition fronts of high temperature phase in low temperature phase were measured. Transition in the interior layers was detected. In order to explain the observations, we propose a model, which involves intrachain defects in the extended chain configuration. This model is an advanced stage of the model proposed by STROBL, basing on the SAXS results.     

Sequence of Phase Transitions in Solid Mbba

Combined neutron diffraction and Raman scattering measurements were carried out on a series of different phases of the same MBBA sample. The change in the diffraction patterns and in the optical spectra are used to indicate the transitions between the different phases investigated in the whole temperature range of interest. Besides the isotropic and nematic liquid crystalline phases, 7 different solid structures were found and a schematic phase diagram was constructed to show the thermal procedur for producing these phases.     

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.     

Phase Transitions in Polypeptide Liquid Crystals: A Reentrant Isotropic Phase

Optical and C-13 NMR examinations of concentrated solutions of poly-γ-benzyl-L-glutamate (PBLG) in a mixed solvent system containing a denaturant acid, show that this polymer liquid crystal has both a low and high temperature isotropic phase. The latter is due to thermal disruption of long range orientational order of the elongated macromolecules. The former reentrant isotropic phase is a result of an intramolecular helix to random coil transition, which leads to a macromolecular conformation inconsistent with liquid crystallinity.     

Phase Transitions in Chlorobenzene-Cis-Decalin Mixtures: A Nuclear Magnetic Resonance,Thermal Analysis and Phase Diagram Study

Using nuclear magnetic resonance and differential scanning calorimetry we have been able to observe the molecular rotation properties of chlorobenzene-cis-decalin mixtures in their glassy, amorphous and crystalline phases. The results indicate: that in “rapidly” cooled samples the behavior of the host dominates the properties of the mixtures; that reorientation of the guest molecule is less restricted in the amorphous phase than in the glassy phase; that when the material crystallizes from the amorphous phase on warming, reorientation again becomes severely restricted. The temperatures at which these phenomena occur agree with the phase diagram that has been determined for these materials. Similar experiments on t butyl chloride-cis-decalin mixtures support the above conclusions. These conclusions are in agreement with the previous dielectric studies.

Our magnetic resonance and thermal analysis experiments support the argument that the behavior of the CD host dominates the behavior of guest polar molecules in rapidly cooled mixtures. At the lowest temperature (110 K) CD forms a glassy phase unaccompanied by any heat of crystallization. On warming this glassy phase transforms near 150 K to an amorphous phase where considerable motion of both host and guest molecules occurs. Above 160 K the material crystallizes and reorientation is once again severely restricted up to the eutectic melting of 210 K. There appears to be no time dependence to these transformations and, as long as one stays below the crystallization temperature, the glassy-amorphous transition is reversible.     

NMR Study of the Phase Transitions in Some Derivatives of Cholesterol and B-Nor Cholesterol

In this paper we analyze by broad line NMR spectroscopy method, the influence of modifying the cholesterol skeleton upon mesomorphic properties and characteristics (phase transition points, mesomorphic ranges, etc.) in some derivatives of cholesterol. From our studies regarding the phase transition points by NMR spectroscopy method, we can assert that derivatives of the B-nor cholesterol have the same behavior as derivatives of the cholesterol.     

Phase Transitions of A Quasi-One-Dimensional Fermi Gas

Phase transitions of a quasi-one-dimensional Fermi gas are studied by the use of the renormalization group method for the fermion system without the bosonization. Intrachain backward and forward scatterings, pair electron hopping between different chains and exchange scattering of electrons in different chains are taken account of. Pair electron hopping gives rise to the singlet and triplet superconductor phase transitions. Electron exchange scattering gives rise to the spin density wave and charge density wave transitions. Calculation is made by the use of the one-dimensional dispersion. Following Menyhárd's method (Ref. 1) for the model with interchain backward scattering only, the change of the fluctuation from the one-dimensional region to the three-dimensional region is described. The transition temperatures are given by the bare couplings at high temperatures.     

Solid-Solid Phase Transitions of Long-Chain n-Alkyltrimethylammonium Halides

Transition properties of some compounds of the type, n-C _n H_2n+1N⁺(CH₃)₃X_-, with n = 10, 12, 14, 18, 22, and X = Cl, Br, and I, were investigated. All these compounds show a solid-solid phase transition with a large enthalpy change in the range of temperature 350 ～ 400K. The transition behaviors were investigated by the aid of DSC, TG, X-ray, and optical microscope. The solid-solid phase transition is regarded to be caused by melting of the layer of hydrocarbon chains of the compounds, while the rigid ionic layer retains the regular arrangement. Some relationships between the physical properties and the structure of the compounds are discussed.     

Conformational Mobility and Phase Transitions in Alkyloxybenzoate of Cholesterol

Abstract

The structural particularities of polymorphic modifications and cholesterol liquid crystal phase have been investigated by theoretical and experimental IR spectroscopy methods. The spectra were recorded in the interval of temperatures 293–523 K within the range of 600–3600 cm^?1. The frequencies of normal modes and intensities in the IR spectra have been calculated for the alkyloxybenzoate of cholesterol conformers, which may be realized under certain temperatures. Comparison of results of theoretical modelling and recorded spectra confirmed suggestion about conformational mobility basically defined with changing of steroid kennel orientation comparatively stayed part of molecule in the different phase state.     

Transitions de Phase en Series Mesogenes:

The polymorphism of the di(4-alkylphenyl) and di(4-alkoxyphenyl) tetrathiafulvalene (TTF) is investigated by optical, crystallographic and calorimetric methods. All the studied derivatives are mesomorphic. The first mesophase is always a smectic G phase; the second one is a nematic N phase for short chains and a smectic C phase for long chains.

The entropies corresponding to the passage high-temperature crystalline phase C₁ → S_G and to the “melting” (C₁ → mesophases → isotropic phase I) increase with the length of the chain and with the presence of the oxygen atom in the radical.     

Concentration Magnetic Phase Transitions in the (La1−xCaxMnO3 System

Comprehensive investigations into crystal structures, electrical and magnetic properties of the (La_1−xCa_x)MnO₃ (x = 0 ÷ 0.6) solid solutions are performed. Two concentration magnetic phase transitions are found: antiferromagnetic-ferromagnetic with x = 0.14 and ferromagnetic (T_c = 150 K) - ferromagnetic (T_c = 260 K) at f = 0.2. It is shown that the first of them is due to the crystal structure O′ O orthorhombic transition, the second - to the increase of ferromagnetic interaction at the expense of additional interaction through conduction electrons. A diagram of the magnetic states for (La_1−xCa_x)MnO₃ at x = 0 / 0.6 is given.     

立方相KTa0.67Nb0.33O3晶体的系列相变研究

采用拉曼散射技术研究了立方相KTa0.67Nb0.33O3晶体的系列相变,从声子角度分析了各相变特点.降温过程中立方-四方和四方-正交相变分别发生在-29℃和-95℃左右,正交-三方相变可能发生在-150℃左右.最后简单讨论了晶体的相变机制和居里点与晶体组分的关系,并比较分析了居里点的实验值与理论值的差异.