Phase transitions in poly(ethylene oxide) and polystyrene at high pressure

Abstract

The temperature and enthalpy of melting for poly(ethy1ene oxide) have, for the first time, been studied as a fuction of pressure up to 1 GPa by means of differential scanning calorimetry. The initial increase of the temperature of melting with increasing pressure is 64 K/GPa, whereas the enthalpy decreases by 40% in the 1 GPa pressure range. Using Clausius-Clapeyrons equation the volume change on melting is estimated to be 1.5 cm³/mol. The glass transition temperature T_g for polystyrene has also been studied by the same technique for pressures up to 0.1 GPa. The measurements show that T_g increases with increasing pressure by 250 K/GPa.     

Pressure dependence of crystal structure and molecular packing in anthracene

Anthracene molecular crystal has been investigated up to a pressure of 10.5 GPa at room temperature using variable shape variable size Monte Carlo simulations in an isothermal–isobaric ensemble. We have reported various structural quantities, such as cell parameters and unit cell volume, as a function of pressure and compared them with the experimental results [J. Chem. Phys. 119, 1078 (2003)]. The pressure dependence of angles θ, δ and χ which describe the relative packing of molecules in the crystal has been calculated. We report that anthracene molecular crystal does not exhibit any first order phase transition up to a pressure of 10.5 GPa which is consistent with the experimental observations by Oehzelt et al. [Phys. Rev. B 66, 174104 (2002)]. The calculated equation of state (EOS) has been fitted to a Murnaghan-type EOS with good agreement. The calculated bulk modulus and the pressure derivative of bulk modulus are 8.2 GPa and 8.9 respectively which are in agreement with the experimentally calculated values.     

High pressure X-ray diffraction study of copper hydride at room temperature

Abstract

High pressure X-ray studies on CuH up to 23 GPa have been performed at room temperature using a gasketed diamond anvil cell. The experimental data on the molar volume of CuH as a function of pressure have been fitted to Murnaghan's equation of state giving a bulk modulus: B₀ = 72.5±2 GPa and B₀ = 2.7 ± 0.3. By comparison with the equation of state for pure copper the effective additive volume of hydrogen has been evaluated as a function of pressure. It decreases from 3.2 cm³/mol H, at ambient pressure reaching a flattening value of 1.7cm³hol H at about 60 GPa. This suggests a continuous transition of CuH from ionic or covalent character at normal pressure to metallic hydride behavior at high pressure     

X-ray difffraction studies on samarium up to one megabar pressure

Abstract

High—pressure crystal structure studies have been performed on Sm up to 100 GPa using synchrotron x-radiation and a diamond anvil cell. The structural sequence Sm-dhcp-fcc-dist.fcc has been confirmed. There is no evidence of any volume collapse. The bulk modulus and its pressure derivative have been determined (B₀ = 30.7 GPa, B₀’ = 2.5).     

Compression of volume and lattice parameters of 2H-CsCdBr3 under high pressure

Abstract

Powder x-ray diffraction experiments have been performed on 2H-CsCdBr₃. at room temperature up to 25 GPa. At normal pressure this compound shows unidimensional electronic properties. Such unidimensional behaviour is not evident in terms of elastic bulk properties under pressure. No phase transformation occurs in this pressure range. The a and c lattice parameters steadily decrease with pressure; their ratio lowers by only 2% up to 25 GPa. The bulk modulus is low, 21.2 GPa, and is in very good agreement with the bulk modulus-volume systematics for ionic compounds. The value of the first pressure derivative is also typical of ionic compounds.     

Crystal Structure Transformations of Rare-Gas Solids Under Pressure

Pressure-induced structural changes in solid krypton (Kr) and xenon (Xe) have been studied using angle dispersive X-ray diffraction in a diamond-anvil cell (DAC) up to 50 GPa. The analysis of the results shows that in solid Kr (Xe) the phase transition from fcc to hcp starts below 3.2 GPa (1.5 GPa). Albeit the hcp/fcc ratio increases under pressure, both phases coexist up to the highest pressure reached in this study. Room temperature (RT) equations of state (EOS) are determined.     

Melting curve of NaCl0.5Br0.5 up to 4.5 GPa

Abstract

The melting curve of NaCl_0.5Br_0.5 has been measured under pressure up to 4.5 GPa. The melting temperatures of Ag and NaCl have been used to determine the pressure in the sample at its melting temperature.     

Long time relaxation effect of liquid castor oil under high pressure conditions

Abstract

The relaxation times of Liquid castor oil have been investigated by observing the scattered light of a He-Ne gas laser during the slow or rapid application of pressure up to 0.7 GPa at 293 K. For the application of pressure above 0.36 GPa the strong increase of the scattered light intensity approximately by a factor of 10² has been observed 12 hours after an application of pressure. This pressure effect is also observed for subsequent pressure cycles, i.e., the pressure effect is reversible. Experimental results are interpreted according to a model of a liquid of long rod molecules.     

High Pressure Optical Absorption in Cs 2 TCNQ 3 Complexes Grown Under the Influence of Magnetic Field

Crystals of the organic semiconductor Cs 2 TCNQ 3 have been grown under the influence of magnetic field of 5 T and their optical properties have been compared with the crystals grown without magnetic field. The magnetic field effect manifests itself as the enhancement of the intradimer charge transfer band S 1 , which appears at around 1.3 eV in the E//a polarization. The high-pressure optical absorption measurements have shown that the S 1 band of the crystal grown at 5 T contains a new component, which is significantly intensified with increasing pressure up to 1 GPa, but diminishes as pressure increases further up to 4 GPa, and remains constant at higher pressures. This new component is additional to the component of S 1 band which has similar properties to that of the crystals grown without magnetic filed, which continuously grows up to 3 GPa and abruptly broadens out at higher pressures. The new component of S 1 is strongly linked to the ferromagnetism in this substance.     

Pressure Dependence of Wurtzite ZnO Structure

From simultaneous X-ray diffraction and EXAFS experiments, structural properties in the Wurtzite phase of ZnO have been measured up to the transition pressure (9 GPa). These results are compared with first-principles calculations and discussed in terms of wurtzite mechanical stability at high pressure.     

A structural study of promethium metal under pressure

Abstract

The structural behaviour of Pm metal has been investigated up to 60 GPa of pressure using a Diamond Anvil Cell (DAC) and the energy dispersive X-ray diffraction technique. The room temperature/pressure structural form of Pm is dhcp and it transforms to a fcc phase by 10 GPa. This cubic phase of the metal converts by 18 GPa to a third phase, which has frequently been referred to as representing a distorted fcc structure. This latter form of Pm was retained up to 60 GPa, the maximum pressure studied, but subtle changes in the X-ray spectra between 50 and 60 GPa hinted that an additional structural change could be forthcoming at higher pressures. From the experimental data a bulk modulus (B₀) of 38 GPa and a B₀′ constant of 1.5 were calculated using the Birch equation. This modulus for Pm is in accord with the moduli reported for the neighboring lanthanide metals.     

High pressure X-ray studies of palladium hydride and deuteride

Abstract

The palladium hydride and deuteride have been investigated in the diamond anvil cell up to 35 GPa using energy dispersive x-ray diffraction method. The search for the neutrons in the case of PdD up to the highest pressure reached was unsuccessful.     

High-pressure phases of thorium and uranium compounds with the rocksalt structure

Abstract

The high-pressure crystal structures of the actinide compounds ThX and UX (X= C, N, P, S, As, Se, Sb, Te) have been studied by X-ray diffraction using synchrotron radiation, in the pressure range up to about 60 GPa Distorted fcc structures were observed for UC (27 GPa), UN (29 GPa), UP (10/28 GPa), US (10 GPa) and ThS (20 GPa). No phase transition has been observed for ThC and ThN. Compounds with As, Se, Sb all transform to the CsCl structure. ThP transform to the CsCl structure at 30 GPa. ThTe has the CsCl structure at ambient pressure and no further phase transition has been observed. UTe transforms to the CsCl structure at 9 GPa.     

Pressure Response of the Higher Fullerene C 84 Studied by Raman and X-ray Scattering

The pressure behavior of the intramolecular phonon modes of the fullerene C 84 and its structural stability have been studied for the first time by means of Raman spectroscopy and synchrotron X-ray diffraction at high pressure up to ～10 GPa. The volume of the cubic unit cell has been measured as a function of pressure. The experimental data fitted by the Murnaghan equation-of-state (EOS) gave K_{0}=19.5\pm 0.9\,\hbox{GPa} and K_{0}^{\prime}=16.4\pm 0.6 . The pressure coefficients and Grüneisen parameters of the intramolecular phonon modes of C 84 have been determined and compared with those of other fullerenes. The data obtained do not show any phase transition and the pressure behavior of the material is entirely reversible in the pressure region investigated.     

Pressure dependence of photoconductivity for hydrogenated amorphous silicon

Abstract

Measurements of steady-state photoconductivity for hydrogenated amorphous silicon (a-Si:H) have been carried out at pressures up to 14 GPa and at room temperature. The ratio of photoconductivity to darkconductivity [sgrave]p/[sgrave]D decreases with increasing pressure. The activation energy for photoconductivity Ep, which is 0.25 eV at ambient pressure, decreases with increasing pressure at the rate -7 meV/GPa. These resultls are discussed with change in density of states.     

Bulk moduli and high-pressure phases of the uranium rocksalt structure compounds: II. The monopnictides

Abstract

The high-pressure crystal structures of the compounds UX, where X = N, P, As and Sb, have been studied using X-ray diffraction in the pressure range up to about 60 GPa Rhornbohedral distortions are observed for UN and Up above 29 GPa and lO GPa, respectively. In Up a further transformation to an orthorhombic phase occurs at 28 GPa. UAs and USb transform to the CsCl structure at 20 GPa and 9 GPa, respectively. The latter transformations show a considerable hysteresis when the pressure is released. The scaling behaviour of the bulk modulus has been studied. It is confirmed that a log-log plot of bulk modulus versus specific volume for the cubic phases gives a straight line with a slope near ? 5/3.     

Structural and optical properties of InSe under pressure

Abstract

We have investigated the high pressure behavior of InSe by x-ray powder diffraction and optical measurements. The rhombohedral γ-polytype of InSe (space group R3m) exhibits a strongly anisotropic compressibility characteristic of the layer-type structure. Mode Gruneisen parameters of intralayer modes have been determined by Raman scattering. At 10.3(5) GPa InSe undergoes a phase transition to the rocksalt structure, which remains stable up to at least 30 GPa. Optical reflectivity measurements show the cubic high pressure phase to have metallic character.     

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.     

High-pressure phases of plutonium monoselenide studied by X-ray diffraction

Abstract

Plutonium monoselenide was studied under high pressure up to 47 GPa, at room temperature, using a diamond anvil cell in an energy dispersive X-ray diffraction facility. At ambient pressure, PuSe has the NaC1-type (B1) structure. The compound has been found to undergo a second-order crystallographic phase transition at around 20 GPa. This phase can be described as a distorted B1 structure, with a rhombohedral symmetry. PuSe transforms to a new phase at around 35 GPa, which can be indexed in the cubic CsCl-type (B2). The volume collapse at this phase transition is 11%. When releasing pressure, we observed a strong hysteresis to the inverse transformation down to 5 GPa. From the pressure-volume relationship, the bulk modulus has been determined to B ₀ = 98 GPa and its pressure derivative as B ₀ = 2.6. These results are compared to those obtained with other actinide monmictides and monochalcogenides.