高压下TiC的弹性、电子结构及热力学性质的第一性原理计算

利用基于密度泛函理论的第一性原理平面波赝势方法 并结合准谐徳拜模型研究了NaCl结构的TiC在高压下的弹性性质、电子结构和热力学性质. 计算所得零温零压下的晶格常数、体弹模量及弹性常数与实验值符合得很好. 零温下弹性常数和弹性模量随压强增大而增大. 通过态密度和电荷密度的分析, Ti-C键随压强增大而增强. 运用准谐德拜模型, 成功计算了TiC在高温高压下的体弹模量、熵、热膨胀系数、徳拜温度、 Grüneisen参数和比热容. 结果表明压强对体弹模量、热膨胀系数和徳拜温度的影响大于温度对其的影响. 热容随着压强升高而减小, 在高温高压下, 热容接近Dulong-Petit极限.     

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.     

Moderate hydrostatic pressure–temperature combinations for inactivation of Bacillus subtilis spores

We report the effect of using moderate hydrostatic pressure, 40–140?MPa, at moderate temperature (38–58°C) to inactivate Bacillus subtilis spores in McIlvaine's citric phosphate buffer at pH 6. We have investigated several parameters: pressure applied, holding time, pressure cycling, and temperature. The kinetics of spore inactivation is reported. The results show that spore inactivation is exponentially proportional to the time the sample is exposed to pressure. Spore germination and inactivation occur at the hydrostatic pressures/temperature combinations we explored. Cycling the pressure while keeping the total time at high pressure constant does not significantly increase spore inactivation. We show that temperature increases spore inactivation at two different rates; a slow rate below 33°C, and at a more rapid rate at higher temperatures. Increasing pressure leads to an increase in spore inactivation below 95?MPa; however, further increases in pressure give a similar rate kill. The time dependence of the effect of pressure is consistent with the first-order model (R²?>?0.9). The thermal resistance values (Z_T) of B. subtilis spores are 30°C, 37°C, and 40°C at 60, 80, 100?MPa. The increase in Z_T value at higher pressures indicates lower temperature sensitivity. The pressure resistance values (Z_P) are 125, 125 and 143?MPa at 38°C, 48°C, and 58°C. These Z_P values are lower than those reported for B. subtilis spores in the literature, which indicates higher sensitivity at pressures less than about 140?MPa. We show that at temperatures <60°C, B. subtilis spores are inactivated at pressures below 100?MPa. This finding could have implications for the design of the sterilization equipment.     

Raman spectra of forsterite and fayalite at high pressures and room temperature

Abstract

Raman spectra of the two pure end-members of olivine (forsterite and fayalite) were studied at high pressures and room temperature in a diamond-anvil cell using both single-crystals and polycrystalline samples in pressure mediums of either an ethanol-methanol mixture or H₂O. Variations with pressure were studied up to 170kbar for fayalite and to 300kbar for forsterite. Two intensive Raman bands of fayalite were definitely observable at high pressures, but only one of them can be reliably determined. Both have a linear variation within experimental uncertainty. Because of interference from the high spectral background, we found that nearly all the weak bands of forsterite could not be reliably determined at high pressures. However, the pressure variations of all bands of forsterite which can be reliably determined are non-linear. The rates of frequency change for the intense bands of forsterite determined in the present experiment are consistent with those of natural forsterites determined by Besson et al. ¹ and Gillet et al. ², but are in a slight discordance with those reported by Chopelas³. Furthermore, there is no evidence for the olivine ? spinel phase transition occurring at room temperature.     

Temperature and Pressure Dependence of Thermal Conductivity Measurement of Polystyrene and Polycarbonate

The thermal conductivity of polymers in the solid and molten phases, as functions of temperature and pressure, is an essential parameter to permit simulation of polymer processing by computer-aided engineering (CAE). A key factor for the thermal conductivity when used in CAE is the Bridgman parameter (g) as a function of temperature. This is experimentally examined for polystyrene (PS) and polycarbonate (PC) in this paper. It was demonstrated that the thermal conductivity results under pressure were well described by the Eiermann's equation. First, the product of the Bridgman parameter (g) and the compressibility (β) as a function of temperature was calculated by fitting the experimental values with the Eiermann's equation. Second, the compressibility (β) as a function of temperature was estimated from the slope, in a plot of specific volume as a function of pressure. Finally, the Bridgman parameter (g) as a function of temperature was obtained from the two previous figures. The Bridgman parameters from the experiments are discussed by comparing them with those from Eiermann's theoretical model.     

Thermodynamic properties of cubic ZrC under high pressure from first-principles calculations

The elastic and thermodynamic properties of Zirconium carbide (ZrC) are investigated by ab initio plane-wave pseudopotential density function theory method. The obtained lattice constant, elastic constant and bulk modulus B are consistent with the experimental and theoretical data. Through the quasi-harmonic Debye model, the dependences of the normalized volume V/V ₀ and the bulk modulus B on pressure P, as well as the specific heat C _V on the temperature T are obtained successfully. The relationships of the thermal expansion α with temperature and pressure are also investigated, which indicate the temperature hardly has any effect on the thermal expansion α at high pressure. Supported by the National Natural Science Foundation of China (Grant No. 10776022)     

Analysis of P-V-T relationships and thermodynamic properties for some alkali halides

In this paper, Pandey approximation for the volume dependence of Anderson-Grüneisen parameter at fixed pressure, Anderson approximation for the temperature dependence of thermal expansivity, the equations of thermal expansivity along isobars derived by Shanker et al., and the presented approximation for the volume dependence of Anderson-Grüneisen parameter along isobars, have been used to study and predict the pressure-volume-temperature (P-V-T) data and the variations of the volume expansion coefficient and isothermal bulk modulus with temperature and pressure for NaCl, CsCl, LiF, NaF crystals, up to 30 GPa and in the temperature range 298-1073 K. The calculated values are compared with each other. It is found that these equations-of-state are valid and present good agreement with the available experimental data.     

Theoretical study of the structural phase transition and elastic properties of HfN under high pressures

The effect of hydrostatic pressure on the structures of HfN at 0 K was investigated by using the projector augmented wave (PAW) within the Perdew–Burke–Ernzerhof (PBE) form of the generalized gradient approximation (GGA). The transition pressure between NaCl (B1) and CsCl (B2) structures is predicted to be 277.3 GPa. This value is consistent with that reported by Kroll, while in contrast to the results obtained by Ojha et al. and Meenaatci et al. Moreover, the elastic properties of B1-HfN and B2-HfN under high pressures are successfully obtained. It is found that the elastic constants, bulk modulus B, shear modulus G, compressional and shear wave velocities increase monotonically with increasing pressure. The Debye temperature Θ calculated from the elastic constants of HfN is in good agreement with the experimental values. The anisotropies of B1-HfN and B2-HfN at zero pressure have also been discussed.     

Phase stability,mechanical and thermodynamic properties of orthorhombic and trigonal MgSiN2: an ab initio study

Structural stability and mechanical and thermodynamic properties of the orthorhombic and trigonal MgSiN₂ polymorphs (or-MgSiN₂ and tr-MgSiN₂) were investigated through density functional theory and quasi-harmonic Debye model (QHDM). Our calculations show that or-MgSiN₂ is energetically the stable polymorph at low pressure, in agreement with previous experimental and theoretical study. Under pressure, a crystallographic transition from the orthorhombic structure to the trigonal one occurs around 25, 17.45 and 19.05 GPa as obtained from the generalized gradient approximation of Perdew-Wang (GGA-PW91), the generalized gradient approximation parameterized recently by Perdew et al (GGA-PBEsol) and the local density approximation developed by Ceperley and Alder and parameterized by Perdew and Zunger (LDA-CAPZ), respectively. Single-crystalline and polycrystalline elastic constants and related properties, namely Vickers hardness, acoustic Grüneisen parameter, minimum thermal conductivity, isotropic sound velocities and Debye temperature, were numerically estimated for both or-MgSiN₂ and tr-MgSiN₂. We have showed that the hardness of tr-MgSiN₂ is comparable to that of the harder materials like c-BN and B₆O. Temperature and pressure dependencies of volume, bulk modulus, thermal expansion, Grüneisen parameter, heat capacities and Debye temperature were investigated using QHDM.     

Variations of lattice constants and thermal expansion coefficients of indium at high pressure and high temperature

ABSTRACT

The effects of pressure and temperature on the lattice constants and thermal expansion coefficients of Indium were studied up to 18.6?GPa and 506?K based on in situ X-ray diffraction method with an externally heated diamond anvil cell. The results show that the measured axial ratio (c/a) decreases with increasing temperature and its temperature dependence decreases with increasing pressure. The thermal expansion coefficient of the a-axis decreases with increasing pressure up to 7?GPa and remains almost constant above 7?GPa, whereas that of the c-axis increases monotonously with pressure and changes from negative to positive at around 7?GPa. The observed behavior suggests that temperature reduces the tetragonal distortion on the lattice, and its effect is dominant below 7?GPa; in contrast, pressure enhances lattice distortion, and tends to have a stronger effect above 7?GPa.     

Generation of microcellular poly(methyl methacrylate) by compressed gases

Abstract

Generation of microcellular poly(methy1 methacrylate) (PMMA) was studied in CO₂ and N₂O at pressures from 2 to 15MPa at three temperatures, 293.2K, 308.2K, and 323.2 K. The average diameter d and average number density N of voids generated by a rapid expansion of compressed gases in PMMA were measured by use of an optical microscope. Effects of gases, temperature, and pressure on the d and N values were examined. Even at pressure below glass transition pressure of PMMA with both gases, voids of diameter being as small as those found at high pressure, 15MPa, were obtained at each temperature. However, the void density of PMMA at lower pressure by both gases was not so good as those obtained at high pressures.     

First-principles calculation of structural stability,lattice dynamic and thermodynamic properties of BeX (X = S,Se and Te) compounds under high pressure

The phase transitions, lattice dynamical and thermodynamic properties of BeS, BsSe and BeTe at high pressure have been investigated with the density functional theory. The calculated equilibrium structural parameters agree well with the available experimental and theoretical values. The phase transition pressures from the zinc-blende (ZB) to the nickel arsenide (NiAs) phase of these compounds are determined. The calculated phonon dispersion curves of these compounds in ZB phase at zero pressure do not show any anomaly or instability. Dynamically, the ZB phase of BeS, BeSe and BeTe is found to be stable near transition pressures P_T. Within the quasiharmonic approximation, the thermodynamic properties including the thermal expansion coefficient, heat capacity at constant volume, heat capacity at constant pressure and entropy are predicted.     

Mechanical stability and thermodynamic properties of OsC from first-principles calculations

The elastic and thermodynamic characteristics of OsC crystal have been predicted through a method of density functional theory within the generalized gradient approximation (GGA). Compared with WC-type OsC, NaCl-type OsC is not only energy unfavorable but also mechanics unstable. The five independent elastic constants (C_ij), bulk modulus (B₀), the dependence of bulk modulus on temperature and pressure as well as the thermal expansion coefficient (α_V) at various temperatures for WC-type OsC are discussed. According to our calculations, WC-type OsC should be an ultra-incompressible material with high bulk modulus about 381 GPa. In addition, the bulk modulus will increase with increasing pressure while decrease with increasing temperature. The researches on the thermal expansion coefficient indicate that there will be a knee point during the process of thermal expansion coefficient variation versus increasing temperature. Our results may provide useful information for theoretical and experimental investigation of OsC.     

Combined effects of pressure and temperature on enzyme stability

Abstract

The effect of high temperature and high hydrostatic pressure on the residual hydrolytic activity of a commercial Rhizomucor miehei lipase has been studied. Inactivation at high temperature and/or high pressure was carried out. Under non-denaturing pressure conditions, results showed that pressurisation protects enzymes against thermal deactivation. This is in accordance with previous results obtained with enzymes from mesophilic sources, such as invertase and galactosidases.     

Molecular dynamics study for the thermal conductivity of diatomic liquid

The thermal conductivity of diatomic liquids was analyzed using a nonequilibrium molecular dynamics (NEMD) method. Five liquids, namely, O₂, CO, CS₂, Cl₂ and Br₂, were assumed. The two-center Lennard-Jones (2CLJ) model was used to express the intermolecular potential acting on liquid molecules. First, the equation of state of each liquid was obtained using MD simulation, and the critical temperature, density and pressure of each liquid were determined. Heat conduction of each liquid at various liquid states [metastable (ρ=1.9ρ_cr), saturated (ρ=2.1ρ_cr), and stable (ρ=2.3ρ_cr)] at T=0.7T_cr was simulated and the thermal conductivity was estimated. These values were compared with experimental results and it was confirmed that the simulated results were consistent with the experimental data within 10%. Obtained thermal conductivities at saturated state were reduced by the critical temperature, density and mass of molecules and these values were compared with each other. It was found that the reduced thermal conductivity increased with the increase in the molecular elongation. Detailed analysis of the molecular contribution to the thermal conductivity revealed that the contribution of the heat flux caused by energy transport and by translational energy transfer to the thermal conductivity is independent of the molecular elongation while the contribution of the heat flux caused by rotational energy transfer to the thermal conductivity increases with the increase in the molecular elongation. Moreover, by comparing the reduced thermal conductivity at various states, it was found that the increase of thermal conductivity with the increase in the density, or pressure, was caused by the increase of the contribution of energy transfer due to molecular interaction.     

Temperature dependence of dielectric constant of crystals with fluorite structure

The experimental data on the temperature variation of dielectric constant of six crystals with fluorite structure are analysed using an approach proposed by Havinga and Bosman for ionic crystals. The temperature variation of dielectric constant is resolved in three components related to the thermal expansion, the pressure dependence of dielectric constant and the temperature variation of polarizability (theA, B, C terms). In the present work, theB term is calculated semiempirically, such that the analysis can be extended to crystals like EuF₂ for which high pressure dielectric constant data are not available. For the first time, such calculations have been made for EuF₂ and PbF₂ at elevated temperatures. TheC term, which is related to the temperature variation ofir polarizability is seen to play a dominant role in determining the temperature variation of dielectric constant.     

Measurement of the Soret,diffusion, and thermal diffusion coefficients of three binary organic benchmark mixtures and of ethanol–water mixtures using a beam deflection technique

We have measured the Soret (S _T ), diffusion (D), and thermal diffusion (D _T ) coefficients of three binary mixtures of dodecane (DD), isobutylbenzene (IB) and 1,2,3,4-tetrahydronaphthalene (TH) for a concentration of 50 wt% at a temperature of 25°C by means of an optical beam deflection cell. This relevant experimental technique was still missing from a recent benchmark campaign for the measurement of the Soret effect. The measured coefficients agree to within a few percent (10% for S _T , D of TH/IB) with the proposed benchmark values. A detailed analysis of the measurement process of the beam deflection cell, which allows for an elegant extension to include temperature gradients within the windows, is given, and improved benchmark values are suggested. In addition, ethanol–water mixtures have been investigated very carefully over a broad concentration and temperature range. Comparison with data of Kolodner and Wiegand gives a generally good agreement with some systematic deviations. Contrary to theoretical predictions, we have not been able to identify a second sign change of S _T at high ethanol concentrations.     

Macrokinetics of decomposition of loose packed RDX in shock and detonation waves

The boundary retardation method was used to study the decomposition of loose packed density RDX behind the front of shock waves with amplitudes ranges from values critical for reaction initiation to those typical of detonation. The threshold pressure P* and temperature T* at which the transition from a relatively slow decomposition in hotspots to fast bulk conversion occurs. It was demonstrated that this transition is associated with a change in the macrokinetics of the conversion of HE material behind the shock front. At pressures below P*, an analogy with the kinetic regularities of the thermal decomposition of RDX at normal pressure is observed. At P > P*, the conversion occurs in the regime of an adiabatic thermal explosion at a very high rate and has no analogues in chemical kinetics. The normal detonation regime is realized at P > P*. It was shown that the macrokinetic characteristics of normal detonation cannot be described within the framework of traditional approaches, with the help of the Arrhenius law or the concept of deflagration propagating from hotspots.     

Elektrische und thermische Leitfähigkeit von Wasserstoff bis 27000 °K

For determination of the heat flux potentialS and of the electrical and thermal conductivityσ andκ as functions of temperature the radial distributions ofS, σ andT are needed. These distributions were evaluated from measurements resp. measured directly on the hydrogen plasma in a cascade arc chamber of high power load at a pressure of 1 atm. These results were published recently. By elimination of the radius as variable the electrical conductivityσ and the heat flux potentialS are determined as functions of temperature. The differentiation of the heat flux potential function with respect to temperature yields the thermal conductivityκ. Theoretical and experimental results of the electrical conductivity agree very well. This is also true of the relative course of the thermal conductivity. On the contrary the absolute values of the measured and theoreticalκ-curve differ by a factor of about two from each other at temperatures above 5,000 °K. This deviation could not yet be cleared. Together with the results of other authors now there exist measurements of the electrical and thermal conductivity of hydrogen at a pressure of 1 atm, up to 27,000 °K corresponding to a degree of ionization of 98%.     

High-pressure effect on the ferroelectric-paraelectric transition in PbTiO<Subscript>3</Subscript>

The crystal structure of lead titanate PbTiO₃ was investigated by energy dispersive X-ray diffraction at high pressures up to 4 GPa in a temperature range of 300–950 K. At the ambient conditions, the PbTiO₃ structure is tetragonal with the space group P4mm (ferroelectric phase). A structural phase transition into the cubic phase with a space group Pm[`3]mPm\bar 3m is observed at T = 747 K. It was found that the phase transition temperature decreases upon applying the high pressure with the coefficient dT _C /dP = -65 K/GPa. Dependences of parameters and volume of the unit cell on the pressure and temperature was found, and the bulk modulus and thermal expansion coefficients for the tetragonal and cubic phases of lead titanate have been calculated.