Structural and thermodynamic properties of AlB2 compound

We employ a first-principles plane wave method with the relativistic analytic pseudopotential of Hartwigsen, Goedecker and Hutter (HGH) scheme in the frame of DFT to calculate the equilibrium lattice parameters and the thermodynamic properties of AlB₂ compound with hcp structure. The obtained lattice parameters are in good agreement with the available experimental data and those calculated by others. Through the quasi-harmonic Debye model, obtained successfully are the dependences of the normalized lattice parameters a/a₀ and c/c₀ on pressure P, the normalized primitive cell volume V/V₀ on pressure P, the variation of the thermal expansion α with pressure P and temperature T, as well as the Debye temperature \Theta_D and the heat capacity C_V on pressure P and temperature T.     

First-principles calculations for transition phase and thermodynamic properties of GaAs

The transition phase of GaAs from the zincblende (ZB) structure to the rocksalt (RS) structure is investigated by ab initio plane-wave pseudopotential density functional theory method, and the thermodynamic properties of the ZB and RS structures are obtained through the quasi-harmonic Debye model. It is found that the transition from the ZB structure to the RS structure occurs at the pressure of about 16.3\,GPa, this fact is well consistent with the experimental data and other theoretical results. The dependences of the relative volume V/V₀ on the pressure P, the Debye temperature \Th and specific heat C_V on the pressure P, as well as the specific heat C_V on the temperature T are also obtained successfully.     

流体静压力对锗隧道二极管伏安特性的影响

本文报导了在流体静压力18000kg/cm²的范围内,锗隧道二极管伏安特性随压力变化的实验结果。测量了十六只锗隧道二极管的峯值电流I_P、峯值电压V_P、谷值电流I_V、谷值电压V_V、指数过剩电流I_X和反向隧道电流等参数与流体静压力的关系。结果表明:峯值电流I_P相对于压力的半对数作图为斜率不同的二段下降直线,在5000—9000kg/cm²范围内有转折点;峯值电压随压力改变较小;在误差范围内谷值电压不随压力而改变。对于大部分被测管子,谷值电流与压力的关系类似于峯值电流与压力的关系;随着压力的增加,指数过剩电流区向高偏压方向移动。讨论了峯值电流及指数过剩电流随压力变化的规律和其他结果。认为转折点的存在是表明隧道跃迁机构的改变;由指数过剩电流区固定电流值测偏压随压力改变,求得禁带宽度的压力系数与其他方法获得的结果很好符合。     

First-principles calculations of structural and thermodynamic properties of BeB2 compound

The lattice parameter bulk modulus and pressure derivative of BeB2 are calculated by using the Cambridge Serial Total Energy Package （CASTEP） program in the frame of density function theory. The calculated results agree well with the average experimental data and other theoretical results. Through the quasi-harmonic Debye model, the dependences of the normalized lattice parameters a/ao, c/c0 and the normalized primitive cell volume V/Vo on pressure P, the variation of the thermal expansion coefficient ~ with pressure P and temperature T, as well as the dependences of the heat capacity Cv on pressure P and temperature T are obtained systematically.     

Transition phase and thermodynamic properties of GaN via first-principles calculations

The transition phase of GaN from zincblende (ZB) structure to rocksalt structure (RS) is investigated by ab initio plane-wave pseudopotential density functional theory method, and the thermodynamic properties of the ZB and RS structures are obtained through the quasi-harmonic Debye model. We find that the transition phase from the ZB structure to the RS structure occurs at the pressure of 42.2 GPa, which is in good agreement with other calculated values. Moreover, the dependences of the relative volume V/V₀ on the pressure P, the Debye temperature Θ and heat capacity C_V on the pressure P, as well as the heat capacity C_V on the temperature T are also successfully obtained.     

Ab initio study of phase transition and thermodynamic properties of PtN

The transition phase of PtN from zincblende (ZB) structure to rocksalt (RS) structure is investigated by ab initio plane-wave pseudopotential density functional theory method, and the thermodynamic properties of the ZB and RS structures under high pressure and temperature are obtained through the quasi-harmonic Debye model. The transition phase from the ZB structure to the RS structure occurs at the pressure of 18.2 GPa, which agrees well with other calculated values. Moreover, the dependences of the relative volume V/V₀ on the pressure P, the Debye temperature Θ and heat capacity C_V on the pressure P, together with the heat capacity C_V on the temperature T are also successfully obtained.     

Structural phase transition (zincblende-rocksalt) and elastic properties in AlY (Y=N, P and As) compounds: Pressure-induced effects

The present paper addresses the pressure-induced structural aspects of ZnS-type (B3) to NaCl-type (B1) structure in AlY (Y=N, P, As). An effective-interionic interaction potential (EIoIP) with long-range Coulomb and three-body interactions and the Hafemeister-and-Flygare-type short-range overlap repulsion extended up to the second-neighbour ions and the van der Waals (vdW) interaction is developed. Emphasis has been given on evaluating the vdW coefficients by the Slater-Kirkwood variational method, as both the ions are polarizable. The lattice model calculations have revealed reasonably good agreement with the available experimental data on the phase-transition pressures (P_t=16, 14, 7.5 GPa) and the elastic properties of AlY (Y=N, P, As). The equation of state curves (plotted between V(P)/V(0) and pressure) for both the B3 and B1 structures obtained are in fairly good agreement with the experimental results. The calculated values of the volume collapses [ΔV(P)/V(0)] are also close to their observed data. Further, the variations of the second-order elastic constants with pressure follow a systematic trend that is almost identical to that exhibited by the observed data measured for other semiconducting compounds with B3→B1 structural phase transitions.     

Die Übergangstemperatur verschiedener Supraleiter zweiter Art unter hydrostatischem Druck

An apparatus for production of hydrostatic pressure is described using a mixture of n-pentane and iso-pentane, which transmits pressure uniformly still at low temperatures. The superconductive transitions of the A 15(β- W type)-compounds Nb₃Sn, Nb₃Al, V₃Si and the B 1(NaCl type)-compound NbN have been measured under pressure up to 18 · 10³ kp/cm². The transition temperatures of the compounds V₃Si and NbN are increasing with pressure. Further measurements have been done on some selected ternary compounds, e.g. Nb₃(Al_1?x Ge _x ), to prove some predictions for the effect of pressure on superconductive transition.     

一种新的快速凝固方法快速卸压淬火

对于固化温度随压力升高而降低的熔体，在适当的初始温度和压力下快速卸压，将使熔体快速固化.给出了通过快速卸压而获得相应过冷速率的计算公式，并用Al-Ge系统对这种新的快速凝固方法进行了评估.实验结果表明用此种方法能获得大于10⁵K·s^-1的过冷速率，因而有利于制备大块亚稳材料甚至非晶.同时，通过快速卸压而实现快速凝固的原理，可用于解释物质在冲击压作用下的非晶化及亚稳相形成. 关键词：     

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.     

Activation volumes of hydrolyses of maltose and maltotriose over an immobilized glucoamylase catalyst

Abstract

Initial rates of hydrolysis of maltose and maltotriose over an immobilized glucoamylase have been measured up to 127 MPa at 25±0.1°C. The observed rates have been analyzed showing the reaction pathways of both hydrolyses to be E+S?ES*?ES7ast;E+P, where E, S, P, ES*, and ES denote the enzyme, the substrate, the product, a substrate-subsite complex, and a substrate-active site complex, respectively. The apparent maximum rate r^mand the apparent Michaelis constant K^m as well as their respective pressure dependences in terms of the apparent activation volume Δ V_app ^# and the apparent volume of reaction Δ V_app have been evaluated. Small absolute values of Δ V_app ^num; and Δ V_app for both reactions have been discussed on the basis of the reaction mechanism.     

First-principles study of structural and thermodynamic properties of osmium

We employ the first-principles plane wave pseudopotential density functional theory method to calculate the equilibrium lattice parameters of osmium and the thermodynamic properties of hcp structure osmium. The obtained lattice parameters are in good agreement with the experimental data investigated up to 58.2 GPa using radial X-ray diffraction (RXRD) together with lattice strain theory in a diamond-anvil cell and the available theoretical data of others. Through the quasi-harmonic Debye model, the dependencies of the normalized lattice parameters a/a₀ and c/c₀ on pressure P, the normalized primitive volume V/V₀ on pressure P, the Debye temperature Θ_D and the heat capacity C_V on pressure P and temperature T, as well as the variation of the thermal expansion α with temperature and pressure are obtained successfully.     

Pressure induced B3-B1 structural phase transition and elastic properties of monopnictides InX (X = N,P, As)

An effective interionic interaction potential is developed to discuss the pressure induced structural phase transformation and mechanical properties of InX (X = N, P, As) semiconducting compounds. The effective interionic potential consists of the long-range Coulomb and three-body interactions and the Hafemeister and Flygare type short-range overlap repulsion extended upto the second neighbour ions and the van der Waals interaction. The present calculations have revealed reasonably good agreement with the available experimental data on the phase transition pressures (P_t = 11.5, 10, 7.5 GPa) and the elastic properties of InX (X = N, P, As). The equation of state curves (plotted between V (P)/V(0) and pressure) for both the structures zincblende (B3) and rocksalt (B1) structures obtained by us are in fairly good agreement with the experimental results. The calculated values of the volume collapses [ΔV(P)/V(0)] are also closer to their observed data.     

Hydrogen permeation of Pd-coated V90Al10 alloy membranes at different pressures in the presence and absence of carbon dioxide

The hydrogen permeation characteristics of alloy membranes based on Pd-coated V₉₀Al₁₀ alloy membrane have been investigated in the pressure range 1-3 atm under pure hydrogen and hydrogen-carbon dioxide gas mixture at 450 °C. Hydrogen permeation experiments have been confirmed that hydrogen flux was 21.1 ml/min/cm² for a Pd-coated V₉₀Al₁₀ alloy membrane (thickness: 0.5 mm) using pure hydrogen as the feed gas. It has been found that Pd-coated V₉₀Al₁₀ alloy membranes exhibit good resistance to hydrogen embrittlement in pure hydrogen atmosphere. After different hydrogen permeation flux tests under different pressure condition in presence of hydrogen-carbon dioxide gas mixture, the characteristics of the Pd-coated V₉₀Al₁₀ alloy membranes were examined by ex-situ analysis techniques. The loss of cell performance observed in the presence of hydrogen-carbon dioxide gas mixture is mainly attributed to both physical and chemical degradations of membrane, which led to structural changes in the Pd-coated V₉₀Al₁₀ alloy membrane.     

Porous PVdF-HFP/P123 electrolyte membrane containing flexible quasi-solid-state dye-sensitized solar cells produced by the compression method

Flexible quasi-solid-state dye-sensitized solar cells (DSSCs) with porous poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP)/polyethylene oxide-co-polypropylene oxide-co-polyethylene oxide (P123) electrolyte membranes were fabricated and their photocurrent–voltage (I–V) characteristics are studied. Flexible TiO₂ photoelectrodes were prepared using the compression method and porous PVdF-HFP/P123 membranes, by the nonsolvent-induced phase inversion technique. To activate the electrolyte membrane, the membrane was immersed in liquid-state electrolyte. Increased compression pressure improved the interconnection between TiO₂ nanoparticles, enhancing the photovoltaic performances of the flexible liquid-state DSSCs to a maximum of 3.92% efficiency. Meanwhile, the overall pore structure of the PVdF-HFP/P123 membranes was controlled by varying the blend ratio of P123 to PVdF-HFP. Membranes higher in P123 content gave larger pores and pore volume, increasing the electrolyte uptake of the porous membrane, and thus the ionic conductivity of the electrolyte membrane as well. The photovoltaic characteristics of the flexible quasi-solid-state DSSCs containing a porous PVdF-HFP/P123 electrolyte membrane showed a maximum at 50 wt% P123 content, which gave a short-circuit current density (J_sc) value of 7.28 mA/cm², an open-circuit voltage (V_oc) of 0.67 V, a fill factor (FF) of 0.61 and an energy conversion efficiency (η) of 2.98%. Furthermore, the device designed in this study showed good durability compared to those based on liquid-state electrolyte.     

First-principles study of elastic and electronic properties of layered ternary nitride SrZrN2 under pressure

The structural, elastic, and electronic properties of SrZrN₂ under pressure up to 100?GPa have been carried out with first-principles calculations based on density functional theory. The calculated lattice parameters at 0?GPa and 0?K by using the GGA-PW91-ultrasoft method are in good agreement with the available experimental data and other previous theoretical calculations. The pressure dependence of the elastic constants and the elastic-dependent properties of SrZrN₂, such as bulk modulus B, shear modulus G, Young's modulus E, Debye temperature Θ, shear and longitudinal wave velocity V_S and V_L, are also successfully obtained. It is found that all elastic constants increase monotonically with pressure. When the pressure increases up to 140?GPa, the obtained elastic constants do not satisfy the mechanical stability criteria and a phase transition might has occurred. Moreover, the anisotropy of the directional-dependent Young's modulus and the linear compressibility under different pressures are analysed for the first time. Finally, the pressure dependence of the total and partial densities of states and the bonding property of SrZrN₂ are also investigated.     

多晶Li3+xV1-xTxO4(T=Ge,Si)离子导电性能的改善

本文用阻抗谱方法研究了Li_3+xV_1-xT_xO₄(T=Si,Ge)多晶的离子导电性,发现一些工艺条件如成型压强、烧结时间和烧结程序对电导率有很大影响。注意分析了这些影响的物理起因。最佳工艺条件是:在大约8t/cm²压强下成型样品。在1000℃连续烧结5至6天,烧结过程中,应尽量避免温度波动。在此条件下制备的Li_3.5V_0.5Ge_0.5关键词：     

On the surface energy of crystals of inert gases

The dependences of the specific surface energy (σ) and its isochoric temperature derivative (?σ/?T) _V on the degree of compression (V/V ₀) of the crystal are calculated on the basis of the Mie-Lennard-Jones pair potential of interatomic interaction. The calculations are performed for all face-centered cubic crystals of inert gases (from Ne to Rn) to the degree of compression V/V ₀ = 0.016 along three isotherms: 1K, T _m and 300 K, where T _m is the melting temperature at zero pressure (V/V ₀ = 1). The activation processes such as the creation of vacancies and self-diffusion are taken into account in the calculations. It is shown that the isotherm σ(V/V ₀) reaching its maximum at (V/V ₀)_max sharply decreases upon further compression. The surface energy becomes negative (σ(V/V ₀) _fr =0) at V/V ₀ ≤ (V/V ₀) _fr < (V/V ₀)_max which should stimulate the process of crystal fragmentation, i.e., an increase in the specific (per atom) intercrystallite surface. It is shown that at high temperatures the condition of fragmentation holds in the crystal in the case of uniform tension, but it is already in the region of the liquid phase. The values of σ, (?σ/?T) _V , the vacancy concentration and the fraction of the diffusion atoms are estimated at the points: V/V ₀ = 1, (V/V ₀)_max and (V/V ₀) _fr at 1 K, Tm and 300 K. The size evolution of the surface and activation parameters is studied using neon as an example.     

AlAs相变及热动力学性质的第一性原理研究

利用基于密度泛函理论的全势能线性糕模轨函法研究了闪锌矿（B3）,NiAs（B8）和岩盐（B1）结构的AlAs的相变、结构性质以及热动力学性质.对B3-B8和B3-B1结构的能量体积曲线做公切线,得到了B3→B8相变压力为5.44 GPa,并预测到B3→B1相变压力为6.46 GPa.同时计算了高压下B8相的结构性质,结果显示当V/V₀≈0.7—1.05时,c/a基本保持恒定（仅有约 0.2%的波动）;当V/V₀≈0.4—0.7,c/a随着V/V₀的减小而近似线性地增大.通过状态方程拟合,得到了AlAs的相对体积V/V₀与压强P的函数关系,B8相的状态方程与实验结果符合很好.最后利用准谐德拜模型得到了AlAs的体弹模量B随压力P的变化关系以及不同压强下热容C_V与温度T的关系. 关键词： 相变 热力学性质 第一性原理     

Orientation kinetics of the hexavacancies—V6 (B80) in silicon

A phenomenological kinetic equation is proposed to describe a process of a hexavacancy (V₆) orientation in silicon samples. The orientation kinetics of V₆ was investigated under a uniaxial compressional stress along the [111] axis of the crystal. Parameters appeared in the matrix equation of the orientation kinetics of V₆ as functions of pressure and annealing temperature were obtained and their values were estimated. In the case of the inequivalent V₆ centers, the pressure dependence of the difference in the magnitude of their binding energies was determined.