Thermodynamic properties of MgO under high pressure from first-principles calculations

The equations of state (EOS) and other thermodynamic properties of the rocksalt (RS) structure MgO are investigated by ab initio plane-wave pseudopotential density functional theory method. The obtained results are consistent with the experimental data and those calculated by others. Through the quasi-harmonic Debye model, in which the phononic effects are considered, the dependences of relative volume V/V₀ on pressure P, cell volume V on temperature T, and Debye temperature Θ and specific heat C_V on pressure P are successfully obtained. The variation of the thermal expansion with temperature and pressure is investigated, which shows the temperature has hardly any effect on the thermal expansion at higher pressure.     

An isothermal equation of state for solids

An isothermal equation of state (EOS) for solids, recently suggested by the authors in the realistic form, V/V₀=f(P), with relative volume as the dependent and the pressure as the independent variable, was shown to have an advantage for some close-packed materials in that it allows B′_∞=(∂B_s/∂P)_s(P→∞) to be fitted, and this is where the usual standard equations fail. In the present study, our EOS is applied to a number of inorganic as well as organic solids, including alloys, glasses, rubbers and plastics; varying widely in their bonding and structural characteristics, as well as in their bulk modulus values. A very good agreement is observed between the data and fits. The results obtained are compared with those from two well-known equations, expressible in the realistic form, proposed by Murnaghan and Luban. Further, the results are also compared with those from the widely used two- and three-parameter EOSs, expressible in the unrealistic form only, P=f(V/V₀), proposed by Birch—and also with those from the EOS model of Keane in which B′_∞ is explicitly expressed as an equation of state parameter. The results obtained from our model compare well to these EOSs. Our EOS, in general, yields the smallest mean-squared deviations between data and fits. The values of B′_∞calculated from our EOS are compared with those from Keane's model. Further, we have studied the variation of B′_∞with temperature using the experimental isotherms of Mo and W at 10 different temperatures ranging from 100 to 1000 K, and observed that the values of B′_∞ yielded by our model and that of Keane vary, as expected, within a narrow range. Furthermore, our EOS is applied to study the stability of the fit parameters with variation in the pressure ranges with reference to the isothermal compression data on Mo and W—and also to study the variation of isothermal bulk modulus with pressure, with reference to the ultrasonic data on NaCl and noted a very good agreement with experiment. In addition, our model is applied, with B₀ and B′₀ constrained to the theoretical values, to the five theoretical isotherms of MgO at 300, 500, 1000, 1500 and 2000 K obtained on the basis of a first principles approach—a good agreement is observed with the predictions, and the values of B′_∞ inferred at different temperatures tend to converge to a constant value.     

Pressure–temperature studies on conductivity of TlX(X=Cl,Br,I) compounds:: I: phase diagram. II: ionic mobility

We have measured the conductivity σ of TlX(X=Cl, Br, I) compounds up to 5.3 GPa and between 300–823 K. The σ–T dependence for all compounds can be divided into three distinct regions: (i) low temperature (LT), <400 K, with unusual negative σ–T dependence, (ii) intermediate temperature (IT), 400<650 K, with positive σ–T dependence and (iii) high temperature (HT), T>650 K, with positive σ–T dependence. The σ–T isobars were used to construct the T–P solid phase diagram for each compound. The LT region data indicate a new meta-stable phase in the 1.0–3.5 GPa range. The LT→IT transition is characterized by an inverse σ–T dependence followed by normal Arrhenius behavior up to and including the HT region. The extrapolation to 1 atm of the P-dependent boundary between IT and HT regions above 3 GPa for each compound in the P–T plot yields a value close to its respective normal (1 atm) T_melt suggesting a solid order–disorder transition type paralleling -AgI behavior. The abrupt drop in conductivity in the LT region for P between 2.5–4.1 GPa of all compounds is at variance with the Arrhenius behavior observed for unperturbed ion migration implying the appearance of a second factor overriding the Arrhenius temperature dependence. Normal Arrhenius σ–T dependence prevails in both IT and HT regions with Q_c values of 85–100 kJ mol⁻¹ and 50–75 kJ mol⁻¹, respectively. The higher conductivities at 0.4 GPa for TlBr and TlI relative to their 1 atm data and the increasing σ with P are in strong contrast to the normal σ-P behavior of TlCl. The dependence of activation volume ΔV^‡ on T for TlCl, i.e. ΔV^‡>0, shows abnormally high values with a maximum at 500 K for P<3.0 GPa but reasonable ΔV^‡ values appear above 3.0 GPa. The ΔV^‡–T dependence for both TlBr and TlI with ΔV^‡<0 is incompatible with an ion transport mechanism suggesting an electronic conduction process and implying an ionic–metallic transition at higher pressures. These contrasting conductivity features are discussed and interpreted in terms of electronegativity differences and bonding character rather than structure.     

二维圆盘颗粒体系声学行为的数值研究

数值测量了卸载过程中二维单分散圆盘颗粒系统的横波、纵波声速、声衰减系数、非线性系数随压强的变化以及声衰减系数随频率的变化.结果表明,二维(2D)圆盘颗粒体系的横波、纵波声速均随压强呈分段幂律标度:当压强P10~(-4)时,横波、纵波声速随压强的增大而减小;当P10~(-4)时,有v_t~P~(0.202),v_l~P~(0.338).进一步得到其剪切模量和体积模量的比值G/B也随压强呈幂律标度,G/B~P~(-0.502),暗示在低压强下,与三维(3D)球形颗粒体系类似,2D圆盘颗粒体系也处于L玻璃态.水平激励和垂直激励下2D圆盘颗粒系统的衰减系数随频率变化也呈现分段行为:当频率f0.05时,衰减系数不随f变化;当f0.05时,横波纵波的衰减系数α~f;当f0.35时,横波衰减系数α_T~f~2,纵波衰减系数α_L~f~(1.5).此外,竖直水平激励下的2D圆盘颗粒系统的非线性系数和衰减系数随压强也呈现与声速类似的分段规律:当P10~(-4)时,横波非线性系数β_T~P~(-0.230),其余都不随压强变化.当P10~(-4)时,两者均随压强增大呈幂律减小:β_T~P~(-0.703),β_L~P~(-0.684),α_T~P~(-0.099),α_L~P~(-0.105).进而得到2D圆盘颗粒系统中散射相关的特征长度?~*随压强呈幂律标度,当P10~(-4)时,?~*~P~(-0.595);当P10~(-4)时,?~*~P~(0.236).     

Diffusion of Na in sodium borate glasses

Diffusion of ²²Na in ion-conducting xNa₂O·(1−x)B₂O₃ glasses (x=0.2 and 0.3) was investigated under standard conditions and under high pressure employing the radiotracer sectioning method. A slight decrease of the diffusion coefficients with increasing time of diffusion annealing is observed and attributed to a structural relaxation of the glass network. The temperature dependence of diffusion was measured below and also in a small temperature range above the glass transition temperature (T_G). Below T_G the diffusion coefficients obey Arrhenius relations. Diffusion in the glass with x=0.3 is fast and associated with an activation enthalpy of 71 kJ mol⁻¹. The diffusion coefficients of the glass with x=0.2 are significantly smaller with an activation enthalpy of 112 kJ mol⁻¹. The activation volume ΔV of Na-diffusion in 0.3Na₂O·0.7B₂O₃ was determined from high pressure diffusion studies at 623 K. A value of 0.52 molar volume of the glass matrix was obtained. According to our knowledge this is the first measurement of an activation volume of diffusion in ion-conducting glasses. The present results will be discussed and compared with dc conductivity data for borate glasses and diffusion results for other oxide glasses reported in the literature.     

P213 BN: a novel large-cell boron nitride polymorph

A new boron nitride polymorph, P2₁3 BN (space group: P2₁3), is investigated by first-principles calculations, including its structural properties, stability, elastic properties, anisotropy and electronic properties. It is found that the new boron nitride polymorph P2₁3 BN is mechanically, dynamically and thermodynamically stable. The bulk modulus (B), shear modulus (G) and Young's modulus of P2₁3 BN are 91 GPa, 41 GPa and 107 GPa, respectively, all of which are larger than that of Y carbon and TY carbon. By comparing with c-BN, the Young's modulus, shear modulus and Poisson's ratio of P2₁3 BN show tiny anisotropy in the (001), (010), (100) and (111) planes. At the same time, in contrast with most boron nitride polymorphs, P2₁3 BN is a semiconductor material with a smaller band gap of 1.826 eV. The Debye temperature and the anisotropic sound velocities of P2₁3 BN are also investigated in this work.     

相位角对容性耦合电非对称放电特性的影响

电非对称效应作为一种新兴技术，被广泛用于对离子能量和离子通量的独立调控.此外，在改善等离子体的径向均匀性方面，电非对称效应也发挥了重要作用.本文采用二维流体力学模型，并耦合麦克斯韦方程组，系统地研究了容性耦合氢等离子体中当放电由多谐波叠加驱动时，不同谐波阶数k下的电非对称效应，重点观察了相位角θ_n对自偏压以及等离子体径向均匀性的影响.模拟结果表明：在同一谐波阶数下，自偏压随相位角θ_n的变化趋势不尽相同，且当k增大（k>3）时，自偏压随最高频相位角θ_k的变化范围逐渐减小.此外，通过调节相位角θ_n，可以改变轴向功率密度和径向功率密度的相对关系，进而实现对等离子体径向均匀性的调节.研究结果对于利用电非对称效应优化等离子体工艺过程具有一定的指导意义.     

Reactive sintering for oriented and connected Bi-2223 superconductive oxides from a mixture of delaminated Bi-2212 and fine powdered supplemental ingredients

Single crystals of NdBa₂Cu₃O_7−δ (Nd123) have been successfully grown by the top-seeded solution-growth (TSSG) method in 1%, 21% and 100% oxygen partial pressure atmosphere ((P(O₂) = 0.01 atm, P(O)₂) = 0.21 atm and P(O₂) = 1.00 atm). Ba---Cu---O solvent with a Ba to Cu ratio of 3:5 was used in a Nd₂O₃ crucible. Nd is supplied by the reaction between the molten solvent and the Nd₂O₃ crucible. Compositions of Nd123 single crystals grown in different oxygen partial pressure atmospheres were analyzed by inductivity coupled plasma atomic emission spectrometry (ICP-AES) and confirmed to be Nd:Ba:Cu = 1.01:1.97:3.00 for P(O₂) = 0.01 atm, Nd:Ba:Cu = 1.07:1.95:3.00 for P(O₂) = 0.21 atm and Nd:Ba:Cu = 1.10:1.90:3.00 for P(O₂) = 1.00 atm, respectively. The Nd123 single crystals grown in different oxygen partial pressure atmospheres were annealed in a pure oxygen gas flow, and the temperature dependence of the DC magnetization for these crystals was measured using a superconducting quantum interference device (SQUID) magnetometer. The Nd123 single crystal grown in P(O₂) = 0.01 atm, and annealed at 340°C for 200 h showed a steep superconductive transition at 96 K. On the other hand, the Nd123 crystal grown in P(O₂) = 0.21, 1.00 atm and, annealed at 340°C for 200 h exhibited a broad transition at 92 K for P(O₂) = 0.21 atm and at 88 K for P(O₂) = 1.00 atm, respectively. Therefore for Nd123 single crystal production with high quality superconductive characteristics, a low oxygen partial pressure atmosphere during crystal growth is found to be effective for minimizing the substitution of Nd ions into Ba sites.     

Temperature and pressure dependence of NMR frequencies in ferromagnetic Heusler alloys containing cobalt and manganese

The ⁵⁹Co and ⁵⁵Mn NMR frequencies ν in Co₂MnZ (Z = Si, Ge, Sn and Ga) were measured as a function of temperature T and pressure P by the cw method. The ν/ν_4.2 value decreased faster for ⁵⁹Co than for ⁵⁵Mn with increasing T/T_C especially in Co₂MnGa, for which ∂ν/∂P was positive at 0°C in contrast to the results in other alloys.