Exploring high pressure structural transformations,electronic properties and superconducting properties of MH2 (M = Nb,Ta)

The high-pressure structures and properties of MH₂ (M = Nb, Ta) are explored through an ab initio evolutionary algorithm for crystal structure prediction and first-principles calculations. It is found that NbH₂ undergoes a phase transition from a cubic Fm$\overline{3}$m structure with regular NbH₈ cubes to an orthorhombic Pnma structure with fascinating distorted NbH₉ tetrakaidecahedrons at 48.8 GPa, while the phase transition pressure of TaH₂ from a hexagonal P6₃mc phase with slightly distorted TaH₇ decahedron to an orthorhombic Pnma phase with attractive distorted TaH₉ tetrakaidecahedrons is about 90.0 GPa. Besides, the calculated electronic band structure and density of states demonstrate that all of these structures are metallic. The Poisson’s ratio, electron localization function, and Bader charge analysis suggest that these phases possess dominant ionic bonding character with the effective charges transferring from the metal atom to H. From our electron–phonon calculations, the calculated superconducting critical temperature T_c of the Pnma-NbH₂ is 6.903 K at 50 GPa. Finally, via the quasi-harmonic approximation method, the phase diagrams at pressure up to 300 GPa and temperature up to 1000 K of MH₂ (M = Nb, Ta) are established, where the transition pressure of Fm$\overline{3}$m-NbH₂ → Pnma-NbH₂ and P6₃mc-TaH₂ → Pnma-TaH₂ were found to decrease with increasing temperature.     

Self-strengthening and high temperature sintering in binder-free silicon nitride

A thermal strengthening process, which occurs during low-temperature heating of binder-free silicon nitride, has been investigated using simultaneous thermal analysis, dilatometry and FTIR and shown to occur in separate stages over clearly identifiable temperatures. Reactions which give the strengthening are the loss of physically and chemically combined water and the decomposition of ammonium carbonate and various hydrosilicates. Compacts have bend strengths of 8–10 MPa after strengthening at 500°C and 30–34 MPa after strengthening at 900°C. High-temperature dilatometry shows several stages of sintering. The maximum rate occurs at 1800°C with shrinkage commencing at 1450°C. Densities of 98.3% theoretical are obtained on heating to 1900°C.     

Evaluation of the calibration errors on cooling of a differential scanning calorimeter using different sets of standard metals

The temperature calibration on cooling of thermal analysis instruments is important for the accurate study of the non-isothermal crystallization kinetics of semi-crystalline polymers. In previous works, a methodology was proposed for performing the calibration on cooling of differential scanning calorimeters (DSCs) with standard metals, and the calibration errors were checked using transitions of high-purity liquid crystals. In this work, alternative, physically meaningful, procedures for carrying out the calibration on cooling are analyzed and validated. The calibration errors are evaluated also with liquid crystalline transitions, when the calibration is performed with standard metals, in a wide temperature range, and when due account is taken for the need of isothermal corrections to the temperature measurements. It is shown that any pair of standard metals may be used to calibrate on cooling, that the calibration errors increase for wider working temperature ranges and that, providing that certain conditions are fulfilled, both calibration procedures yield similar results.     

Electrochemical Determination of Ascorbic Acid in Room Temperature Ionic Liquid BPPF6 Modified Carbon Paste Electrode

A room temperature ionic liquid N‐butylpyridinium hexafluorophosphate (BPPF₆) was used as a binder to make an ionic liquid modified carbon paste electrode (IL‐CPE), which showed good characteristics such as simple preparation procedure, fast electrochemical response and good conductivity. The electrochemical oxidation of ascorbic acid (AA) on the new IL‐CPE was carefully studied. The oxidation peak potential of AA on the IL‐CPE appeared at 109 mV (vs. SCE), which was about 338 mV decrease of the overpotential compared to that obtained on the traditional carbon paste electrode (CPE) and the oxidation peak current was increased for about four times. The electrochemical parameters of AA on the IL‐CPE were calculated with the charge transfer coefficient (α) and the electrode reaction rate constant (k_s) as 0.87 and 0.800 s^?1, respectively. Based on the relationship of the oxidation peak current and the concentration of AA a sensitive analytical method was established with cyclic voltammetry. The linear range for AA determination was in the range from 1.0×10^?5 to 3.0×10^?3 mol/L with the linear regression equation as I_p (μA)=?2.52–0.064C (μmol/L) (n=13, γ=0.9942) and the detection limit was calculated as 8.0×10^?6 mol/L (3σ). The proposed method was free of the interferences of coexisting substances such as dopamine (DA) and amino acids etc., and successfully applied to the vitamin C tablets determination.     

New Temperature Integral Approximate Formula for Non-isothermal Kinetic Analysis

A new approximate formula for temperature integral is proposed. The linear dependence of the new fomula on x has been established. Combining this linear dependence and integration-by-parts, new equation for the evaluation of kinetic parameters has been obtained from the above dependence. The validity of this equation has been tested with data from numerical calculating. And its deviation from the values calculated by Simpson's numerical integrating was discussed. Compared with several published approximate formulae, this new one is much superior to all other approximations and is the most suitable solution for the evaluation of kinetic parameters from TG experiments. This revised version was published online in August 2006 with corrections to the Cover Date.     

Dynamics of the formation of two-dimensional ordered structures

The growth of ordered domains in lattice gas models, which occurs after the system is quenched from infinite temperature to a state below the critical temperatureT _c, is studied by Monte Carlo simulation. For a square lattice with repulsion between nearest and next-nearest neighbors, which in equilibrium exhibits fourfold degenerate (2×1) superstructures, the time-dependent energy E(t), domain size L(t), and structure functionS(q, t) are obtained, both for Glauber dynamics (no conservation law) and the case with conserved density (Kawasaki dynamics). At late times the energy excess and halfwidth of the structure factor decrease proportional tot ^–x, whileL(t) t ^x, where the exponent x=1/2 for Glauber dynamics and x1/3 for Kawasaki dynamics. In addition, the structure factor satisfies a scaling lawS(k,t)=t ^2xS(kt^x). The smaller exponent for the conserved density case is traced back to the excess density contained in the walls between ordered domains which must be redistributed during growth. Quenches toT>T _c, T=T_c (where we estimate dynamic critical exponents) andT=0 are also considered. In the latter case, the system becomes frozen in a glasslike domain pattern far from equilibrium when using Kawasaki dynamics. The generalization of our results to other lattices and structures also is briefly discussed.     

Low-temperature electrothermal vaporization of thenoyltrifluoroacetone complex of Sc(III) and Y(III) for sample introduction in an inductively coupled plasma atomic emission spectrometry,and their determination in biological samples

A new method for inductively coupled plasma atomic emission spectrometry (ICP-AES) determination of trace Sc and Y, based on gaseous compound introduction into the plasma as their thenoyltrifluoroacetone (TTA) complexes by electrothermal vaporization was developed. Using the reagent TTA as chemical modifier can not only enhance the analytical signals, but also reduce the vaporization temperature. At a temperature of 1,000 °C the trace Sc and Y can be vaporized completely into ICP. The factors affecting the formation of the chelate and its vaporization behavior, such as drying time, vaporization temperature/time, reaction medium and the amount of TTA, were investigated in detail. Under the optimized conditions (drying temperature/time 100 °C/10 s, vaporization temperature/time 1,000 °C/4 s), the limits of detection for Sc and Y were 19 pg and 34 pg (3), respectively, and the relative standard deviations for Sc and Y were 4.2% (c _Sc=0.2 g mL^–1; n=7) and 2.6% (c _Y=0.5 g mL^–1; n=7). The linear ranges of the calibration graphs cover three orders of magnitude. The method was applied to the analysis of the biological reference materials (GBW 07602, bush branches and leaves; GBW 07604, poplar leaves), and the results obtained were in good agreement with the certified values.     

Effect of carbonate incorporation on the structural and superconducting properties of the double chain compound Y2Ba4Cu7O15−x

Structural investigations on powder samples of Y₂Ba₄Cu₇O_15–x with different carbonate content have been performed. Powder x-ray Rietveld refinements showed the remarkable influence of carbonate incorporation on the lattice parameters. Most important is the decrease of T_c with increasing carbonate content. We assign these effects to an incorporation of the carbonate ion into the crystal lattice, copper vacancies at the Cu(1) position and a possible misorientation of the copper oxygen single chains. No change of the structure (e. g. superstructure) could be found.     

立规聚甲基丙烯酸热表征研究

本文对不同立构的聚甲基丙烯酸(PMAA)进行了热表征。实验结果表明,在30℃～200℃内未出现玻璃化转变。间同PMAA分别在-245℃和-280℃发生脱水反应和脱羧,而全同PMAA只在-185℃观察到脱水反应。这种热稳定性的明显差别与不同立构PMAA链上相邻羧酸距离有关。实验数据证实PMAA脱水反应为无规反应,服从一级动力学反应方程。脱水温度和间同立构含量成正比,脱水反应活化能间同PMAA比全同PMAA高～7Kcal/mol。     

Bifurcation phenomena near homoclinic systems: A two-parameter analysis

The bifurcations of periodic orbits in a class of autonomous three-variable, nonlinear-differential-equation systems possessing a homoclinic orbit associated with a saddle focus with eigenvalues ( ±i,), where ¦/¦ < 1 (Sil'nikov's condition), are studied in a two-parameter space. The perturbed homoclinic systems undergo a countable set of tangent bifurcations followed by period-doubling bifurcations leading to periodic orbits which may be attractors if ¦/¦ < 1/2. The accumulation rate of the critical parameter values at the homoclinic system is exp(-2¦/¦). A global mechanism for the onset of homoclinicity in strongly contractive flows is analyzed. Cusp bifurcations with bistability and hysteresis phenomena exist locally near the onset of homoclinicity. A countable set of these cusp bifurcations with scaling properties related to the eigenvalues±i of the stationary state are shown to occur in infinitely contractive flows. In the two-parameter space, the periodic orbit attractor domain exhibits a spiral structure globally, around the set of homoclinic systems, in which all the different periodic orbits are continuously connected.