Isostructural phase transition (IPT) in CaMoO4 with Scheelite structure

The ceramic compound CaMoO₄ is synthesized via a solid-state reaction technique. Rietveld refinement studies were done on the powder X-ray diffraction data of CaMoO₄ and revealed that the compound is crystallized in the tetragonal Scheelite structure with I4₁/a space group. The differential scanning calorimetry (DSC) studies on CaMoO₄ divulged an anomaly around 440 °C. This anomaly is further probed using the temperature-dependent Raman and dielectric spectroscopic measurements and are corroborating with the results obtained from DSC. A detailed investigation on the temperature-dependent Raman spectroscopic data revealed that the A_1g mode of CaMoO₄ showed a soft phonon behavior up to the phase transition temperature. It is observed that the A_1g mode displayed phonon hardening behavior with further increasing the temperature. The anomaly is attributed to an isostructural phase transition (IPT), a rarely observed phenomenon in the compounds with Scheelite structure. The IPT in CaMoO₄ is elucidated with a phonon softening mechanism.     

Annealing temperature-dependent structural and electrical properties of (Ta2O5)1-x - (TiO2)x thin films,x ≤ 0.11

(Ta₂O₅)_1-x- (TiO₂)_x (TTO_x) thin films, with x = 0, 0.03, 0.06, 0.08, and 0.11, were deposited using magnetron direct current (DC) sputtering method onto the P/boron-silicon (1 0 0) substrates by varying areas of Tantalum and Titanium metallic targets, in oxygen environment at ambient temperature. The as-deposited thin films were annealed at temperatures ranging from 500 to 800 °C. Generally, the formation of the Ta₂O₅ structure was observed from the X-ray diffraction measurements of the annealed films. The capacitance of prepared metal– oxide– semiconductor (MOS) structures of Ag/TTO_x/p-Si was measured at 1 MHz. The dielectric constant of the deposited films was observed altering with varying composition and annealing temperature, showing the highest value 71, at 1 MHz, for the TTO_x films, x = 0.06, annealed at 700 °C. With increasing annealing temperature, from 700 to 800 °C, the leakage current density was observed, generally decreasing, from 10^?5 to 10^?8 A cm^?2, for the prepared compositions. Among the prepared compositions, films with x = 0.06, annealed at 800 °C, having the observed value of dielectric constant 48, at 1 MHz; and the leakage current density 2.7 × 10^?8 A cm^?2, at the electric field of 3.5 × 10⁵ V cm^?1, show preferred potential as a dielectric for high-density silicon memory devices.     

Optimized Biocatalytic Synthesis of 2-Selenopyrimidine Nucleosides by Transglycosylation**

Selenium-modified nucleosides are powerful tools to study the structure and function of nucleic acids and their protein interactions. The widespread application of 2-selenopyrimidine nucleosides is currently limited by low yields in established synthetic routes. Herein, we describe the optimization of the synthesis of 2-Se-uridine and 2-Se-thymidine derivatives by thermostable nucleoside phosphorylases in transglycosylation reactions using natural uridine or thymidine as sugar donors. Reactions were performed at 60 or 80 °C and at pH 9 under hypoxic conditions to improve the solubility and stability of the 2-Se-nucleobases in aqueous media. To optimize the conversion, the reaction equilibria in analytical transglycosylation reactions were studied. The equilibrium constants of phosphorolysis of the 2-Se-pyrimidines were between 5 and 10, and therefore differ by an order of magnitude from the equilibrium constants of any other known case. Hence, the thermodynamic properties of the target nucleosides are inherently unfavorable, and this complicates their synthesis significantly. A tenfold excess of sugar donor was needed to achieve 40−48 % conversion to the target nucleoside. Scale-up of the optimized conditions provided four Se-containing nucleosides in 6–40 % isolated yield, which compares favorably to established chemical routes.     

Revealing the dimensional stability mechanisms of SiC/Al composite under long-term thermal cycling

Long-term thermal cycling causes irreversible dimensional changes of the material, which in turn affects the reliability of precision instruments. In this paper, dimensional stability mechanisms of SiC/Al composites during thermal cycling were revealed using high-precision thermal dilatometer, XRD and spherical aberration correction transmission electron microscope (Cs-TEM). First, how the factors including dislocations, internal stress and precipitates affect the dimensional change of SiC/Al composites were separately introduced. Then, the integrated effect of these factors affecting the dimensional stability of SiC/Al composites was further discussed. Among them, the integrated effect of dislocation-internal stress in SiC/pure Al composites leads to an increase in dislocation density and average lattice constant, which leads to an increase in dimensional change. The integrated effect of dislocation-internal stress-precipitates in SiC/2024Al composites leads to a decrease in the average lattice constant and some changes in the precipitation behavior (including the type, density and lattice constant of the precipitates), which ultimately leads to a decrease in dimensional change. The dimensional change of the two types of composites was semi-quantitatively estimated. Finally, the reasons for the significantly higher dimensional stability of the SiC/2024Al composites were given.     

Probing the effect of R-cation radii on structural,vibrational, optical,and dielectric properties of rare earth (R=La,Pr, Nd) aluminates

The present study correlates the effect of R-cation radii on structural, vibrational, optical, and dielectric properties of rhombohedral rare earth aluminates RAlO₃ (R = La, Pr, Nd). The polycrystalline samples of RAlO₃ have been synthesized using sol-gel synthesis technique. Pure rhombohedral phase of RAlO₃ samples has been confirmed with X-ray diffraction. Systematic decrements in the lattice parameter, bond length, and bond angle have been observed, giving rise to structural distortion due to decrease in ionic radii of R-cation. The phononic properties of RAlO₃ have been investigated through Raman spectroscopy, where the degree of distortion of AlO₆ octahedra can be analyzed with the peak position of E_g and A_1g modes. An increase in the energy bandgap with decreasing R-cation radii shows an interconnection with the decrease in Al–O bond length. Interestingly, the decreasing dielectric constant with decreasing ionic radii of R-cation has been correlated with the difference in electronegativity of cation(R³⁺)-anion(O^2?) pair. Also, a positive linear relationship between dielectric constant and energy bandgap has been investigated using Penn model.     

低阶煤颗粒-气/油泡间的诱导时间研究

为表征低阶煤颗粒-气/油泡间矿化过程的差异,通过Sutherland理论下固体颗粒进入泡沫产品的总概率(E)和浮选速率常数(k)之间关系,并结合低阶煤颗粒-气/油泡的浮选速率试验,求得了低阶煤颗粒-气/油泡间的诱导时间。浮选实验研究表明,在相同的捕收剂消耗量下低阶煤-油泡浮选产率均高于低阶煤-气泡浮选产率。诱导时间测试表明,低阶煤颗粒-油泡间的诱导时间(35 ms)要明显低于低阶煤颗粒-气泡间的诱导时间(93 ms)。上述实验结果表明,油泡表面的疏水性要强于传统浮选气泡表面的疏水性。然而,进一步利用Sutherland理论中固体颗粒进入泡沫产品的总概率和浮选速率常数之间的数学关系,并结合低阶煤颗粒-气/油泡的浮选速率试验求得的低阶煤颗粒-气/油泡间的诱导时间分别为9.67和8.46 ms,其与诱导时间测试仪分别测量的诱导时间差异很大。这主要是由于在实际浮选过程中气/油泡的上升速度分别为23.26和22.68 cm/s,其远高于2015EZ型诱导时间仪测试过程中气/油泡碰撞速度(2.0 cm/s)。因此,诱导时间理论计算表明气泡-颗粒间的碰撞速度对颗粒-气泡间的诱导时间影响很大。上述研究结果表明油泡浮选效果优于传统浮选的内在原因在于低阶煤颗粒-油泡间的诱导时间小于低阶煤颗粒-气泡间的诱导时间。     

Combined constant speed control method for a wind generator equipped with hydraulic energy storage

A wind generator equipped with hydraulic energy storage (WG‐HES) uses hydraulic transmission systems instead of gearbox transmissions, thus eliminating high‐power converters and reducing the tower‐top cabin weight. When there is no wind or the wind speed is extremely low, the pressured oil released by accumulators is used to drive a motor to operate at a constant speed, thereby generating constant‐frequency power. However, few studies have examined the constant speed control characteristics for generating electricity using only an accumulator group. In this study, a combined constant speed (CCS) proportional–integral–derivative (PID) control method based on “variable displacement and throttling” is proposed, which includes two closed loops and one regulating loop. First, a simulation model of the CCS PID control method for a variable motor was established in the Simcenter Amesim program. The influence of different PID parameters on the anti‐interference ability of the constant speed control of the motor was analyzed under a given load step. Then, we obtained the range of control parameter values and a set of optimal values. Second, the effectiveness of the CCS control method and the accuracy of the simulation results were verified on a 600‐kW WG‐HES system prototype. The results verified that the CCS control method has good anti‐interference ability and can meet the requirements of constant speed control for a variable motor under the best PID parameters. These results can provide a basis for developing control strategies for WG‐HESs when there is no wind or at low wind speeds.     

Chemical reaction kinetics dataset of Cs-I-B-Mo-O-H system for evaluation of fission product chemistry under LWR severe accident conditions

In order to improve LWR source term under severe accident conditions, the first version of a fission product chemistry database named ‘ECUME’ was developed. The ECUME is intended to include several datasets of major chemical reactions and their effective kinetic constants for representative severe accident sequences. It is expected that the ECUME can serve as a fundamental basis from which fission product chemical models can be elaborated for use in the severe accident analysis codes. The implemented chemical reactions in the first version were those for representative gas species in Cs-I-B-Mo-O-H system from 300 to 3000 K. The chemical reaction kinetic constants were evaluated from either literature data or calculated values using ab-initio calculations. The sample chemical reaction calculation using the presently constructed dataset showed meaningful kinetics effects at 1000 K. Comparison of the chemical equilibrium compositions by using the dataset with those by chemical equilibrium calculations has shown rather good consistency for the representative Cs-I-B-Mo-O-H species. From these results, it was concluded that the present dataset should be useful to evaluate fission product chemistry in Cs-I-B-Mo-O-H system under LWR severe accident conditions, where kinetics effects should be considered.     

Composition-dependent xBa(Zr0.2Ti0.8)O3-(1-x)(Ba0.7Ca0.3)TiO3 bulk ceramics for high energy storage applications

This work reports the composition dependent microstructure, dielectric, ferroelectric and energy storage properties, and the phase transitions sequence of lead free xBa(Zr_0.2Ti_0.8)O₃-(1-x)(Ba_0.7Ca_0.3)TiO₃ [xBZT-(1-x)BCT] ceramics, with x?=?0.4, 0.5 and 0.6, prepared by solid state reaction method. The XRD and Raman scattering results confirm the coexistence of rhombohedral and tetragonal phases at room temperature (RT). The temperature dependence of Raman scattering spectra, dielectric permittivity and polarization points a first phase transition from ferroelectric rhombohedral phase to ferroelectric tetragonal phase at a temperature (T_R-T) of 40?°C and a second phase transition from ferroelectric tetragonal phase - paraelectric pseudocubic phase at a temperature (T_T-C) of 110?°C. The dielectric analysis suggests that the phase transition at T_T-C is of diffusive type and the BZT-BCT ceramics are a relaxor type ferroelectric materials. The composition induced variation in the temperature dependence of dielectric losses was correlated with full width half maxima (FWHM) of A₁, E(LO) Raman mode. The saturation polarization (P_s) ≈8.3?μC/cm² and coercive fields ≈2.9?kV/cm were found to be optimum at composition x?=?0.6 and is attributed to grain size effect. It is also shown that BZT-BCT ceramics exhibit a fatigue free response up to 10⁵ cycles. The effect of a.c. electric field amplitude and temperature on energy storage density and storage efficiency is also discussed. The presence of high T_T-C (110?°C), a high dielectric constant (ε_r ≈?12,285) with low dielectric loss (0.03), good polarization (P_s ≈?8.3?μC/cm²) and large recoverable energy density (W?=?121?mJ/cm³) with an energy storage efficiency (η) of 70% at an electric field of 25?kV/cm in 0.6BZT-0.4BCT ceramics make them suitable candidates for energy storage capacitor applications.     

正电子湮没研究Al、Nb共掺CaCu3Ti4O12陶瓷高介电常数机理

关于CaCu₃Ti₄O₁₂陶瓷的高介电常数机理，目前广泛接受的是非本征的内阻挡层电容模型。该模型认为在多晶中元素变价、缺陷和非化学计量比等导致的半导化晶粒被绝缘晶界层，即内阻挡层所包围。其中内阻挡层的厚度对材料的介电性能影响较大，而扫描电子显微镜（SEM）测试表明样品晶界呈稀烂的果酱状，SEM难以测量晶界区域绝缘内阻挡层厚度。本文采用正电子湮没技术表征其厚度，通过对CaCu₃Ti₄O₁₂陶瓷共掺不同浓度的Al、Nb（CaCu₃Ti_4-xAl_0.5xNb_0.5xO₁₂，x=0.2%、0.5%、5.0%）改变其晶粒和晶界的微观结构，研究CaCu₃Ti₄O₁₂陶瓷高介电常数机理。正电子湮没结果显示，掺杂样品符合多普勒展宽谱S参数的变化趋势与平均寿命的变化趋势一致。x=0.5%掺杂样品的介电常数最高，其平均寿命、S参数和湮没长寿命成分均最小，阻挡层最薄。实验结果验证了描述CaCu₃Ti₄O₁₂陶瓷高介电常数机理的内阻挡层电容模型的预测。