Investigation of phase stability and oxide ion performance in new perovskite-type bismuth vanadate

Samples of the BICDVOX system, formulated as Bi₄Cd_xV_2−xO_{11−(3x/2)−δ} in the Cd substitution range 0 ≤ x ≤ 0.25 were synthesized using the standard solid state reaction.The correlation between phase stability and oxide ion performance were investigated by variable temperature XRPD, DSC and AC impedance spectroscopy. The substitution of V⁵⁺ by Cd²⁺ exhibited different phase transitions upon varying composition. For compositions with x ≤ 0.05, two successive transitions; α↔β↔γ are evident, while the β↔γ transition exists in the composition range 0.05 < x < 0.175. However, some temperature dependent phenomena confirmed the exixtence of the γ′↔γ transition, coupled with the tetragonal symmetry stabilization for x ≥ 0.175. The maximum oxide ion conductivity at lower temperatures was observed for x = 0.20. It has also been found that the slow V⁴⁺ → V⁵⁺ re–oxidation results in increased defect trapping effects in the system at higher temperatures.     

Growth and characterization of new oxide and fluoride crystals for optical applications

High quality oxide and fluoride single crystals for optical applications have been grown by the Czochralski technique. Lattice parameter investigation of grown Gd₃Yb _x Ga_5−x O₁₂ suggested that this crystal will be a superior material as substrate for optical isolators with large Faraday effect. Growth conditions of (La,Sr)(Al,Ta)O₃ single crystals are discussed. These crystals have excellent lattice matching with GaN, a promising material for optoelectronic devices. Ce-doped fluoride single crystals—LiCaAIF₆, LiYF₄ and BaLiF₃—have been grown for solid state UV laser applications. Growth results and optical characterization are discussed.     

Phenomenological modeling and design of new acentric crystals for optoelectronics

The sets of 600 noncentrosymmetric simple and binary oxides and 270 sulfides have been observed and classified. The fields have been defined on the plane of the shortest chemical bond lengths between cations and anions in which appearance of the crystals not having center of inversion is possible. Interrelation between nonlinear optical susceptibility χ⁽²⁾ and chemical bonding in oxides and sulfides has been considered. The intervals of the shortest bond lengths cation–anion optimal for high rank χ⁽²⁾ have been estimated for the compounds.     

Growth and stability of pure and amino doped TGS crystals

Pure and amino (L-alanine and L-valine) doped TGS crystals were grown by the slow cooling method. The rates of nucleation as indicated by the induction period were measured. Effects of dopants on the solubility, stability and induction periods were investigated in stirred solutions. The interfacial energy for pure and doped solutions at 30°C was calculated. High quality single crystals of dimension 9×5×4 cm³ were grown.     

Metals with structural vacancies: prediction of radiation stability

 A solution to the problem of radiation stability of metallic materials for nuclear power reactors is suggested. It is by selecting and creating alloys with structural (unhealable) vacancies, whose concentration is determined precisely by the stoichiometry of alloys, but being independent of temperature and any other external influences. The advantages as well as difficulties arising from the technical application of radiation stable alloys proposed are considered. Received: 8 April 1997/Accepted: 28 May 1997     

Growth of larger and more perfect single crystals of KClO4 in silica gel

As part of a continuing effort on crystal growth in gels, this paper describes the growth of large transparent single crystals of KClO₄ by the improved design. The effect of various anionic and cationic components on nucleation, growth and quality of these crystals has been studied. It has been found that a combination of KNO₃ and HClO₄ as the reactants resulted in the best crystals in terms of crystal size, quality and inter-crystalline separation. The effect of various impurities on nucleation, growth and quality of these crystals has been studied. It has been found that the impurities which enhance the solubility of KClO₄ have a positive effect on the size and quality of the crystals. A new etchant, consisting of concentrated HCl and H₂SO₄ in the volume ratio 2:3 has been found to reveal as-grown as well as freshly introduced dislocations.     

Synthesis and characterization of cuprous sulfide crystals with novel morphology

Cuprous sulfide (Cu_2−xS) crystals in different stoichiometries were synthesized by hydro- and solvo-thermal methods at 125 °C using Na₂S₂O₃ as sulfur source in pure water, mixed solvents of ethylenediamine (en) and water, and pure en, respectively. The products were characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersion spectrometer (EDS), transmission electron microscope (TEM) and selected area electronic diffraction (SAED). Owing to different sulfur sources, crystal structures and morphologies of cuprous sulfides were different from those developed by some former researchers. Novel twelve-fold symmetrical Cu₇S₄ single crystals were synthesized at an en/water volume ratio of 3:1, and they were built up by two layers of about 80-100 nm in thickness. Moreover, the possible growth process had been discussed based on the analyses of detailed configuration of the products.     

Controllable phase transformation and improved thermal stability of nickel on tungsten substrate by electrodeposition

Present study reports a controllable phase transformation of nickel(Ni) from amorphous to cubic crystal structures on tungsten(W) substrate by electrodeposition. X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy were used to characterize the microstructure, micro-constituents and surface morphology of as-prepared Ni. The microstructure of Ni was strongly affected by the applied overpotential and deposition time. It is demonstrated that by controlling these two parameters either amorphous or cubic crystal structure of Ni on the W substrate could be obtained. The crystallization mechanism is discussed based on Gibbs crystal growth theory and Ostwald's rule. It is concluded that W substrate, acting as a heat sink, can effectively promote the thermal stability of amorphous Ni, based on the data from differential scanning calorimetry and Kissinger's model. This work contributes to the elucidation of the crystallization mechanism of Ni on W powder substrates, and proves that, better than alloying with other elements, incorporating powder substrates will significantly improve the crystallization temperature, hence the thermostability of amorphous Ni.     

Preparation of dendritic-like Ag crystals using monocrystalline silicon as template

Symmetric dendritic silver structures with controlled morphology were successfully synthesized by a solvothermal method with the assistance of monocrystalline silicon. The morphology and structure of the dendritic silver were characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), and scanning electron microscopy (SEM). It was found that the architecture of silver crystals could be controlled via simply adjusting the experiment parameters: AgNO₃ concentration, reaction time and temperature. Moreover, structural characterizations suggested that the dendritic silver structures preferentially grew along (1 1 1) and (2 0 0) directions, leading to the formation of dendritic structures with 1-2 μm in stem diameter and 10-50 μm in length. Additionally, the formation process of the dendritic silver structures was studied, and a possible formation mechanism was proposed based on the experimental results.     

Development of a new esomeprazole delayed release gastro-resistant pellet formulation with improved storage stability

This study describes the development of a new esomeprazole (ESO) delayed release gastro-resistant formulation with improved storage stability. A three-step (drug-, sub(seal)- and enteric-) coating process was employed with the aid of a fluid bed coater. Several formulation factors (namely, size and quantity of starting non-pareil sugar spheres, binder quantity during drug-layering, sub(seal)-coating polymer type, and quantity and enteric coating quantity) were evaluated and the whole process was modeled with the aid of feed-forward back-propagation artificial neural networks (ANNs). Results showed that the selection of small-sized starting spheres (45/60 mesh size) leads to pellet agglomeration, while as sub(seal)-coating weight gain increases a reduction in ESO dissolution rate is observed. The enteric-coating applied (Eudragit L30D-55) showed good gastro-resistant performance in both 0.1 N HCl and pH 4.5 media, while immediate release profiles with more than 85% of ESO being released in less than 30?min were obtained. The effect of cellulose-based sub(seal)-coating polymers, (namely, hydroxypropyl cellulose and hydroxypropylmethyl cellulose) on formulation’s storage stability at 40?±?2?°C/75?±?5%RH indicated that only hydroxypropylmethyl cellulose was able to stabilize ESO delayed-release formulations in terms of assay, dissolution, impurities, and gastro-resistance performance. Finally, scanning electron microscopy (SEM) analysis revealed smooth and homogeneous external surface/coating layers in all three levels (drug-, sub(seal)-, and enteric- coating), while x-ray diffraction showed no polymorphic transformations.     

Some structural aspects of neodymium praseodymium oxalate single crystals grown in hydro silica gels

The mixed crystals of neodymium praseodymium oxalate are grown by the diffusion of a mixture of aqueous solutions of neodymium nitrate and praseodymium nitrate (as an upper reactant) into the set gel embedded with oxalic acid. By varying the concentration (by volume) of rare earth nitrates in the upper reactant, the incorporation of Nd and Pr in the mixed crystals has been studied. Tabular crystals with the well defined hexagonal basal planes are observed in the mixed crystals of varying concentrations. X-ray diffraction patterns of these powdered samples reveal that these mixed crystals are ‘isostructural’, while IR and FTIR spectra establish the presence of oxalate groups. TGA and DSC analyses show the correctness of the chemical formula for the mixed crystals, by the release of water molecules (endothermic) and of CO and CO₂ (exothermic), with the rare earth oxides as the stable residue. X-ray fluorescence (XRF) and energy dispersive X-ray analyses (EDAX) establish the presence of heavy rare earth elements qualitatively and to a good extent quantitatively. X-ray photoelectron spectroscopic (XPS) studies confirm the presence of rare earth elements (Nd and Pr) as their respective oxides. The findings of these techniques of characterization are in excellent agreement with the proposed empirical structure for the mixed rare earth oxalates. The implications are discussed.     

高掺杂氧化镝的BSA玻璃的制备稳定性研究

为了研究高掺杂稀土情况下B2O3-SiO2-Al2O3体系玻璃的成玻璃性能,玻璃受到不同的化学溶液侵蚀时的抗腐蚀能力,及其腐蚀的机理与规律.通过采用扩张选点方法,探讨了的玻璃的形成区域图;采用UV3101-PC型分光光度仪,DTA和粉末失重法等测试手段研究了玻璃的化学稳定性.通过比较不同的H 浓度,不同场强的稀土离子,以及玻璃表面覆盖层等影响因素对玻璃化学腐蚀速率的影响规律,结果表明,BSA玻璃具有较好的玻璃形成能力;化学侵蚀过程中由于稀土离子的氢氧化物扩散与H 离子交换作用会影响玻璃化学侵蚀程度,因此玻璃耐酸性最差,耐碱性最好;稀土离子的场强越大,玻璃的抗腐蚀能力越强,化学稳定性越好;随着时间的延长由于玻璃表面产生了覆盖层,从而使得玻璃的溶解速率减缓.     

Effects of geometric structure, orientation and size on structural stability and thermal behavior of zinc oxide nanowires

The structural stability, orientation effect and melting characteristic of zinc oxide (ZnO) nanowires are simulated by using the molecular dynamics with many-body tightbinding potential. The structural stability is affected by the geometric shape of the cross section of a nanowire. The nanowire with a hexagonal cross section is more stable than that with another cross section type, namely, a rectangular, triangular, rhombohedral, octagonal, and circular cross section. The structural stability and melting temperature of a nanowire is sensitive to its diameter because of the surface energy and unfavorable coordination. Remarkably, it is observed that hexagonal ZnO nanowires transform to metastable circular-type structures at temperatures lower than the melting point.     

Effect of Ni on the structural, optical, thermal and dielectric properties of ADP single crystals

The effects of the addition of Ni²⁺ on the growth and various properties of ammonium dihydrogen phosphate single crystals grown from aqueous solution by the slow evaporation method have been studied. The grown crystals were subjected to HRXRD, UV-Vis, TG/DTA and dielectric studies. The structural perfection of the grown crystal has been analyzed by high resolution X-ray diffraction rocking curve measurements. UV-Vis studies show that the grown crystal has good transparency in the entire visible region which is an essential requirement for a nonlinear crystal. Higher decomposition temperature was observed from TG/DTA. Dielectric constant and dielectric loss were measured for the grown crystal for different frequencies and temperatures.     

A first-principles study on the structural stability of Al2Ca Al4Ca and Mg2Ca phases

Energetics and electronic structures have been determined from first-principles calculations for Al₂Ca Al₄Ca Mg₂Ca phases. These calculations show that Al₂Ca phase has the strongest alloying ability as well as the highest structural stability, next Al₄Ca, finally Mg₂Ca, which is also well explained through the densities of states (DOS) of these compounds.     

Solution methods and initialization techniques in SFE analysis of structural stability

Computational efficiency is a significant issue in simulation-based stochastic stability analysis of structures with random material properties. The efficiency of the analysis is affected by the selection of eigenproblem solution method and, for a specific eigensolution, how the iterations are initialized. This study applies the inverse and shifted inverse iteration methods to solve the eigensystem for the lowest eigenpair (the smallest buckling load and corresponding buckled shape). The efficiency and accuracy of these two methods are investigated in combination with several initialization strategies to start the solution processes. Among these strategies is a novel tree-type ordering strategy. The impact of the use of the solution methods and initialization strategies on the efficiency of the stochastic stability analysis is investigated and is illustrated in analyses of three systems: a sway frame, a column with a spring support at the mid-span, and a two-bay frame structure.     

分散扶正与保径的新型PDC钻头设计与现场试验

PDC钻头因具有较高的破岩效率而被广泛应用,但在硬地层以及软硬交错、含砾等复杂地层中,由于受力变化频繁和工作稳定性降低,PDC齿易发生冲击崩损而导致钻头使用寿命显著降低。针对PDC钻头在上述复杂地层中寿命短的问题,提出分散扶正与保径的PDC钻头新方案,并对PDC钻头进行工作稳定性分析、主切削结构设计与优化、分散扶正与保径结构设计以及钻头流场分析等。针对大段砂砾岩层的恶劣条件,开发研制的以分散保径结构为主要特征的新型PDC钻头在现场试验中取得了成功,单只钻头总进尺达1 339.16 m,其中包括605 m砂砾岩层,节约6次起下钻,钻头钻速高、寿命长,且井眼质量好。研究结果表明：分散扶正与保径技术能显著提升钻头的工作稳定性,使PDC钻头对硬地层、不均质地层的适应性得到明显改善,是提高复杂难钻地层PDC钻头工作性能的有效技术手段。     

Crystal growth and dielectric characterization of crystals derived from the solid-solution Ba(1−x)NaxTi(1−x)NbxO3 (BTNN)

Single crystals of (1 − x)BaTiO₃ + xNaNbO₃ (BTNN) for x = 0.84 were obtained by high temperature solution growth using Na₂B₄O₇ as solvent. The room temperature crystal structure of BTNN 16/84-phase was determined from X-ray single crystal diffraction data, in the tetragonal system with space group P4bm. The refinement from 246 independent reflections led to the following parameters: a = b = 5.5845(3) Å, c = 3.9453(2) Å, V = 123.041(11) Å³, Z = 2, with final cR_wp = 0.150 and R_B = 0.041. The structure of BTNN 16/84-phase can be described as a three-dimensional framework built up from (Nb-Ti)O₆ octahedra with Na and Ba in the dodecahedral site of perovskite-like type. Some mm³-sized crystals have been selected and various dielectric measurements (ferroelectric, pyroelectric, and piezoelectric) have been performed. Transition from paraelectric to ferroelectric state at around 460 K has been observed to be in good agreement with ceramics of closer composition. Dielectric, piezoelectric and pyroelectric measurements on crystal confirm the ferroelectric behaviour of BTNN 16/84.     

Analysis of VUV and optical spectra of Cs2NaYF6 crystals doped with Tm

This study presents a detailed interpretation and analysis of the reported interconfigurational spectra of Tm³⁺ in Cs₂NaYF₆ [V.N. Makhov, N.M. Khaidukov, D. Lo, J.C. Krupa, M. Kirm, E. Negodin, Opt. Mater. 27 (2005) 1131]. Since only spin-forbidden d–f emission bands are observed for Tm³⁺ in this host, it is unsuitable for use as a scintillator because the emission lifetime is too long. The d–f emission spectrum is well-explained by calculation and most of the intensity is located in one band: 4f¹¹5d¹ (high-spin) → 4f^{12 3}H₆. Measurements from the bands in the d–f excitation spectrum do not provide the accurate separation energy of the high and low-spin states. Strict O_h point group selection rules are operative for the optical spectra. The electronic states of the 4f¹¹5d¹ configuration (briefly, d-electron states, hereafter) are calculated to span from 58,318 cm⁻¹ to 86,900 cm⁻¹. At least five structured bands are observed in the excitation spectrum and their intensities are fairly well simulated by calculation. The 4f¹² → 4f¹³ (np₆)⁻¹ charge transfer band is assigned between 140 and 120 nm (83,000–71,000 cm⁻¹) and excitation into this band leads to f–f emission, bypassing the d-electron states.     

Thermal stability of indium tin oxide thin films co-sputtered with zinc oxide

The thermal stability of indium tin oxide (ITO) films and ITO co-sputtered with zinc oxide (ZnO) films at different zinc atomic ratios in various atmospheres are investigated. The resistivity of the annealed ITO films decreased with increased annealing temperatures. The improved electrical properties were attributed mainly to the increase in carrier concentration originating from the significant formation of oxygen vacancies in the ITO films. In contrast, due to the lower oxidation potential of zinc ions, the resistivity of the annealed co-sputtered films showed no significant reduction and an increase with annealing temperatures. The film decomposition due to the high degree outdiffusion of oxygen atoms and aggregation of In atoms observed from the metal-like In phase in the diffraction patterns was responsible for the drastic thermal degradation in the electrical and optical properties of the samples annealed at elevated temperatures in reducing gas atmosphere. In contrast, the superior thermal stability of the co-sputtered films, at an atomic ratio of 60% annealed in reducing gas atmospheres, was ascribed to the stable Zn₃In₂O₆ crystalline structure that appeared in the diffraction pattern. The absorption edge observed from the optical transmittance of these annealed films also showed evidence of carrier concentration evolution in various annealing atmospheres. The lower oxidation potential of the zinc atoms introduced into the ITO films was concluded to be efficient in compensating for the formation of oxygen vacancies resulting in the alleviated decomposition behavior during thermal annealing.