Structural evolution of (Ca0.35Sr0.65)TiO3 perovskite at high pressures

Lattice parameters of a synthetic powder sample of Ca_0.35Sr_0.65TiO₃ perovskite have been determined by the method of Le Bail refinement, using synchrotron X-ray diffraction patterns collected at pressures up to 15.5 GPa with a membrane-driven diamond anvil cell. At ambient conditions, diffraction data were consistent with the I4/mcm structure reported previously in the literature for the same composition. Diffraction data collected at high pressures were consistent with tetragonal (or, at least, pseudo-tetragonal) lattice geometry, and no evidence was found for the development of any of the orthorhombic structures identified in other studies of (Ca, Sr)TiO₃ perovskites. Additional weak reflections, which could not be accounted for by the normal I4/mcm perovskite structure, were detected in diffraction patterns collected at pressures of 0.9-2.5 GPa, and above ∼13.5 GPa, however. Small anomalies in the evolution of unit cell volume and tetragonal strain were observed near 3 GPa, coinciding approximately with breaks in slope with increasing pressure of bulk and shear moduli for a sample with the same composition which had previously been reported. The anomalies could be due either to new tetragonal↔tetragonal/pseudo-tetragonal phase transitions or to subtle changes in compression mechanism of the tetragonal perovskite structure.     

Free energies of transfer of complexes of the type MCl2py4 between pyridine and other solvent media

Solubility isotherms are reported for the NiCl₂·4py, MnCl₂·4py, and MnCl₂·2py solid pyridinates in a number of pyridine+diluent mixtures at 25°C. Activity coefficients of the solvent components have been derived from the total vapor pressures measured by a static method. The standard free energies of transfer for the NiCl₂py₄ and MnCl₂py₄ complexes are the same, within the experimental error, in the pyridine+aprotic diluent mixtures, while marked differences are observed in the pyridine+chloroform mixtures. Marked deviations are observed for chloroform and 1,2-dichloroethane from a correlation between the standard free energy of transfer of the complexes, on one hand, and the Hildebrand's solubility parameter of the solvent, on the other, the latter correlation being roughly valid for aprotic solvents. The deviations are tentatively ascribed to hydrogen bond formation of the type H... between the protic solvents and the coordinated pyridine molecules, enhanced by the d electron delocalization.     

煤中有机硫形态结构和热解过程硫变迁特性的研究

利用热解 质谱并结合固定床热解反应装置，对煤中有机硫的形态主其对加氢热解过程 变迁特性的影响，进行了较系统的研究。结果表明，煤中有机硫的形态结构在褐煤中主要以脂肪族、芳香族硫化物为主，而在 煤中则主要以各种不同芳构化程度的噻吩结构为主，初步表明煤中有机硫形态结构随煤变质程度的变迁呈较强的连续递变性。煤热解过程中硫在呼产物中的变迁和分布与煤中有机硫的形态结构特点密切相关。较高芳构化噻吩结构不完全的氧     

Ein Beitrag über Ba3Pt4HgO11: Das erste Erdkalimetall-Oxoplatinat(II,V)/Oxomercurat

A Contribution on Ba₃Pt₄HgO₁₁: The First Alkaline-Earth Oxoplatinate(II,V)/Oxomercurate Single crystals of Ba₃Pt₄HgO₁₁ were prepared by oxygen high pressure technique (4 200–3 600 bar) and investigated by X-ray methods. It crystallizes with hexagonal symmetry, space group D? P6 2c, a = 6.021, c = 17.374 Å, Z = 2. Ba₃Pt₄HgO₁₁ represents a new structure type, showing structural relationships to Ba₂Hg₃Pd₇O₁₄ and to the precious metal 6L-perovskites. The Hg²⁺ ions show dumb-bell like coordination, Pt²⁺ a square-planar surrounding and Pt⁵⁺ face shared double octahedra.     

CdHgO2: Ein Oxomercurat mit Verwandtschaft zur Crednerit-Struktur

CdHgO₂: An Oxomercurate related to the Crednerite Structure Single crystals of CdHgO₂ were prepared by oxygen high pressure technique (600°C, 3900 bar) and investigated by X-ray technique. It crystallizes with monoclinic symmetry, space group C–C2/m; a = 5.933, b = 3.452, c = 5.875 Å, β = 91.26°; Z = 2. The Hg²⁺ ions show dumb-bell like coordination, Cd²⁺ an octahedral one. CdHgO₂ shows strong relationship to the Crednerite structure. The orientation of the O? Hg? O dump-bells to the CdO₆ octahedra layers is discussed with respect to related oxomercurates.     

Pressure effect on grain boundary wetting at various temperatures

Bicrystals of Fe-6 at.% Si alloy containing <001> 5 tilt grain boundaries with a deposited zinc layer have been annealed at various hydrostatic pressure at four temperatures between 700° and 905°C. After the anneals the dihedral angle of the grain boundary groove formed at the site of the grain boundary intersection with the solid-melt interphase boundary has been measured. The transition from complete to incomplete wetting of the grain boundary by the zinc-rich melt (dewetting phase transition) has been found to occur as the pressure increased at all temperatures studied. The temperature dependence of the dewetting transition pressure p _w has been determined. That dependence has a minimum at a temperature of 790°C, which is close to the peritectic temperature in the Fe–Zn system (782°C). A thermodynamic analysis of the wetting phenomena in the two-component system, based on Becker's regular solution model for the surface tension of the interphase boundary, explains the minimum in the p _w (T) dependence.     

有磁和无磁状态下YIG和YAG晶体高压下的声速和衰减

 YAG晶体是一种无磁石榴石,YIG晶体是铁磁石石榴石。通过对YAG和YIG晶体在高压加磁场和不加磁场条件下,研究铁磁石榴石和无磁石榴石晶体的超声行为。采用“回波重合法”测量声速,通过比较回波的幅度进行衰减的测量。我们发现,不存在磁场时,有磁石榴石和无磁石榴石在高压条件下声速和声衰减有类似的变化行为。我们也发现,无论有无高压,在YAG晶体中不存在磁声相互作用,而在YIG晶体中,则存在磁声相互作用。     

Quantitative millimetre wavelength spectrometry at pressures approaching atmospheric: II. Determination of oxygen at atmospheric pressure

A millimetre wavelength (MMW) Fabry-Perot cavity spectrometer described in earlier work has been applied to the measurement of oxygen absorption at 60 GHz and atmospheric pressure in a gas matrix of nitrogen. The spectrometer has also been modified such that the MMW source is stabilised by a sub-harmonic microwave signal transmitted by an infrared carrier on a single mode telecommunications fibre optic. This is a step towards developing an instrument comprising minimal electronic components that can perform MMW spectrometry remotely. Oxygen determinations were achieved by monitoring the change in the quality factor (Q) of a resonant Fabry-Perot cavity due to the presence of an absorbing sample. The MMW absorption of the sample was determined by incrementing the frequency modulation (FM) deviation of the source frequency scanning the cavity resonance profile. The response curve of absorption signal versus fraction of oxygen in nitrogen was found to be linear throughout the working range of 1-100% O₂ (v/v) in N₂ with a slope of (1.407±0.007)×10⁻⁴ m⁻¹ (% O₂)⁻¹. The detection limit (3× standard deviation of the background) was found to be ∼0.8% (v/v). The MMW technique employed is advantageous since, unlike common MMW techniques, there is no vacuum requirement. Application of this method, to the monitoring of oxygen in gas mixtures of practical importance, is proposed. Values of the oxygen spectral absorption coefficients of lines between 55 and 60 GHz were measured at reduced pressure and found to be within ±2% of previous literature values. A pressure correction coefficient for O₂ absorption at 60 GHz in the 45-121 kPa range was obtained and found to be (1.354±0.014)×10⁻⁴ m⁻¹ kPa⁻¹.     

Dynamic surface tension of micellar solutions studied by the maximum bubble pressure method. 1. Experiment

The effect of the micelles on the dynamic surface tension of micellar surfactant solutions is studied experimentally by means of the maximum bubble pressure method. Different frequencies of bubbling ranging approximately between 1 and 30 s^–1 are applied. The time dependence of the surface tension is calculated using a dead time correction. Water solutions of two types of surfactants with different concentrations are investigated: sodium dodecyl sulfate and nonylphenol polyglycol ether. The surface tension relaxes more quickly in the presence of micelles. The characteristic times of relaxation of the surface tension seem to be in the millisecond range. The time constants observed experimentally are explained in terms of the theory of surfactant diffusion affected by micellization kinetics.