Cohesive and anharmonic elastic properties of mixed fluorite crystals

Summary The cohesive and anharmonic elastic properties of four mixed fluorite crystals (Ca _x Sr_1−x F₂, Sr _x Ba_1−x F₂ Ba _x Ca_1−x F₂ and Cd _x Pb_1−x F₂) have been investigated by means of a three-body potential (TBP) model which consists of the long-range Coulomb and three-body interactions and the short-range van der Waals attraction and overlap repulsion effective up to the second-neighbour ions. Due to the lack of measured data on cohesive energy, third-order elastic constants and pressure derivatives of the secondorder elastic constants of mixed fluorites, the accuracy of the present results has been tested by comparing them with the so-called experimental results generated by the application of Vegard’s law to their corresponding experimental values for the host fluorites.

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Riassunto Sono state ricercate le proprietà elastiche coesive e anarmoniche di quattro cristalli misti di fluorite (Ca _x Sr_1∮x F₂, Sr _x Ba_1−x F₂, Ba _x Ca_1−x F₂ e Cd _x Pb_1−x F₂) per mezzo di un modello del potenziale a tre corpi (TBP) che consiste di interazioni di Coulomb a lungo raggio e a tre corpi, di attrazione di van der Waals a corto raggio e di repulsione di sovrapposizione efficace fino agli ioni del secondo vicino. A causa della mancanza di dati misurati sull’energia coesiva, di costanti elastiche di terz’ordine e di derivate di pressione delle costanti elastiche di secondo ordine, l’accuratezza dei risultati attuali è stata provocata confrontandoli con i cosidetti risultati sperimentali generati dalla applicazione della legge di Vegard ai loro valori sperimentali corrispondenti per i fluoriti ospiti.

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Резюме С помощью трех-частичной потенциальной модели исследуются когезионные и ангармоничные упрыгие свойства четырех смешанных кристаллов флюорита (Ca _x Sr_1−x F₂, Sr _x Ba_1−x F₂, Ba _x Ca_1−x F₂ и Cd _x Pb_1−x F₂). Используемая модель состои т из длиннодейтсвующего кулоновского и трех-частичного веаимодействий и короткодействующего притяжения Ван дер Ваальса и перекрывающегося отталкивания, эффективного вплоть до вторых соседних ионов. Из-за недостатка зкспериментальных данных для когезионной энергии упругих постоянных третьего порядка и производных по давлехию упрутих постоянных второго поядка для смешанных флюоритов, проверяется точность полученных результатов посредством сравнения их с так называемыми экспериментальными результатами, образованными с помощью применения закона Вегарда к соответствующим экспериментальным величинам для первичных кристаллов флюоритов.

     

LDM长距离显微镜

长距离显微镜破除了只能近距离观测的传统，使微观观测可在高温、高压、有腐蚀气体的环境中进行，可广泛用于材料微观观测、化工、医学、司法鉴定等各个领域，本文着重介绍中科院上海天文台研制成功的ＬＤＭ－Ⅱ型长距离显微镜光学、机械结构特点及各种性能指标，用户正利用其独特的功能从事各种不同领域的工作。     

Domain Structures in Minerals

Domain structures in mineral crystals could be categorized into three groups and several subgroups within each group, based on characteristics of domain structures and mechanisms causing domain structures: (ⅰ) domain structures constituted by domains with the same (or identical) crystal structure and chemical composition, including anti-phase domain structures, twinning domain structures, inversion domain structures, and translationtwinning domain structures; (ⅱ) domain structures constituted by two or more than two kinds of domains with the same chemical composition but different crystal structures; and (ⅲ) domain structures constituted by two kinds of compositional and structural different domains, including exsolution-induced and polysomatic reaction-induced domain structures. Different types of domain structures may display different phenomena in their TEM images and SAED patterns, due to different crystallographic characteristics of different domain structures. The domain structures in minerals     

On the Synthesis and Basicity of 1,3-Diaminoisoquinolines

Summary.  A series of 6- and 7-substituted derivatives of 1,3-diaminoisoquinoline were synthesized by the reaction of N,N-diethylarylacetamides with POCl₃ and then with N,N-dimethylcyanamide. The products were identified by means of spectroscopic methods and their pK _a dissociation constants were determined. Corresponding author. E-mail: kudelkoa@zeus.polsl.gliwice.pl Received July 7, 2002; accepted July 22, 2002     

Influence of glycerol on the formation of lyotropic mesophases —microscopic texture observations for determining preliminary phase diagrams of binary K-soap/glycerol systems

Analogously to aqueous K-soap/water systems already examined, the glycerol-containing systems KC _n /G (KC _n ;n=12, 14, 16, 18, 22; G=glycerol) are also able to build up hexagonal, lamellar, optically isotropic, gel-like and crystalline phases. These preliminary phases have been identified by texture observations of contact samples and singular concentrations with a polarizing microscope. The appertaining phase regions have been plotted in the binary phase diagrams.Correspondences and differences between these systems have been elucidared by drawing a comparison. Mosaic texture and oily streaks are typical of the lamellar phase. Spherulites are mainly found in the heterogeneous two-phase region lamellar/isotropic. The textures of the hexagonal phase are of fan-like morphology. The appearance of the gel phase texture resembles globular or curd-like structures.The influences exerted by the increasing chain lengths of the K-soaps (KC _n ,n=12–22) on the phase regions in the binary systems (KC _n /G) can be described as follows. The concentrations required for forming the hexagonal and the lamellar phase respectively are shifted toward lower K-soap concentrations. The concentration range in which the hexagonal phase is stable is diminished. The temperature range in which the hexagonal phase is stable becomes larger. The upper temperature limit of the lamellar phase region is lowered.Binary aqueous and glycerol-containing K-soap systems have the following common features: The hexagonal phase is built up at low soap concentrations. The lamellar phase is formed at high soap concentrations. The lamellar phase is formed at high soap concentrations. An optically isotropic region is inserved between the lamellar and the hexagonal phase in aqueous and glycerol-containing systems of the types KC₁₄, KC₁₆ and KC₁₈. The temperature of the transition hexagonalisotropic phase (HS) runs through a maximum value. On increasing the chain length the formation of the hexagonal phase is shifted in the direction of lower soap concentrations.Aqueous and glycerol-containing K-soap mixtures differ in the following essential points: The lyotropic mesophases (H, L, I) of aqueous systems are formed at considerably lower soap concentrations than the corresponding phases of glycerol-containing systems. The lamellar phases of aqueous systems reach the regions of very low soap concentrations. The lyotropic mesophases of aqueous systems are built up at temperatures lower than the corresponding ones of glycerol-containing mixtures. In aqueous systems the concentration range of the lamellar phase increases with increasing chain length, in contrast to glycerol-containing systems where it is diminished.     

Determination of pKa values for (E)-2-hydroxy-5-(aryldiazenyl) benzaldehydes in dimethyl sulfoxide: Cyclic voltammetry and density functional theory calculations

The (E)-2-hydroxy-5-(aryldiazenyl) benzaldehydes (azo dyes 1–4 ) were synthesized in high purity. As they are insoluble in water, the usual analytical methods cannot be utilized to determine their pK_a values. Cyclic voltammetry was experimentally used to determine their pKa values in DMSO solvent. In addition, computational methods and a conductor-like screening model (COSMO) were used to calculate the solvent effect. , , K_exchange, and pK_a values were estimated for the azo dyes being studied using the BP86, TPSS, B3LYP, PBE0, TPSSh, and PW6B95 density functionals in def2-TZVP basis sets. The obtained mean absolute deviations (MADs) indicate that the results of BP86, PBE0, and PW6B95 functionals are in good agreement with experimental values.     

Thermoanalytical and microscopic investigations of the thermal dehydration of α-nickel (II) sulphate hexahydrate

Thermoanalytical (TA) and hot-stage microscopic techniques were employed to investigate the complicated behaviour of the non-isothermal dehydration of single crystals of α-NiSO₄·6H₂O. Non-isothermal dehydration to the tetrahydrate proceeds in two stages: (1) surface nucleation and growth of nuclei, followed by advancement of reaction fronts inward; (2) random nucleation and growth near the reaction front as well as in the bulk. Corresponding TA curves were interpreted to represent diffusional removal of evolved water vapour through the surface layer created in stage (1). The dehydration process of the tetrahydrate to the monohydrate is explained on the basis of textural structures produced in the previous step. Crack formation in the surface layer and rapid escape of the water vapour were observed in this step.     

Fluorescent microscopic determination of cadmium in water samples with the self-ordered ring of α,β,γ,δ-tetra(5-sulfophenyl)porphine formed on the solid support of glass slides

A self-ordered ring (SOR) technique is first proposed for the determination of trace metal ions based on the capillary effect of solvent on a solid support. At pH 9.1, α,β,γ,δ-tetra(5-sulfophenyl)porphine could form an SOR on the surfaces of hydrophobic glass slides with the aid of poly(vinyl alcohol), and the fluorescence intensity of the SOR was found to be quantitatively quenched by Cd(II). An SOR method for the determination of Cd(II) was established in the range 1.0×10⁻¹⁴ to 2.0×10⁻¹³ mol, and the limit of detection was 5 fmol (3σ). Water samples were analyzed with an R.S.D. of 3.2-3.8%. The quantification basis of the SOR method, the relationships between the radius of the SOR and volume of the droplet are theoretically discussed.     

Small deviations from local equilibrium for a process which exhibits hydrodynamical behavior. I

The symmetric simple exclusion process where infinitely many particles move randomly on , jump with equal probability on nearest-neighbor sites, and interact by simple exclusion is considered. It is known that the only extremal invariant measures are Bernoulli, that each measure, in a suitable class, after a macroscopic time is locally described, at a zero-order approximation, by a Bernoulli measure with parameter depending on macroscopic space and time, and that the so-defined equilibrium profile satisfies the heat equation. Small deviations from local equilibrium in the hydrodynamical limit are investigated. It is proven, under suitable assumptions, that at first order the state is Gibbs with one- and two-body potentials whose strength depends only on macroscopic space and time and on the equilibrium profile. More precisely, the one-body potential is linear (on the microscopic positions of the particles) and proportional to the macroscopic space gradient of the equilibrium parameter at that time, so that Fourier law holds. The two-body potential varies on a macroscopic scale and does not depend on the microscopic positions of the particles; it is given by the value of the covariance of the Gaussian macroscopic density fluctuation field.     

H~2S对硫酸溶液中铁腐蚀作用的CNDO/2研究

动电位扫描得出工业纯铁在含H~2S的H~2SO~4溶液中腐蚀的电化学行为。应用CNDO/2法确定了阴、阳极电位下H~2S,HS^-在金属Fe晶面上的稳定吸附取向与最佳吸附间距,通过对吸附物总能量、结合能、净电荷分布的计算,得出H~2S体系阴、阳极反应被加速的微观机制。阳极电位下,大量HS^-为S原子的平行吸附方式,HS^-负电荷大部分向Fe转移,促进铁的溶解。阴极电位下,少量H~2S则为H原子的平行吸附方式,Fe表面负电荷向H~2S分子中与Fe作用的H转移,促进析氢。在CNDO/2法计算的基础上,圆满地解释了实验结果。