On the crystal structure type of 2 CsCl · CoCl2 · 2 H2O

The following three-component systems have been studied: CsCl MnCl₂ H₂O at 25 °C; 2 CsCl · CuCl₂ · 2 H₂O—2 CsCl · CoCl₂ H₂O at 10 °C and 2 CsCl · MnCl₂ · 2 H₂O—2 CsCl · CoCl₂ H₂O at 25 °C and 10 °C. It was established that Co²⁺-ions do not substitute isodimorphously the Cu²⁺-ions in the tetragonal salt 2 CsCl · CuCl₂ · 2 H₂O, whereas in the case of the triclinic salt 2 CsCl · MnCl₂ · 2 H₂O they can substitute isodimorphously the Mn²⁺-ions. The theoretical considerations supported by the results obtained allow to predict the existence of the double salt 2 CsCl · CoCl₂ · 2 H₂O as well as the type of its crystal structure — triclinic, space group P1 .     

Hydrothermal synthesis and formation of 4ZnO·B2O3·H2O whiskers via a new route

4ZnO·B₂O₃·H₂O whiskers were prepared from 2ZnO·3B₂O₃·3.5H₂O under hydrothermal process at 160 °C for 10 h. The synthesized product was characterized by XRD, SEM, TG‐DSC and FT‐IR. SEM results showed that the synthesized 4ZnO·B₂O₃·H₂O whiskers' length was about 3–10 μm and the diameter was 0.2–0.3 μm. Further study on the whiskers' growth process and mechanism showed that the formation of the whiskers went through three stages and the morphology of 4ZnO·B₂O₃·H₂O changed from irregular particles to rod‐like structures and finally to whiskers. The variation of the morphology of the 4ZnO·B₂O₃·H₂O whisker with the concentration of the starting material was investigated. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Etch pit morphology and calcium sulphate growth on {111} faces of calcium fluoride crystals etched in sulphuric acid

An investigation of the etching behaviour of cleaved octahedral faces of calcium fluoride crystals in sulphuric acid of different concentrations and at various temperatures is carried out. It is observed that the morphology of dislocation etch pits depends on the temperature and concentration of the acid. With an increase in the acid concentration, growth of whiskers, elongated platelets, hexagonal and dice-shaped elevations, spherulites and sheaves is observed. Temperature of the etchant also has an effect on their formation. By X-ray diffraction techniques, the compounds forming the whiskers and elongated platelets, and hexagonal and dice-shaped features are identified as CaSO₄ · 2 H₂O and CaSO₄, respectively. The mechanism of the growth of CaSO₄ · 2 H₂O and CaSO₄ and the change in the morphology of selective etch pit are discussed.     

Thermodynamische Berechung des Systems Ge/H2O/H2 und experimentelle Untersuchung mit der Nahabstandsanordnung

In the temperature range from 950 to 1200 K K_p-values result from 5 · 10⁻⁵ to 6,9 · 10⁻³ for the heterogeneous reversible reaction Ge_(s) + H₂O_(g) ⇋ GeO_(g) + H₂O_(g), the average reaction enthalpy being 46,5 ± 05 kcal/mol. Etching rates calculated with these equilibrium constants for closed systems are 20-25% larger than the experimental etching rates for (110)-Ge in the sandwich device. The ratio of the etching rates is for (111)-, (100)- and (110)-Ge 1:1,4:1,8; the average reaction enthalpy calculated experimentally is 46 ± 1 kcal/mol for the temperature range 1000-1200 K. The dependence of transport rate on distance between source and substrate characterizes the sandwich device as a quasi-closed system with the diffusion as the rate controlling step of the material transport.     

Chemical durability of Na2OCaOSiO2 glasses in acid solutions

The resistance of Na₂OCaOSiO₂ glasses to acid solutions has been studied. The compositions studied were Na₂O · 4SiO₂, Na₂O · x CaO · (4?x) SiO₂ and a common electrode glass containing 22.63Na₂O and 5.58 CaO, mol%. The reaction was made at 40°C for about 3 h in 1N solutions of HCl, HNO₃ and H₂SO₄. Powdered glass samples were used and the reaction was followed by analyzing the solution for soda, lime and silica.The extraction rates of each constituent were measured. The effect of acid concentration was also studied for each glass using 10^?3–10N solutions of the three acids for a fixed time. The quantity of calcium extracted increased slowly at first with increasing calcium content in the glass, but rapidly when the lime content exceeded ≈10 mol%. Above this concentration, both calcium and sodium appears to pass into solution in the same proportion in which they are present in the glass. The extraction rate was found to depend on the type and concentration of the acid used, being least in H₂SO₄ and much higher and almost equal in both HCl and HNO₃.An attempt was made to correlate the results of decomposition of the soda-lime-silica glasses to their membrane potentials in acidic solutions.     

A study of the mechanisms of defect formation in K2Ni(SO4)2 · 6H2O/K2Co(SO4)2 · 6H2O bicrystals grown from aqueous solutions

The K₂Co(SO₄)₂ · 6H₂O-K₂Ni(SO₄)₂ · 6H₂O system has been studied, and a series of K₂Ni(SO₄)₂ · 6H₂O/K₂Co(SO₄)₂ · 6H₂O bicrystals have been grown. The processes of defect formation at the substrate/layer interface K₂Co(SO₄)₂ · 6H₂O/K₂Ni(SO₄)₂ · 6H₂O are studied by probe microanalysis, X-ray topography, and optical microscopy. It is found that inclusions and threading dislocations are formed at the interface, due to which elastic stresses relax in the crystal. Nickel is nonuniformly distributed in the layer; its concentration decreases with an increase in the layer thickness, which is indicative of substrate dissolution in the initial stage of interaction. A way for the elastic mismatch stresses to relax in heterostructures of brittle crystals obtained from solutions at low temperatures is proposed which implies the formation of inclusions at the substrate/layer interface. Original Russian Text ? M.S. Grigor’eva, A.é. Voloshin, E.B. Rudneva, V.L. Manomenova, S.N. Khakhanov, V.Ya. Shklover, 2009, published in Kristallografiya, 2009, Vol. 54, No. 4, pp. 679–687.     

Influence of supersaturation on the kinetics of crystallisation of ZnC2O4 · 2H2O

The kinetics of crystallisation of ZnC₂O₄ · 2 H₂O was investigated at 25°C and at different supersaturations. Zinc oxalate was prepared from pure zinc sulphate and oxalic acid solutions. The specific surface energy at the crystal-solution interface was calculated from the induction period and the Volmer relationship, while the critical nuclei dimension was found by means of the Thomson-Gibbs equation. With the decrease in supersaturation the size of the nuclei does not increase to infinity, but changes by 1–2 unit cells within a given supersaturation range.     

Investigations on the HCl gas-phase etching of differently doped and oriented gaas crystals

The influence of the orientation and dopant on the dissolution of GaAs surfaces in H₂–HCl gas mixtures has been investigated. For this purpose the etch rates, temperature regions of different etching behaviour and the corresponding activation energies were determined for temperatures ranging from 540 °C to 945 °C. The etch rate anisotropy is correlated with the three existing temperature regions of different dissolution mechanisms. The orientation-dependent transition temperatures are influenced by the dopant and can be related to the thermodynamic data of the dopant.     

Transport Properties of (NH4)2 CuCl4.2H2O Low Dimensional Single Crystals

The X‐ray diffraction and Infrared (IR) spectral studies of (NH₄)₂ CuCl₄.2H₂O single crystals reveals that these crystals contains tetragonal crystal structure with the unit cell dimensions of a = 7.58Å, c = 7.95Å, z= 2, β =90° and two water molecules in the unit cell. The temperature dependence of thermally stimulated depolarization current (TSDC) and dc electrical conductivity (σ) studies of this two‐dimensional (NH₄)₂ CuCl₄.2H₂O single crystal have been carried out in 77K–300K temperature region. The TSDC thermograph shows only one sharp peak at 248K with a peak current of 130nA, which is attributed to the Maxwell‐Wagner peak. The activation energy (U), relaxation time (τ) are calculated as 0.78eV and 3.44×10^‐15 s respectively. Dc electrical conductivity studies of these crystals show a first order phase transition at about 248K.     

Some characteristic features of formation of composite material based on KDP single crystal with incorporated Al2O3·nH2O nanoparticles

Composite material based on KDP (KH₂PO₄) crystal matrix with incorporated aluminum oxyhydroxide Al₂O₃·nH₂O nanoparticles is obtained and peculiarities of the formation of KDP:Al₂O₃·nH₂O composite structure are studied by selective etching, optical and scanning electron microscopy. Influence of the nanoparticles on the formation of defect subsystem is analyzed. The obtained material is shown to have a zonal structure with a period independent of the concentration of nanoparticles. By means of FTIR‐spectroscopy, interaction of nanoparticles with KH₂PO₄ solution is studied. A model of the capture of nanoparticles by the {100} KDP crystal face is proposed.     

Electrical conductivity of Cs<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> crystals

The electrical conductivity of Cs₂CuCl₄ single crystals, synthesized by crystallization from aqueous solutions in the CsCl–CuCl₂–H₂O system, has been investigated. The temperature dependence of the electrical conductivity of crystals in a temperature range of 338–584 K exhibits no anomalies. The electrical transfer activation enthalpy is ΔH_σ = 0.72 ± 0.05 eV and the conductivity is σ = 3 × 10^–4 S/cm at 584 K. The most likely carriers in Cs₂CuCl₄ are Cs⁺ cations, which transfer electric charge according to the vacancy mechanism.     

Study of optical and transport properties of K2CuCl4 · 2H2O single crystal

Optical absorption, transport properties and EPR of K₂CuCl₄ · 2H₂O single crystals have been studied. The optical absorption in UV, and visible region are characterized by a charge transfer band, and in the near infrared region at 3998, 4336, and 4480 cm⁻¹ are attributed to transitions between the stark levels of copper(II) ion in an extended octahedral crystal field. An anisotrophic ‘g’ value was observed with g_∥ = 2.12 and g_∥ = 2.24 by EPR method. The spin orbit coupling constant is found to be 500 cm₋₁. D.C. electrical conductivity measurements with temperature reveal an anisotropy characteristic of a two-dimensional layered structure and exhibit a first order irreversible structural phase-transition at 377 K, i.e. from tetragonal to monoclinic crystal system. X-ray diffraction studies and density calculations from the crystal structure data in both the phases suggest that the first order irreversible transition occurs following the loss of the two water molecules of hydration.     

Thermal expansion,pyroelectricity and linear optical properties of Li2SeO4·H2O and Li2SO4·H2O

Large single crystals of polar Li₂SeO₄·H₂O were grown at 343 K from aqueous solution. Temperature dependent thermal expansion coefficients of Li₂SeO₄·H₂O and Li₂SO₄·H₂O were determined within the temperature range 133 K–313 K and coefficients of the pyroelectric effect within the temperature range 183–343 K. Refractive indices between 365 nm and 1530 nm as well as unpolarized absorption spectra of Li₂SeO₄·H₂O and Li₂SO₄·H₂O were measured and phase‐matching curves for second harmonic generation were calculated. Both compounds allow type I and type II phase‐matching at wavelengths from about 650 nm to the near infrared region. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of Ca on HoPO4·nH2O (n = 1 and 2) crystallization from phosphoric acid solution

Ca‐substituted holmium phosphate, isomorphic with tetragonal form of HoPO₄·H₂O was synthesized by crystallization from boiling phosphoric acid (2 M H₃PO₄) solution containing 0.02M of Ho and 0–0.2 M of Ca. Calcium concentration, higher than 0.2 M Ca in solution resulted in biphasic solid crystallization: tetragonal HoPO₄·H₂O and orthorhombic HoPO₄·2H₂O. Ca incorporation in the solid according to substitution mechanism: Ca²⁺ + H⁺ ↔ Ho³⁺ was limited to ∼3 wt.% and was coupled with simultaneous incorporation of HPO₄²⁻. Ca for Ho substitution caused an expansion of the tetragonal unit cell of HoPO₄·H₂O, resulted from differences in the ionic radii (r_Ca > r_Ho). Effects of thermal treatment at 900 °C were as follows: (i) the orthorhombic admixture of HoPO₄·2H₂O re‐crystallized into tetragonal anhydrous HoPO₄, (ii) Ca–at first dissolved in crystal structure of HoPO₄·H₂O was expelled from it during re‐crystallization to form Ca(PO₃)₂, and that was associated with a contraction of the unit cell; a ‐ and c‐ axes went down to the level of Ca‐free anhydrous tetragonal form of HoPO₄. (iii) HPO₄²⁻ present in the solids as prepared underwent condensation according to reaction 2HPO₄²⁻ → P₂O₇⁴⁻ + H₂O. Scanning electron micrographs revealed significant changes in size and morphology of the crystals ranging from spherical globules of HoPO₄·H₂O formed in Ca‐free H₃PO₄ with increasing diameter in the presence of lower Ca concentration to rod‐like crystals organized in bundles resembling the “scheaf of wheat”, while crystallized from phosphoric acid solution with higher than 0.2 M Ca.     

Kinetics of luminescence of CsI single crystals scavenged by Y3+

CsI single crystals were grown from the melt scavenged by Y³⁺ (YCl₃) addition in 6.7·10⁻⁴–6.7·10⁻³ mol·kg⁻¹ range. The addition of the scavenger amounts comparable with the total concentration of the oxygen‐containing admixtures in molten CsI results in complete destruction of the latter. Because of this, the intensity of the band with a maximum at 2.8 eV in radioluminescence spectra caused by the oxygen‐containing admixtures (anion vacancies) considerably decreases, and the fraction of the slow 2μs‐component corresponding to these admixtures becomes lower than 0.01 (0.007). The addition of larger quantities of YCl₃ leads to the appearance of a wide band with a maximum at 2.8 eV caused by cation vacancies, and the intensity of the slow 2μs‐component increases to 0.02. The maximum ratio of two faster components with the decay constants equal to 7 and 30 ns reaches 0.65:0.33 at Y³⁺ concentration in CsI melt equal to 6.7·10^‐3 mol·kg^‐1, the effective luminescence time of fastest components is ca 14 ns. The dependence of the ‘Fast/Total ratio’ on Y³⁺ concentration passes through its maximum (0.81) corresponding to the equivalence of Y³⁺ and O²⁻ concentrations in the growth CsI melt.     

Vickers microhardness of K<Subscript>2</Subscript>Co(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O single crystals and fracture geometry around impressions of vickers,knoop, and spherical indenters

The microhardness on the (010) and (001) planes in K₂Co(SO₄)₂ · 6H₂O crystal has been measured by the Vickers indentation method. Its values are, respectively, 11500 and 1300 MPa. No microhardness anisotropy of the first kind is revealed on either plane. The fracture geometry under indentation by a spherical indenter and Vickers and Knoop indenters is studied. The crystal has lower brittleness than the isomorphic Cs₂Ni(SO₄)₂ · 6H₂O crystal.     

Etching studies on {100} faces of MgO crystals in H3PO4 acids

The effect of temperature (20–100°C) and concentration of H₃PO₄ etching solutions on the etching behaviour of {100} faces of MgO crystals in investigated. It is observed that the formation of etch pits and pyramids and the values of dissolution rate depend on the etching conditions. The density of the pyramids in 33.08 N H₃PO₄ solution was found to be maximum at 20°C. From the plots of logarithm of dissolution rate versus inverse of absolute temperature, the values of activation energy and pre-exponential factor for the dissolution process are computed. It is found that for H₃PO₄ concentrations upto 22.05 N the value of the activation energy remains constant but that of pre-exponential factor increases with acid concentration. At higher concentrations, the activation energy decreases. The results are systematically described and discussed.     

Synthesis of magnesium oxysulfate whiskers in the presence of sodium dodecyl benzene sulfonate

Uniform magnesium oxysulfate (5Mg(OH)₂·MgSO₄·3H₂O) whiskers with a length of 10‐15 µm and a diameter of 0.4‐1.0 µm were synthesized in the presence of sodium dodecyl benzene sulfonate (Na‐SO₃‐C₆H₄‐C₁₂H₂₅) at 200°C for 1 h, using MgSO₄·7H₂O and NaOH as the reactants. Mg(OH)₂ precursor with poor crystallization and small crystal size was formed owing to the adsorption of sodium dodecyl benzene sulfonate on the Mg(OH)₂ surface. The quick dissolution of Mg(OH)₂ precursor in the subsequent hydrothermal reaction inhibited the occurrence of the sector‐like byproduct and promoted the formation of magnesium oxysulfate whiskers with uniform morphology. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Double Salt Formation in the Cu(HCOO)2–Sr(HCOO)2–H2O System

The solubility in the Cu(HCOO)₂–Sr(HCOO)₂–H₂O system has been studied by the method of physico-chemical analysis at 25 and 50 °C. It has been established that two double salts are formed in the system: CuSr₂(HCOO)₆ · H₂O at 25 °C and CuSr(HCOO)₄ · 4 H₂O at 50 °C. The latter salt has not yet been described in the literature. It has been characterized by X-ray powder diffraction and DT and TG analysis. CuSr(HCOO)₄ · 4 H₂O crystallizes in the triclinic system with lattice parameters a = 12.376(6) Å, b = 13.394(4) Å, c = 11.508(6) Å, α = 93.38(3)°, β = 94.01(3)°, γ = 75.04(3)°. Dehydration proceeds in two stages.     

Kinetics of dissolution and calcium sulphate growth on {111} faces of calcium fluoride crystals etched in sulphuric acid

The effect of temperature (20–100°C) and concentration of H₂SO₄ etching solutions on the etching behaviour of {111} faces of calcium fluoride crystals is investigated. Whisker growth of calcium sulphate is observed. Temperature of the etchant also has an effect on their formation. The kinetics of dissolution at the sites of dislocations and general dissolution have been studied. Studies on induction period and its dependence on the concentration of the acid and temperature are also described. It is observed that: (i) at low and high acid concentrations, the dissolution is diffusion controlled while it is predominantly reaction-rate controlled in the intermediate concentration range and (ii) the growth rate of calcium sulphate whiskers decreases with time and their induction period decreases with increase in the temperature of the solution. The implications are discussed.