The crystallisation of alkaline-earth metal oxides from metal chloride melts: Solubility-temperature phase diagram analyses and preliminary experimental studies

The solubility v temperature phase diagrams for magnesium, calcium, strontium and barium oxide solutions, in lithium, sodium and potassium chloride melts and in the alkaline earth metal chloride melts, have been analysed. The solutions in the alkali metal chlorides are pseudo-binary reciprocal ternary mixtures; the more soluble barium and strontium oxides showed small deviations, calcium oxide showed larger deviations while the extremely sparingly-soluble magnesium oxide showed extensive deviations from ideality. These deviations were related to electrostatic interactions in solution, that depended in turn on some function of reciprocal solute and solvent caiton radii. The solutions in the alkalineearth metal chlorides are binary mixtures with MO · 4 MCl₂ solvate formation. — Some preliminary crystallisation experiments were carried out, by slow cooling of saturated solutions in the metal chloride melts: calcium and strontium oxide crystallisation from lithium chloride melts and barium oxide crystallisation from all three alkali metal chloride melts would be worth further investigation.     

Electrochemical growth and properties of LaMn1−xCoxO3 (0 < x ≤ 1) single crystals

Single crystals of LaMn_1−xCo_xO₃ (0 < x < 1) with distorted perovskite structure have been obtained by the electrodeposition technique at anode from flux melt using Cs₂MoO₄‐MoO₃ binary system as solvent. An investigation of magnetic and electrical properties of the obtained crystals as well as its comparison with those for ceramic samples of the same composition were carried out. A much weaker interplay between magnetic and electrical properties and a smaller ∼8% magnetoresistance were found in the ternary oxide crystals slightly doped by Co on the verge of transition to ferromagnetic state in comparison to the data have been reported for LaMnO_3+δ single crystals. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Czochralski-growth of germanium crystals containing high concentrations of oxygen impurities

Oxygen-containing germanium (Ge) single crystals with low density of grown-in dislocations were grown by the Czochralski (CZ) technique from a Ge melt, both with and without a covering by boron oxide (B₂O₃) liquid. Interstitially dissolved oxygen concentrations in the crystals were determined by the absorption peak at 855 cm⁻¹ in the infrared absorption spectra at room temperature. It was found that oxygen concentration in a Ge crystal grown from melt partially or fully covered with B₂O₃ liquid was about 10¹⁶ cm⁻³ and was almost the same as that in a Ge crystal grown without B₂O₃. Oxygen concentration in a Ge crystal was enhanced to be greater than 10¹⁷ cm⁻³ by growing a crystal from a melt fully covered with B₂O₃; with the addition of germanium oxide powder, the maximum oxygen concentration achieved was 5.5×10¹⁷ cm⁻³. The effective segregation coefficients of oxygen in the present Ge crystal growth were roughly estimated to be between 1.0 and 1.4.     

Reduction of grown-in dislocation density in Ge Czochralski-grown from the B2O3-partially-covered melt

Germanium (Ge) single crystals with an extremely low density of grown-in dislocations were grown by the Czochralski (CZ) technique with boron oxide (B₂O₃) liquid. Because attachment of particles floating on the melt surface to a growing Ge crystal leads to generation of dislocations during the growth, partial covering of the Ge melt surface with B₂O₃ liquid was attempted. Such attachment of particles was drastically suppressed or the particles were caught by the introduction of B₂O₃ liquid, and a particle-free Ge melt was realized in the central region of the melt surface. Ge single crystals were successfully grown from such melt, the grown-in dislocation density being 0–1×10³ cm⁻², which was remarkably lower than that in Ge crystals grown by a conventional CZ technique. The contaminations by B and O atoms of the grown crystal detected by SIMS analysis were very low. These Ge crystals have the potential for application to be applied as high-quality, dislocation-free substrates of GaAs solar cells for various usages including in space.     

Crystallization and optical properties of CaWO4 and SrWO4

Single crystals of calcium tungstate and strontium tungstate have been grown by double decomposition flux reaction technique using lithium chloride as flux. Growth conditions are optimized to synthesize well faceted crystals. Effect of primary and secondary flux density in the growth charge has been studied. Thermogravimetric study reveals that the grown crystals are highly stable in the temperature range 25 – 1000°C. Analysis of optical absorption normal to the ab‐plane in the spectral range of 200 – 800 nm reveals the true absorption edge, the nature of transition being the allowed indirect one at 4.60 eV and 4.56 eV respectively for CaWO₄ and SrWO₄. The crystals have been characterized by determining useful pertinent optical and dielectric parameters. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth Kinetics of Barium Sulphate in Suspension

The growth rate of barium sulphate seed crystals from stirred solutions was studied conductometrically at 25°C by a stopped-flow technique. The supersaturation ranged from 3 × 10⁻⁷ to 3 × 10⁻⁸ mol BaSO₄/cm³. The seed crystals were grown in the system during the initial (steady-state) period of the experiment. Crystal size distributions were determined by optical microscopy. The growth rate of barium sulphate under the conditions of the experiments can be expressed by a quadratic function of supersaturation. The results, which suggest an interface rate-controlling mechanism, are discussed with respect to published data.     

Experimental Study of Interface Inversion of Tb3ScxAl5‐xO12 Single Crystals Grown by the Czochralski Method

Thermal conditions and rotation rate were examined experimentally for obtaining a flat interface growth of high melting‐point oxide (Tb₃Sc_xAl_5‐xO₁₂ ‐ TSAG) by the Czochralski method. The critical crystal rotation rate can be significantly reduced, of about twice at low and very low temperature gradients comparing to medium temperature gradients in the melt and surroundings of the crystal. The interface shape of TSAG crystals is not very sensitive on crystal rotation rate at small rotations and becomes very sensitive at higher rotations, when the interface transition takes place. The range of crystal rotation rates during the interface transition from convex to concave decreases with a decrease of temperature gradients. At low temperature gradients interface inversion crystals takes place in very narrow range of rotation rates, which does not allow one to growth such crystals with the flat interface. Even changing crystal rotation rate during the growth process in a suitable manner did not prevent the interface inversion from convex to concave and thus did not allow to obtain and maintain the flat interface.     

Single crystal growth from the melt and magnetic properties of hexaferrites–aluminates

Single crystals of aluminum substituted barium hexaferrite were grown by the floating zone method with optical heating. Single crystals were produced from a melt of stoichiometric composition. The process was carried out under a pressure of 50 atm of oxygen. In the system BaO–(x)Al₂O₃–(6?x)Fe₂O₃ the region of single phase crystal growth from the melt is limited by the value x=3. For higher substitutions single-phase crystallization is not observed. The grown single crystals are cylindrical boules with a diameter of 4–5 mm and with lengths up to 50 mm. To avert cracking the crystals have been annealed during the process of growth at 1100 °C. The content of FeO in the composition of single crystals of barium hexaferrite, grown by zone melting under an oxygen pressure of 50 atm, is approximately 0.3 wt%. In the system of hexaferrite–aluminates the macroscopic magnetic moment of the material disappears at x=3.     

Effects of the Li-evaporation on the Czochralski growth of γ-LiAlO2

Two-inch-diameter γ-LiAlO₂ single crystals were grown from the melt by Czochralski method. The crystals were examined by optical methods, high-resolution X-ray diffraction and transmission electron microscopy (TEM). Inductively coupled plasma optical emission spectrometry (ICP-OES) was used to determine the Li/Al ratio in the residual melts. The Li-evaporation from both melt and grown crystal is the main problem in the γ-LiAlO₂ growth and has to be controlled by acting on the vertical temperature gradient. Shallow gradients increase the Li-evaporation from the crystal surface resulting in boules with a milky rim. On the other hand, steep gradients may induce cracks in the boule and enhance the Li₂O escape from melt with consequent variation of the composition. ICP-OES investigations reveal that melt compositions can vary in the range from 46.5 to 50 mol% Li₂O to obtain transparent LiAlO₂ crystals. Beyond this value, the formation of inclusions inside the crystals is probable. We have established an optimized growth assembly, which allows remaining the melt composition stoichiometric. The as-grown crystals exhibit defects like subgrains, twins and a core of voids and fine-grained inclusions. The latter could be characterized by TEM as submicron LiAl₅O₈ crystallites.     

A Study of precipitation morphology in NaCl:Sr and NaCl:Ba crystals

Single crystals of sodium chloride grown from melt containing different concentrations of strontium and barium have been observed to contain a second phase precipitating throughout the interior in the form of thin rods and well defined polygonal platelets. Two types of rods have been observed, one type oriented along 〈100〉 and the other along 〈110〉 directions. The platelets are variously in the form of hexagons, octagons, and rhombs. The precipitates disappear on quenching the crystal and reappear on aging the crystals under suitable conditions.     

Growth aspects of barium oxalate monohydrate single crystals in gel medium

Single crystals of barium oxalate monohydrate (BaC₂O₄.H₂O, BOM) were grown in pure form by controlled diffusion of Ba²⁺ using the gel technique at different temperatures. Starting from aqueous Ba²⁺ chloride (BaCl₂) and acetic acid (C₂H₂O₄) in gel, this method offers a low‐cost and an easiest alternative to other preparation methods for the production of barium oxalate bulky single crystals. The optimal conditions for the growth of BOM crystals in silica gel were found by investigating different growth parameters such as gel pH, gel aging and crystallization temperature. Irrespective of all such crystallization environments, growth rate of the crystals were initially less and then exhibited supersaturation effect leading to non‐linearity. Gel aging and temperature has profound effect on nucleation density that resulted less number of crystals of maximum size in the gel matrix. Perfect single crystals were grown on gels of higher pH. The macropore morphology and porosity was controlled by changing age of the gel. It has been found that temperature has a fabulous effect in controlling the nucleation density by altering the supersaturation conditions for the formation of critical nuclei. The entire growth kinetics informed that the grown crystals were derived by the one dimensional diffusion controlled process. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Part 1: Kinetics and mechanism of the crystallization process

The kinetics of spontaneous crystallization of sodium chloride from aqueous‐ethanol solutions were studied. During the crystallization the electrical conductance and optical transmission of the supersaturated solutions were measured automatically. For monitoring of the total surface of growing potassium chloride crystals at the crystallization the turbidimetric method was used. The growth rate and activation energy were determined. The crystal growth rate was proportional to supersaturation. When the volume fraction of ethanol in solution increased from 14.85 to 29.72%, the activation energy of the growth process did not change and was about 50 kJ· mol^‐1. Aggregation of the crystals was found. The aggregation kinetics of the crystals may be described approximately by the famous Smoluchowski equation for coagulation of colloidal particles. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spontaneous crystallization of potassium chloride from aqueous and aqueous‐ethanol solutions Part 1: Kinetics and mechanism of the crystallization process

Kinetics of spontaneous crystallization of potassium chloride from aqueous and aqueous‐ethanol solutions were studied. During the crystallization of the salt the electrical conductance and optical transmission of the supersaturated solutions were measured automatically. For monitoring of the total surface of growing potassium chloride crystals at the crystallization the turbidimetric method was used. The growth rate and activation energy of the crystals were determined. The crystal growth rate was proportional to supersaturation. When the volume fraction of ethanol in the solution increased from 0 to 25.76%, the activation energy of the growth process did not change and was about 60 kJ·mol^‐1. Aggregation of the crystals was found. The aggregation kinetics of the crystals may be described approximately by the famous Smoluchowski equation for coagulation of colloidal particles. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Size and morphology controlled synthesis of barium sulfate

In this work submicron barium sulfate (BaSO₄) particles were synthesized successfully by chemical precipitation technique. We focused on the effects of pH and additives on the size and morphology of BaSO₄ crystals. Polyacrylic acid, polyvinyl sulfonic acid and ethylenediaminetetraacetic acid were used as crystal growth modifiers. BaSO₄ crystals were characterized using scanning electron microscopy, X‐ray diffraction, and Fourier transform infrared resonance techniques. The results show that the submicron BaSO₄ particles have been synthesized successfully and the particle size of the barium sulfate was effectively controlled under the experimental conditions. Experimental studies revealed that the additive concentration and pH had great effect on the morphology and size of barium sulfate.     

Crystal Growth and Structural Refinements of the Y2SiO5, Y2Si2O7 and LaBSiO5 Single Crystals

The laser crystals of chromium doped yttrium oxyorthosilicate (YSO) were grown from the melt by Czochralski technique. The crystals of YSO, yttrium pyrosilicate and stillwellite-like lanthanum borosilicate were obtained from high temperature solutions. Lithium and potassium di- and trimolybdates were used as fluxes in the growth experiments on silicate crystals. In the case of borosilicate crystals, the choice of fluxes was based on the potassium trimolybdate with an excess of potassium fluoride. The composition of grown crystals was studied by electron microprobe analysis, and structural characteristics were determined for all the single crystals.     

Effect of different metal ions on structural,thermal, spectroscopic and optical properties of ATCC and ATMC single crystals

A novel metal‐organic coordination complex nonlinear optical crystals, tri‐allylthiourea cadmium chloride [(CdCl₂(AT)₃] and tri‐allylthiourea mercury chloride [(HgCl₂(AT)₃] abbreviated as ATCC, ATMC (AT is Allylthiourea i.e.,CH₂=CHCH₂NHCSNH₂) has been synthesized and grown as single crystals. It was synthesized in deionised water and further recrystallized to improve its purity. Single crystals of the allylthiourea co‐ordination complex nonlinear optical crystals tri allylthiourea cadmium chloride (ATCC) with dimensions of 14x14x10 mm³ and tri allylthiourea mercury chloride (ATMC) with dimensions of 15x15x12 mm³ were grown successfully from aqueous solution by solvent evaporation as well as by temperature lowering method. It exhibits powder SHG efficiencies higher than that of a well known organic NLO crystal Urea. The solubility of the as grown crystals was estimated from the aqueous solution and the effect of different metal ions on the grown crystals, structural, thermal, spectral and optical properties were analyzed. XRD studies the reveals the same structure of both materials. Influence of the different central metal (Cd and Hg) atoms, changing the thermal properties of the materials when NLO complexes formed with the common ligand allylthiourea. The metal co‐ordination was confirmed form the spectroscopic analysis. From the UV transmittance studies, red shift was from the transparency cut‐off wavelengths. The value is 285nm for ATCC is and is 335nm ATMC, Non‐linear an optical study confirms the suitabilities of the as grown crystals for the non linear optical applications. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal,phase transition and FTIR spectroscopic studies in tetraethylammonium trichlorocadmiate crystals

Single crystals of tetraethylammonium trichlorocadmiate were grown by slow evaporation of aqueous solutions at room temperature. The bright and transparent crystals obtained were characterized through FTIR spectroscopy, thermo gravimetric (TG and DTA) and low temperature DSC analyses. A fitting decomposition pattern for the title compound was formulated based on the TG thermogram which shows a two‐stage weight loss between 300°C and 800°C. In this temperature range the DTA curve shows endothermic dips supporting the formulated decomposition pattern. The thermal anomalies observed in the low temperature DSC both during the heating and cooling cycles indicate the occurrence of the first and second order structural phase transitions in the compound. The FTIR and far IR spectra show characteristic vibration frequencies due to [N(C₂H₅)₄]⁺ and CdCl₃^‐ ions. Detailed structural analysis of the compound is under progress. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and basic dielectric data of high quality TSCC crystals

Tris-sarcosine calcium chloride (TSCC) single crystals were grown from water solutions by the isothermal evaporation method. The growth solutions contained sarcosine and CaCl₂ either in stoichiometric or nonstoichiometric ratio. The required phase diagram sarcosine–CaCl₂ H₂O at 40 °C was determined by the synthetic method. PFT 400 MHz NMR was used for the analysis of organic impurities in sarcosine and TSCC. The crystals grown from both types of solutions had maximum values of the dielectric permittivity 10 to 200 times larger than those measured by other authors at comparable measuring frequencies and fields. It is discussed in terms of crystal quality.     

DNA模板调控纳米无机材料生长

以DNA为模板诱导纳米无机晶体的生长是近年来一个新的研究方向.DNA模板具有完善和严密的分子识别功能,使其组装过程具有高度的选择性.通过人为控制DNA的形状、长度和序列,可以制备出不同结构的纳米功能材料.本文讨论了DNA模板诱导硫化镉、四氧化三铁、硫酸钡、氯化镁和二氧化硅等纳米无机晶体的生长.