Seeded batch crystallization of ammonium aluminum sulfate from aqueous solution

Seed crystals of ammonium aluminum sulfate ((NH₄)Al(SO₄)₂··12H₂O) were grown in aqueous solution by cooling. The temperature of a crystallizer was lowered with no control by circulating cooling water through the jacket. It fell in an exponential manner. The effects of seed amount and size on the product crystal size distribution were examined. The product crystals obtained were of narrow and uni-modal size distribution with suppressed secondary nucleation if seed crystals were loaded more than a critical value. The critical value was determined and well compared with previously reported values for other material systems. This crystallization technique does not need any prior knowledge of the kinetics of crystal growth and nucleation. It is simple and robust, and can be easily applied to an existing crystallizer without installing any additional control systems.     

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.     

Crystal structure of aluminum sulfate hexadecahydrate and its morphology

A single‐crystal structure of aluminum sulfate hexadecahydrate (Al₂(SO₄)₃·16H₂O) was captured with a polarizing microscope. The structure was similar to a hexagonal plate and consistent with the predicted morphology derived from the modified AE model. An octagonal plate morphology was first obtained in a vacuum but was transformed into hexagonal plate‐like when the effect of the solvent with two disappearing {1 1 0} and {1 0 −1} faces was considered.     

Induction periods and mechanism and kinetics of nucleation of barium tungstate crystal growth from sodium tungstate melts in platinum crucibles

Induction periods (t) and mechanism and kinetics of nucleation in barium tungstate crystallization from sodium tungstate melts in platinum crucibles were studied. A theoretical relation has been developed to express the dependence of t on the cooling rates (R_T) and the rate (R_c) of development of excess solute concentration. At any crystallization temperature the average rate-constant (k_n) for heterogeneous nucleation was related to R_c by (k_n/p)^1/(p+1) = 1/(tR_c^γ), where γ is a constant and p is the average number of particles in the critical nuclei. The critical temperature (T), critical supersaturation (S) and γ values were estimated.     

Differential thermal analysis studies on the crystallization of strontium tungstate melts. Variation of rate constants with crystallization temperatures and cooling rates

Kinetics of strontium tungstate crystallization from sodium tungstate melts were studied in platinum crucibles (by DTA) by continuous cooling from initial crystallization temperatures T₀ = 800° to 1000° to below the eutectic temperature at cooling rates R_T = 0.67° to 3.3° min⁻¹. Heterogeneous nuclei first formed slowly onto metal platinate particles within the solution during induction periods (t ); the main crystal growth then started after the development of some exces solute concentration (ΔC ) at the induction temperature (T ). The actual growth after t was diffusion rate-controlled. The diffusion rate-constants (k_Dt) for growth after the induction periods along the major axis were estimated; the increased with T₀ and R_T. These values were higher than those for diffusion-controlled crystal growth of strontium tungstate from sodium tungstate melts in alumina crucibles but much smaller than the real diffusion rate-constants (k_Dl)_real.     

Investigation of the crystallization of the system KAl(Cr)(SO4)212 H2O under various conditions

The crystallization of the isomorphous system KAl(Cr)(SO₄)₂ · 12 H₂O under various conditions has been studied. It has been found that the rate of linear crystallization of the face (100) passes through a maximum on the interval of Cr³⁺ concentrations 0.02–0.08 g ions/l which is shifted to the right with increasing temperature. Under the same conditions, the equilibrium coefficient of distribution of the microcomponent D has been determined in single crystals. D decreases with the increase of the Cr³⁺ concentration and the crystallization temperature. These results can be explained with the formation of complexes of Cr³⁺ in the solution which decreases the active concentration of the ion and are selectively adsorbed on the face (100). At the same Cr³⁺ concentration (0.058 g ion/l), the temperature dependence of the rate of growth of the face (100), as well as the influence of supersaturation on the rate of growth of the faces (100) and (111), have been studied. The apparent activation energy of crystallization of the face (100) has been determined to be E = 11.2 Kcal. · mol⁻¹. The data obtained are compared with analogical results for pure KAl(SO₄)₂ 12 H₂O.     

Mechanisms of Interaction of Molybdenum and Tungsten Polyoxide with Aluminum Oxide Melt under Reducing Conditions

The main chemical reactions between Mo and W polyoxides and Al₂O₃ melt in a controlled Ar + H₂ atmosphere (T = 2400 K, P = 1 bar) during sapphire growth by horizontal directional solidification have been investigated. Under these thermodynamic conditions, the melt and products of its dissociative evaporation may actively react with the tungsten heater and molybdenum thermal screens of the crystallization system. It is shown that the polyoxides formed during evaporation do not directly interact with the melt; this interaction occurs only with participation of reagents exhibiting pronounced reducing properties (Al, H₂, H, WO, Al₂O, AlH, AlH₂, AlH₃). It is established that most of processes occur with participation of aluminum hydrides. A particular role of Mo(W) dioxide–W(Mo) polyoxide functional pairs in the interaction with the melt is determined.

     

Structural and spectral studies on gypsum crystals under simulated conditions of phosphoric acid production with and without organic and inorganic additives

In the dihydrate process to produce phosphoric acid, phosphate ore [Ca₁₀F₂(PO₄)₆] is leached with sulfuric and weak phosphoric acids to produce phosphoric acid and gypsum as a by‐product. Crystallization of gypsum occurs as the leaching is taking place. The effect of organic and inorganic additives on the structure and spectrum of gypsum crystals under simulated conditions of phosphoric acid production is studied using x‐ray diffraction and infrared spectroscopy. Structure and spectrum of formed gypsum crystals in the absence of additives are slightly different from the standard gypsum crystals (card No. 6‐0046), which reflect the effect of preparation medium on the crystal structure of gypsum crystals. Presence of additives such as cetyl trimethyl ammonium bromide and 1,2‐dihydroxybenzene‐3,5‐disulfonic acid, Al³⁺ and Mg²⁺ increase the crystallinity of gypsum, while presence of additives such as citric acid and sodium dodecyl sulfate decrease the crystallinity of gypsum. Presence of Al³⁺ and Mg²⁺ as additives lead to the formation of calcium sulfate hemihydrate beside calcium sulfate dihydrate. Presence of sodium dodecyl sulfate as an additive inhibits the crystallization of gypsum and leads to the formation of anhydrite and calcium sulfate hemihydrate.     

Fluctuation of crystallization at center part of floating molten zone under reduced gravity condition

Fluctuation of crystallization was observed at floating molten zone under reduced gravity condition on airplane. The zone material was Ba(B_0.9Al_0.1)₂O₄. A pair of Pt tubes was used at the upper and the lower positions, and the molten zone was formed between two Pt tubes. Double peak temperature profile could be performed using two Pt tubes. Crystallization of the molten Ba(B_0.9Al_0.1)₂O₄ was started at center part of side surface of floating molten zone under reduced gravity condition. The formed crystal was melted again during the crystallization by the gravity fluctuation at the center part of the floating molten zone. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Simulation of metastable zone width and induction time for a seeded aqueous solution of potassium sulfate

The metastable zone width (MSZW, ΔT_m) and induction time (t_ind) were determined with computer simulation for seeded batch crystallization of potassium sulfate from aqueous solution. The MSZW and induction time determined with simulation showed the same behavior as experimental values reported in the literature; log (ΔT_m) increased linearly with an increase in log R (R: cooling rate) and t_ind decreases in proportion to (ΔT)⁻ⁿ (ΔT: supercooling, n: nucleation order in the secondary rate expression of B=k_n(ΔT)ⁿ). The secondary nucleation parameters (k_n and n) were deduced both from the simulated MSZW and induction times by using the previously proposed model [J. Cryst. Growth, 2010, 312, 548–554]. The secondary nucleation rate calculated with the deduced parameters was in agreement with that calculated with the parameters input for simulation.     

A cooling rate dependent structure of amorphous (AuxCu1−x)91La9

A novel class of metallic glasses of the form (Au_xCu_1?x)₉₁La₉ (x = 0.5, 0.25, 0.6) and (Au_0.5Cu_0.5)_1?yLa_y (y = 10, 11) have been prepared by rapid cooling from the melt. Investigation by means of X-ray diffraction and TEM shows a dependence of the structure on the cooling rate and suggests a phase separated amorphous structure. For sufficiently low cooling rates, crystallization seems to follow phase separation.     

Crystallization study of molybdate phosphate glasses by thermal analysis

Vitreous samples were prepared in the binary system NaPO₃–MoO₃ and their characteristic temperatures were determined by Differential Scanning Calorimetry. Glasses with high amounts of MoO₃ (>45 mol%) exhibit an intense crystallization peak and the composition 50 NaPO₃–50 MoO₃ was chosen for the crystallization study. Two different methods based on thermal analyzes were used to determine the mechanism of crystallization in these molybdenum–phosphate glasses. In the first procedure, thermal analyses by DTA were performed on samples with different grain sizes and the crystallization tendency deduced in function of superficial area. The second method used the classical non-isothermal crystallization study: DSC measurements were performed under several heating rates to access activation energy for crystallization and Avrami parameter n. Critical cooling rate was calculated and compared with experimental data obtained from DTA analysis upon cooling.     

Synthesis and crystal structure of a novel polymeric silver(I) complex

The complex of [Ag₂(μ–L)₂(μ–NO₃)₂]_n, where L?=?2–methyl–5–(2–pyridyl)–1,3,4–oxadiazole, has been synthesized and characterized by single–crystal X–ray diffraction analysis. The crystals are in triclinic system with space group P–1. Complex [Ag₂(μ–L)₂(μ–NO₃)₂]_n is a polymeric silver(I) complex bridged through the 1,3,4–oxadiazole rings and the nitrate ions, and the center Ag1(I) atoms have distorted trigonal bipyramidal geometries [AgN₃O₂].     

Continuous cooling crystallization kinetics of a molten blast furnace slag

The crystallization characteristics and kinetics of a molten blast furnace slag during continuous cooling were investigated. Samples of molten blast furnace were continuously cooled both in tiny amounts in a differential scanning calorimetry (DSC) equipment and in bulk states in a cooling mold. The mineragraphy and morphology were investigated by means of X-ray diffraction (XRD) and scanning electron microscope (SEM). The continuous cooling crystallization kinetics were studied using different models based on DSC data. The results show that akermanite (2CaO·MgO·2SiO₂) and gehlenite (2CaO·Al₂O₃·SiO₂) are the major minerals in the continuously cooled crystalline blast furnace slag. The mechanism of crystallization of the blast furnace slag during continuous cooling is dominated by both surface nucleation and one-dimensional growth with bulk nucleation, which is significantly different to that during heating. The activation energy of crystallizations of akermanite and gehlenite was determined by Kissinger and Matusita methods. The values obtained are much higher than that yielded during heating.     

Electroactive complex in thermally treated Ge-Si 〈Cu,Al〉 crystals

It is shown by Hall measurements that quenching complexly doped Ge_{1 − x} Si _x 〈Cu, Al〉 (0 ≤ x ≤ 0.20) crystals from 1050–1080 K leads to the formation of additional electroactive acceptor centers in them. The activation energy of these centers increases linearly with an increase in the silicon content in the crystal and is described by the relation E _k ^x = (52 + 320x) meV. Annealing these crystals at 550–570 K removes the additional acceptor levels. It is established that the most likely model for the additional electroactive centers is a pair composed of substituent copper and aluminum atoms (Cu _s Al _s ) or interstitial copper and substituent aluminum atoms (Cu _i Al _s ). It is shown that the generation of additional deep acceptor levels must be taken into account when using the method of precise doping of Ge_{1 − x} Si _x 〈Al〉 crystals with copper.     

Crystallization Control of Molten Ba(B0.9Al0.1)2O4 from Supercooled Pendant Drop

Crystallization process of molten Ba(B_0.9Al_0.1)₂O₄ from supercooled pendant drop was investigated on a viewpoint of a supercooling and a solid phase formation. Molten pendant drop was crystallized by a rod touching at an crystallization temperature under an adequate degree of supercooling. Three kinds of rods were used. Each rod was made of Pt, hBN and graphite which had different wettability to the molten drop. There were three kinds of phases on a solid Ba(B_0.9Al_0.1)₂O₄, such as a high temperature crystal phase, a low temperature crystal phase and a glass phase. All phases could be formed by the present method.     

Estimation of activation parameters for diffusion-controlled crystallization of barium tungstate from sodium tungstate melts by differential thermal analysis

The proximity (d₁₂) between a diffusing species and its host crystal necessary for a successful diffusion for diffusion-controlled crystallization of barium tungstate from sodium tungstate melts in platinum crucibles was estimated. These distances increased with increased cooling rates (R_T) and crystallization temperatures (T₀). Energy (E), enthalpy (ΔH_a), entropy (ΔS_a) and free-energy (ΔG_a) of activation and the pre-exponential factor (k₀) were evaluated using an ordinary Arrhenius equation k_D1 = k₀e^−E/RT, where k_D1 was the diffusion rate-constant. These parameters were virtually unaffected by the changes in T₀ and R_T.     

Writing of crystal line patterns in glass by laser irradiation

We examined the laser-induced crystallization to form the fresnoite type Ba₂TiGe₂O₈ crystal line patterns in transition metal ion doped BaO–TiO₂–GeO₂ glass. Ba₂TiGe₂O₈ crystal line was written in 0.6FeO–33.3BaO–16.7TiO₂–50GeO₂ glass by continuous wave yttrium–aluminum–garnet (YAG) laser irradiation. We obtained polarization dependence of Raman spectra in crystal line pattern. Second harmonic generation (SHG) indicated unique fringe patterns from Ba₂TiGe₂O₈ crystal lines.     

The dependence of surface morphology of GaSb- and AlxGa1–xSb epitaxial layers on the conditions of LPE growth

The present work shows the dependence of surface morphology of the GaSb and Al_xGa_1–xSb epitaxial layers on the conditions of LPE growth. It is found that for LPE growth at 500 °C a supersaturation of 5—10 °C and a cooling rate of 0.24—0.4°C/min for GaSb epitaxial layers and 0.8—1.2 °C/min for Al_xGa_1–xSb epitaxial layers is necessary to obtain a flat and smooth surface.     

Stability Determinant of Anisotropic Phases

The thermodynamic stability of crystal determinant D) and nonstability D_{n st}⁽¹⁴) of the fourteenth order, their adiabatic and corresponding isodynamical coefficients are discussed.