Crystallization kinetics of MgSO4 · 7 H2O in presence of tenside

The effect of sodium dodecyl sulfate (SDS) on crystallization kinetics and crystal habit of MgSO₄ · 7 H₂O from aqueous solutions at 25 °C was investigated in batch experiments. It highly depends on the supersaturation level. Both increasing supersaturation and rising concentration of the tenside promote the production of needle-like crystals but the influence of the driving force is much more pronounced. SDS increases the crystallization rate and the linear crystal growth rate in length direction of the crystals. To a high degree it also influences properties of the crystallizing solution such as surface tension and viscosity.     

The role of hydration and complexing in the mechanism of impurity influence on crystal growth

The influence of impurities of chlorides and nitrates of divalent Ca²⁺ and Ba²⁺ cations on the kinetic growth of potassium dihydrophosphate KH₂PO₄ crystals at a saturation temperature of 323 K and relative supersaturation of 0.03 has been investigated experimentally. It is established that the impurity acts differently, depending on the face index, the impurity concentration, cation hydration, and the stability of the complexes formed in the solution by impurity salt ions. A model is proposed to explain the different influence of impurity ions on the growth of crystal faces. This influence is determined by the different hydration of cations and enhanced association of cations and anions of impurity salts in the surface layer with a lower dielectric constant.     

Crystallization of zinc lactate in presence of malic acid

The influence of malic acid, which acts as an impurity on the cooling crystallization of zinc lactate is investigated in this paper by monitoring the relative supersaturation and the number of crystals during crystallization. The presence of malic acid increases the solution solubility and makes the metastable zone wider; it also changes the habit of the crystal. The purity of the final products is shown to be influenced by the amount and size of seed crystals, cooling rate, seeding temperature and final temperature, but appears to depend mainly on the particle size and level of supersaturation. Residual supersaturation thresholds are observed that depend on the final temperature. A model is proposed to predict the steady-state supersaturation value from the final temperature at a given impurity concentration. This model is based on Kubota and Gibbs equations.     

The combined effects of supersaturation and Ba2+ on the batch cooling crystallization of potassium dihydrogen phosphate

The combined effects of supersaturation and Ba²⁺ on potassium dihydrogen phosphate (KDP) were investigated in batch cooling suspension crystallization. Growth size, morphology, and impurity Ba²⁺ adsorbed in the KDP crystals were measured with changing Ba²⁺ concentration and supersaturation. Significant changes in shapes and volume of the grown crystals have been observed. The results further confirmed that the size and shape of crystals were greatly determined by supersaturation. Ba²⁺ ions significantly modified the growth habit of KDP crystals. The concentration of Ba²⁺ ions adsorbed in the crystals increases with the increasing Ba²⁺ ions in the solutions and supersaturation. The foggy phenomena caused by the addition of Ba to the KDP solution were also described. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Semi-Batch Precipitation of Calcium Oxalate Monohydrate

Calcium oxalate monohydrate (COM) formation on the semi-batch precipitation of CaCl₂ and Na₂C₂O₄ solutions in the stoichiometric ratio carried out at pH = 6 and 37 or 70°C, respectively, was studied. When a certain level of supersaturation in the system is reached, individual COM crystals of a rather uniform size are formed. These crystals then grown and form ‘loose’ agglomerates that later develop into compact and spherical particles. The particle size distribution (PSD) rapidly shifts during early stages of precipitation towards larger sizes as a result of crystal growth and agglomeration. Later the PSD reaches a shape and position on the size axis that remain virtually constant with progressing precipitation. COM agglomerates consisting of mainly intergrown crystals are formed by mechanism of primary and secondary agglomeration. The primary agglomeration can constitute an important factor in urolithiasis.     

Kinetics of sodium fluosilicate precipitation

The formation of Na₂SiF₆ by discontinuous precipitation of dilute H₂SiF₆ with a 40% excess of an aqueous solution of NaCl under various conditions was studied. The values of induction time, number of crystals formed, their final size and their habit were determined during precipitation from solutions, whose initial supersaturation was 2 < S < 11. At S < 7–8 the crystals were formed by heterogeneous nucleation, whereas at S ≳ 7–8 homogeneous nucleation mechanism began to prevail. Once formed, the Na₂SiF₆ crystals were growing according to the screw-dislocation mechanism till they reached visible size; the corresponding values of kinetic order of nucleation and of the growth rate constant were g = 1.35 and k_g = 4.32 × 10⁻⁸ cm^2.05 sec⁻¹ g^−0.35, resp. The value of interfacial tension on the phase boundary Na₂SiF₆ crystal — saturated solution was determined (σ ∼ 52 erg/cm²). The resulting Na₂SiF₆ crystals conformed to log-normal distribution irrespective of conditions of precipitation. The dependence of the final size of crystals on supersaturation exhibited a maximum at S ∼ 6. Crystals of Na₂SiF₆ had a hexagonal habit, which was near to a spherical form at lower supersaturations, while dendritic crystals were formed at higher supersaturations.     

A study of primary nucleation of calcium oxalate monohydrate: I‐Effect of supersaturation

There are various organic and inorganic constituents in kidney stones. Among them, calcium oxalate monohydrate (COM) is the primary inorganic constituent of kidney stones. However, the mechanisms of formation of kidney stones are not well understood. In this regard, a basic study is carried out for better understanding of nucleation, crystal growth and/or aggregation of formed COM crystals. The primary nucleation of calcium oxalate monohydrate is studied at the laboratory scale using turbidity measurements. Calcium chloride and potassium oxalate solutions are mixed and then added to a Turbidimeter tube for continuous recording of turbidity. Induction time (time to induce formation of detectable crystals) is estimated from time‐turbidity graphs. The effect of some urinary species, such as oxalate and calcium, on nucleation and crystallization characteristics of COM is determined by particle size distribution analysis, measuring weight of crystals and calculation of relative supersaturation. The classical nucleation theory is applied at high supersaturation ratios (SR) ranging from 1.6 to 2.2. The results indicate that nucleation rate increases with increasing supersaturation ratio from 0.81 × 10²⁸ nuclei/cm³.sec at 1.6 SR, to 18.02 × 10²⁸ nuclei/cm³.sec at 2.2 SR. On the other hand, free energy change and radius of critical nucleus are decreased as supersaturation ratio is increased. The nucleation rates are higher than those reported in literature. Such discrepancy is discussed on the bases of differences in experimental techniques. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and mechanical properties of KН2PО4 single crystals with embedded nanoparticles and organic molecules

Single crystals of KDP crystals with embedded Urea molecules and TiO₂ nanoparticles have been grown from aqueous solution by the temperature lowering method. The effect of the organic molecules and nanoparticles on the structural and mechanical properties has been studied. It has been observed that addition of Urea molecules improves laser induced damage threshold and mechanical strength of the crystal, while TiO₂ nanoparticles have the opposite effect. The structure and composition of KDP:Urea crystal are studied by three‐crystal X‐ray diffraction analysis, which reveals the existence of a correlation between the increase of the microhardness value and the change of the crystal lattice parameter. The surface features of KDP:TiO₂ crystals are analyzed by scanning electron microscopy that reveals the presence of quasi‐equidistant growth bands caused by capture of the nanoparticles. It is shown that the rise of TiO₂ nanoparticles concentration up to 10⁻⁴ wt.% and higher resulted in 3‐fold reduction of the laser damage threshold of KDP:TiO₂ relative to pure KDP in [001] and [100] crystallographic directions. It is found that microhardness and fracture toughness decrease at the nanoparticles concentration of 10⁻³ wt.% due to crack formation at crystal lattice discontinuities. The grown crystals also have been subjected to dielectric studies.     

Growth mechanism of crystals from aqueous solutions

Microscopic processes occurring on the surface of a growing crystal or a dissolving one were observed by microcinematography. The crystals under observation were grown either in a drop of solution by evaporation or in a constant-temperature microscope stage at a chosen supersaturation. Small (approx. 0.1 mm) and large (approx. 10 mm) crystals of NaCl, Pb(NO₃)₂, NaNO₃, CdI₂, KDP and ADP were studied. It is concluded qualitatively that the layers, in general polygonal, originating in one or several active centres, are formed on the crystal face, never at the corners or edges. – The average velocity of layer motion was studied quantitatively in dependence on their thickness and supersaturation. The layer motion at constant supersaturation considerably fluctuated. – Surface patterns created by moving layers agree in most cases with predictions of the dislocation theory. Two categories of steps were found on the surface: ”︁real”︁ macrosteps and shock waves. – The velocity of layer motion for most compounds lies within (1–10) · 10⁻⁴ cm · s⁻¹.     

On the Mechanism of Crystal Growth from Undercooled Melts

The mechanism of crystal growth from undercooled melts is studied experimentally by means of a simple capillary technique. Thymol and Na₂S₂O₃ · 5 H₂O are used as model substances. Dislocation-free crystal faces of these compounds are obtained by continuous growth in the capillary or by prolonged annealing under appropriate conditions. Two-dimensional mechanism of growth was experimentally verified on such perfect crystal planes. The conditions under which the surface nuclation mechanism operates are described accounting for the supersaturation, the influence of impurities etc. Transition from two-dimensional into spiral growth of purposedly defected crystal faces is demonstrated and investigated. The mechanism of formation of perfect crystals is discussed and further experimental evidence on the possibility of two-dimensional growth from melts is given.     

Kinetic studies on the influence of temperature and growth rate history on crystal growth

Crystallization experiments of sucrose were performed in a batch crystallizer to study the effect of temperature and growth rate history on the crystal growth kinetics. In one of the growth methods adopted, the isothermal volumetric growth rate (R_V) is determined as a function of supersaturation (S) at 35, 40 and 45 ºC. In the other, crystals are allowed to grow at constant supersaturation by automatically controlling the solution temperature as the solute concentration decreased. Using the latter method R_V is calculated as the solution is cooled. The obtained results are interpreted using empirical, engineering and fundamental perspectives of crystal growth. Firstly, the overall activation energy (E_A) is determined from the empirical growth constants obtained in the isothermal method. The concept of falsified kinetics, widely used in chemical reaction engineering, is then extended to the crystal growth of sucrose in order to estimate the true activation energy (E_T) from the diffusion‐affected constant, E_A. The differences found in the isothermal and constant supersaturation methods are explained from the viewpoint of the spiral nucleation mechanism, taking into account different crystal surface properties caused by the growth rate history in each method. Finally, the crystal growth curve obtained in the batch crystallizer at 40 ºC is compared with the one obtained in a fluidized bed crystallizer at the same temperature. Apparently divergent results are explained by the effects of crystal size, hydrodynamic conditions and growth rate history on the crystallization kinetics of sucrose. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The influence of concentration and supersaturation ratio of CuI·HI on CuI crystal growth by decomplexation method

The fundamental role of solubility and supersaturation of solute for crystal growth from solution has been widely realized. In order to optimize the process of CuI crystal growth by CuI·HI decomplexation in HI acid, the solubility and supersaturation curves of CuI in HI‐H₂O mixed solvent were measured, and then a modified concentration programming scheme was designed, which could grow high quality CuI single crystals of 2.5 mm on edge successfully. In this scheme, the concentration distribution of CuI·HI complex and HI acid in silica gel along their diffused direction were measured with spectrophotometer, and the evolution of CuI·HI complex supersaturation ratio was analysed. It was found that the excess CuI·HI complex concentration would lead to the high supersaturation ratio and the formation CuI dendrites. The condition for regular CuI single crystal growth in silica gel was measured as follow: when the crystal nuclei appears, the CuI·HI complex concentration in HI‐H₂O solvent should be kept in the range of 0.033–0.050 mol/L and its corresponding supersaturation ratio is 1.24–1.45, and then they should be respectively declined to a range of 0.025–0.033 mol/L and 1.14–1.26 at the stage of crystal growth. The results may provide a useful clue for further improvement of the experimental scheme. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study on the Growth of Triglycinsulphate Single Crystals

Crystallization of TGS at 52.0°C - above the transition point - has been studied in a wide range of supersaturation of the solution (σ = 0 to 10⁻²). The rates of growth of {110} and {001} faces were measured as a function of supersaturation at constant hydrodynamical conditions (Re = 3.4 · 10⁻³). Further, the influence of hydrodynamical conditions on the growth of {110} faces at constant supersaturation (σ = 4.2 · 10⁻³) was established. The parameters of the experimentally found dependences are determined on the basis of the surface-diffusion model of BURTON . CABRERA and FRANK . From these dependences follows that the growth rate of the {110} faces is already almost limited by the volume diffusion of TGS molecules towards the crystal surface, while in the case of {001} faces the surface diffusion mechanism of crystallization is clearly manifested. Dislocation densities in the crystals have been determined by means of etching technique. The number of dislocations increases with increasing supersaturation; hence, supersaturation of the solution together with the processes taking place in the regeneration zone surrounding the seed determine the number of dislocations in the crystal volume and thus the resulting structural perfection of single crystals. Investigation of the spontaneous redistribution of domains showed that the growth rate of TGS crystals influences the dielectric properties to much smaller extent than does chemical purity.     

Growth kinetics and adsorption trapping of impurity during crystallization of NH<Subscript>4</Subscript>Cl in the NH<Subscript>4</Subscript>Cl-CuCl<Subscript>2</Subscript>-H<Subscript>2</Subscript>O-CONH<Subscript>3</Subscript> system

The growth of NH₄Cl crystals and their trapping of copper impurity in the NH₄Cl-CuCl₂-H₂O-CONH₃ quaternary system have been experimentally studied. The epitaxial adsorption of copper complexes on (100) faces leads to a sharp decrease in the growth rate in good correspondence with the Bliznakov-Chernov equation. The copper impurity enters the crystal composition in amounts up to 6.5 mol %. The impurity distribution coefficient nonlinearly changes with the copper concentration in the solution: it is much larger than unity at low concentrations and sharply decreases with an increase in supersaturation. Such behavior is indicative of the adsorption mechanism of copper trapping by NH₄Cl crystals. Single-crystal X-ray study shows that the impurity is incorporated in NH₄Cl crystals in the form of oriented intergrowths of different complex coppercontaining compounds. The concentration and variety of impurity phases increase with an increase in the copper content in the solution and decrease with an increase in supersaturation. Heterogeneous 2D isomorphous trapping of copper impurity by NH₄Cl crystals induces high (up to 60 MPa) internal stresses in them, as a result of which anomalous birefringence and splitting of crystals occur.     

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)     

Polymorphic composition and morphology of calcium carbonate as a function of ultrasonic irradiation

This paper reports on the precipitation of CaCO₃ polymorphs, having various crystal morphologies under different conditions. In particular, systems that were subject to ultrasonic irradiation were compared to the corresponding reference systems in the absence of such a treatment. The application of ultrasonic irradiation predominantly resulted in a change of particle size distribution and polymorphic composition of the precipitate, in comparison to the reference systems. Thus, it was found that the supersaturation and temperature influenced the size distribution, in both the reference and sonicated systems. A mixture of calcite, vaterite and aragonite was obtained in all reference systems, at 25 °C. At this temperature, the sonication caused the vaterite content to increase, while aragonite was not detected. In reference and sonicated systems at 80 °C, only aragonite precipitated. The results also indicate that the principle parameter responsible for the morphology of vaterite was the initial supersaturation: at higher supersaturation spherical vaterite particles precipitated, while at lower supersaturation hexagonal platelets were obtained. The morphological investigations also indicated different mechanisms of vaterite formation in the systems in which precipitation was initiated at higher supersaturation: spherulitic growth of vaterite was observed in sonicated systems, while the aggregation of primary particles was predominant in the reference systems. At lower supersaturation, the effect of c(Ca²⁺)/c(CO₃²⁻) on the morphology of hexagonal platelets of vaterite was observed as well. By varying the c(Ca²⁺)/c(CO₃²⁻), significant changes of the polymorphic composition were observed only in the sonicated systems, at 25 °C.     

Kinetic investigations within the transition region from polyhedral to skeletal growth mode (I). Growth kinetics of the basal face of zinc single crystals under diffusion conditions

The effect of diffusion in the vapour phase on the kinetics of growth of zinc single crystals in the presence of argon has been studied. The shift of the basal face in normal direction as a function of the time has been measured at constant temperature and supersaturation and argon pressures varying within the range 5–250 Torr as well as in vacuum 1 × 10⁻⁶ Torr. It has been established that the crystal size R changes with the time t following a linear and a parabolic law in the kinetic and the diffusion regimes, respectively. The kinetic critical size R_k for the transition from a kinetic to a diffusion regime has been experimentally obtained. A relatively good agreement is found between the experimentally established and theoretically calculated values of the critical size. The problems related to the transition of the basal faces of zinc single crystals from a kinetic to a diffusion growth mode is discussed.     

Hydrothermal synthesis and luminescent properties of YBO3:Tb3+ uniform ultrafine phosphor

The pure hexagonal phase YBO₃:Tb³⁺ phosphors with good crystallinity and uniform size were prepared by hydrothermal reaction (HR). The particle size and morphology can be well controlled by adjusting the concentration of ammonium acetate and varying the reaction temperature and time. The phosphor prepared by HR emits an intense green light at 543 nm, which is stronger than that from crystals synthesized by solid-state reaction (SR). The influence of Tb³⁺-doping concentration on the crystallization and luminescent properties were investigated. The results showed that the samples exhibited a higher quenching concentration of Tb³⁺ in comparison with those prepared by the SR. The phenomena were also discussed.     

Kinetics of crystal growth of mirabilite in aqueous supersaturated solutions

The crystallization of sodium sulfate decahydrate (Na₂SO₄·10H₂O, mirabilite) from supersaturated solutions was investigated using stable supersaturated solutions seeded with mirabilite seed crystals. The experiments were done in batch, stirred reactors in which the supersaturated solutions were prepared either by dissolution of sodium sulfate anhydrous at 32 °C followed by cooling to 18 or 20 °C or by mixing equal volumes of equimolar ammonium sulfate and sodium hydroxide solutions at 20 °C. Inoculation of the solutions supersaturated only with respect to mirabilite with seed crystals was accompanied with temperature increase of the thermostated solution. Despite the fact that crystal growth was initiated with seed crystals, the process started past the lapse of induction times inversely proportional to the solution supersaturation. The rates of crystal growth were measured both from the temperature rise and from the concentration–time profiles, which were linearly correlated. The measured crystal growth rates showed a parabolic dependence on supersaturation at low supersaturations. For higher values this dependence changed to linear, a behavior consistent with the BCF spiral crystal growth model. The morphology of the crystals growing at 20 °C showed typical prismatic habit, while at 18 °C when crystallized from cooled sodium sulfate solutions changes in the crystal habit to a leaf like morphology were observed.     

LPE growth of DH laser structures with the double source method

For the reproducible processing of double heterojunction injection laser structures to stripe geometry laser diodes, e.g. by proton bombardment, the thickness of the p-Ga_0.7Al_0.3As confining layer and of the p-GaAs top layer are of great importance. It is shown that the thickness control of these layers grown by liquid phase epitaxy can be improved considerably by introducing two source crystals into the growth system. Both source crystals are brought into contact with the solutions consecutively and prior to the seed. If this method is combined with the use of relatively thin melts (about 2 mm), a growth scheme may be chosen such that the growth rates of the p-GaAlAs and of the p-GaAs layers have reached a practically constant value on the seed crystal, independent of the initial degree of supersaturation. This behaviour is found to be in accordance with the diffusion-limited growth model applied for thin solutions, including a temperature dependence for both the diffusion constant and the slope of the liquidus curve. The results indicate that a second solid phase may appear in the p-GaAlAs solutions at a supersaturation as small as 4°C, which reduces the growth rate on the substrates by a factor of about 2. This situation is different from that of GaAs solutions, where a second phase appears only at a much higher degree of supersaturation. For the p-GaAlAs and the p-GaAs layers a thickness control of ⁺_-0.2 μm is thus achieved with this growth method, without the necessity of very precise temperature control and weighing so as to keep the total supersaturation less than 0.2°C.