Understanding the growth mechanism of CuI crystals during gel growth experiments

Cuprous iodide crystals have been grown with decomplexation method in silica gel. Various crystal morphologies, such as polycrystalline aggregate, skeletal, dendrite, hopper crystals and regular tetrahedron crystals, were observed in different growth regions with an optical microscope. Their surfaces were photographed using a binocular metallographic microscope and the results were explained with the crystal growth mechanism which was determined by supersaturation. These observations support the general hypothesis that the concentration of reactant affects the relative growth rate by controlling the nucleation and diffusion. The mutual influence of the crystals grown in different regions was also discussed. Additionally, the suitable condition for getting regular tetrahedron crystals or large hopper crystals was obtained by changing the concentration of CuI·HI complex in the later period of crystal growth. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Determination of the supersaturation in the LiIO3–HIO3–H2O system using a refractive index value at near saturation concentration

The exact determination of supersaturation is essential for the studies of crystal growth processes in solutions. Due to peculiarities in the solubility of LiIO₃, the refractive index of the solution is chosen as a measure of the supersaturation instead of undercooling. The experimental setup is based on a refractometer and a special setup to create supersaturation in the cuvette by means of successive evaporation of small amounts of solvent. The refractive index is measured at different solution concentrations and pH and the data are correlated as dependences of concentration and pH on the refractive index. The accuracy of the method and the adequacy of the model are discussed.     

Growth Kinetics of Adenine Sulphate Crystals

The kinetics of growth and dissolution of adenine sulphate in 1.5 mol · 1⁻¹ H₂SO₄ at different super- and undersaturations has been studied. The solubility of adenine sulphate in H₂SO₄ was determined over the temperature range 20–50 °C. The growth rate of the (100) face is by about 25% higher than that of (111) and the crystal habit is changed by a high supersaturation almost to a bipyramide. The surface diffusion was determined as a prevailing processes and the BaS model gives the best fit with experimental data.     

Investigation of nucleation kinetics and crystal defects of HMX

The nucleation kinetics of HMX (cyclotetramethylene tetranitramine, C₄H₈N₈O₈) in γ‐butyrolactone was studied in cooling process by induction time method. The laser scattering method was used to measure the solubility data and metastable region of HMX in γ‐butyrolactone. The induction time was measured over a range of supersaturation at different temperatures. Then, the nucleation mechanism of HMX in γ‐butyrolactone was investigated by analysis the relationships between induction time and supersaturation. The results indicated homogeneous nucleation dominated at high supersaturation of S >1.35, while the heterogeneous nucleation dominated at low supersaturation of S < 1.35. The values of interfacial tension at different final temperatures were calculated to indicate the ability of HMX to be crystallized. The growth mechanism of HMX was investigated by the data fitting applying different growth mechanism models and identified as two‐dimensional nucleation‐mediated (2D) growth. Finally, the effects of supersaturation and temperature on the crystal defects were analyzed based on the nucleation kinetics. When the temperature is below 303.15K, homogeneous nucleation dominated the nucleation process at higher supersaturation. Fine HMX crystals with more defects were produced. On the contrary, heterogeneous nucleation mechanism dominated at lower supersaturation. large regular HMX crystals with fewer defects were formed when the temperature is above 318.15K.     

Growth Habit and Habit Variation of γ‐CuI Crystallites under Hydrothermal Conditions

The octahedra were observed in the γ CuI crystallites synthesized by hydrothermal method using 1.6g (C₂H₅OO)₂Cu and 2.66g KI as precursors at 200 °C for 12 hours in the de‐ionized water. The effect of additives on the morphology of γ‐CuI crystallites was investigated. Results show that the morphology of γ‐CuI crystallites prepared in the mixed solution of de‐ionized water and alcohol at 200 °C for 12 hours is the tetrahedron. In order to disclose the effect of the additive on the growth habit of γ‐CuI crystallites, the microcosmic growth mechanism of γ‐CuI crystal is investigated from the complex of I^‐ and Cu⁺ ions to each other. It is concluded that the effect of alcohol on the morphology of γ‐CuI crystallites is carried out through changing the relative rate of complex of anion and cation to each other at the interface. Based on the above analysis, the growth habit of γ‐CuI crystallites and the habit variation under hydrothermal conditions are explained reasonably.     

Crystallization kinetics of MgSO4 · 7 H2O at higher ranges of the driving force

By means of batch crystallization technique the crystallization kinetics of MgSO₄ · 7 H₂O at 25 °C at higher ranges of the supersaturation from pure aqueous solutions was investigated. It was observed that the growth rate highly depends on the habit of crystals and on their ratio of length to width, respectively. This ratio is a function of the initial supersaturation of each crystal.     

The induction time,interfacial energy and growth mechanism of maltitol in batch cooling crystallization

Maltitol is crystallized with seeds by cooling mode in industry, often with large amount of fine crystals and wide crystal size distribution. To eliminate the fine nucleation, it's necessary to understand the nucleation kinetics. In this work, the solubility of maltitol in water was measured by the gravimetric method, the nucleation kinetics of maltitol in batch cooling crystallization was investigated using focus beam reflectance measurement (FBRM), and a novel method was proposed to determine the induction time from the trend of the crystal median chord given by FBRM. Based on the relationship between the induction time and the supersaturation, the nucleation mechanism was obtained, including homogenous nucleation at high supersaturation and heterogenous nucleation at low supersaturation. Additionally, combining the classical nucleation theory (CNT) and Arrhenius’ principle, the crystal‐solution interfacial energy and the energy barrier of homogenous nucleation were calculated. From the scanning electron microscope (SEM) images, the growth mechanism of maltitol was identified as surface nucleation growth and the surface entropy factor calculated from the kinetic analyses of t_ind data corroborated this growth mechanism.     

Effect of impurity adsorption on the growth of Rochelle salt crystals

The influence of impurities of copper compounds on the growth of Rochelle salt crystals of the composition KNaC₄H₄O₄ · 4H₂O is studied. The growth rates of the faces of various simple forms experimentally measured as functions of the CuCO₃ concentration in solution at a constant supersaturation and temperature are compared with the theoretical models of impurity adsorption on the faces of a growing crystal. Deceleration of the growth of various faces of a Rochelle salt crystal is satisfactorily described by the Bliznakov equation with the use of the Langmuir, Frumkin-Fowler, and de Boor adsorption isotherms for all the faces except for {010}. However, such a comparison does not allow one to reveal the cause of adsorption or its type on different faces. Photometric scanning of Rochelle salt solutions with copper-compound impurity showed that a small addition of alkali (0.06–0.4 g/l) to the solution results in the appearance in the absorption spectra of both the solution nd the crystal grown from it of a maximum at the wavelength 660–670 nm. The intensity of this maximum increases with an increase in the copper concentration. The EPR data, the absorption spectra of the solution and the crystal, and the modified crystal shape showed that the addition of alkali to the solution results in the formation of new copper complexes that more actively decelerate the growth of Rochelle salt faces.     

About supersaturation and growth rates of hydrargillite Al(OH)3 in alumina caustic solutions

Growth rates of hydrargillite crystals, Al(OH)₃, growing from concentrated caustic solutions, are traditionally plotted and discussed as a function of the difference between actual concentration and solubility of alumina. This way to express supersaturation is probably due to practical or technical reasons, as hydrargillite is mainly grown in industrial plants. However, as the solubility of hydrargillite is greatly affected by the presence of caustic soda there are as many growth rate curves as there are solutions at different soda concentrations, if supersaturation is expressed as a concentration difference. In the present paper we show that all growth rates, measured in different caustic solutions, lie on a single curve if supersaturation is normalized with respect to solubility, i.e. expressed as a ratio of actual concentration over solubility. Accordingly, growth rates become independent of the caustic concentrations when growth takes place at the same supersaturation.     

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.     

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.     

Growth Rate anisotropy of the K2(S,Cr)O4 Mixed Crystals Grown from Aqueous Solution

The ratio of growth rates of the K₂(S,Cr)O₄ crystals in the [100] and [001] directions (the anisometry coefficient) is proportional to the initial effective supersaturation of the solutions from which the crystals were grown. The values of the factors of asymmetry and excess of distribution of the crystal anisometry coefficient are affected by the composition of solution. The change in the values of these factors is caused by the change in the value of the initial supersaturation of solution according to the specific features of the solubility diagram.     

Crystallization and Characterization of Orthorhombic β‐MgSO4 · 7H2O

In solution, the growth rate and the crystal habit are influenced by a number of factors such as supersaturation, temperature, pH of the solution, cooling rate, agitation, viscosity, initial state of the seed crystal and the presence of impurities. The crystallization of orthorhombic β‐MgSO₄ · 7H₂O, from low temperature aqueous solution by slow cooling process was studied. The metastable zone width, the induction periods (τ) for different supersaturations and the effect of pH on the growth rate of the crystals were investigated. The increase of pH yielded bigger crystals. The structural, optical, thermal and mechanical properties of β‐MgSO₄ · 7H₂O have been studied using FT‐IR, X‐ray diffraction, TGA‐DTG and micro hardness analyses.     

Determination of the solid liquid interfacial energy and thereby the critical nucleus size of paracetamol in different solvents

The effect of the type of solvent on the solid liquid interfacial energy was determined by performing induction time measurements of paracetamol in methanol, 1‐propanol, acetone and water at a constant supersaturation temperature of 30 °C and different levels of supersaturation (a/a*) ranging from 1.03 to 1.24. At equal supersaturation level and temperature the induction time increases with decreasing solubility whereas the solid liquid interfacial energy decreases with increasing solubility. The interfacial energy has a minimum value of 1.45 mJ/m² in the solvent where paracetamol has a maximum solubility (methanol) whereas it has its maximum value of 2.91 mJ/m² in the solvent with minimum solubility. The interfacial energy is a function of the solubility has been established. The critical radius for homogeneous nucleation was found to be minimum in the solvent of highest solubility. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Understanding the effect of solvent polarity on the habit modification of monoclinic paracetamol in terms of molecular recognition at the solvent crystal/interface

The habit change of monoclinic paracetamol crystallized from solutions with different solvents such as water, ethanol, methanol, acetone, isopropyl alcohol, tetrahydrofuran, cyclohexanone, acetonitrile and 1, 4 ‐ dioxane was investigated. Change in solubility, pH and nucleation time of paracetamol in these solvents at ambient condition was studied. The polymorphic form of the nucleated paracetamol was observed under in‐situ optical microscopy. Solutions with different solvents having different chemical nature and polarity yielded paracetamol crystals with different habits: columnar morphology from polar protic water and prismatic morphology from other selected polar protic, aprotic and in non‐polar solvents. The significant differences on the growth rate of various crystal habit faces of the monoclinic paracetamol grown from different solvents are attributed in context with the solubility of the solute, solvent polarity, evaporation number of the solvent, rate of generation of supersaturation and the role of hydrogen bonding interaction between the solvent molecules and protruding solute molecules on the crystal surface. Among the solution with different solvents, bulk monoclinic paracetamol single crystal was grown from ethanolic solution using seed rotation technique by controlled cooling method.     

Growth of KDP crystals from solutions with mechanical impurities

Growth of KDP crystals from aqueous solutions with SiO₂ particles whose size ranges from 10^–2 to 400 μm in the static and dynamic modes has been studied. The effect of mother-solution supersaturation and particle size and concentration on the process of particle capture by a growing crystal is considered as well as types of inhomogeneities formed in the crystal under the influence of these factors. It is shown that the larger the particle size, the higher the probability of particle capture by a crystal. The influence of supersaturation, growth rate, face morphology, and particle concentration on particle capture and defect formation in crystals is also discussed.     

Understanding supersaturation‐dependent crystal growth of L‐alanine in aqueous solution

The dependence of crystal growth rate of L‐alanine on solution supersaturation was investigated by combining experiments and molecular dynamics (MD) simulations. The experimental results show that lower supersaturated solution yields more elongated L‐alanine crystals along the c‐axis, i.e., the aspect ratio (c/b) of the crystal decreases with the increase of solution supersaturation, which is due to the higher supersaturation inducing a rise in the relative growth rate between the main side surface (the (120) surface) and the main end surface (the (011) surface). MD simulations on the two surfaces in contact with different supersaturated solutions revealed that the solute molecules tend to be more efficiently attached to the (011) surface than to the (120) surface at both supersaturations studied, as the interaction between the solute molecules and the L‐alanine molecules in the first layer of the (011) surface is stronger than that of the (120) surface. However, higher supersaturation leads to larger relative interaction energy between the (120) and (011) surfaces, suggesting an increase in the relative growth rate of the two surfaces (R₍₁₂₀₎/R₍₀₁₁₎) with supersaturation, which is in agreement with the experimental results.     

Effect of the addition of alcoholic miscible co‐solvents on the properties of ascorbic acid in its supersaturated aqueous solution

In the current study results are presented on the influence of the solvent composition on the properties of ascorbic acid in its supersaturated aqueous solutions. In examining the role of addition of 20 wt.% ethanol or 1‐propanol to the ascorbic acid water system, it was emphasized that the solubility is reduced significantly due to the addition of alcoholic co‐solvents. Using UNIFAC simulation, tt was found that the addition of alcoholic co‐solvents to the aqueous ascorbic acid solution and in the state of equilibrium reduces significantly the activity coefficient of ascorbic acid. In the supersaturated ascorbic acid solutions, the calculated activity ratio (γ/γ_eqm) by means of UNIFAC simulations as a function of supersaturation ratio (x/x_eqm) point out that the addition of alcoholic co solvents lead to an increase in the thermodynamic driving force. The measured metastable zone widths in the presence of alcoholic co‐solvents displays that alcoholic co‐solvents acts on increasing the width of the metastable zone. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

Growth of corundum single crystals by the top-seeded solution growth technique (TSSG)

Single crystals of corundum were grown by the top-seeded solution growth technique from a cryolite, Na₃AlF₆, solvent. The relationship between the growth rate (mg/h) of a crystal and the temperature difference (= supersaturation) or the rotation rate of a seed crystal was investigated, and optimum growth conditions for obtaining single crystals with good quality are discussed.