Investigations on the nucleation kinetics of bis glycine sodium nitrate

The nucleation parameters such as, energy per unit volume, radius of critical nucleus, critical free energy barrier, number of molecules in the critical nucleus and nucleation rate have been evaluated for bis glycine sodium nitrate single crystals. The interfacial energy of the solution at various temperatures has been estimated from existing solubility data. The metastable zone width and induction period measurements have been carried out experimentally.     

Thermodynamics of Crystal Nucleation in an External Electric Field

The influence of electric field on crystal nucleation in a saturated solution has been studied both theoretically and experimentally. The classical equations for nucleation have been used to determine the free energy of formation, critical radius of the cluster and the concentration of the critical nuclei. The theory shows that an externally applied electric field can modify the free energy of formation of a crystalline cluster in its aqueous solution. The impact of the field will be stronger on large molecules. Two experimental set ups have been designed to study the nucleation of crystals in saturated aqueous solutions, in the presence of electric fields. Experiments conducted using a metal coordination compound bis‐ thiourea zinc chloride show that electric fields of strength around 10⁵ V/m would increase its nucleation.     

Investigations on nucleation,thermodynamical parameters and growth of Benzimidazole crystals from low temperature solution

Metastable zonewidth and induction period measurements of Benzimidazole (BMZ) are presented. The nucleation parameters such as interfacial tension, radius of the critical nucleus and critical free energy change have been calculated for the solution grown Benzimidazole (BMZ) single crystals at different supersaturation ratios. The grown BMZ crystals were characterized by the differential scanning calorimetric studies for analysis of thermal properties. The dielectric behaviour of the crystal was studied at different temperature and frequency. The laser damage threshold studies show that BMZ crystal has higher laser damage threshold. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigations on the Nucleation Kinetics of L-Arginine Phosphate single crystals

The nucleation parameters, such as radius of the critical nucleus and critical free energy change have been evaluated for LAP single crystals. The interfacial tension determined by conducting the induction period measurements has been used for the evaluation of nucleation parameters. The determined interfacial tension is found to be comparable with theoretical literature values.     

Nucleation kinetics of the formation of low dimensional calcium sulfate dihydrate crystals in isopropyl alcohol medium

Calcium sulfate dihydrate, constituted as uniform crystals of low dimensions, is a potential biomaterial for clinical applications like bone graft substitution and drug delivery. In this work, isopropyl alcohol has been used as a solvent to obtain low dimensional calcium sulfate dihydrate crystals from calcium nitrate ‐ sulfuric acid system. Reactants in 0.5 molar concentration at ambient conditions generated uniform rod‐shaped crystals of length 3–5 µm. Analysis using X‐ray Diffractometry and Fourier Transform Infrared Spectrometry showed the material to be well crystallized, phase‐pure calcium sulfate dihydrate. The nucleation kinetics has been studied by observing the induction time of phase formation in solutions of millimolar concentrations through turbidimetry at 300 K. The data have been analysed using classical nucleation theory to deduce parameters like interfacial tension (or surface free energy), nucleation rate and critical radius. The surface free energy obtained (5.6 mJ/m²) is comparatively lower than that reported for aqueous precipitation, which could be attributed to the presence of isopropyl alcohol. On escalating the supersaturation ratio, the nucleation rate drastically increased and the critical radius decreased exponentially. Particles formed at supersaturation 1.39 showed a monomodal distribution centered at 8.2 nm in Dynamic Light Scattering analysis. Comparable particle sizes were obtained in Transmission Electron Microscopy.     

Precipitation and dissolution of KCaCl3 impurity in NaCl crystals

Impurity precipitation in NaCl crystals containing CaCl₂ and KCl in various proportions is studied by means of flotation density measurements. The paper is concerned with the determination and dissolution, the kinetics and activation energy, and the mechanism of nucleation. Two temperature regions for solid solution decomposition were revealed. The characteristic stages in density variation upon isochronal annealing are shown to be correlated with radical changes in the X-ray diffraction patterns. Evidence is given that the nucleation is heterogeneous for the stable phase and homogeneous for the metastable one. – The activation energy in the low-temperature region has been found to be 0.8 ± 0.1 eV, which suggests precipitation to be diffusion-limited. From the kinetics studies it follows that the composition of the metastable phase corresponds to KCaCl₃ and the rate-controlling stage in stoichiometric crystals is a K⁺ diffusion.     

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.     

马来酸氢十六酯(HHM)在过饱和溶液中的成核过程

本文研究了马来酸氢十六酯(HHM)在以甲苯为溶剂的过饱和溶液中的成核过程.测定了以诱导时间表示的成核速率.用经典的成核理论计算了固-液表面张力、成核自由能和临界成核半径.指出HHM晶体在甲苯为溶剂的过饱和溶液中的成核速率随着温度和过饱和比的提高而增大.溶剂的性质也将改变成核速率的大小.     

Electrolytic nucleation of copper and brass on platinum single crystal spheres

The nucleation of copper from cyanide electrolytes on platinum single crystal cathodes was investigated by a pulse method. Using pulse widths of 10 ms to 1 min the critical overvoltage for nucleation varies between 35 and 60 mV. The nucleation rate depends not only on the pulse width and amplitude but also to a high degree on the crystallographic orientation of the substrate. The Gibbs free energy of nucleation is about 3–7 kT and 1–7 atoms are in one nucleus. The deposition of copper-zinc alloys from cyanide solutions was also studied. It was found that the nucleation rate and the content of copper in the deposited brass crystals depend on the composition of the electrolyte solution, the electrode potential and the crystallographic orientation of the substrate.     

Effect of the Presence of Crystals on Nucleation Parameters

Metastable zone width measurements in aqueous solutions of 18 well soluble substances have been used for the characterization of the nucleation process in absence and in presence of crystals. As could be expected, it has been confirmed that the specific surface energy of the critical nucleus is only slightly decreased by the presence of crystals. The effect is almost negligible for the critical nucleus size. Both of these quantities can be correlated with the solubility of the substance.     

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.     

Kinetics of precipitation of nickel ammonium sulphate hexahydrate from aqueous solutions

The precipitation of nickel ammonium sulphate [Ni(NH₄)₂(SO₄)₂·6H₂O] prepared by mixing of equimolar aqueous solutions of (NH₄)₂SO₄ and NiSO₄ has been studied at 25 °C. Precipitation induction periods and the number of crystals formed per unit volume have been determined experimentally as functions of supersaturation for values of S_{a, H} < 2.6. The mechanisms of nucleation and crystal growth are assessed by comparing the experimental results with theoretical predictions. In this system, heterogeneous nucleation and crystal growth are assessed by comparing the experimental results with theoretical predictions. In this system, heterogeneous nucleation appears to operate at S_{a, H} < 1.3, whereas at S_{a, H} > 1.6 crystals are generated predominantly by homogeneous nucleation and grow by a polynuclear mechanism. The interfacial tension of nickel ammonium sulphate crystals in contact with their supersaturated solution is estimated to be about 20 mJ/ m².     

Determination of Nucleation Parameters of YBCO from High Temperature Solution

The growth kinetics of YBCO single crystal from high temperature solution of YBCO-BaO/CuO solute-solvent system has been studied. Based on regular solution model and classical nucleation theory the thermodynamical data investigated for the system are used to determine the nucleation parameters: interfacial energy, metastable zone-width (supercooling temperature), free energy change, critical nucleation radius etc. which leads to the understanding of the nucleation phenomena of YBCO.     

Investigation of single crystal growth of GaPO4 by the flux method

GaPO₄ crystals have been grown by a spontaneous nucleation method and the top-seeded solution growth method using three different solvents, 3MoO₃-Li₂O, 3MoO₃-K₂O and 2KPO₃-5MoO₃-3LiF. All of the as-grown crystals were characterized by means of X-ray powder diffraction. The results show that all the crystals were well crystallized and belong to the point group 32, and 2KPO₃-5MoO₃-3LiF flux is the best for nucleation and growth of transparent GaPO₄ crystals. The infrared spectrum of GaPO₄ single crystal obtained by the flux method shows that there is no incorporation of OH groups during the crystallization, which is beneficial for high temperature piezoelectric applications.     

Influence of the pH-Value on the Metastable Zone Width of Potassium Sulphate

Aqueous solution of the potassium sulphate with addition of sulphuric acid or potassium hydroxide has been chosen for the metastable zone width measurements in order to check how the solution structure affects the nucleation. Hydration analysis of corresponding sub-systems indicated involved structure changes. The solubility of K₂SO₄ increases with addition of H₂SO₄ and decreases with addition of KOH. The hydration analysis has shown that low acid concentrations have an inexpressive effect on the structure of solution. Much distinct effect exhibit low concentrations of the hydroxide. The metastable zone width decreases with increasing the value of pH. This decrease is less perceptible in the acidic region but more distinct in the alkaline region. The same holds for the critical nucleus size L* and the specific surface energy σ*. The behaviour quoted above supports the conception that the pH affects the solution structure and that the latter has a significant effect on the nucleation.     

Studies on growth,induction period,interfacial energy and metastable zonewidth of m‐nitroaniline

Single crystals of m‐Nitroaniline (mNA) were grown by slow cooling solution growth technique. Induction period, interfacial energy and metastable zonewidth have been evaluated. The solubility of mNA has been estimated at different temperatures in acetone and ethanol. Interfacial energy has been estimated using the experimentally determined induction period values. It is observed that the nucleation rate increases with the increase of supersaturation. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Kinetics of crystallization in binary solutions

A two-dimensional nucleation is required to grow the crystals of low energy planes. Expressions for the size and free energy of the two-dimensional nucleus corresponding to a saddle point in binary system are derived. The concentration of the critical nuclei in the system is related to the critical free energy of the two-dimensional nucleus. A circular island of atoms on the growing surface is considered and the flux of atoms on the surface going to the growing walls of the island from either direction is calculated. The rate of advance of the curved step is determined and hence the velocity of the straight step in the A-B crystal-binary solution interface is found.     

The effect of cooling rate on size,quality and morphology of KTiOPO4 (KTP) crystals grown by different nucleation techniques

KTP crystals have been grown by two nucleation techniques namely spontaneous nucleation in flux medium and nucleation on Pt rod using K₆P₄O₁₃ flux.10 °C/h, 7 °C/h, 0.8 °C/h, 0.4 °C/h and 0.2 °C/h cooling rates were applied for spontaneous nucleation and crystals up to 15 × 7 × 4 mm³ in size were grown. 1 °C/h and 0.8 °C/h cooling rates were also used for nucleation on Pt rod and crystals up to 8 × 6 × 3 mm³ in size were grown. The effect of cooling rate on size, morphology and optical quality of grown crystals by both techniques were studied. For nucleation on Pt rod upper and lower rotation rates limits and an optimum rotation rate were distinguished for each cooling rate. Quality of the grown crystals by both techniques was characterized by optical transmission analysis.     

Impact of malonic acid on the segregation of glycine polymorphs – Analytical assisted molecular approach

Proton dissociation assisted negative polarity of malonic acid molecules admist glycine zwitterions leads to orgination of γ nucleation in the solution. Alteration in the nucleation behaviour and segregation of glycine polymorphs in the presence of malonic acid over a wide range of concentrations has been investigated both by experimental and analytical approaches. Complete changeover in the nucleation behaviour from 100% α to 100% γ is observed at the critical concentration of the additive. Shifting in the overall charge environment of the system towards cationic in the presence of malonic acid favours the nucleation of γ through induced charge compensation in the solution. Tuning of merohedral twinning in γ nucleation by the additive concentration has been well revealed in the present work. CNT based analytical approach employed elucidates well the experimental observations through the estimated interfacial energy, volume excess free energy, critical radius, activation energy barrier and nucleation rates of α and γ polymorphs. Structural affirmation of the nucleated polymorphs was carried out by powder x‐ray diffraction.     

Heterogeneous Nucleation of Hen‐Egg‐White Lysozyme — Molecular Approach

The heterogeneous nucleation of hen‐egg‐white lysozyme (HEWL) crystals has been repeatedly investigated using a double‐(thermal)‐pulse technique, thus detaching nucleation from growth stage. n(t) dependencies of the nucleus number n, on templates of poly‐L‐lysine, vs time, t were plotted and the steady‐state nucleation rates I were determined. They were compared with the results obtained earlier for surfaces rendered hydrophobic (by means of hexamethyl‐disilazane) as well as for bare glass surfaces. In the present paper we determine the number of HEWL molecules in the (heterogeneously formed) critical nucleus. It turned out that it is build of 3 (to 4) HEWL molecules on glass substrate and 8 molecules for both hexamethyl‐disilazane and poly‐L‐lysine templates. The energy Ak required for heterogeneous formation of a critical nucleus on poly‐L‐lysine has been calculated, on the basis of the steady‐state nucleation rates I. Intermolecular binding energy in the HEWL crystal lattice has been estimated again (approximately 10‐9 erg/molecule). This time the basis was the adhesion of HEWL crystals to poly‐L‐lysine substrate.