Promotion of crystal growth rate in aqueous solution by direct contact with gas corona discharge

A new technique to promote crystal growth in aqueous solution using gas plasma is proposed. In this method, short‐lived radical species produced in solution which is contacted with gas corona discharge play a role to increase chemical potential of inorganic solute. In an experimental examination, single crystal of KDP was grown in a supersaturated solution which receives oxygen ions and radicals from adjacent corona discharge in air. KDP crystal has two unique growth faces (100) and (101), and the growth rates of both faces were increased considerably by generating the corona discharge. The both growth rates with and without corona discharge were well converged by one function based on chemical potential supersaturation. This result revealed that the solution in contact with gas corona discharge has a larger capacity of chemical potential than that without the discharge. Short‐lived species induced by gas corona discharge are considered to be anti‐solvents to cause this effect. The crystal growth process proposed here is considered to be an excellent method in terms of low impurity inclusion because such short‐lived species do not remain in the final crystal products and solution. (© 2004 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)     

Kinetic anomalies of mixed crystal growth and their effect on the crystal isomorphic composition

Growth rate anomalies in aqueous solution growth of NaClO₃ and KClO₃ were first revealed by V. V. Sipyagin in 1967 and attributed to “kinetic anomalies”. These phenomena were confirmed in a series of other studies and for a variety of substances. Therefore, some universality of these anomalies was supposed that should be due to structural transformations in the liquid solutions. In this paper, we present for the first time results on growth rate oscillations found in mixed crystal growth and their impact on the isomorphic composition of solid solutions. Thick (100) Na(Cl,Br)O₃ layers were grown at fixed supercooling conditions onto NaClO₃ seeds in a microcrystallization cell equipped with an optical microscope. In the temperature range of 33 – 41 °C, four kinetic anomalies were found in solutions of a chlorate: bromate molar ratio of 20: 1 at supercoolings of 2.0 K and 3.0 K. Lattice parameter measurements of the grown Na(Cl,Br)O₃ layers revealed a linear dependence of lattice constant vs. growth rate. By measuring Vegard's law (lattice parameter vs. solid solution composition) we were able to determine the oscillations in mixed crystal composition that accompany the kinetic anomalies in solid solution systems. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth rate of single acetaminophen crystals in supersaturated aqueous solution under different operating conditions

Single crystal growth experiments were conducted to investigate the growth rate of acetaminophen (paracetamol) crystals under carefully controlled conditions of temperature, supersaturation and pH value. The relative growth rate of the different faces was studied. Growth Rate Dispersion (GRD) was observed by studying the effect of supersaturation and temperature on the growth rate. The growth rate in all directions was found to be temperature dependant. Elongation of the crystals was measured due to the faster growth in the Y‐ direction and Xa direction compared to in the Xb direction. Dissolution of the crystals was observed at pH values greater than 8.5, and a growth rate retardation was observed when increasing the pH from 5.6, which is the normal value without additions, to higher values in both acidic and basic mediums up to 8.5. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The influence of supersaturation on crystal morphology – experimental and theoretical study

The surface docking approach of molecular modeling for prediction of crystal morphology in the presence of additives is further developed in this work. It is modified in order to take into account the influence of supersaturation on the crystal habit. With the introduction of the BCF theory and the 2‐D growth mechanism in the above mentioned approach predictions have been carried out for paracetamol and caprolactam crystals, respectively. The verifications by crystals grown from solutions as simulated by the computer model give good agreements. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

The influence of crystallization conditions on the onset of dendritic growth of calcium carbonate

Understanding the crystallization of calcium carbonate is relevant in numerous fields like biomineralization, geology and industrial applications where calcium carbonate forms. In order to enhance the knowledge about the formation of calcium carbonate with focus on the vaterite polymorph, in this work calcium carbonate has been crystallized in aqueous solutions at temperatures from 5 °C to 90 °C. Special attention has been directed to higher temperatures for which the effect of the initial supersaturation on the resulting crystal morphologies and the onset of dendritic growth have been studied. In analogy to snow crystal formation, it has been found that in a certain temperature range hexagonal plate‐like crystals form at low supersaturation whereas dendritic patterns start to appear at higher supersaturation. The symmetrical branches characteristic for dendritic growth get less pronounced as the temperature is decreased. The results reported here related to the interdependence between supersaturation, crystal morphology and growth mechanisms, can be used in future works to predict particle formation and to design crystal architectures. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ferrous Tartrate recognition of sodium chloride {111} and its effect on crystal growth

The surface morphology and growth pattern of some molecules could be altered by the recognition of ferrous tartrate (FeC₄H₄O₆, FeTA). We have explored this phenomenon in the aspect of growth rate and morphology alteration of sodium chloride crystals where few researches have been done. In this paper, the crystallization behavior of NaCl with added FeTA was studied by supersaturation test, conductivity, scanning electron microscopy (SEM), and X‐ray diffraction (XRD). The results showed that the supersaturation of NaCl solution could be increased to about 5.5 % in presence of FeTA prior to the onset of crystallization. Furthermore, SEM images and XRD results indicated that the addition of FeTA could change the morphology of NaCl crystal from cubic to octahedron by impeding the growth of {111} and {110} faces. Besides, the interaction between NaCl {111} face and FeTA was discussed and the possible spatial structure of FeTA was speculated through the lattice parameters of NaCl.     

Low temperature photoluminescence studies on semiorganic tris thiourea copper (I) chloride single crystal

Semiorganic tris thiourea copper (I) chloride (TTCC) single crystals have been synthesized from copper (II) chloride via slow evaporation technique. The stoichiometry of the grown anhydrous complex crystal has been confirmed by elemental CHNS (C, H, N and S) and atomic absorption spectrophotometric (AAS) analysis. The crystal structure with space group has been confirmed by single crystal and powder X‐ray diffraction (XRD) studies. The FTIR study assigned the presence of functional groups and confirmed the co‐ordination of metal ions with thiourea. It also confirmed the transition from Cu²⁺ to Cu⁺ when thiourea combined with Copper (II) chloride. The optical transparency of the crystal has been studied by UV‐Vis spectrum and deduced the energy gap. The room temperature Photoluminescence (PL) spectrum reported maximum emission line at 410.92 nm and Stokes shift has been determined as 75 nm or 16.5 eV. Low temperature luminescence study from 300 K to 77 K exhibited three blue emission peaks and one green emission peak. The green emission band has been assigned to recombination of an electron in a shallow trap and Cu²⁺. Blue emission has been attributed to S^2‐ vacancies. The interesting hysteresis loop has been exhibited by the variation of energy gap with low temperature. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystallization rate control for alkali halide crystal growth by the VGF technique with a skull layer

This study describes the ability to use the melt‐level control for stabilization of the crystallization rate during NaI crystal growth by the VGF technique with a skull layer. It is shown that a conventional linear decrease of the heater temperature leads to a nonuniform crystallization rate and deterioration of crystal quality. A method and algorithm of temperature control for the stabilization of the crystallization rate during crystal growth is proposed. The series of growth experiments with NaI(Tl) crystals proved the efficiency of this approach and ability to obtain scintillators with high registration efficiency, about 6.3% energy resolution for a ¹³⁷Cs (662 keV) source.     

High temperature synthesis and crystal structure of new representatives of the huntite family

Single crystals of REE, Al borates, new and known representatives of huntite family are obtained by annealing of REEBO₃ on Al₂O₃ surface at 1100°C. Phase identification for REE=Pr, Eu, Tb, Tm, Ho, Yb has been carried out using unit cell parameter determination on single crystals. Crystal structures of C 2/c (PrAl₃(BO₃)₄) and C 2 (EuAl₃(BO₃)₄) ‐ two polytypic modifications, previously determined for other REE's have been studied. Formation of one or another polytype in similar thermodynamic conditions is probably dependent on electronic structure of rare earth ion. Crystal field stabilization energy in crystal fields of different symmetry is a possible factor of polytype stability (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of surface tension‐driven flow on BaB2O4 crystal growth from high temperature melt‐solution

The surface tension driven‐flow in BaB₂O₄ (BBO) melt‐solution is visualized by differential interference microscope coupled with Schlieren technique, and the streamline of the steady thermocapillary convection is found to be in form of an axially symmetric pattern. Based on the observation of BBO crystal rotation caused by the convective vortex, the widths of interfacial concentration, heat and momentum boundary layer are calculated. The effect of thermocapillary convection on boundary layer thickness is also investigated. Results show that the width of boundary layer decreases linearly with the increasing of dimensionless Marangoni number. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Rapid growth of KDP crystal from aqueous solutions with additives and its optical studies

Potassium Chloride (KCl) and Ethylene diamine tetraacetie acid (EDTA) as new additives were added into the KDP solutions in a small amount (5M% and 0.01M% respectively). The solubility curve and metastable zone width of KDP solution with 5M%KCl was determined and we explained the mechanism of rapid growth of KDP crystal with KCl additve. The clear transparent crystal of KDP with a dimension of 54 × 54 × 42 mm have been grown rapidly by cooling solution method in 2 days. The crystal grown from additives added solution was subjected to optical transmission and laser damage threshold studies as compared with the crystal grown by traditional growing method. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A novel method of temperature control for a crystal growth puller

A facile method to control the contracting rate of the thermal expansible bars for pulling crystal is first suggested. The thermal expansible bars, set in a modified Dewar flask whose vacuum degree is controlled, are heated to designed temperature and then switch off the power to let it cool down at a desired rate, which depends largely on the changeable vacuum degree. This new approach is expected to completely eliminate the effects, which possibly reduces the smooth extent of thermal expansion, caused by the minor temperature fluctuations during crystal growth process and to realize the utmost smooth and slow pulling rate. It is expected to install this apparatus in optical floating zone furnace, instead of traditional motor, to grow peritectic crystal, such as crystal Bi‐2223, since for the peritectic reaction, in principle, the extremely slow growing rate is considerably essential.     

Effect of supersaturation on the crystallization of phenylbutazone polymorphs

The article describes the effect of degree of supersaturation, σ, on the crystallization of specific polymorphs of phenylbutazone from its methanolic solution at 20 °C. At low initial supersaturation, σ ≤ 2.0, the fraction of the metastable α polymorph in the crystallized product exceeds that of the δ polymorph, while at σ ≥ 5.0, the fraction of the stable δ polymorph increases in the crystallized product. The results are explained by the effect of supersaturation on the relative rates of nucleation and crystal growth of the polymorphs. Furthermore, the mechanism of nucleation and crystal growth also change with supersaturation. Supersaturated methanolic solutions of phenylbutazone exhibit a critical temperature at which the nucleation rates of the polymorphs decrease drastically. This effect is partly explained by the decreased mobility of phenylbutazone molecules at lower temperatures. Nucleation is most rapid when the crystallization temperature is close to the transition temperature, T_t(α ⟷ δ), between the polymorphs, α and δ. The nucleation rate decreases as the temperature difference between T_t(α ⟷ δ) and the crystallization temperature increases. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the origin of supersaturation barriers during the growth of single crystals from aqueous solutions containing impurities – a review

A generalised treatment of the appearance of supersaturation barriers σ_d, σ* and σ** during the growth of single crystals is outlined from the standpoint of well‐defined critical values of relative step velocities on a face. The final theoretical expressions are based on the premise that: (1) there are critical values of the relative step velocities associated with different average distances between adsorbed impurity particles during instantaneous, time‐dependent and time‐independent adsorption of the impurity on the growing surface, (2) the growth rate of a face is proporptional to velocity of steps on the growing face, and (3) Freundlich and Langmuir adsorption isotherms apply for different impurities. The theoretical expressions are then used to critically analyse the experimental data on supersaturation barriers observed during the growth of ammonium oxalate monohydrate and potassium dihydrogen phosphate single crystals from aqueous solutions containing different impurities. It was found that: (1) Langmuir adsorption isotherm is more practical for the analysis of the experimental data of the dependence of supersaturation barriers σ_d, σ* and σ** on the concentration c_i of an impurity, and (2) the ratios σ_d/σ* and σ*/σ** of successive supersaturation barriers for an impurity either increases or remains constant with an increase in impurity concentration c_i, and may be explained in terms of the mechanism of adsorption of impurity particles. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

KDP晶体生长的溶液流动和物质输运计算

本文采用有限容积法,对KDP晶体生长过程中溶液的流动和物质输运进行了数值模拟.结果表明:随着入口溶液流动速度的增大,籽晶的上表面因自然对流而引起的抽吸作用减小,表面过饱和度的最小值沿x正向发生右移,其上表面的剪切力先减小后增大.随着入口溶液过饱和度的增大,籽晶上表面剪切力增大.不同尺寸的籽晶表面过饱和度的分布差异较大.籽晶的生长边界层厚度与溶液流动密切相关,入口溶液流动速度越大,厚度越小,但其受入口溶液过饱和度的影响较小.     

Effect of the seed crystallographic orientation on AlN bulk crystal growth by PVT method

The growth of AlN crystals by PVT method was investigated using TaC crucible in the temperature range of 2250‐2350 °C. AlN boules with 30 mm in diameter were successfully grown on the crucible lid by self‐seeded growth. The AlN boules consist of the spontaneously nucleated AlN single crystal grains with the {1010} natural crystalline face. The fast growth rate of more than 1 mm/h was achieved. AlN crystals grown on (11 0)‐, (10 0)‐, and (0001)‐face AlN seeds were investigated. Different experimental phenomena have been observed under particular condition. The crystal grown on (11 0)‐face seed has different natural crystalline face from the seed. For the crystal grown on (10 0) or (0001) seed, the crystal natural crystalline face is same as the crystallographic orientation of the seed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of Mn(II) ions on the growth of ammonium oxalate monohydrate crystals from aqueous solutions: II. Growth kinetics

The experimental results of the effect of concentration of Mn(II) ions on the growth kinetics of different faces of ammonium oxalate monohydrate single crystals from aqueous solutions at a constant temperature and different predefined supersaturations are described and discussed. It was observed that: (1) at a given supersaturation σ, Mn(II) ions lead to a decrease in the growth rates of different faces of AO crystals, (2) the growth of a particular face of the crystals occurs above a critical supersaturation σ_d but there is also another supersaturation barrier σ* when the rate abruptly increases with σ, (3) the values of σ_d and σ* increase with increasing concentration of the impurity, and (4) the values of σ_d depend on the growth kinetics of a face but those of σ* are independent of face growth kinetics. The experimental R(σ) data for different Mn(II) concentrations c_i were analysed according to the model involving complex source of cooperating screw dislocations and concepts of instantaneous and time‐dependent impurity adsorption. It was found that: (1) for a given face the differential heat of adsorption Q_diff is higher during instantaneous impurity adsorption than that during time‐dependent adsorption, and (2) the values of Q_diff involved during instantaneous adsorption are related with face growth kinetics but those during time‐dependent adsorption are independent of face growth kinetics.     

Metastability and crystal growth kinetics on L‐arginine phosphate

Stability of saturated L‐Arginine Phosphate (LAP) solution studied as a function of supercooling rate and crystal growth kinetics investigated as a function of supersaturation are reported in this communication. Solution stability was studied by observing the metastable zone width at different cooling rates employing a polythermal method. Analysis of the experimental data yielded the kinetic constant of nucleation and the order of nucleation. Crystal growth rates studied on small seed crystals with regular morphology, under normal growth conditions and at different supersaturation levels were found to satisfy BCF surface diffusion model. Crystal growth rates were investigated normal to the (100), (010) and (00 ) faces. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)