Study of lactose crystallization in water‐acetone solutions

This paper describes a study on the process of lactose crystallization using a water‐acetone solution. The selection of lactose was based on its significance for the pharmaceutical and food industries and on the fact that the crystallization of this organic compound has been little studied and is, unlike inorganic compounds, complex. The objective was to achieve lactose batch crystallization of solutions by analyzing the crystal growth under different operating conditions. To determine solubility curves, the experiments were carried out based on gravimetric methods. All the crystallization experiments were performed according to the methodology proposed by Nývlt in 1985, who uses the temperature at which the first crystals appear (nucleation) to establish the width of the metastable zone and the induction time. The results showed that crystals with different average diameters, shape factors, and recovered mass were obtained for different water‐acetone compositions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

Investigation of structural perfection and faceting in highly Er‐doped Yb3Al5O12 crystals

The undoped Yb₃Al₅O₁₂ (YbAG) single crystals and doped with 1.5, 10 and 30 at% erbium were grown by the Czochralski method. The YbAG crystals offer efficient emission of laser beam of 2.94 µm and 1.55 µm important for practical applications in communication and medicine. The crystals were investigated by various synchrotron X‐ray diffraction methods including white beam topographic methods, monochromatic beam topography and recording of the rocking curves. The experiments were performed at E2 and F1 experimental stations in HASYLAB. The investigations proved a good crystallographic perfection of the crystals, in most cases revealing only segregation fringes and growth facets. The crystallographic identification of the facets was performed together with direct evaluation of growth front radius from the transmission section topographs. Relative lattice parameter changes connected with erbium segregation were found to be less than 2 × 10^‐5 inside the segregation fringes and 8 × 10^‐5 in the facets. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of zinc doping on pentaerythritol tetranitrate single crystals

In this study, the effect of zinc impurity on the organic high explosive pentaerythritol tetranitrate (PETN) single crystal has been investigated with optical microscopy and ex situ atomic force microscopy (AFM). The optical images show that the crystal shape has a transition with a predictable trend from long crystal to compact one as the zinc concentration is increased. Also, the 2‐dimentional (2‐D) growth hillocks are observed clearly on (110) face with contact AFM. The crystal growth occurs on monomolecular steps generated by 2‐D nucleation and followed by layer‐by‐layer expansion, and the macro‐steps formed onto the surface before spreading laterally as step bunches. The zinc ions are incorporated in growth steps as the zinc concentration is increased. The mechanism of inorganic impurity on molecular crystallization growth is still unclear. However, the incorporation of impurities may significantly affect growth kinetics of defect structure, and the bulk properties of molecular crystals. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of the variations in the crystallization front shape during growth of gadolinium gallium and terbium gallium crystals by the Czochralski method

Numerical investigation of the variations in the crystallization front shape during growth of gadolinium gallium and terbium gallium garnet crystals in the same thermal zone and comparison of the obtained results with the experimental data have been performed. It is shown that the difference in the behavior of the crystallization front during growth of the crystals is related to their different transparency in the IR region. In gadolinium gallium garnet crystals, which are transparent to thermal radiation, a crystallization front, strongly convex toward the melt, is formed in the growth stage, which extremely rapidly melts under forced convection. Numerical analysis of this process has been performed within the quasistationary and nonstationary models. At the same time, in terbium gallium garnet crystals, which are characterized by strong absorption of thermal radiation, the phase boundary shape changes fairly smoothly and with a small amplitude. In this case, as the crystal is pulled, the crystallization front tends to become convex toward the crystal bulk.     

Advancements (and challenges) in the study of protein crystal nucleation and growth; thermodynamic and kinetic explanations and comparison with small-molecule crystallization

This paper reviews advancements and some novel ideas (not yet covered by reviews and monographs) concerning thermodynamics and kinetics of protein crystal nucleation and growth, as well as some outcomes resulting therefrom. By accounting the role of physical and biochemical factors, the paper aims to present a comprehensive (rather than complete) review of recent studies and efforts to elucidate the protein crystallization process. Thermodynamic rules that govern both protein and small-molecule crystallization are considered firstly. The thermodynamically substantiated EBDE method (meaning equilibration between the cohesive energy which maintains the integrity of a crystalline cluster and the destructive energies tending to tear-up it) determines the supersaturation dependent size of stable nuclei (i.e., nuclei that are doomed to grow). The size of the stable nucleus is worth-considering because it is exactly related to the size of the critical crystal nucleus, and permits calculation of the latter. Besides, merely stable nuclei grow to visible crystals, and are detected experimentally. EBDE is applied for considering protein crystal nucleation in pores and hydrophobicity assisted protein crystallization. The logistic functional kinetics of nucleation (expressed as nuclei number density vs. nucleation time) explains quantitatively important aspects of the crystallization process, such as supersaturation dependence of crystal nuclei number density at fixed nucleation time and crystal size distribution (CSD) resulting from batch crystallization. It is shown that the CSD is instigated by the crystal nucleation stage, which produces an ogee-curve shaped CSD vs. crystal birth moments. Experimental results confirm both the logistic functional nucleation kinetics and the calculated CSD. And even though Ostwald ripening modifies the latter (because the smallest crystals dissolve rendering material for the growth of larger crystals), CSD during this terminal crystallization stage retains some traces of the CSD shape inherited from the nucleation stage. Another objective of this paper is to point-out some biochemical aspects of the protein crystallization, such as bond selection mechanism (BSM) of protein crystal nucleation and growth and the effect of electric fields exerted on the process. Finally, an in-silico study on crystal polymorph selection is reviewed.     

Experimental investigation of different configurations for the seeded growth of SiC crystals via a VLS mechanism

The growth of SiC crystals or epilayers from the liquid phase has already been reported for many years. Even if the resulting material can be of very high structural quality and the possibility to close micropipes was demonstrated, handling the liquid phase still is a challenge. Moreover, it is highly difficult to stabilize the C dissolution front and then to stabilize the growth front over a long growth time. Based on the Vapour‐Liquid‐Solid (VLS) mechanism, we present a new configuration for the growth of SiC single crystal which should allow first to simplify the liquid handling at high temperature and second to precisely control the crystal growth front. The process consists in a modified top and bottom seeded solution growth method, in which the liquid is held under electromagnetic levitation and fed from the gas phase. 3C‐SiC crystals exhibiting well‐faceted morphology were successfully obtained at 1100‐1200 °C with exceptional growth rates, varying from 1 to 1.5 mm/h in Ti‐Si melt. It was shown that the nucleation density decreases simultaneously with increasing propane partial pressure. At 1200‐1400 °C, thick homoepitaxial 6H‐SiC layers were successfully obtained in Co‐Si and Ti‐Si melts, with growth rate up to 200 µm/h. Large terraces with smooth surfaces are observed suggesting a layer by layer growth mode, and the influence of the system pressure was demonstrated. It was shown that the terrace size decrease simultaneously with increasing propane partial pressure which suggests the beginning of a two dimensional to three dimensional growth mode transition. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Correlation of the structural imperfection and morphology of Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> crystals grown by the low-gradient Czochralski method

This paper reports on the results of investigations into the morphological structure of the facets of Bi₄Ge₃O₁₂ crystals grown by the Czochralski method under the conditions of low temperature gradient (0.1–1 K/cm). A correlation between the morphological features of the facets at the crystallization front and the formation of defects in the bulk of the crystal is revealed. It is demonstrated that the {112} facets remain regular while the growing surface deviates from the (112) crystallographic plane by an angle of up to 1°. At larger deviations, there occurs a crossover from the stable facet growth to the growth of macrosteps or normal growth depending on the growth conditions.     

Zur Züchtung von β-Kupferphthalocyanin-Einkristallen aus der Gasphase

An apparatus useful for many kinds of vapour phase growth used in order to clarify reasons for bad reproducibility and constancy of growth conditions by an growing method known since 1936 and reasons for cavity growth. The characteristics of growth are described dependent on different growing methods and on various kinds of nucleation and crystal growth. The introduction of new growing methods allows the production of larger crystals. The growth of the needle-like crystals is governed by diffusion. The shape of the crystals does not differ qualitatively from their equilibrium shape. The crystals grow with smooth surfaces. Only the front surfaces show morphological imperfections, if the crystals exceed a critical size.     

Twins in GaAs Crystals Grown by the Vertical Gradient Freeze Technique

The growth of facets and the generation of twins on <100> VGF (vertical gradient freeze technique) grown GaAs were investigated using DSL (diluted Sirtl-like etchant with light) photoetching and transmission X-ray topography. Due to the polarity of the (111) plane in GaAs, As facets are larger and more irregular than Ga facets and twins always occur on As facets. Twins are initiated at the change of boundary condition which is affected by temperature gradient and crucible shape. The mechanism of twin generation is explained by considering the edge concavity at the solid-liquid interface and the supercooling required for initial nucleation of a facet. Twins are more often produced in Si-doped crystals than undoped ones due to the constitutional supercooling.     

Modeling of the shape of polyethylene oxide single crystals and determination of the kinetic crystallization parameters: Theoretical and experimental approaches

The curvature of faces of polymer single crystals is described by the system of Mansfield equations, which is based on the Frank-Seto growth model. This model assumes the velocity of nucleus steps to be the same for their propagation to the right and left and is valid only for symmetric crystallographic planes. To describe the shape of polyethylene oxide single crystals grown from melt and limited by the {100} and {120} folding planes, it is assumed that the layer velocities to the right and left are different on {120} faces. This approach allows modeling, with a high accuracy, of the observed shapes of polymer single crystals grown at different temperatures, which makes it possible to determine unambiguously the fundamental crystallization parameters: the dimensionless ratio of the secondary homogeneous nucleation rate to the average velocities of nuclei along the crystallization planes and the ratio of nucleus velocities to the right and left. In addition, it was found that a known macroscopic single-crystal growth rate can be used to determine the absolute values of the secondary homogeneous nucleation rate and the velocities of nuclei along the growth plane.     

The growth of controlled profile crystals by Stepanov's method

Single crystals in the shapes of plates, tubes and rods of various cross sections are widely used in many areas of science and technology. Of great importance is the production of such single crystal specimens directly from the melt. By Stepanov's method, the desired shape of the crystal is obtained by the proper selection of a device which shapes the melt column which rises due to the capillary effect. The capillary parameters determine the shape of the profile curve. The thermal parameters, taking into account the equilibrium crystal shape, define the position and shape of the crystallization front. The use of the shaper makes the process self-stabilizing. A negative feedback which damps out perturbations appears in the crystal-melt system and thus permits the production of controlled profile crystals with constant cross-section along their length. Thermoelastic stresses created in ribbons and rods as a result of temperature-induced misfit deformations are considered. The generation of dislocations in crystals occurs mainly due to stresses arising near the crystallization front. Various versions of the method and their applications to some materials are discussed.     

The growth of single crystals of Ni-W alloy under conditions of high temperature gradient

The structure of single crystals of the NV-4 nickel alloy containing 32–36 wt % W is investigated. The temperature gradient at the crystallization front and the velocity of the crystallization front are the variable parameters of directional crystallization. The degrees of structural perfection of the single crystals grown under different conditions are compared. The crystallization parameters providing growth of single crystals that have high structural perfection and can be successfully used as seeds for the growth of single-crystal blades are determined. Typical defects formed upon directional crystallization of single crystals of the Ni-W (35 wt %) alloy are examined. The studied defects are classified, and the factors responsible for the disturbance of the single-crystal structure are analyzed.     

Comparison Study of Mixing Effect on Batch Cooling Crystallization of 3‐Nitro‐1,2,4‐triazol‐5‐one (NTO) Using Mechanical Stirrer and Ultrasound Irradiation

The insensitive explosive 3‐Nitro‐1,2,4‐triazol‐5‐one (NTO) has been recrystallized from water in an effort to prepare crystals with smaller size and narrower distribution in a batch cooling crystallizer. Two mixing devices, i.e., a mechanically stirred system with and without ultrasound in aqueous media were employed to compare the mixing effect on the crystallization. Under ultrasound irradiation, the metastable zone width was significantly reduced by more than 2 fold and the crystal size was shifted from 140∼160 μm to 50∼70 μm with a narrower CSD compared to the mechanically stirred system. However in the mechanical stirrer, the mixing effect on NTO crystallization was negligible if the impeller speed was sufficient to suspend all crystals in the crystallizer. It was found that the crystal growth was not influenced by mixing. We suggest that the NTO crystals were formed by primary heterogeneous nucleation that is common in batch cooling system. Finally, the population balance model (PBM), with the empirical nucleation and growth kinetic expressions, was solved numerically to predict the crystal size and the CSD with batch time, and the results were in good agreement with the experimental data.     

Parity violation and parity conservation in unstirred crystallization: Effect of first crystals

Statistics of nucleation of chiral forms was studied to establish the effect of the number of first crystals and their handedness on distributions of enantiomers. Various bimodal, trimodal and unimodal distributions are obtained in unstirred crystallization, depending on the number of initial crystals and growth conditions. The binomial distribution satisfactorily describes experimental distributions of enantiomeric excess and may be used to predict distributions and probabilities of nucleation of enantiomers. The first nucleated crystals determine the handedness of secondary crystals, and number of initial crystals governs statistics of chiral nucleation. According to the binomial distribution if single crystals nucleate as the first, the bimodal distributions result with D and L peaks. If LD, LL, and DD pairs are nucleated as first, trimodal distributions with D, R, and L peaks are created, and if groups of crystals of various handedness nucleate as the first the unimodal distributions of enantiomeric excess with racemate R peaks are formed. Chiral nucleation experiments on sodium bromate were the basis for the theoretical considerations and verifications of predictions resulting from binomial distributions on probabilities of the creation of L and D crystals, and racemates, and the presence of D, L, and R peaks in the distributions. Growth conditions affect the number of the first crystals and effectiveness of cloning, and as a result, the distributions of enantiomers. Formation of pure enantiomers and/or racemates proves that the conservation of chiral symmetry, and the breakage of chiral symmetry can occur in unstirred crystallization. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Specific features in shaping Bi<Subscript>12</Subscript>GeO<Subscript>20</Subscript> crystals grown by low thermal gradient Czochralski technique

Germanosillenite (BGO) crystals have been grown by the low thermal gradient Czochralski technique [1] at crystallization rates of v = 0.05–4 mm/h. The evolution regularities of the faceted front forms have been studied taking into consideration their growth conditions (crystallization rate and thermal conditions). The orientations of the faces forming the crystallization front during crystal growth in the 〈111〉 direction have been determined. The relationship between the front morphology (and, therefore, growth conditions) and the quality of crystals formed is established. The quality of the BGO crystals grown is evaluated by X-ray topography.     

Layered crystals of apo‐ and holoferritin grown by alternating crystallization

We report on the use of alternating crystallization for deposition of layers of different (though closely related) proteins in a single crystal. Investigations were carried out with the unique protein couple consisting of two forms of ferritin, apoferritin and holoferritin from horse spleen, which, despite being of quite different molecular masses, still possess identical organic shells. Crystals of both proteins were used as substrates for subsequent contiguous growth of the partner protein in perfect alignment. We observed continuous growth of combined (onion‐like) single crystals; artificial structures of biological macromolecules can be designed in this way. The homoepitaxial layered growth shows in an unambiguous way that protein crystallization depends only on the surface protein conformation and amino‐acid composition, but not on the internal molecule structure. The limitations of protein crystal growth for designing layered structures of biological macromolecules were revealed by growing of heterogeneous protein crystals onto pre‐existing protein crystalline substrates. Tetragonal crystals of hen egg‐white lysozyme were grown onto cubic apoferritin crystals used as substrates. It was observed that the lysozyme crystals were not lattice‐matched to the ‘host’ apoferritin crystals; this led to mere aggregates of different crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of CdBr2 crystals by zone-melting and study of their growth features

A detailed surface microtopographic study has been carried out on the (0001) faces of melt-grown CdBr₂ single crystals. Mainly the growth of the crystals takes place by continuous solidification at the solid-liquid interface. Rarely, the growth occurs by two-dimensional nucleation and still more rarely by spiral mechanism. Most spirals are seen to be polygonized such that the polygonization extends right upto the centres of the spirals.     

Vapour growth and morphology of PbBr2 crystals

In this paper, the vapour transport of PbBr₂ under vacuum during vacuum distillation refining and its condensation on the wall of the vessel were described. The macro‐ and micro morphologies of PbBr₂ crystals grown in the vessel (glass tube) were studied. The crystal shape changed dramatically depending on the positions of condensation in the vessel, i.e., the crystal shape varied from an isometric polyhedron to columnar crystals with facets, and to a massive crystal without facets with a rise in the wall temperature. These results were interpreted in terms of the concentration gradient of the molecules in the vessel, surface roughening and/or surface melting of the crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Application of Rosin–Rammler model for analysis of CSD in sugar crystallization

Crystal‐size distribution (CSD) is one of the most important parameters in sugar production. The objective is to grow crystals of uniform sizes or narrow CSD. CSD appears to be determined by the growth‐rate history of the crystals and the relative supersaturation (SS) of the solution from which crystals growth takes place. Three methods for preparation of nucleation seeds were described and used for industrial crystallization of raw and white sugars; these are wet milling filtered sugar (ML), agitating saturated solution (AS) and powdered sugars (PD). Rosin–Rammler (RR) and mathematical models were adopted to investigate CSD and the uniformity of the produced crystals. Higher uniformity coefficients were reported for the AS seeded crystals than the other two seeding methods. Furthermore, higher crystal contents were obtained for the AS seeded white sugar batches in comparison.