Vapour growth and epitaxy of minerals and synthetic crystals

Surface microtopographs of the following crystals, both natural and synthetic, grown from pure vapour phase (PV), by chemical vapour transport (CVT), from high temperature solution (HTS) and hydrothermal solution (HS) are compared according to the criteria of (1) whether spirals are circular or polygonal and (2) how wide is the step separation of the spiral; SiC (PV, CVT, both synthetic), hematite (CVT, HTS, natural and synthetic), corundum (CVT, HTS, synthetic), mica minerals (PV, CVT, HS, natural and synthetic) and beryl (CVT, HTS, HS, natural and synthetic). Clear differences in morphology and step separation were found between crystals grown from vapour phase and solutions, between PV and CVT, as well as between natural and synthetic crystals. The differences are analysed in conjunction with the recent developments of computer simulations on spiral morphology. The results show interaction between solid and fluid plays very important role in determining the spiral morphology. Oriented intergrowth between different crystals well known among minerals, such as epitaxy, topotaxy, co-axial intergrowth, exsolution etc. are briefly summarized. It is also briefly explained how these relations are used in understand the growth or cooling histories of natural minerals.     

On the Morphological Changes and Twinning of ZnS (Sphalerite) Crystallites under Hydrothermal Conditions

Morphological characteristics and twinning mechanism of ZnS crystals under hydrothermal conditions have been investigated in this paper. It was shown that under hydrothermal conditions the morphology of ZnS crystallites changes along the four‐fold axis directions, and the crystals are observed in a positive or negative tetrahedron, or in a combination of positive and negative tetrahedra depending on the growth conditions. The positive tetrahedral areas on the crystallites get larger with increase of the concentrations of OH^‐ and S^2‐ in solutions, whereas the twinned crystallites of ZnS taking an elliptic shape with (111) as composition plane are easily formed in weak basic solutions. It can be found that the morphologies of ZnS crystals are in accordance with the crystallization orientations of positive or negative coordination tetrahedra ([S‐Zn₄]⁶⁺, [Zn‐S₄]^6‐) in the crystal although, in some cases, the practical morphology could be greatly affected by growth conditions, and the twinning mechansim can be suggested based on the linkage of growth units of positive and negative coordination tetrahedra, which were formed in the solution. The present investigations further indicated that the crystal chemistry approach based on the linkage/incorporation of growth units previously proposed by us can be sucessfully applied to interpret the growth mechanisms of the crystals and to control a desirable morphology.     

Concept of specific supersaturation (specific supercooling) and practical aspects of its application

It is demonstrated that the normal growth rate of crystals from solutions and melts depends on the area of the crystallization front. New growth parameters, namely, the specific supersaturation and the specific supercooling, are introduced, and the quantitative dependence of the normal growth rate on these parameters is determined. It is noted that the normal growth rate affects the formation of defects. The criteria and the range of the possible use of the specific supersaturation (specific supercooling) for optimizing the conditions of crystal growth from solutions and melts are revealed.     

Surface nanoscale relief of mineral crystals and its relation to nonautonomous phase formation

The features of the nanoscale relief of crystals formed under natural and experimental conditions are considered by examples of pyrite, sphalerite and its solid solutions, and native gold. Nonautonomous phases (NAPs), which differ from the bulk mineral by their chemical composition, stoichiometry, and structure, are fixed within an approximately half-micron surface layer. For pyrite crystals, the NAP composition and morphology vary depending on the genetic conditions. In the case of sphalerite, hierarchical fractal structures arise on the crystal surface due to the formation of NAPs of sulfate or sulfoxide composition. An increased content of admixed elements (Cd, Hg) is observed on the surface at the largest NAP development. Gold sulfide NAPs are observed to be stable at a relatively high temperature under hydrothermal conditions.     

On the growth mechanism of sodalite single crystals grown by the hydrothermal method on single crystal seeds coated with informative informative interfacial layers

The growth mechanism of the early formation stages of sodalite single crystals grown by the method of hydrothermal synthesis on single crystal seeds coated with interfacial layers of polycrystalline silver has been studied at an electronmicroscopic scale. Coating with interfacial layers leads to a very weak adhesion between the overgrown single crystal and the surface of the interfacial layer on top of the seed, thus providing a unique possibility of detaching the overgrown single crystals from seeds and investigating the very early crystallization stages by the morphology of the growth surface. In local microregions of seed surfaces coated with interfacial layers discrete particles arise differing from one another in morphology, this being primarily associated with the electrical heterogeneity of seed surfaces. During crystallization, the space between the discrete particles was filled with the hydrothermal solution which represented a liquid interfacial layer exhibiting informative properties occurred under the influence of electrically active elements of the seed surface. At the boundary separating the liquid interfacial layers with particular informative properties from the rest of the solution volume, at early crystallization stages, together with the formation of discrete particles directly on the coated seed surface, growth of a continuous sodalite single crystal took place. The informative properties of seed surfaces, which are regularly modified due to coating with interfacial silver layers, determine the occurrence on local regions of seed surfaces (under appropriate crystallization conditions) of one or the other polymorphous modification: either hexagonal – cancrinite, or cubic – sodalite.     

Effect of CuCl2 on hydrothermal crystallization of calcium sulfate whiskers prepared from FGD gypsum

Using purified flue‐gas desulfurization (FGD) gypsum as raw material, effects of CuCl₂ on crystal morphology, phase structure, aspect ratio and crystallization of hydrothermal products prepared via hydrothermal crystallization in H₂SO₄‐H₂O solutions were investigated. The results show that dosage of CuCl₂ has a significant effect on the morphology, aspect ratio and crystallization of calcium sulfate whiskers (CSWs), but no effect on their phase transformation . At a dosage of 15 g CuCl₂/kg FGD gypsum, the produced calcium sulfate whiskers had diameters ranging from 1 to 3 μm with average aspect ratio greater than 200 . Transmission electron diffraction patterns and highly magnified surface morphology of CSWs were found different from those of self‐assembly crystals. Compared to self‐assembly crystals, the produced CSWs showed a single crystal structure and their surface was very smooth.     

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.     

Lanthanum borogermanate glass-based active dielectrics

Favorable properties of stillwellite-like LaBGeO₅ stimulated many attempts to realize them on an industrial scale. However, the growth of stillwellite single crystals is problematic and, because of strong structural anisotropy, dense stillwellite ceramics were not synthesized to date. Unique properties of crystalline LaBGeO₅ may be realized via bulk or grain-oriented crystallization of lanthanum borogermanate (LBG) glasses. Nucleation, bulk and surface crystallization including grain-oriented crystallization of LBG glasses are briefly reviewed. Dependence of crystallization behavior of LBG glasses on the synthesis conditions was found to be closely linked with alumina impurities that suppress texture forming but improve glass-forming ability. The latter offers an opportunity to obtain LBG-based glasses of optical quality, containing more than 30 mol% rare-earth oxides, for laser and magneto-optical applications. A wide range of active dielectrics in the LBG system covering non-linear optical nano-structures, planar wave guides and textures with excellent pyroelectric activity are expected to be developed.     

Part 1: Kinetics and mechanism of the crystallization process

The kinetics of spontaneous crystallization of sodium chloride from aqueous‐ethanol solutions were studied. During the crystallization the electrical conductance and optical transmission of the supersaturated solutions were measured automatically. For monitoring of the total surface of growing potassium chloride crystals at the crystallization the turbidimetric method was used. The growth rate and activation energy were determined. The crystal growth rate was proportional to supersaturation. When the volume fraction of ethanol in solution increased from 14.85 to 29.72%, the activation energy of the growth process did not change and was about 50 kJ· mol^‐1. Aggregation of the crystals was found. The aggregation kinetics of the crystals may be described approximately by the famous Smoluchowski equation for coagulation of colloidal particles. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spontaneous crystallization of potassium chloride from aqueous and aqueous‐ethanol solutions Part 1: Kinetics and mechanism of the crystallization process

Kinetics of spontaneous crystallization of potassium chloride from aqueous and aqueous‐ethanol solutions were studied. During the crystallization of the salt the electrical conductance and optical transmission of the supersaturated solutions were measured automatically. For monitoring of the total surface of growing potassium chloride crystals at the crystallization the turbidimetric method was used. The growth rate and activation energy of the crystals were determined. The crystal growth rate was proportional to supersaturation. When the volume fraction of ethanol in the solution increased from 0 to 25.76%, the activation energy of the growth process did not change and was about 60 kJ·mol^‐1. Aggregation of the crystals was found. The aggregation kinetics of the crystals may be described approximately by the famous Smoluchowski equation for coagulation of colloidal particles. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of initial oxidation state on crystallization of basaltic glass

Iron-rich silicates mined as basalt may be processed as glass fibers and, woven to textile mats, it may be used as heat insulation. High-temperature stability is however a limiting factor because at least three process of alteration occur upon heat treatment that affect mechanical and chemical properties, micron to nano-crystallization, oxidation and cation-enrichment at the glass surface with a few microns depth. We here evaluate the crystallization behavior of synthetic Fe³⁺-rich basalt (SB) heat treated in air (negligible oxygen potential) in comparison with previously studied Fe²⁺-rich natural basalt (NB) heat treated in air and in Ar (i.e., high and low oxygen potential, respectively). Initial crystals growing in Fe²⁺-rich basalt are micron-sized dendrites, and with temperature of heat treatment they become increasingly granular and are identified as pyroxene. Pyroxene in SB form smaller dendrites; crystallization textures and nucleation and growth rates, derived from crystal size distribution, are independent of the temperature of heat treatment in the range between 850 and 1030 °C. Here, the activation energy of pyroxene vanishes, though crystallization rates are smaller than those of NB. Whereas in NB pyroxene growth occurs diffusion limited, in SB it is likely to be limited by the attachment of ions to new crystal surface.     

On the mechanism of trace-element uptake during the hydrothermal growth of sulfide mineral crystals

The stable species of cadmium and mercury are formed in iron and lead sulfides at elevated temperatures and pressures under hydrothermal conditions. Their formation proceeds through different mechanisms. The most general mechanism involves the uptake of trace elements in the form of structural species due to isomorphous exchange. The results obtained for cadmium in pyrrhotite indicate that structural defects substantially affect the incorporation of impurities into the crystal structure. It is found that trace elements are accumulated on the surface in the absence of defects and are incorporated into the crystal bulk in the form of structural impurities in the presence of defects. Moreover, at elevated temperatures and pressures, trace elements can form their own (surface nonautonomous) phases. These phases are formed not only at trace-element concentrations close to saturation (Cd in Fe_1.0S) but also under conditions far from saturation as a result of the interaction of trace elements with the oxidized surface of the mineral (the cadmium uptake by galena with the formation of either a sulfate surface phase or a sulfate-chloride surface phase). An important mechanism of trace-element uptake by sulfides during the hydrothermal growth of crystals is associated with external and internal adsorption of impurities by defects. This adsorption manifests itself both in an increase in the content of sorbed mercury in galena at a high sulfur activity due to the interaction of mercury with lead vacancies and in the formation of dislocation cadmium species, which results in an increase in the coefficient of cadmium distribution in the crystal-solution system.     

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.     

Structure of KTiOPO<Subscript>4</Subscript> single crystals grown by the top-seeded solution and spontaneous flux crystallization methods

This paper reports on the results of precision X-ray structural investigations of KTiOPO₄ single crystals grown by one method (crystallization from a solution in the melt) in two variants (the spontaneous formation of crystallization centers or top-seeded solution growth during slow cooling of saturated solution melts). It is shown that spontaneous flux crystallization leads to the formation of a larger number of defects. Potassium atoms are found to be disordered. The splitting of the K1 and K2 potassium positions is equal to 0.347(4) and 0.279(3) Å, respectively, for the crystals grown by the top-seeded solution method and 0.308(5) and 0.321(4) Å, respectively, for the crystals grown through the spontaneous flux crystallization.     

Growth of Gallium Orthophosphate Single Crystals under Hydrothermal Conditions

Gallium orthophosphate (GaPO₄) single crystals have been grown from phosphoric acid solutions under hydrothermal conditions. The crystals have been studied in terms of twinning because of the strong effect of this structural defect on the piezoelectric properties. The growth rates of individual faces have been compared to each other by considering the dipyramidal habit of the grown crystals.     

Developing a Fluorescence-based Approach to Screening for Macromolecule Crystallization Conditions

Current macromolecule crystallization screening methods rely on the random testing of crystallization conditions, in the hope that one or more will yield positive results, crystals. Most plate outcomes are either clear or precipitated solutions, which results are routinely discarded by the experimenter. However, many of these may in fact be close to crystallization conditions, which fact is obscured by the nature of the apparent outcome. We are developing a fluorescence-based approach to the determination of crystallization conditions, which approach can also be used to assess conditions that may be close to those that would give crystals. The method uses measurements of fluorescence anisotropy and intensity. The method was first tested using model proteins, with likely outcomes as determined by fluorescence measurements where the plate data showed either clear or precipitated solutions being subjected to optimization screening. The results showed a ~83% increase in the number of crystallization conditions. The method was then tried as the sole screening method with a number of test proteins. In every case at least one or more crystallization conditions were found, and it is estimated that ~53% of these would not have been found using a plate screen.     

Growth conditions and electrical properties of KDP crystals: II. Dielectric permittivity measurements

The dielectric properties of potassium dihydrophosphate single crystals, which were grown from crystallization solutions at different pH, have been studied. The dielectric response of the single crystals is shown to vary substantially depending on the growth conditions and can be significantly different for samples from different growth sectors of the same single crystals and even within one sector. The results of this study are useful for optimizing the growth conditions of these single crystals.     

Crystallization of the E. coli polyamine-induced protein: a novel procedure based on the concept of ionic strength reducers

Nucleation and growth of macromolecular crystals occur in supersaturated solutions the properties of which depend on numerous parameters that influence macromolecular solubility. Detailed knowledge of the effects of those parameters is essential for crystallization. The concept of the so-called “ionic strength reducers” provides insight into the changes of solubility induced by organic solvents and hydrophilic polymers in aqueous electrolytic solutions. A simple and efficient procedure is presented which exploits the properties of ionic strength reducers in the crystallization of proteins. Using this procedure in the crystallization of the E.coli polyamine-induced protein, superior crystals compared to conventional techniques have been obtained. The procedure combines microseeding with dialysis techniques and is applicable to other proteins, particularly in cases where conditions favoring both for nucleation and growth cannot be found, or in cases where excessive nucleation leads to the growth of a large number of very small crystals.     

Some observations on forms of NaA and NaX zeolites growing in the presence of triethanolamine

Using modified preparation conditions for silicate and aluminate solutions some differences in the result of large A- and X-type zeolites crystallization utilizing Charnell's procedure have been obtained. A-type zeolite crystals show clearly {110} faces. X-type zeolite occurs in mixed phase together with A-type zeolite as separate as well as overgrown crystals. These observations can be explained by structure defects in A-type crystals and by presence of polysilicate or/and too high aluminium content in the gel.     

微波辅助水热合成条件对直接合成纳米HZSM-5晶体性质的影响

利用微波辅助水热合成法直接制备了纳米HZSM-5晶体.采用XRD、FT-IR、SEM、BET和NH3-TPD等手段对合成样品进行了分析表征,研究了晶化温度和时间对合成产物晶体性质的影响.结果表明,晶化温度和时间对微波辅助水热直接合成产物微观形貌、晶粒尺寸和分散度影响明显.较低的晶化温度和较短的晶化时间均难以形成形貌规则的HZSM-5晶体.随着晶化温度的升高,合成样品逐渐变为球形晶粒、晶粒尺寸逐渐增大、分散度逐渐提高,继续提高晶化温度达180 ℃时,晶粒长大使比表面积稍有降低;随着晶化时间的延长,样品的微孔和介孔增多,比表面积和孔容逐渐增大,继续延长晶化时间,晶体内微孔可能的收缩和晶粒的长大使得样品孔容和比表面积减小.160 ℃和1.5 h条件下制备的HZSM-5分子筛晶体形貌呈球形,晶粒尺寸约为60 nm,分散程度较好;其比表面积、孔容和平均孔径分别为398.45 m2·g-1、0.63 cm3·g-1和6.27 nm;晶体表面具有弱酸特征.