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Precipitates of a series of alkaline earth metal (barium and strontium) carbonates, chromates, phosphates, and sulfates were formed at high supersaturation by diffusion through silica hydrogel, agarose hydrogel, and the freshly developed agarosesilica mixed gels. The reaction vessels could be a small test tube, a recently designed standard micro slide cassette and a enlarged supercassette. Homogeneous nucleation is thought to have taken place, and particle development led to the formation of an unusual category of materials, known as Induced Morphology Crystal Aggregates [IMCA], at high pH under far-from-equilibrium conditions. Standard procedures were developed in order to produce homogeneous gels. Particle development led to characteristic style of pattern formation, which I have called monster, spiral, and flake. Among these IMCA, barium carbonate, chromate, and sulfate were moderately easy to grow. Barium phosphate was very difficult to grow as IMCA due to formation of poorly crystalline spherulites. IMCA of strontium carbonate, chromate and sulfate could be developed at high basic pH in the presence of silicate. Strontium carbonate sheet morphology displays a unique property, double internal layer structure, which was identified by backscattering electron imaging (BEI). Selected electron diffraction (SAD) revealed a new crystal phase which was called "Dentonite". Precipitate particles were isolated using a non-destructive isolation technique. Optical microscopy was widely used to examine particles in situ and scanning electron microscopy and X-ray dispersive energy (EDX) spectroscopy were applied to particles ex situ, together with ESCA for surface analysis. Growth patterns were found to be strongly dependent on pH. Other related pattern formation processes were also investigated including normal and dendritic structures, spherulitic structures and periodic pattern formation. Some interpretations were proposed in terms of mechanism. Chemical additive effects were examined experimentally in the calcium phosphate system. The effect of external ionic strength was investigated, and it was found that a certain concentration of sodium chloride (0.2 M) approximately equals a fraction of pH unit (-0.2).

Thesis. 1978. Ph.D.--Massachusetts Institute of Technology. Dept. of Materials Science and Engineering. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / Ph.D.

Although the precipitation of aluminium trihydroxide as gibbsite, via the Bayer process has been widely studied, the mechanism of crystal growth is poorly understood. This work focus on the morphology of gibbsite and the relative growth rates of individual crystal faces.Initial work was carried out to characterize aluminium trihydroxide and it was found that bayerite, another polymorph, precipitated at temperatures below 50 [degrees] C and its morphology depended on the method of precipitation. Gibbsite however, precipitated above this temperature and its morphology depended on the type of alkali aluminate solutions used. The method of precipitation does not affect the morphology, only the size of the precipitate formed. The morphology of gibbsite can be altered by the addition of organic compounds which are known to inhibit gibbsite precipitation. Some of these compounds were found to selectively inhibit the growth of individual crystal faces, thus altering the overall morphology of gibbsite. Boehmite, a polymorph of aluminium hydroxide, can be produced by partial dehydration of gibbsite at 300T. The morphology of boehmite consisted of diamond shaped crystals.The influence of cation incorporation on the morphology of gibbsite was studied experimentally and computationally (molecular modelling). These studies showed that there is a linear relationship between the amount of cation incorporated and atomic radii and between the amount of cation incorporated and the defect energy calculated. The equilibrium morphology of gibbsite predicted in the absence of media matched the morphology of gibbsite grown slowly from sodium aluminate, implying that the amount of sodium incorporation is low in these crystals.The growth rates of individual crystal faces were measured in situ, and found to be a function of supersaturation squared for the prismatic faces, possibly indicating ++ / that E growth occurs by spiral growth mechanism. The growth of the basal face was found to follow the spiral growth mechanism below a relative supersaturation of 0.815 and the birth and spread mechanism above this level. The activation energies and kinetic coefficients for the individual prismatic faces were also determined.Growth rate dispersion was observed in these microscopic studies, but the question of size dependency remains unanswered.The overall growth rates of gibbsite crystal, determined using rapid dynamic light scattering, was found to be an exponential function of supersaturation indicative of a birth and spread growth mechanism.

Lactose is the major carbohydrate in milk. The presence of lactose in whey constitutes a significant pollution problem for dairy factories. At the same time, there is an increasing market for high quality crystalline lactose. The main problem of lactose crystallisation, compared to sucrose, which is also a disaccharide, is that it is very slow, unpredictable and cannot easily be controlled. Compared to sucrose crystallisation, which has been extensively studied, lactose crystallisation lacks the fundamental research to identify the mechanisms of growth and effect of additives. An important difference from most other crystal growth systems is that ([alpha]-lactose hydrate crystals never grow from a pure environment; their growth environment always contains beta lactose. [alpha]-lactose monohydrate crystallises much more slowly because of the presence of [beta]- lactose in all solutions. Although there have been some studies on growth rates and the effect of additives, there has not been any reported work on the fundamentals of lactose crystallisation and the mechanisms that operate on the molecular level. The aim of this thesis is to gain a greater understanding at the fundamental processes, which occur at the molecular level during the crystallisation of lactose, in order to improve control at a macroscopic level. / The growth rates of the dominant crystallographic faces have been measured in situ, at three temperatures and over a wide range of supersaturation. The mean growth rates of faces were proportional to the power of between 2.5-3.1 of the relative supersaturation. The rate constants and the activation energies were calculated for four faces. The [alpha]-lactose monohydrate crystals grown in aqueous solutions exhibited growth rate dispersion. Crystals of similar size displayed almost 10 fold difference in the growth rate grown under identical conditions for all the faces. Growth rate dispersion increases with increasing growth rate and supersaturation for all the faces. The variance in the GRD for the (0 10) face is twice the variance of the GRD of the (110) and (100) faces and ten times higher than the (0 11) face at different supersaturations and temperatures. The influence of [beta]-lactose on the morphology of [alpha]-lactose monohydrate crystals has been investigated by crystallising [alpha]-lactose monohydrate from supersaturated DMSO ethanol solutions. The slowness of mutarotation in DMSO allowed preparation of saturated solutions with a fixed, chosen [beta]-lactose content. It was found that [beta]-lactose significantly influences the morphology of [alpha]- lactose monohydrate crystals grown from DMSO solution. At low concentrations of [beta]-lactose, the fastest growing face is the (011) face resulting in long thin prismatic crystals. At higher [beta]-lactose concentrations, the main growth occurs in the b direction and the (020) face becomes the fastest growing face (since the (011) face is blocked by [beta]-lactose), producing pyramid and tomahawk shaped crystals. / Molecular modeling was used to calculate morphologies of lactose crystals, thereby defining the surface energies of specific faces, and to calculate the energies of interactions between these faces and [beta]-lactose molecules. It was found that as the replacement energy of [beta]-lactose increased, the likelihood of [beta]-lactose to dock onto faces decreased and therefore the growth rate increased. The attachment energy of a new layer of [alpha]-lactose monohydrate to the faces containing [beta]-lactose was calculated for the (010) and (011) faces. For the (0 10) face, the attachment energy of a new layer was found to be lower than the attachment energy onto a pure lactose surface, meaning slower growth rates when [beta]-lactose was incorporated into the surface. For the (011) face, attachment energy calculations failed to predict the slower growth rates of this face in the presence of [beta]-lactose. AFM investigation of [alpha]-lactose monohydrate crystals produced very useful information about the surface characteristics of the different faces of the [alpha]-lactose monohydrate crystal. The growth of the (010) face of the crystal occurs by the lateral addition of growth layers. Steps are 2 nm high (unit cell height in the b direction) and emanate from double spirals, which usually occurred at the centre of the face. Double spirals rotate clockwise on the (010) face, while the direction of spirals is counterclockwise on the (010) face. A polygonised double spiral, showing anisotropy in the velocity of stepswas observed at the centre of the prism-shaped a-lactose monohydrate crystals grown in the presence of 5 and 10 % [beta]-lactose. / The mean spacing of the steps parallel to the (011) face is larger than those parallel to the (100) face, indicating higher growth rates of the (011 )face. The edge free energy of the (011) face is 6.6 times larger than the (100) face in the presence of 5% [beta]-lactose. Increase of [beta]-lactose content from 5% to 10 % decreases the edge free energy of the growth unit on a step parallel to the (011) face by 10 %. Tomahawk-shaped [alpha]-lactose monohydrate crystals produced from aqueous solutions where the [beta]-lactose content of the growth solution is about 60 % have shown clockwise double spirals as the source of unit cell high steps on the (010) face of the crystal. However , the spirals are more circular than polygonised, unlike the prism shaped crystals and the mean step spacing of the (011) face is less than the steps parallel to the (110) face, indicating the growth rate reducing effect of [beta]-lactose on the (011) face. The (100) face of the [alpha]-lactose monohydrate crystal grows by step advancement in relative supersaturations of up to 3.1. Steps are 0.8 nm high and parallel to the c rection. Above this supersaturation, rectangular shaped two-dimensional nuclei, 10 nm high, were observed. The (011) face of the crystal grown at low supersaturations (s= 2.1) displayed a very rough surface with no steps, covered by 4-10nm high and 100-200[micro]m wide formations. Triangular shaped macrosteps were observed when the crystal was grown in solutions with s=3.1. In situ AFM investigation of the (010) face (T = 20[degree]C and s = 1.18) has shown that growth occurs by lateral addition of growth units into steps emanated by double spirals. / The growth rate of the (010) face from in situ AFM growth experiments was calculated to be 1.25 gm/min. The growth rate of crystals grown in the in situ optical growth cell under identical conditions was 0.69 pm/min. The difference in growth rates can be attributed to the size difference of seed c stals used. The (010) face of a [alpha]-lactosemonohydrate crystal grown at 22.4 C and s=1.31 displayed triangular-shaped growth fronts parallel to the (011) face. The steps parallel to the (O11) face grow in a triangular shape, and spaces between triangles are filled by growth units until the end of the macrosteps is reached. No such formations were observed on steps parallel to the (110) face. Formation of macrosteps, 4-6 nm high, emanating from another spiral present on the surface was also observed on the (010) face of a crystal grown under these conditions.

Yttrium garnet is an excellent laser host crystal due to its excellent optical, thermal, mechanical properties and high chemical stability. As a rare-earth ion with the simplest energy level construction, Yb3+ belongs to the 4f13 electronic configuration. It possess some important advantages such as long fluorescence lifetime, no excited-state absorption, low quantum defect and larger intrinsic laser slope efficiency. Besides, yttrium garnet crystal doping ytterbium ion can especially dope with high concentrations and lower heat generation. In this thesis, a series of different doping concentration of Yb¡GYAG by Czochralski pulling technique are grown and perform some accurate experiments including Raman, IR, XRD and EXAFS in order to make sure the impact effect of doping on the lattice structure. The study includes following ¡]1¡^the effect of different doping Yb3+ from pure YAG to YbAG¡]2¡^the distances of Yb-O, Yb-Al, Yb-Y, Yb-Yb when Yb3+ ions replace Y3+ ions¡]3¡^the changes of absorption energy level in YAG crystal due to different concentrations of Yb3+ ion.

Thesis (Ph. D.)--University of Texas at Austin, 2000. / Vita. Includes bibliographical references.

Spatial correlation functions, which quantify spatial relationships among porphyroblasts over a range of length scales, can be used in combination with other techniques of quantitative textural analysis to constrain crystallization mechanisms in metamorphic rocks. The utility, reliability, and robustness of these functions, however, depend critically upon correct methods of calculation and application to geological samples. Application of the L' -function, Pair Correlation Function, and Mark Correlation Function (Stoyan and Stoyan, 1994) to artificial arrangements of crystals yields results consistent with their predetermined ordering and clustering qualities. These results serve as a foundation for the interpretation of more complex simulated and natural crystal arrays. Analysis of artificial and simulated crystal arrays in which ordering signals are obscured in various ways (displacing crystals in an ordered array by increasing amounts, reducing the number of crystals, and increasing the sample's aspect ratio) demonstrates that these scale-dependent functions are robust indicators of effects diagnostic of certain crystallization mechanisms, even in complex circumstances. The effects of clustering of nucleation sites, however, can strongly obscure any underlying signal that might reveal crystallization mechanisms. The L' -function and the Pair Correlation Function are sensitive to short-range ordering of crystals, which may reflect suppression of nucleation in the vicinity of growing porphyroblasts. The Mark Correlation Function is sensitive to size-isolation correlations, which may reflect retardation of growth among crystals competing for nutrients. Interpretation of these functions, however, requires careful attention to proper calculation of Monte Carlo simulations, which are used to identify values of the functions that constitute a null-hypothesis region for comparison to samples with unknown ordering and clustering characteristics. To yield functional values commensurate with those calculated for a particular natural rock specimen, each simulation must match as closely as possible several critical features of the natural rock, including the set of crystal radii, limitations on the observability of crystals, and the shape and size of the bounding surface of the sample. Crystallization mechanisms in seven previously studied garnetiferous rocks from three localities (Carlson et al., 1995; Denison and Carlson, 1997) have been re-assessed using both scale-dependent correlation functions and single-valued spatial statistics, both evaluated by comparison to rigorously computed null-hypothesis regions. The results confirm previous inferences that the nucleation and growth rates of the garnet porphyroblasts in these specimens were governed by rates of diffusion through the intergranular medium. / text