Thesis supervisor: Christoph Beckermann. Includes bibliographic references (p. 135-143).

In this study, two semi-analytical models of microsegregation were developed to predict the concentration fields of solute in the liquid and solid regions for dendritic solidification of binary metallic alloys. Both models assume that the growing dendrites are cylindrical in shape. This assumption is more realistic compared to the common assumptions of plate-like dendrites that most of the earlier researchers employed in their microsegregation modeling study. The solute redistribution profile, in the developing solid layer, necessary to determine the back diffusion parameter was derived from Fick's second law for the model without coarsening. The application of this parameter in a wide range of conditions and the use of its basic form in the model with coarsening was verified. The concept of coordinate transformation and enhancement of back-diffusion Fourier number were used in deriving the model which took into account the coarsening of dendrites. The models are then extended to deal with rapid solidification, peritectic transformations and multi-component systems and the results were compared with relevant experimental data. A good agreement between the model predictions and experimental results was found. / The second part of this study was focused on developing a fully numerical microsegregation model. The numerical model built upon a previously proposed phase change model which relied upon a coordinate transformation technique. The model was extended to deal with moving boundaries with solute diffusion. A suitable computational procedure was developed to solve the model equations which are strongly coupled to each other. To verify the accuracy of the present algorithm with regard to the capability of tracking the moving interfaces, analytical solution of the Stefan problem was used for verification purposes. A good agreement between the model predictions and the analytical solution was found. Evolution of concentration fields during solidification was calculated in the growing solid as well as in the shrinking liquid regions for rectangular, cylindrical and spherical dendrite geometries. The effects of various cooling conditions and relevant parametric values on microsegregation were analyzed and discussed.

The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Title from PDF of title page (University of Missouri--Columbia, viewed on October 21, 2009). Thesis advisor: Dr. Hongbin Ma. Includes bibliographical references.

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Thesis (Ph. D.)--Ohio State University, 2007. / Title from first page of PDF file. Includes bibliographical references (p. 123-126).

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Surface behavior of poly (epsilon-caprolactone) (PCL) have been studied at the air/water interface (A/W). PCL is a hydrophobic and crystalline polyester with a glass transition temperature around -60 degrees centigrade, a melting point around 55 degrees centigrade, excellent biocompatibility, and low toxicity. In the past decade, PCL based systems have attracted considerable interest for controlled-release drug delivery and as scaffolds for tissue engineering, that require a fundamental understanding of PCL's degradation mechanisms and crystallization properties. PCL spherulites were commonly observed in previous bulk studies. This thesis focuses on PCL crystallization in Langmuir monolayers. Brewster angle microscopy (BAM) studies show that square, distorted rectangular, and dendritic crystals form at the A/W interface. While dendritic structures have been observed in poly (ethylene oxide) (PEO) thin film on solid substrates, this study of PCL is the first time that dendritic morphologies have been observed at the A/W interface for a linear flexible-coil polymer. As far as we know, the crystallization of flexible-coil polymers at the A/W interface is a brand new area of research. These findings may provide an interesting model system for studying crystallization in confined geometries and the effect of crystallinity on enzyme catalyzed hydrolysis of this important biodegradable polymer at the A/W interface. The main objectives of this thesis were to investigate the phase behavior of PCL at the A/W interface, gain a deeper understanding of the nucleation and growth mechanism of PCL crystallization at the A/W interface through surface pressure-area isotherms and isobaric area relaxation analyses, and interpret the effects of molecular weight on the nucleation and growth mechanism, and morphologies of semicrystalline PCL crystallized in Langmuir monolayers at the A/W interface. / Master of Science

Hyaluronic acid (HA) is one of the primary chemical building blocks of the extracellular matrix and thus is an attractive material for biomedical applications. FDA approved HA-based materials are available as dermal fillers, joint viscosupplements, vitreous substitutes, and abdominal adhesion barriers. The engineering of new HA-based materials and applications is an active area of research. Here we develop several new types of HA-based hydrogels with unique and useful properties. To address the challenge of delivering hydrophobic drugs from hydrophilic hydrogel matrices we have grafted HA hydrogels with [Beta]-cyclodextrin to create hydrogels capable of binding poorly water soluble drugs. To create HA hydrogels with unique anisotropic swelling behavior we have developed a dual-crosslinking technique in which a super-swelling chemically crosslinked hydrogel is patterned with low-swelling photocrosslinked domains. When this dual-crosslinked hydrogel is swelled it contorts into a new shape because of differential swelling among photopatterned regions. To address the challenge of creating hydrogel scaffolds with biomimetic branched porosity we have invented a "crystal templating" technique. This technique grows dendritic crystals throughout a biopolymer solution, crosslinks the biopolymer around the crystals, and washes the crystals away to yield a hydrogel with a dendritic macroporous network. Lastly, we invented a method for patterning a substrate with a microarray of hydrogel compartments. A microarray of living cells is obtained when cells are seeded on the hydrogel patterned substrate. This method addresses the need for an inexpensive, simple method for obtaining living cell microarrays that does not require clean room labs and lithographic expertise. Each of these new materials were based on hyaluronic acid hydrogels but the methods are generalizable to hydrogels of other polymers too. In conclusion, the novel methods in this dissertation are a significant contribution to the engineering of HA-based materials. / text