A vacuum deposition system was built enabling flexible polymer sheet, wound on a roll-to-roll transport mechanism, to be coated by any or all of three planar magnetron sputtering sources. Using this machine a large variety of coatings were produced in long lengths onto heat sensitive substrates and with controlled stoichiometry. Within the system the coating was monitored soon after deposition which allowed fast response to changing film properties, a critical factor in the continuous production of high quality coatings. An area of current interest has been the production of large area optical filters, the basis of which is the deposition of thin metal and thin metal oxide films. Of particular interest have been the 'heat mirror' type filters, the transparent conducting oxides and more recently the electrochromic devices. All these have been deposited at high rates onto flexible polyester substrates ostensibly at room temperature. Analysis of the films has been carried out by a variety of techniques in order to establish the precise chemical composition and structure of the films. Once optimum conditions had been established for individual films multilayer filters were produced and their optical performance determined. In the case of the 'heat mirror' type filters their performance was compared to theoretical predictions.

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I am deeply indebted to my parents and family for their much needed support and concern about my well being. I wish to thank Dr. Laurence for all of his time, patience, and knowledge which enabled me to complete this research. I would also like to thank Dr. Middleman for his support and advice which were much appreciated. I am grateful for all the advice of Tong and Pradeep and for their interest in the progress of my research. Finally, a special thanks to all my friends for their help in making the last two years a fun filled adventure. This research was funded by the Department of Polymer Science and Engineering at the University of Massachusetts and a grant from the Eastman-Kodak Company.

Biofouling has been an economically and environmentally costly problem to mankind ever since they set sail. Biofouling causes frictional drag leading to slow vessel speeds, and increased fuel costs. Antifouling (AF) coatings containing biocides have been used for decades, however, since some biocides have shown undesired effects towards the environment, a non-toxic solution to combat fouling is desired. Subsequently, fouling release (FR) coatings quickly gained acceptance as a non-toxic approach to contend with biofouling. Unlike AF coatings, FR coatings not necessarily prevent settlement of organisms, they permit weak adhesion which is easily released by water shear or light grooming. The siloxane-polyurethane (SiPU) coatings based on the concept of self-stratification is a non-toxic and durable approach to prepare FR coatings. In this work, several approaches were considered to optimize surface properties of SiPU coatings. Incorporation of phenyl-methyl silicone oils led to improved FR properties towards several marine organisms in laboratory assays and in ocean field immersion. Enhancement in FR properties may be attributed to slowly exuding silicone oil providing surface lubricity, weakening the adhesion of marine organisms. Addition of diphenyldimethyl siloxane in to SiPU coatings at different ratios resulted in micro-scale surface topographical features which negatively affected microfouling-release while several coatings displayed good FR performance towards macrofouling organisms. In another study, decreasing the acid group content helped to improve FR performance towards barnacles, but FR performance towards diatoms were compromised. Novel amphiphilic siloxane-polyurethane (AmSiPU) coatings from polyisocyanate pre-polymers modified with polydimethyl siloxane and polyethylene glycol displayed excellent FR properties towards several marine organisms during laboratory assays. These AmSiPU coatings show promise as contenders to commercial FR standards. Initial development of SiPU coatings with hydrophilic surfaces showed promise, as the coatings showed rapidly rearranging surfaces with comparable FR performance to commercial standards which claim hydrophilic surface properties. During freshwater field immersion trials, SiPU coatings displayed excellent mussel FR performance up to 3 years. Surface analysis suggested that solvent content affected self-stratification and morphology of SiPU coatings. The SiPU coating system is a highly tunable, tough, environmentally friendly, and practical FR solution which can evolve along with non-toxic commercial marine coatings. / Office of Naval Research (Grant number N00014-12-1-0482) / SSPC / Valpar / American Coatings Association / North Dakota State University. College of Science and Mathematics

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Various physical parameters of solvents within two component, PMMA + Solvent films are analyzed for their impact upon the coating uniformity of spin deposited PMMA films. Towards this end, a model is presented for describing the surface behavior of spin-on films during the latter stages of deposition, correlating the tendency of a film toward non-uniform deposition to physical characteristics of the spin-on solution. A finite difference solution to this model is presented for two-component, spin-on films that is shown to effectively predict the uniformity of the resulting thin-film layers. The model is then used to determine the impact of specific film parameters upon the predicted spin-on uniformity of the film. Based upon these results, the interdependency between evaporation rate, solvent viscosity, surface tension and rotation rate in determining the uniformity of the spin-on film is evaluated by comparing the model predictions against those found in actual spin-on, two component films. The results from this model are used to provide a physical explanation for why certain surface non-uniformities begin to develop during spin coating.