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126 TAYLOR CARBONELL DESIMONE acetate (PVAC)-b-poly(1,1,2,2-tetrahydroperfluorooctyl acrylate) (PTAN) (23). Three regions were observed on the phase diagram of the copolymer: (a) a two- phase region at low CO2 density, (b) solutions of spherical micelles at intermediate CO2 densities, and (c) solutions of unimers at high CO2 densities. The aggregation number (the number of copolymer chains in a micelle) decreased with an increas- ing density of supercritical CO2 in region (a). An increase of the CO2 density corresponds to the improvement of solvent quality for both blocks of the copoly- mer (PVAC and PTAN). The hydrodynamic radii of micelles and unimers were measured using dynamic light scattering in regions (b) and (c), respectively. This light-scattering study is the first one reporting a solvent density–induced transition, a critical micelle density, between spherical micelles at lower supercritical CO2 density and unimers at higher CO2 density. The light-scattering technique appears to be a very powerful tool for the analysis of carbon dioxide density–induced micel- lization transition (Figure 8, see color insert). This phenomenon is unique to super- critical fluids and demonstrates a convenient control over the polymer solubility. 3. BY THE DESIGN OF CO2-SOLUBLE POLYMERS APPLICATION OPPORTUNITIES ENABLED 3.1 A New Coatings Technology Based on Liquid CO2 Hundreds of millions of pounds of solvents are manufactured each year for use in coatings applications. A wide range of coating materials and processes can utilize environmentally friendly CO2 as a potential replacement for traditional solvents used as delivery media. PFPE-based coating materials are viewed with particular interest for a number of reasons including their exceptional performance in aggressive environments (as compared to other fluoropolymer coatings) and their solubility in dense carbon dioxide. The applications currently envisioned include coatings for buildings/bridges, fouling-release coatings, spin coating for microlithography, and lubricants for magnetic drives. A few of these applications will be discussed in more detail below. 3.1.1 New Environmentally Friendly Lithographic Processes The properties of fluoroacrylate polymers can be controlled in CO2 to provide polymers with a range of glass transition temperatures, functionalities, molecular weights, and architectures (9). The synthetic control of fluoropolymer synthesis in CO2 provides the opportunity to develop new coatings and polymerization technologies. Spin coating photoresists from liquid CO2 is a novel idea that could have a great impact on the electronics industry. This industry currently uses one million gallons of solvent each year on a single fabrication line. The use of these solvents requires extensive safety and waste processing equipment. To impact this industry with the benefits of CO2 technology, photoresists need to be identified and synthesized forPDF Image | OPPORTUNITIES FOR POLLUTION PREVENTION
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