@article{yarbrough_rolland_desimone_callow_finlay_callow_2006, title={Contact angle analysis, surface dynamics, and biofouling characteristics of cross-linkable, random perfluoropolyether-based graft terpolymers}, volume={39}, ISSN={["1520-5835"]}, DOI={10.1021/ma0524777}, abstractNote={The conventional approach to prevention of marine biofouling has been the use of antifouling paints and coatings which function through the release of toxins in the immediate vicinity of the ship. Such technology, while admittedly effective, has proven to be responsible for an alarming increase in the levels of organotin and other toxic materials in and around dry docks, harbors, and shipping lanes which experience significant commercial and tourist traffic. Therefore, our objective is the rational design of minimally adhesive, mechanically stable, nontoxic fouling release coatings as responsible and practical alternatives to antifouling technologies. Herein we report on the synthesis and characterization of a series of cross-linkable perfluoropolyether (PFPE) graft terpolymers containing various alkyl (meth)acrylate monomers with glycidal methacrylate as the cure-site monomer. These materials were targeted for use as coatings to prevent marine biofouling. A series of terpolymers were prepared through application of the macromonomer approach, allowing for control of cross- link density, Tg, and modulus. Structure/property relationships were established through compositional variation with regard to the three classes of monomers. The first monomer class was an alkyl (meth)acrylate used to create the continuous phase of the microphase-separated graft terpolymers. Variation between methyl methacrylate (MMA) and n-butyl acrylate (BA) provided materials with a low (-10 °C) and a high (95 °C) Tg for the continuous phase. This was a means of isolating the effect of modulus and Tg on surface properties, while the basic chemical nature of the monomer remained unchanged. The second monomer class contained a curable functional group. Through incorporation of glycidyl methacrylate (GMA) in the monomer feed and manipulation of curing conditions, the relative effect of cross-link density on surface dynamics has been evaluated. The third monomer class was the PFPE macromonomer itself. The incorporation of this macromonomer was used to enhance the release properties of the resulting materials which relied on surface enrichment of the low surface energy PFPE component. Dynamic surface properties of these materials have been evaluated through dynamic surface tensiometry (DST). Herein, it has been demonstrated that contact angle hystersis can be significantly mitigated (i.e., ir is maximized) by as much as 50° through variation in bulk polymer composition, the chemical nature of monomers, cross-link density, modulus, and environmental conditions at the time of cure. The antifouling and fouling-release potential of the experimental coatings were also evaluated by laboratory assays employing the green fouling macroalga UlVa. The results from these initial studies suggest promising antifouling properties, especially with regard to spore settlement which was strongly inhibited on the experimental surfaces. Additionally, those that did settle were only weakly attached with one sample set exhibiting fairly moderate release of the young UlVa plants.}, number={7}, journal={MACROMOLECULES}, author={Yarbrough, JC and Rolland, JP and DeSimone, JM and Callow, ME and Finlay, JA and Callow, JA}, year={2006}, month={Apr}, pages={2521–2528} }
 @article{zhou_dominey_rolland_maynor_pandya_desimone_2006, title={Molded, high surface area polymer electrolyte membranes from cured liquid precursors}, volume={128}, ISSN={["0002-7863"]}, DOI={10.1021/ja064391e}, abstractNote={Polymer electrolyte membranes (PEMs) for fuel cells have been synthesized from easily processable, 100% curable, low molecular weight reactive liquid precursors that are photochemically cured into highly proton conductive solid membranes. The liquid precursors were directly cured into membranes of desired dimensions without the need for further processing steps such as melt extrusion or solvent casting. By employing chemical cross-linking, high proton conductivities can be achieved through the incorporation of significant levels of acidic groups without rendering the material water-soluble, which plagues commonly used non-cross-linked polymers. Fabrication of membrane electrode assemblies (MEAs) from these PEMs resulted in fuel cells that outperformed those based on commercial materials. Moreover, these liquid precursors enabled the formation of three-dimensional, patterned PEMs with high fidelity, micron-scale features by using soft lithographic/micromolding techniques. The patterned membranes provided a larger interfacial area between the membrane and catalyst layer than standard flat PEMs. MEAs composed of the patterned membranes demonstrated higher power densities over that of flat ones without an increase in the macroscopic area of the fuel cells. This can potentially miniaturize fuel cells and promote their application in portable devices.}, number={39}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Zhou, Zhilian and Dominey, Raymond N. and Rolland, Jason P. and Maynor, Benjamin W. and Pandya, Ashish A. and DeSimone, Joseph M.}, year={2006}, month={Oct}, pages={12963–12972} }
 @article{rolland_hagberg_denison_carter_desimone_2004, title={High-resolution soft lithography: Enabling materials for nanotechnologies}, volume={43}, ISSN={["1433-7851"]}, DOI={10.1002/anie.200461122}, abstractNote={The availability of commercially viable nanofabrication processes is key to realizing the potential of nanotechnologies, especially in the fields of photonics, electronics, and proteomics. The imprint lithographic (IL) technique is a case in point, an alternative to photolithography for manufacturing integrated circuits, nanofluidic and other devices with sub100-nm features. However, it is becoming increasingly clear that new materials are needed to advance IL methods to their putative limits. We recently reported the fabrication of organic-solvent resistant, microfluidic devices with features on the order of hundreds of microns made from photocurable perfluoropolyethers (PFPEs). PFPE-based materials are liquids at room temperature and can be photochemically cross-linked to yield highly fluorinated, solvent resistant, chemically robust, durable, elastomers with a modulus of 4.0 MPa. Herein we report the successful use of PFPE-based materials in high-resolution imprint lithography. Imprint lithography can be roughly broken into two areas: 1) so-called soft lithographic techniques, such as solventassisted micro-molding (SAMIM), micro-molding in capillaries (MIMIC), and microcontact printing (MCP), and 2) rigid imprint techniques, such as nanocontact molding (NCM), “step and flash” imprint lithography (S-FIL), and nanoimprint lithography (NIL). Polydimethylsiloxane (PDMS)}, number={43}, journal={ANGEWANDTE CHEMIE-INTERNATIONAL EDITION}, author={Rolland, JP and Hagberg, EC and Denison, GM and Carter, KR and DeSimone, JM}, year={2004}, pages={5796–5799} }
 @article{wood_michel_rolland_desimone_2004, title={New fluoropolymer materials}, volume={125}, ISSN={["1873-3328"]}, DOI={10.1016/j.jfluchem.2004.09.029}, abstractNote={We report the synthesis of two classes of fluoropolymers that could impact several key lithographic techniques; one has potential applications in next generation photolithography (193 nm, 157 nm, and immersion lithography) and the other in lithographic techniques which are emerging as viable alternatives to photolithography for future applications (i.e., soft lithography).}, number={11}, journal={JOURNAL OF FLUORINE CHEMISTRY}, author={Wood, CD and Michel, U and Rolland, JP and DeSimone, JA}, year={2004}, month={Nov}, pages={1671–1676} }