Eliminating the Enhanced Mobility at the Free Surface of Polystyrene: Fluorescence Studies of the Glass Transition Temperature in Thin Bilayer Films of Immiscible Polymers Export

@article{roth07, abstract = {Abstract: By selective placement of fluorescent dyes, we have measured the glass transition temperature (Tg) of individual layers within supported bilayer films of different polymers to determine the extent to which strong free-surface effects and substrate interactions are mediated by a narrow interface between immiscible polymers. We have discovered that the impact a free surface has on Tg within an ultrathin PS layer is extremely sensitive to the polymer species used in the underlayer. The large Tg reduction of \~{}32 K relative to bulk Tg observed for a 14 nm thick surface layer of polystyrene (PS) supported on bulk PS is virtually eliminated when a 14 nm thick surface layer of PS is placed on an underlayer of poly(methyl methacrylate) or poly(2-vinylpyridine) (P2VP), even of bulk thickness. Thus, the cooperative segmental mobility associated with the Tg of the PS free-surface layer is greatly hindered by the narrow, several-nanometer-wide interfacial region formed with the dissimilar polymer underlayer. This indicates that the dynamics of nanoscale layers can be strongly modified by adjacent layers or domains of unlike polymers via propagation of effects across an interfacial layer of cooperatively rearranging regions containing segments of the two immiscible polymers, which has important implications for multilayer films and nanostructured blends. Conversely, the Tg of an ultrathin P2VP film is unaffected by the presence of a PS capping layer, indicating that strong attractive interactions of P2VP with hydroxyl groups on the surface of the silica substrate dominate over a much weaker free-surface effect in P2VP.}, address = {Department of Chemical and Biological Engineering and Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208-3120, and Department of Polymer Materials and Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands}, author = {Roth, C. B. and Mcnerny, K. L. and Jager, W. F. and Torkelson, J. M.}, citeulike-article-id = {1835912}, citeulike-linkout-0 = {http://dx.doi.org/10.1021/ma062864w}, citeulike-linkout-1 = {http://pubs.acs.org/doi/abs/10.1021/ma062864w}, doi = {10.1021/ma062864w}, journal = {Macromolecules}, keywords = {confinement, polymer}, month = {April}, number = {7}, pages = {2568--2574}, posted-at = {2007-10-29 15:23:38}, priority = {2}, title = {Eliminating the Enhanced Mobility at the Free Surface of Polystyrene: Fluorescence Studies of the Glass Transition Temperature in Thin Bilayer Films of Immiscible Polymers}, url = {http://dx.doi.org/10.1021/ma062864w}, volume = {40}, year = {2007} }

TY - JOUR ID - roth07 L3 - citeulike-article-id:1835912 N2 - Abstract: By selective placement of fluorescent dyes, we have measured the glass transition temperature (Tg) of individual layers within supported bilayer films of different polymers to determine the extent to which strong free-surface effects and substrate interactions are mediated by a narrow interface between immiscible polymers. We have discovered that the impact a free surface has on Tg within an ultrathin PS layer is extremely sensitive to the polymer species used in the underlayer. The large Tg reduction of ~32 K relative to bulk Tg observed for a 14 nm thick surface layer of polystyrene (PS) supported on bulk PS is virtually eliminated when a 14 nm thick surface layer of PS is placed on an underlayer of poly(methyl methacrylate) or poly(2-vinylpyridine) (P2VP), even of bulk thickness. Thus, the cooperative segmental mobility associated with the Tg of the PS free-surface layer is greatly hindered by the narrow, several-nanometer-wide interfacial region formed with the dissimilar polymer underlayer. This indicates that the dynamics of nanoscale layers can be strongly modified by adjacent layers or domains of unlike polymers via propagation of effects across an interfacial layer of cooperatively rearranging regions containing segments of the two immiscible polymers, which has important implications for multilayer films and nanostructured blends. Conversely, the Tg of an ultrathin P2VP film is unaffected by the presence of a PS capping layer, indicating that strong attractive interactions of P2VP with hydroxyl groups on the surface of the silica substrate dominate over a much weaker free-surface effect in P2VP. IS - 7 JF - Macromolecules AD - Department of Chemical and Biological Engineering and Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208-3120, and Department of Polymer Materials and Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands EP - 2574 TI - Eliminating the Enhanced Mobility at the Free Surface of Polystyrene: Fluorescence Studies of the Glass Transition Temperature in Thin Bilayer Films of Immiscible Polymers VL - 40 SP - 2568 KW - confinement KW - polymer AU - Roth, CB AU - Mcnerny, KL AU - Jager, WF AU - Torkelson, JM PY - 2007/04/03/ UR - http://dx.doi.org/10.1021/ma062864w ER -