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Segmental Dynamics In Poly(Methyl Acrylate) On Silica: Molecular-Mass Effects, Burak Metin, Frank D. Blum
Segmental Dynamics In Poly(Methyl Acrylate) On Silica: Molecular-Mass Effects, Burak Metin, Frank D. Blum
Chemistry Faculty Research & Creative Works
The effect of molecular mass on the segmental dynamics of poly(methyl acrylate) (PMA) adsorbed on silica was studied using deuterium quadrupole-echo nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry. Samples adsorbed on silica (all about 1.5 mg PMA/m2 silica) were shown to have more restricted segmental mobility, and higher Tg's, than the corresponding bulk PMA samples. Around the glass-transition region, adsorbed samples exhibited segmental mobility, which could be classified as heterogeneous due to a superposition of more-mobile and less-mobile components present in the deuterium NMR spectra. This heterogeneity was consistent with a motional gradient with more-mobile segments near the …
Dynamics Of Adsorbed Poly(Methyl Acrylate) And Poly(Methyl Methacrylate) On Silica, Frank D. Blum, Wuu-Yung Lin, Crystal E. Porter
Dynamics Of Adsorbed Poly(Methyl Acrylate) And Poly(Methyl Methacrylate) On Silica, Frank D. Blum, Wuu-Yung Lin, Crystal E. Porter
Chemistry Faculty Research & Creative Works
Deuterium NMR and modulated differential scanning calorimetry (MDSC) were used to probe the behavior of ultrathin adsorbed poly(methyl acrylate) (PMA). The spectra for the bulk methyl-labeled PMA-d3 were consistent with the motions of the polymer segments being spatially homogeneous. For the polymers adsorbed on silica, multicomponent line shapes were observed. The segmental mobility of the surface polymers increased with increased adsorbed amounts. In contrast to the behavior of the polymers in bulk, the adsorbed lower-molecular-mass PMA-d3 was less mobile than the adsorbed high-molecular-mass polymer. The presence of a polymer overlayer was sufficient to suppress the enhanced mobility of the more-mobile …