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Nonlinear optical spectroscopic studies of polymer surface properties and competition adsorption of toluene and heptane on silica surfaces Hua, Rui

Abstract

Surface properties of polymers and competition adsorption of toluene and heptane on silica were studied using IR-visible sum frequency generation (SFG) vibrational spectroscopy. SFG is intrinsically surface sensitive because the second-order optical process is forbidden in media with inversion symmetry, such as bulk polymers and liquids. This nonlinear optical technique provides surface vibrational spectra under ambient conditions without the need of an ultra-high vacuum environment. Polymer surface properties, including surface relaxation temperature of poly(methyl methacrylate) (PMMA) and surface electronic states of poly[2-methoxy, 5-ethyl (2’-hexyloxy) para phenylenevinylene] (MEH-PPV), were investigated. It was found that there are significant differences between the surface and bulk properties for these polymers. For PMMA, a new surface structure relaxation was identified at 67°C, which does not match any known structure relaxation temperatures for bulk PMMA and is 40°C below the bulk glass transition temperature. For MEH-PPV, SFG electronic spectra, which were obtained by scanning the frequencies of incident visible and JR beams, indicated that the electronic states at the polymer/solid and air/polymer interfaces are red-shifted with respect to that of the bulk. Finally, SFG was employed to study the competition adsorption of toluene and heptane on silica surfaces. Experimental data showed that heptane adsorbed favorably compared to toluene. Using a Langmuir adsorption isotherm, the changes of Gibbs free energy for the adsorption processes were calculated to be —12.1 ± 1.8 (kJ/mol) for toluene and —16.5 ± 2.3 (kJ/mol) for heptane.

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Attribution-NonCommercial-NoDerivatives 4.0 International

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