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Calorimetric evidence for a mobile surface layer in ultrathin polymeric films: poly(2-vinyl pyridine)
Calorimetric evidence for a mobile surface layer in ultrathin polymeric films: poly(2-vinyl pyridine)
Madkour, Sherif; Yin, Huajie; Füllbrandt, Marieke; Schönhals, Andreas
Inst. Chemie
Specific heat spectroscopy was used to study the dynamic glass transition of ultrathin poly(2-vinyl pyridine) films (thicknesses: 405-10 nm). The amplitude and the phase angle of the differential voltage were obtained as a measure of the complex heat capacity. In a traditional data analysis, the dynamic glass transition temperature T-g is estimated from the phase angle. These data showed no thickness dependency on T-g down to 22 nm (error of the measurement of +/- 3 K). A derivative-based method was established, evidencing a decrease in T-g with decreasing thickness up to 7 K, which can be explained by a surface layer. For ultrathin films, data showed broadening at the lower temperature side of the spectra, supporting the existence of a surface layer. Finally, temperature dependence of the heat capacity in the glassy and liquid states changes with film thickness, which can be considered as a confinement effect.
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- This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.