Calorimetric evidence for a mobile surface layer in ultrathin polymeric films: poly(2-vinyl pyridine)

Soft Matter
Sherif MadkourAndreas Schönhals

Abstract

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 Tg is estimated from the phase angle. These data showed no thickness dependency on Tg down to 22 nm (error of the measurement of ±3 K). A derivative-based method was established, evidencing a decrease in Tg 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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Citations

Aug 25, 2016·The Journal of Physical Chemistry. B·Meinong ShiYumei Ding
Dec 13, 2016·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Xiaoxia Guo, Kongshuang Zhao
Feb 22, 2018·The Journal of Physical Chemistry Letters·Wojciech OgiegloNieck E Benes
Oct 7, 2017·ACS Applied Materials & Interfaces·Sherif MadkourAndreas Schönhals
Mar 13, 2018·Langmuir : the ACS Journal of Surfaces and Colloids·Naisheng JiangMesfin Tsige
Jan 3, 2020·The Journal of Physical Chemistry. B·Pavel PleskunovAndrei Choukourov
Dec 15, 2020·The Journal of Physical Chemistry Letters·Emmanuel Urandu MapesaJoshua Sangoro

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