화학공학소재연구정보센터
Polymer, Vol.105, 64-71, 2016
Size-dependent elastic modulus of ultrathin polymer films in glassy and rubbery states
The stiffness-related properties of glassy and rubbery polymer films can behave differently when confined at the nanometer scale. However, direct measurements of the glassy and rubbery modulus of nanometer-sized polymer films are still limited and the existing models for explaining the thickness dependence of the polymer modulus remain in significant disagreement. By means of nanomechanical mapping with an atomic force microscopy, we report a direct measurement of the glassy and rubbery modulus of nanometer-sized poly(vinyl acetate) (PVAc) films supported by substrates of different moduli: Si and poly(vinyl alcohol). At similar to 15 degrees C below the bulk PVAc glass transition temperature (T-g), the modulus of PVAc films is found to be independent of the thickness as thin as similar to 10 nm. In contrast, the modulus of rubbery films measured at similar to 20 degrees C above the T-g significantly increases when the film thickness is reduced to less than 100 nm, irrespective of the substrate modulus. Such an increase becomes more dramatic near the rubbery plateau regime of PVAc films. Among existing models, we demonstrate that the theoretical framework suggesting an increasing separation between the a-relaxation, sub-Rouse modes and Rouse modes induced by nanoconfinement is more appropriate when describing our experimental observation. (C) 2016 Elsevier Ltd. All rights reserved.