Journal of Polymer Science Part B: Polymer Physics, Vol.47, No.24, 2509-2519, 2009
Streamlined Ellipsometry Procedure for Characterizing Physical Aging Rates of Thin Polymer Films
Existing studies in the research literature showing conflicting changes in physical aging rates with decreasing film thickness in nanoconfined polymer films highlight the need for a single experimental technique to efficiently characterize physical aging rates in thin polymer films of varying chemical structure. To that end, we have developed a streamlined ellipsometry procedure to measure the structural relaxation of thin glassy polymer films. We evaluate different methods of calculating a physical aging rate beta from the measured thickness h(t) and index of refraction n(t) data. We present extensive measurements of beta as a function of aging temperature and aging time for polystyrene (PS) films supported on silicon, and determine that the physical aging rate beta can be easily and reliably determined from beta = -1/h(0) dh/d(log t), where h(0) is the initial measure of the film thickness at an aging time of 10 min. We have also carried out oxygen permeation studies on poly(methyl methacrylate) (PMMA) films from 800 mu m down to 190 nm in thickness, and find no change in the permeability with film thickness or physical aging at room temperature for up to 65 days, which suggests that gas permeation may be insensitive to physical aging in such low free volume polymers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B. Polym Phys 47, 2509-2519, 2009
Keywords:ellipsometry;gas permeation;glass transition;physical aging;poly(methyl methacrylate);polymer thin films;polystyrene;structural relaxation