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Cooling Rate Dependent Ellipsometry Measurements to Determine the Dynamics of Thin Glassy Films
Published on: January 26, 2016
Can the glass transition in bulk polymers be modeled by percolation picture?
Yaşar Yilmaz1, Demet Kaya, Onder Pekcan
1Department of Physics, Istanbul Technical University, Maslak, 80626 Istanbul, Turkey. yyilmaz@itu.edu.tr
Abstract:
Recent observations (Eur. Phys. J. E 9, 135 (2002)) showed that the vitrification process, which sets in during the linear bulk methyl methacrylate (MMA) polymerization carried out below glass transition temperatures, can be modelled by static percolation picture. To generalize this observation for different kind of bulk linear or crosslinked polymers not enough data are present in the literature. To cover partly this deficit we studied the glass transition of MMA and styrene (Sty) crosslinking copolymerization in varying ratios of MMA and Sty. Both the fluorescence intensity I and the lifetime tau of pyrene (Py) used as a nanosecond in situ fluoroprobe were monitored during the gelation time. Both I and tau increase dramatically as a result of the reduced mobility of the probes trapped in the "glassy" regions, appearing near the glass transition point. The average size of the glassy regions just below, and the strength of the infinite network formed upon the connection of the glassy regions above the glass transition point tg obey power law relations. The data around tg were interpreted on the basis of the percolation theory and we observed that the corresponding exponents gamma and beta give static percolation values independent of the polymer composition.
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