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Thermally Stimulated Current Studies of Transitions in Amorphous Polymers

  • Chapter
Order in the Amorphous “State” of Polymers

Abstract

Thermally Stimulated Current (TSC) studies allow us to investigate the transition spectra of amorphous polymers. The relaxation modes observed around and above the glass transition (T g ) have common features: (1) The TSC peak isolated around T g corresponds to a distribution of relaxation times following an Arrhenius equation. The width of the distribution characterizes the distribution of the order parameter. (2) The TSC peak observed some 50° above T g is well described by a Fulcher-Vogel equation. This mode, which can also be distributed, has been associated with the dielectric manifestation of the liquid-liquid transition (T ll ).

The influence of several parameters on the transition spectra (molecular weight, chemical structure, and metastability) has been followed.

Influence of Molecular Weight Polyisobutylene has been taken as an example. For samples of molecular weight M w > 9,300, the temperature positions of the TSC peaks associated with T g and T w are practically constant, as in other “non-flow techniques” such as adiabatic or differential scanning calorimetry. Influence of Chemical Structure Poly(cyclohexyl methacrylate) has been chosen as a model. In this case, the analysis of the T u peak shows a significant increase in the thermal expansion coefficient. This result is coherent with thermal expansivity data from Simha et al. It is attributed to the bulkiness of the side group resulting in a larger excluded volume. Influence of Meiastability Metasiability has been induced in polystyrene by applying static pressure or “Rheomolding®.” These treatments are accompanied by a spectacular decrease in the T critical temperature. This evolution is indicative of low temperature mobility.

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Authors and Affiliations

  1. Solomat S.A, Ballainvilliers, 91160, France

    A. Bernes

  2. Michigan Molecular Institute, Midland, Michigan, 48640, USA

    R. F. Boyer

  3. Laboratoire de Physique des Solides, Associe au C.N.R.S., Universite Paul Sabatier, 118 Route de Narbonne, 31062, Toulouse Cedex, France

    D. Chatain & C. Lacabanne

  4. Solomat Corporation, Glenbrook Road, Stamford, Connecticut, 06906, USA

    J. P. Ibar

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  1. Michigan Molecular Institute, 1910 West St. Andrews Road, Midland, Michigan, 48640, USA

    Steven E. Keinath  & Robert L. Miller  & 

  2. Dow Chemical Company, 1702 Building, Midland, Michigan, 48674, USA

    James K. Rieke

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Bernes, A., Boyer, R.F., Chatain, D., Lacabanne, C., Ibar, J.P. (1987). Thermally Stimulated Current Studies of Transitions in Amorphous Polymers. In: Keinath, S.E., Miller, R.L., Rieke, J.K. (eds) Order in the Amorphous “State” of Polymers. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-1867-5_14

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