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The Glassy Amorphous State

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Fundamental Polymer Science

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Abstract

Liquid polymers are transformed into a glass if the chain structure is irregular and the polymer in unable to crystallise, not even at the slowest possible cooling rate, or if the polymer (also being a polymer with a regular structure) is cooled at such a high rate that does not permit crystallisation. The transformation of the liquid to a glass occurs at the glass transition temperature, which is accompanied by a 200 to 1000-fold increase in the Young’s modulus. A comprehensive account is presented for the factors (repeating unit, molecular architecture, plasticizing compounds, etc.) that affect the glass transition temperature. The glass transition is a second order phase transformation, but not in the strict Ehrenfest sense. The glass transition is a kinetic phenomenon and glassy polymers undergo slow structural and property changes approaching equilibrium referred to as physical aging. The gradual approach towards equilibrium in volume and enthalpy is thoroughly described, which also includes the KAHR model. The current theories for the glass transition can be divided into three main groups: free volume, kinetic and equilibrium theories; all three are comprehensively described. Molecular dynamic simulation and related techniques as well as micro-level experimental techniques such as positron annihilation lifetime spectroscopy and neutron scattering have provided further insight about the structure and dynamics of polymer glasses.

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  1. Fibre and Polymer Technology School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, Stockholm, Sweden

    Ulf W. Gedde & Mikael S. Hedenqvist

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Gedde, U.W., Hedenqvist, M.S. (2019). The Glassy Amorphous State. In: Fundamental Polymer Science. Graduate Texts in Physics. Springer, Cham. https://doi.org/10.1007/978-3-030-29794-7_5

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