Microscopic Mechanisms of Strain Hardening in Glassy Polymers

Vorselaars, B., Lyulin, A. V. and Michels, M. A. J. (2009) Microscopic Mechanisms of Strain Hardening in Glassy Polymers. Macromolecules, 42 (15). pp. 5829-5842. ISSN 0024-9297 doi: 10.1021/ma802709d

Abstract/Summary

The mechanisms underlying the increase in stress for large mechanical strains of a polymer glass, quantified by the strain-hardening modulus, are still poorly understood. In the present paper we aim to elucidate this matter and present new mechanisms. Molecular-dynamics simulations of two polymers with very different strain-hardening moduli (polycarbonate and polystyrene) have been carried out. Nonaffine displacements occur because of steric hindrances and connectivity constraints. We argue that it is not necessary to introduce the concept of entanglements to understand strain hardening, but that hardening is rather coupled with the increase in the rate of nonaffine particle displacements. This rate increases faster for polycarbonate, which has the higher strain-hardening modulus. Also more nonaffine chain stretching is present for polycarbonate. It is shown that the inner distances of such a nonaffinely deformed chain can be well described by the inner distances of the worm-like chain, but with an effective stiffness length (equal to the Kuhn length for an infinite worm-like chain) that increases during deformation. It originates from the finite extensibility of the chain. In this way the increase in nonaffine particle displacement can be understood as resulting from an increase in the effective stiffness length of the perturbed chain during deformation, so that at larger strains a higher rate of plastic events in terms of nonaffine displacement is necessary, causing in turn the observed strain hardening in polymer glasses.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/1735
Item Type	Article
Refereed	Yes
Divisions	Science > School of Mathematical, Physical and Computational Sciences > Department of Mathematics and Statistics
Uncontrolled Keywords	MOLECULAR-DYNAMICS SIMULATION; ANGLE NEUTRON-SCATTERING; CONFORMATIONAL CHARACTERISTICS; PERSISTENCE LENGTH; CHAIN DIMENSIONS; AMORPHOUS POLYCARBONATE; ATACTIC POLYSTYRENE; DEFORMATION; TEMPERATURE; BEHAVIOR
Publisher	American Chemical Society
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