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Atomistic Simulation Of Energetic And Entropic Elasticity In Short-Chain Polyethylenes, David Keffer, T. C. Ionescu, V. G. Mavrantzas, B. J. Edwards

David Keffer

The thermodynamical aspects of polymeric liquids subjected to uniaxial elongational flow are examined using atomistically detailed nonequilibrium Monte Carlo simulations. In particular, attention is paid to the energetic effects, in addition to the entropic ones, which occur under conditions of extreme deformation. Atomistic nonequilibrium Monte Carlo simulations of linear polyethylene systems, ranging in molecular length from C₂₄ to C₇₈ and for temperatures from 300 to 450 K, demonstrate clear contributions of energetic effects to the elasticity of the system. These are manifested in a conformationally dependent heat capacity, which is significant under large deformations. Violations of the hypothesis …