Mechanical Properties of End-crosslinked Entangled Polymer Networks using Sliplink Brownian Dynamics Simulations

Julian Oberdisse (1) , Giovanni Ianniruberto (2) , Francesco Greco (3) , Guiseppe Marrucci (2)

1 LCVN - Laboratoire des colloïdes, verres et nanomatériaux
2 Dipartimento di Ingegneria Chimica
3 Istituto per i Materiali Compositi e Biomedici

The mechanical properties of a polymeric network containing both crosslinks and sliplinks (entanglements) are studied using a multi-chain Brownian dynamics simulation. We coarse-grain at the level of chain segments connecting consecutive nodes (cross- or sliplinks), with particular attention to the Gaussian statistics of the network. Affine displacement of nodes is not imposed: their displacement as well as sliding of monomers through sliplinks is governed by force balances. The simulation results of stress in uniaxial extension and the full stress tensor in simple shear including the (non-zero) second normal stress difference are presented for monodisperse chains with up to 18 entanglements between two crosslinks. The cases of two different force laws of the subchains (Gaussian chains and chains with finite extensibility) for two different numbers of monomers in a subchain (no = 50 and no = 100) are examined. It is shown that the additivity assumption of slip- and crosslink contribution holds for sufficiently long chains with two or more entanglements, and that it can be used to construct the strain response of a network of infinitely long chains. An important consequence is that the contribution of sliplinks to the small-strain shear modulus is about ⅔ of the contribution of a crosslink.

Mots clés: entanglement; network theory; computer modelling

Domaines: Matière Molle [cond-mat.soft]

Julian Oberdisse, Giovanni Ianniruberto, Francesco Greco, Guiseppe Marrucci. Mechanical Properties of End-crosslinked Entangled Polymer Networks using Sliplink Brownian Dynamics Simulations. Rheologica Acta, 2006, 46, pp.95-109. ⟨10.1007/s00397-006-0096-0⟩. ⟨hal-00019328⟩