Understanding and predicting structure–property relations in polymeric materials through molecular simulations

Abstract

The development of computational methods for predicting thermal, mechanical and rheological properties of polymers from chemical constitution calls for hierarchical strategies, which are capable of addressing the broad spectra of length and time scales governing the behaviour of these materials. This paper reviews three recently developed strategies that appear particularly promising: (a) use of connectivity-altering Monte Carlo algorithms for rapid equilibration of atomistic models of long-chain polymer systems and calculation of their structural and thermodynamic properties; (b) mapping of molecular dynamics trajectories onto the Rouse and reptation models for the prediction of linear viscoelastic properties; (c) kinetic Monte Carlo simulations of large network specimens, generated on the basis of self-consistent field theoretical analysis, for tracking large-scale deformation and fracture of polymer–polymer interfaces. How connections can be established between the atomistic, mesoscopic (entanglement network) and macroscopic (continuum) descriptions is discussed. Validations of the simulation results against experiment are presented and questions pertaining to materials design are addressed.

Acknowledgments

I am grateful to my former doctoral students Drs Vagelis Harmandaris, Manolis Doxastakis and Nikos Karayiannis, to my collaborators Drs Vlasis Mavrantzas, Andreas Terzis, Alfred Uhlherr (CSIRO Australia), Alexander Stroeks (DSM Research, The Netherlands) and Christos Tzoumanekas, to Professor Hans Christian Öttinger, Dr Martin Kröger and Dr Jorge Ramírez (ETH Zürich), and to Professor Dimitri Vlassopoulos (U. Crete). Financial support provided by the European Union through the Brite-EuRAM project MPFLOW, the Growth programmes DEFSAM and PERMOD, and the TMR Network NEWRUP, by DSM Research B.V. (Geleen, The Netherlands), and by the General Secretariat of Research and Technology of Greece through the PENED programme (Contracts 218-95 EΔ, 95-96 EΔ) is gratefully acknowledged.