Wenlin Zhang

Predicting the Flory-Huggins χ Parameter for Polymers with Stiffness Mismatch from Molecular Dynamics Simulations

The Flory–Huggins χ parameter describes the excess free energy of mixing and governs phase behavior for polymer blends and block copolymers. For chemically-distinct nonpolar polymers, the value of χ is dominated by the mismatch in cohesive energy densities of the monomers. For blends of chemically-similar polymers, the entropic portion of χ, arising from non-ideal local packing, becomes more significant. Using polymer field theory, Fredrickson et al. predicted that a difference in backbone stiffness can result in a positive χ for chains consisting of chemically-identical monomers. To quantitatively investigate this phenomenon, we perform molecular dynamic (MD) simulations for bead-spring chains, which differ only in stiffness. From the simulations, we apply a novel thermodynamic integration to extract χ as low as 10-4 per monomer for blends with stiffness mismatch. To compare with experiments, we introduce a standardized effective monomer to map real polymers onto our bead-spring chains. The predicted χ agrees well with experimental values for a wide variety of pairs of chemically-similar polymers.

Predicting Flory-Huggins χ from Simulations

We introduce a method, based on a novel thermodynamic integration scheme, to extract the Flory-Huggins χ parameter as small as 10^{-3}kT for polymer blends from molecular dynamics (MD) simulations. We obtain χ for the archetypical coarse-grained model of nonpolar polymer blends: flexible bead-spring chains with different Lennard-Jones interactions between A and B monomers. Using these χ values and a lattice version of self-consistent field theory (SCFT), we predict the shape of planar interfaces for phase-separated binary blends. Our SCFT results agree with MD simulations, validating both the predicted χ values and our thermodynamic integration method. Combined with atomistic simulations, our method can be applied to predict χ for new polymers from their chemical structures.

Nematic Order Imposes Molecular Weight Effect on Charge Transport in Conjugated Polymers

Nematic order, in the bulk or at interfaces, is ubiquitous for semiflexible conjugated polymers. Nevertheless, the effect of liquid crystalline order on charge transport remains unclear. Using an analytical model, we demonstrate that nematic order leads to an enhancement in charge mobilities when compared to isotropic chains. Furthermore, we predict a quadratic dependence of the charge mobility on molecular weight of the chains. Analysis of the probability of forming hairpin defects also shows how the persistence length affects charge transport in conjugated polymers. We speculate that the prevalence of nematic order in conjugated polymers explains the reported increase in charge mobilities with molecular weight.