Maja Lazar Mihajlovic

Dynamic self-consistent field theory for unentangled homopolymer fluids.

We present a lattice formulation of a dynamic self-consistent field (DSCF) theory that is capable of resolving interfacial structure, dynamics, and rheology in inhomogeneous, compressible melts and blends of unentangled homopolymer chains. The joint probability distribution of all the Kuhn segments in the fluid, interacting with adjacent segments and walls, is approximated by a product of one-body probabilities for free segments interacting solely with an external potential field that is determined self-consistently. The effect of flow on ideal chain conformations is modeled with finitely extensible, nonlinearly elastic dumbbells in the Peterlin approximation, and related to stepping probabilities in a random walk. Free segment and stepping probabilities generate statistical weights for chain conformations in a self-consistent field, and determine local volume fractions of chain segments. Flux balance across unit lattice cells yields mean field transport equations for the evolution of free segment probabilities and of momentum densities on the Kuhn length scale. Diffusive and viscous contributions to the fluxes arise from segmental hops modeled as a Markov process, with transition rates reflecting changes in segmental interaction, kinetic energy, and entropic contributions to the free energy under flow. We apply the DSCF equations to study both transient and steady-state interfacial structure, flow, and rheology in a sheared planar channel containing either a one-component melt or a phase-separated, two-component blend.

Interfacial slip in sheared polymer blends.

We have developed a dynamic self-consistent field theory, without any adjustable parameters, for unentangled polymer blends under shear. Our model accounts for the interaction between polymers, and enables one to compute the evolution of the local rheology, microstructure, and the conformations of the polymer chains under shear self-consistently. We use this model to study the interfacial dynamics in sheared polymer blends and make a quantitative comparison between this model and molecular dynamics simulations. We find good agreement between the two methods.