Gelation Impairs Phase Separation and Small Molecule Migration in Polymer Mixtures.

Surface segregation of the low molecular weight component of a polymeric mixture is a ubiquitous phenomenon that leads to degradation of industrial formulations. We report a simultaneous phase separation and surface migration phenomena in oligomer-polymer ( O P ) and oligomer-gel ( O G ) systems following a temperature quench that induces demixing of components. We compute equilibrium and time varying migrant (oligomer) density profiles and wetting layer thickness in these systems using coarse grained molecular dynamics (CGMD) and mesoscale hydrodynamics (MH) simulations. Such multiscale methods quantitatively describe the phenomena over a wide range of length and time scales. We show that surface migration in gel-oligomer systems is significantly reduced on account of network elasticity. Furthermore, the phase separation processes are significantly slowed in gels leading to the modification of the well known Lifshitz-Slyozov-Wagner (LSW) law ℓ ( τ ) ∼ τ 1 / 3 . Our work allows for rational design of polymer/gel-oligomer mixtures with predictable surface segregation characteristics that can be compared against experiments.