Structure and Dynamic Evolution of Interfaces between Polymer Solutions and Gels and Polymer Interdiffusion: A Molecular Dynamics Study (2412.11346v1)

Abstract: Letting free polymers diffuse from solution into a crosslinked polymer gel is often a crucial processing step in the synthesis of multiphase polymer-based gels, e.g., core-shell microgels. Here we use coarse-grained molecular dynamics simulations to obtain molecular insights into this process. We consider idealized situations where the gel is modeled as a regular polymer network with the topology of a diamond lattice, and all free polymers and strands have the same length and consist of the same type of monomer. After bringing the gel and the polymer solution into contact, two time regimes are observed: An initial compression of the gel caused by the osmotic pressure of the solution, followed by an expansion due to swelling. We characterize the time evolution of density profiles, the penetration of free polymers into the gel and the connection between the gel and solution phase. The interfacial structure locally equilibrates after roughly 100 chain relaxation times. At late times, the free chains inside the gel undergo a percolation transition if the polymer concentration in the gel exceeds a critical value, which is of the same order as the overlap concentration. The fluctuations of the interface can be described by a capillary wave model that accounts for the elasticity of the gel. Based on this, we extract the interfacial tension of the gel-solution interface. Interestingly, both the interfacial tension and the local interfacial width increase with increasing free polymer concentration - in contrast to liquid-liquid interfaces, where these two quantities are typically anticorrelated.