Influence of polymer architecture and polymer-wall interaction on the adsorption of polymers into a slit-pore.
The effects of molecular topology and polymer-surface interaction on the properties of isolated polymer chains trapped in a slit were investigated using off-lattice Monte Carlo simulations. Various methods were implemented to allow efficient simulation of molecular structure, confinement force, and free energy for a chain interacting with such "sticky" surfaces. The simulations were performed in the canonical ensemble, and the free energy was sampled via virtual slit-separation moves. Six different chain architectures were studied: linear, star-branched, dendritic, cyclic, two-node (i.e., containing two tetrafunctional intramolecular crosslinks), and six-node molecules. The first three topologies entail increasing degrees of branching, and the last three topologies entail increasing degrees of intramolecular bonding. The confinement force, monomer density profile, and conformational properties for all these systems were compared (for identical molecular weight N) and analyzed as a function of adsorption strength. The compensation point where the wall attraction counterbalances the polymer-slit exclusion effects was the focus of our study. It was found that the attractive energy at the compensation point, epsilon(c), is a weak increasing function of the chain length for excluded-volume chains. The value of epsilon(c) differs significantly for different topologies, and smaller values are associated with better-adsorbing molecules. Due to their globular shape and numerous chain ends, branched molecules (e.g., stars and dendrimers) experience a relatively small entropic penalty for adsorption at low adsorption force and moderate confinement. However, as the adsorption force increases, the more flexible linear chains reach the compensation point at a weaker attractive energy because of the ease with which monomers can be packed near the walls. In moderate to weak confinement, molecules with intramolecular cross-links, such as cyclic, two-node, and six-node molecules, always adsorb better than the other chains (with the same N). Especially at strong adsorption, two-node and six node molecules are highly localized in the region near the walls. Under strong confinement conditions, chain rigidity becomes the dominating factor and the more flexible linear chain adsorbs the best at all adsorption strengths. These results provide useful insights for controlling confinement and depletion forces of polymers with different molecular architectures in the presence of attractive polymer-surface interactions.
School of Chemical Engineering, Cornell University, Ithaca, New York, 14850-5201, USA.
Zhong
Z
Chen
Fernando A
FA
Escobedo
D000327:Adsorption; D003198:Computer Simulation; D004735:Energy Transfer; D046911:Macromolecular Substances; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D011108:Polymers / Q000737:chemistry*; D016062:Porosity; D013499:Surface Properties
D046911:Macromolecular Substances; D011108:Polymers