Langevin dynamics simulation on optimal conditions for large and stable loops of adsorbed homopolymers on substrates.

Adsorption of polymer chains on a solid surface is a universal interfacial behavior. Loops in the adsorbed chains are considered to exert a significant effect on the overall properties of a substrate-supported polymer film via entanglement with non-adsorbed chains in the film. In this work, the size and stability of loops formed by adsorbed homopolymer chains on an attractive substrate were studied by Langevin dynamics simulations. The size of loops decreases while the stability increases with increasing attraction strength of the substrate. In contrast, with an increase in the polymer concentration, the size of loops increases but the stability decreases. However, both the size and stability of loops increase with increasing chain length. Simulation results show that the optimal conditions for forming large and stable loops are long homopolymer chains, substrates with moderate attraction strength, and moderate polymer concentration.

A simulation study on the subdiffusion of polymer chains in crowded environments containing nanoparticles.

Polymer chains in crowded environments often show subdiffusive behavior. We adopt molecular dynamics simulations to study the conditions for the subdiffusion of polymer chains in crowded environments containing randomly distributed, immobile, attractive nanoparticles (NPs). The attraction is strong enough to adsorb polymer chains on NPs. The results show that subdiffusion occurs at a low concentration of polymer chains (cp). A transition from subdiffusion to normal diffusion is observed when cp exceeds the transition concentration , which increases with increasing concentration of NPs while decreases with increasing size of NPs. The high concentration and small size of NPs exert a big effect on the subdiffusion of polymer chains. The subdiffusive behavior of polymer chains can be attributed to the strong adsorption of polymer chains on the attractive NPs. For the subdiffusion case, polymer chains are adsorbed strongly on multiple NPs, and they diffuse via the NP-exchange diffusion mechanism. However for the normal diffusion case, polymer chains are either free or weakly adsorbed on one or a few NPs, and they diffuse mainly via the adsorption-and-desorption diffusion mechanism.

Glass transition and dynamics of semiflexible polymer brushes.

The glass transition and dynamics of densely grafted semiflexible polymer brushes are studied by molecular dynamics simulation. The glass transition temperature (Tg) increases with the polymer rigidity. The local glass transition temperature (Tg,local) is estimated from the temperature-dependent dynamics of individual segments including the lateral position fluctuation and lateral mean square displacement. Different from the flexible polymer brush, Tg,local of semiflexible polymer brushes is roughly independent of the segment height. Our simulation reveals that the glass transition is in synchronism with an abrupt change of the chain conformation in semiflexible polymer brushes. When the temperature drops to near Tg, the semiflexible polymer chains elongate, tilt, and become more ordered. Moreover, enhanced segmental dynamics is observed at temperatures just above Tg for the semiflexible polymer brushes.

Simulation on diffusivity and statistical size of polymer chains in polymer nanocomposites.

The dynamical and conformational properties of polymer chains are affected significantly by strongly attractive nanoparticles. The adsorption of polymer chains on nanoparticles not only reduces the dynamics but also changes the conformation of polymer chains. For orderly distributed nanoparticles of size roughly the same as the radius of gyration of polymer chains, the variation of the diffusivity is highly related to that of the statistical size and can be explained mainly from the adsorption of polymers. In particular, both the polymer's size and diffusivity reach the minimum when the number of polymer chains matches the number of nanoparticles where polymer chains are mostly adsorbed on separate nanoparticles. The behavior of diffusivity can be explained from the cooperation of polymer adsorption and nanoparticle-exchange motion. Adsorption of the polymer chain slows down the diffusion, whereas the nanoparticle-exchange motion accelerates the diffusion of polymer chains.