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Grest, Gary S.

Publications and source records attributed to Grest, Gary S..

Measuring Topological Constraint Relaxation in Ring-Linear Polymer Blends

Polymers are an effective test bed for studying topological constraints in condensed matter due to a wide array of synthetically available chain topologies. When linear and ring polymers are blended together, emergent rheological properties are observed as the blend can be more viscous than either of the individual components. This emergent behavior arises since ring-linear blends can form long-lived topological constraints as the linear polymers thread the ring polymers. Here, in this work, we demonstrate how the Gauss linking integral can be used to efficiently evaluate the relaxation of topological constraints in ring-linear polymer blends. For majority-linear blends, the relaxation rate of topological constraints depends primarily on reptation of the linear polymers, resulting in the diffusive time τ d,R for rings of length N R blended with linear chains of length N l to scale as τ d,R ~ N$^2_R$N$^{3.4}_L$.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

From ionic clusters dynamics to network constraints in ionic polymer solutions

Physical networks formed by ionizable polymers with ionic clusters as crosslinks are controlled by coupled dynamics that transcend from ionic clusters through chain motion to macroscopic response. Here, the coupled dynamics, across length scales, from the ionic clusters to the networks in toluene swollen polystyrene sulfonate networks, were directly correlated, as the electrostatic environment of the physical crosslinks was altered. The multiscale insight is attained by coupling neutron spin echo measurements with molecular dynamics simulations, carried out to times typical of relaxation of polymers in solutions. The experimental dynamic structure factor is in outstanding agreement with the one calculated from computer simulations, as the networks are perturbed by elevating the temperature and changing the electrostatic environment. In toluene, the long-lived clusters remain stable over hundreds of ns across a broad temperature range, while the polymer network remains dynamic. In conclusion, though the size of the clusters changes as the dielectric constant of the solvent is modified through the addition of ethanol, they remain stable but morph, enhancing the polymer chain dynamics.

36 MATERIALS SCIENCE↗

Commensurate states on incommensurate lattices

A simple one-dimensional model related to flux quantization on superconducting networks or charged particles on a substrate is proposed to investigate whether commensurate states can exist on incommensurate lattices. For both periodic and quasi-crystalline patterns, a set of low-energy states is found which is related to decimation symmetry and periodicity. It is suggested that the present quasi-periodic arrays which possess a decimation operation can be generalized to more-dimensional quasi-crystalline systems.

Grest, Gary S.↗