0000000000496570
AUTHOR
Mathieu Solar
The dielectric α -relaxation in polymer films: A comparison between experiments and atomistic simulations
The question of whether the glass transition temperature in thin polymer films depends on the film thickness or not has given rise to heated debate for almost two decades now. One of the most puzzling findings is the seemingly universal thickness independence of the dielectric α-relaxation observed for supported films. It is puzzling not only in view of the fact that other techniques or other geometries sometimes showed a significant shift of as a function of film thickness, but more so, because computer simulations for all types of polymer film models revealed changes in the structure and dynamics close to a hard surface or a free surface. Our results suggest to explain this apparent contr…
Dielectric Relaxation of a Polybutadiene Melt at a Crystalline Graphite Surface: Atomistic Molecular Dynamics Simulations
Dielectric experiments are an indispensable tool to further our understanding of the relaxation behavior of polymers, not only in bulk samples but also in confined situations. A chemically realistic Molecular Dynamics simulation, in which all information about molecular motions is available, can shed light onto the questions of heterogeneity and anisotropy of the underlying molecular relaxation processes which lead to the ensemble averaged experimental dielectric signal. In this contribution, we present a careful analysis of the dielectric response of a weakly polar and confined polymer, 1,4-polybutadiene between graphite walls. The relaxation of the segmental dipole moments was obtained in…
Polymer Dynamics in a Polymer-Solid Interphase: Molecular Dynamics Simulations of 1,4-Polybutadiene At a Graphite Surface
A chemically realistic model of 1,4-polybutadiene confined by graphite walls in a thin film geometry was studied by molecular dynamics simulations. The chemically realistic approach allows for a quantitative determination of a variety of experimentally accessible relaxation functions (e.g., dielectric, NMR, or neutron scattering responses). The simulations yield these experimental observables. Additionally, the simulations can be resolved as a function of distance to the solid interface on a much finer scale than experimentally possible, providing a detailed mechanistic picture of the segmental and large scale motions of polymers in the interfacial region between bulk polymer melts and soli…