Interfacial diffusion phenomena of cyclic and linear polymers

Diffusion of cyclic and linear polymers at interfaces was studied. Interdiffusion of cyclic polystyrene/cyclic deuterated polystyrene was measured by dynamic secondary ion mass spectroscopy as functions of temperature and molecular weight. Diffusion coefficient of cyclic polystyrene with weight-average molecular weight of 113k is twice as large as that of the corresponding linear one at all the temperatures employed. This result clearly shows that both the linear and cyclic polystyrenes have the same temperature dependence of segmental frictional coefficient. At an iso-free volume condition, diffusion coefficient of cyclic polystyrene is larger than that of the linear one at a given molecular weight. The short-time interdiffusion at an interface of linear polystyrene / linear deuterated polystyrene having different molecular weights was examined by time-resolved neutron reflectivity measurements. The model scattering length density profiles obtained by solving a partial differential equation for the diffusion process were used to analyze the data. The results indicate that even though the molecular weights of both components are larger than the critical molecular weight for entanglement, the initial interfacial broadening of bilayer films with different molecular weight proceeds with asymmetric mobility being inversely proportional to the molecular weight.