Kinetics of phase separation in ramified polymer blends of arbitrary topology

We present here a theoretical study of kinetics of phase separation within a mixture made of two chemically incompatible ramified polymers. For simplicity, we assume that they have the same topology. We are interested in the variation of the relaxation rate, _q, versus the wave number q, in the vicinity of the spinodal temperature. The kinetics is governed by local (Rouse) and reptation motions (faster and slower modes). For qR_G 1 (R_G being the gyration radius), kinetics is entirely controlled by local motions where each chain moves inside its own tube, and we show that the corresponding characteristic frequency, ^{-1}_q, scales as ^{-1}_{q G}q⁶, where _G is a known topological factor. For qR_G 1, however, kinetics is rather dominated by long-wavelength (reptation) motions where unlike ramified polymers creep inside a long tube. For this case, we find that ^{-1}_q ( 0 )q² (_c - ), where ( 0 ) is another known topological factor that represents the total mobility of free monomers belonging to connected chains and reticulation points, and _c accounts for the critical value of the segregation parameter. Finally, the derived relaxation rate must be compared to that relative to a linear polymer mixture.