Kinetics and dynamic properties of equilibrium polymers

The statistical mechanics and scission-recombination mechanism of self-assembling linear micelles are investigated by Brownian dynamics using a newly proposed mesoscopic model representing the micelles as equilibrium polymer chains. A semidilute concentration regime, yet dynamically unentangled, is considered over a wide range of scission/recombination rates. We focus on the analysis of short and long time behaviors of the scission and recombination mechanisms. Our results show that at time scales larger than the life time of the average chain length, the kinetics is in agreement with the mean-field kinetic model proposed by Cates and Candau [J. Phys.: Condens. Matter 2, 6869 (1990)] provided the kinetic constants are estimated as effective ones. These values do take into account through a transmission coefficient that a fraction of scission/recombination events is correlated over a short time (diffusion controlled mechanism) and thus turn out to be ineffective reactive events by annihilation effects. By studying macroscopic relaxation phenomena such as the average micelle length evolution after a T jump, the monomer diffusion, and the zero shear stress relaxation function, we confirm that the effective kinetic constants found are indeed the relevant parameters when macroscopic relaxation is coupled to the kinetics of micelles.