On the interplay between the slowdown of dynamics and the kinetics of aggregation: The case study of a reactive...

Modeling the kinetics of aggregation requires a proper strategy to take into account not only the reactivity of reagents but also the ability they have to diffuse. The lack of direct information about diffusion represents the most serious experimental obstacle to the use of diffusion-corrected mean-field equations, which is usually overcome by using information on the structural relaxation dynamics. A very accurate description of the entire kinetics of aggregation can be made by introducing a single time scale of diffusion, set by the structural relaxation time τ of the system according to ∼τ(ξ), with ξ a fractional exponent. Here, we apply this modeling to the case of a reactive binary mixture made of diglycidyl ether of bisphenol-A and 1,3-phenylenediamine, where the reaction proceeds along an autocatalyic (hydroxyl catalyzed) and a non-catalytic (impurity catalyzed) pathway and find that a very small value of the exponent ξ = 0.27 ± 0.03 is needed to reproduce all the data. Our results help revise some preconceived ideas: contrary to widely held assumptions, we find that (i) the time scale of diffusion neither increases proportionally to the structural relaxation time nor is related to τ by a power law with the same fractional exponent as that relating τ to conductivity; (ii) no direct connection exists between the transition to diffusion-control and the development of a gel network or formation of a glassy phase; and (iii) there is no significant difference in the enthalpy barrier for bond formation in the presence of hydroxyl or other than hydroxyl catalyst groups.