Chain length effects in the excluded volume of polymer chains having a generalized molecular architecture

Abstract

A generalized treatment is presented for computing the coefficient of the first-order perturbation theory for the expansion factor, α_S, in polymers of any chain length, n, and architecture. Results show substantial deviations from the longchain asymptote. Plots between the interpenetration factor, ψ, and α_S³ are different for different values of n, the spread decreasing with branching. It is found that the branching parameter g is insufficient to characterize the excluded volume effect and more detailed, unperturbed segment density distributions are necessary.