Renormalized one-loop theory of correlations in polymer blends

Abstract

The renormalized one-loop theory is a coarse-grained theory of corrections to the self-consistent field theory (SCFT) of polymer liquids, and to the random phase approximation (RPA) theory of composition fluctuations. We present predictions of corrections to the RPA for the structure function $S(k)$ and to the random walk model of single-chain statics in binary homopolymer blends. We consider an apparent interaction parameter $χ_{a}$ that is defined by applying the RPA to the small $k$ limit of $S(k)$. The predicted deviation of $χ_{a}$ from its long chain limit is proportional to $N^{-1/2}$, where $N$ is chain length. This deviation is positive (i.e., destabilizing) for weakly non-ideal mixtures, with $χ_{a} N \alt 1$, but negative (stabilizing) near the critical point. The positive correction to $χ_{a}$ for low values of $χ_{a} N$ is a result of the fact that monomers in mixtures of shorter chains are slightly less strongly shielded from intermolecular contacts. The depression in $χ_{a}$ near the critical point is a result of long-wavelength composition fluctuations. The one-loop theory predicts a shift in the critical temperature of ${\cal O}(N^{-1/2})$, which is much greater than the predicted ${\cal O}(N^{-1})$ width of the Ginzburg region. Chain dimensions deviate slightly from those of a random walk even in a one-component melt, and contract slightly with increasing $χ_{e}$. Predictions for $S(k)$ and single-chain properties are compared to published lattice Monte Carlo simulations.