Phase transitions in polymer blends and block copolymer melts: Some recent developments

Abstract

The classical concepts about unmixing of polymer blends (Flory-Huggins theory) and about mesophase ordering in block copolymers (Leibler's theory) are briefly reviewed and their validity is discussed in the light of recent experiments, computer simulations and other theoretical concepts. It is emphasized that close to the critical point of unmixing non-classical critical exponents of the Ising universality class are observed, in contrast to the classical mean-field exponents implied by the Flory-Huggins theory. The temperature range of this non-mean-field behavior can be understood by Ginzburg criteria. The latter are also useful to discuss the conditions under which the linearized (Cahn-like) theory of spinodal decomposition holds. While Flory-Huggins theory predicts correctly that the critical value of the Flory χ-parameter scales with chain length N (for symmetrical mixtures) χc ∝ 1/N, it strongly overestimates the prefactor and its use for fitting experimental data yields spurious concentration dependence. Also the chain radii depend on both χ and the composition of the mixture, thus invalidating the random phase approximation (RPA). Particular strong deviations from the RPA are predicted for block copolymer melts, where chains may stretch out in a dumbbell-like shape even in the disordered phase, before the microphase separation transition is approached. This review concludes with an outlook on interfacial phenomena and surface effects on these systems and other open problems in this field.