Surface enrichment in a miscible polymer blend: An experimental test of self-consistent field and long-wavelength approximation models

Neutron reflectivity (NR) and low-energy forward recoil spectrometry (LE-FRES) were used to study surface enrichment in miscible blends of deuterated polystyrene, d-PS, and poly(styrene-co-4-bromostyrene), PBr0.049S, having a 0.049 mole fraction of 4-bromostyrene units. The d-PS component was found to segregate preferentially to the polymer blend/air interface, whereas no enrichment of either component was detected at the polymer blend/silicon interface. The experimental values of the surface concentration, phi(1), and the surface excess, z*, of d-PS were interpreted using both the theory of Schmidt and Binder (SE) (J. Phys. II (Paris) 1985, 46, 1631) and the self-consistent field (SCF) approach of Genzer et al. (Phys. Rev. E 1994, 50, 2373). Although both SE and SCF models were found to be in good qualitative agreement with the experimentally measured values of phi(1) and z*, we demonstrate that the latter proves to be in better quantitative agreement with the experimental results. Moreover, a comparison of the SE and SCF volume fraction profiles of d-PS revealed that the SCF model described more accurately the experimental profile. We also demonstrated that adding long-range interactions to the surface potential in the SCF model produced just minor changes in the shape of the d-PS profile near the surface.