Entropic segregation of short polymers to the surface of a polydisperse melt.

Chain ends are known to have an entropic preference for the surface of a polymer melt, which in turn is expected to cause the short chains of a polydisperse melt to segregate to the surface. Here, we examine this entropic segregation for a bidisperse melt of short and long polymers, using self-consistent field theory (SCFT). The individual polymers are modeled by discrete monomers connected by freely-jointed bonds of statistical length a , and the field is adjusted so as to produce a specified surface profile of width [Formula: see text]. Semi-analytical expressions for the excess concentration of short polymers, [Formula: see text], the integrated excess, [Formula: see text] , and the entropic effect on the surface tension, [Formula: see text], are derived and tested against the numerical SCFT. The expressions exhibit universal dependences on the molecular-weight distribution with model-dependent coefficients. In general, the coefficients have to be evaluated numerically, but they can be approximated analytically once [Formula: see text]. We illustrate how this can be used to derive a simple expression for the interfacial tension between immiscible A- and B-type polydisperse homopolymers.