Liquid‐like structure of polymer solutions near the overlap concentration

The light scattering structure factor S(q, c) has been measured for a series of concentrations near the overlap value c* for solutions of high molecular weight poly(α-methyl styrene) in the good solvent toluene. Scattering functions near and above overlap are characterized by a maximum as a function of scattering vector q. Scattering functions have also been calculated for these conditions using the measured second virial coefficientand radiusof gyration, as reported previously for dilute solutions. The scattering function is factored into an intramolecular part that is described by a Debye functionwith no adjustable parameters and an intermolecular part that depends on the coil–coilpair correlation function, as suggested by Flory and Bueche. The pair correlation function is calculated using the Percus–Yevick theory of liquids and the Flory–Krigbaum potential for coil–coilinteractions, as suggested by Frank Stillinger. Good agreement is obtained for the most concentrated dilute solutions, but as the overlap concentration is approached significant discrepancies are observed. The thermodynamic value of the scattering function, S(0, c), is overestimated by the theory. This discrepancy is discussed in terms of the importance of three-body interactions, the failure of the Flory–Krigbaum potential in semidilute solutions and the limited precision of the standard protocol for calculating the measured scattering function in nondilute solutions. The observed maximum in the scattering function near overlap is not quantitatively reproduced by the theory. This discrepancy is discussed in terms of the failure of the shape of the Flory–Krigbaum potential to accurately reflect the energy of overlap for chains separated by distances near twice the radiusof gyration. The mean-field nature of the potential ignores the increased probability of interactions of linear neighboring segments. Well into the overlap region, the calculated scattering function poorly describes the observed results. The failure of the Flory–Bueche approximation in semidilute solutions is discussed as well as the effect of a changing radiusof gyrationas a function of concentration on the intramolecular scattering function. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 703–710, 2006