Determination of chain stiffness and polydispersity from static light-scattering

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Abstract

Chain stiffness is often difficult to distinguish from molecular polydisperity. Both effects cause a downturn of the angular dependence at large q2 (q = (4π/λ)sin θ/2) in a Zimm plot. A quick estimation of polydisperity becomes possible from a bending rod (BR) plot in which lim (c → 0) qRθ/Kc is plotted against q(〈S2z)1/2 = u. Flexible and semiflexible chains show a maximum whose position is shifted from umax = 1.41 for monodisperse chains towards larger values as polydispersity is increased, while simultaneously, the maximum height is lowered. Stiff chains display a constant plateau at large q, its value is πML where ML is the linear mass density. Using Koyama's theory, the number of Kuhn segments can be determined from the ratio of the maximum height to the plateau height, if the polydispersity index z = (Mw/Mn − 1)−1 is known. Thus, if the weight-average molecular weight Mw, is known, the contour length Lw, the number of Kuhn segments (Nk)w, the Kuhn segment length lk and the polydispersity of the stiff chains can be determined. The influence of excluded volume is shown to have no effect on this set of data. The reliability of this set can be cross-checked with the mean-square radius of gyration 〈s2z which can be calculated from the Benoit-Doty equation for polydisperse chains. Rigid and slightly bending rods exhibit no maximum in the BR plot, and the effect of polydispersity can no longer be distinguished from a slight flexibility if only static scattering techniques are applied.

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