First and Second Concentration-Dependent Coefficients of Translational Diffusion and Sedimentation for Poly(α-methylstyrene) in a Good Solvent

Autor: Taisaku Hashimoto, Yoshisuke Tsunashima, Tateo Nakano
Rok vydání: 1996
Předmět:
Zdroj: Macromolecules. 29:3475-3484
ISSN: 1520-5835
0024-9297
DOI: 10.1021/ma951319k
Popis: The first and second concentration-dependent coefficients of translational diffusion, kD and kD2, and of sedimentation, ks and ks2, for poly(α-methylstyrene) fractions of high molecular weight in benzene at 30 °C were determined by dynamic light scattering and sedimentation velocity measurements. In the molecular weight, Mw, range of 3.76 × 105 ≤ Mw ≤ 6.85 × 106, the first coefficients are positive, as reported previously, but the second are negative, which has not been previously observed. These molecular weight dependences are described by power laws (k ∝ Mwa), but the exponents for kD (0.769) and ks (0.663) and for kD2 (1.54) and ks2 (1.48) are smaller than the predicted values in the good-solvent limit, 0.80 and 1.60, respectively. Expressed in the volume-fraction frame of reference, the coefficients are not constant, which contradicts the hard sphere approximation for swollen chains, and are represented well by universal functions of X, the ratio of the thermodynamic interaction radius derived from t...
Databáze: OpenAIRE