Journal of Polymer Science: Part B: Polymer Physics
We studied translational diffusion of dilute monodisperse spheres (diameters 14 < d < 455 nm) in aqueous 1 MDa hydroxypropylcellulose (0 ≤ c ≤ 7 g/L) at 25°C using quasielastic light scattering. Spectra are highly bimodal. The two spectral modes (“slow,” “fast”) have different physical properties. Probe behavior differs between small (d < Rh) and large (d ≥ Rg) probes; Rh and Rg are the matrix polymer hydrodynamic radius and the radius of gyration, respectively. We examined the dependences of spectral lineshape parameters on d, c, scattering vector q, and viscosity η for all four probe-size and mode-type combinations. We find three time scale-separated modes: (1) a large-probe slow mode has properties characteristic of particle motion in a viscous medium; (2) a large-probe fast mode and small-probe slow modes share the same time scale, and have properties characteristic of probe motion coupled to internal chain dynamics; and (3) a small-probe fast mode has properties that can be attributed to the probe sampling local chain relaxations. In the analysis, we also attempted to apply the coupling/scaling (CS) model of Ngai and Phillies [Ngai, K. L., Phillies, G. D. J. J. Chem. Phys.,105, 8385 (1996)] to analyze our data. We find that the second mode is described by the coupling/scaling model for probe diffusion; the first and third modes do not follow the predictions of this model.
Streletzky, Kiril A. and Phillies, George D.J., "Relaxational Mode Structure for Optical Probe Diffusion in High Molecular Weight Hydroxypropylcellulose" (1998). Physics Faculty Publications. 261.
This is the accepted version of the following article: Kiril A. Streletzky and George D. J. Phillies, "Relaxational mode structure for optical probe diffusion in high molecular weight hydroxypropylcellulose," Journal of Polymer Science Part B: Polymer Physics 36 (17), 3087-3100 (1998). , which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/(SICI)1099-0488(199812)36:17%3C3087::AID-POLB9%3E3.0.CO;2-2/pdf