"Relaxational Mode Structure for Optical Probe Diffusion in High Molecu" by Kiril A. Streletzky and George D.J. Phillies
 

Document Type

Article

Publication Date

12-1-1998

Publication Title

Journal of Polymer Science: Part B: Polymer Physics

Abstract

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.

Comments

The partial support of this work by the National Science Foundation under Grant DMR94-23702 is gratefully acknowledged.

DOI

10.1002/(SICI)1099-0488(199812)36:17<3087::AID-POLB9>3.0.CO;2-2

Version

Postprint

Volume

36

Issue

17

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