Dynamic Light Scattering and Diffusion of Polymers

The rotational diffusion coefficient Dr of a rodlike polymer in isotropic solutions can be measured by electric, flow, and magnetic birefringence, dynamic light scattering, and dielectric dispersion. However, if the polymer has some flexibility, its internal motion makes it difficult to extract Dr for the end-over-end rotation of the chain from data of these measurements. In other words, Dr can be measured only for nearly rodlike polymers. 

T. Chang, C. C. Han, L. M. Wheeler, and T. P. Lodge. Comparison of diffusion coefficients in ternary polymer solutions measured by dynamic light scattering and forced Rayleigh scattering. Macromolecules, 21 (1988), 1870-1872. 

We have identified three diffusion coefficients. These are the self-translational diffusion coefficient D, cooperative diffusion coefficient Dc, and the coupled diffussion coefficient fly. fl is the cooperative diffusion coefficient in the absence of any electrostatic coupling between polyelectrolyte and other ions in the system, fly is the cooperative diffusion coefficient accounting for the coupling between various ions. For neutral polymers, fly and Dc are identical. Furthermore, we identify fly as the fast diffusion coefficient as measured in dynamic light scattering experiments. The fourth diffusion coefficient is the slow diffusion coefficient fl discussed in the Introduction. A satisfactory theory of flj is not yet available. 

For small chains in solution the translational diffusion significantly contributes to the overall decay of Schain(Q>0- Therefore precise knowledge of the centre of mass diffusion is essential. Combing dynamic light scattering (DLS) and NSE revealed effective collective diffusion coefficients. Measurements at different concentrations showed that up to a polymer volume fraction of 10% no concentration dependence could be detected. All data are well below the overlap volume fraction of (p =0.23. Since no -dependence was seen, the data may be directly compared with the Zimm prediction [6] for dilute solutions ... 

The results obtained by the present mechanical measurements are also consistent with the previous experimental results of the dynamic light scattering studies of the collective diffusion coefficient of gels and the rheological studies of the shear modulus of gels. The studies published by different researchers indicate that the concentration dependence of the collective diffusion constant of the polymer networks of gel and that of the elastic modulus are well represented by the following power law relationships [2, 3, 5]... 

Evanescent wave dynamic light scattering (EWDLS) can be used to study the rapid motion of submicron particles near and on interfaces. Two situations have been studied restricted diffusion of spherical particles moving near an interface, and composition fluctuations of polymers attached to the interface. 

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