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Dynamics of Polystyrene in Confining Geometry: Transition from Dilute to Semidilute

Published online by Cambridge University Press:  15 February 2011

Iwao Teraoka
Affiliation:
Department of Polymer Science and Engineering, University of Massachusetts, Amherst, MA 01003
Kenneth H. Langley
Affiliation:
Department of Physics and Astronomy, University of Massachusetts, Amherst, MA 01003
Frank E. Karasz
Affiliation:
Department of Polymer Science and Engineering, University of Massachusetts, Amherst, MA 01003
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Abstract

Dynamics of polystyrene molecules inside controlled pore glasses, a typical confining geometry, was studied by dynamic light scattering over a wide range of concentrations of polystyrene in solutions in equilibrium with the porous glasses. Index-matching of the solvent to the silica glasses effectively facilitates the acquisition of information on the dynamics of polymer chains inside the pore without compromising that information by multiple light scattering. When the concentration outside the pore is much smaller than the overlap concentration v*, the apparent diffusion coefficient Dporc of polymers within the pore shows little dependence on concentration. As the outside concentration increases and approaches v*, Dporc rapidly increases. This tendency is more pronounced for polystyrene samples that have higher molecular weights and are predicted to have a lower concentration inside the pore. With further increases of concentration beyond v*, Dporc approaches the apparent diffusion coefficient outside the pore. Moreover, Dporc becomes almost the same for the three different molecular weights of polystyrene fractions studied and depends primarily on the weight concentration of the solute outside the pore. These features are typical of a semidilute solution regime for flexible polymers. The rapid increase in Dporc, is ascribed to a drastic increase of the polymer concentration inside the pore, which results from an equilibration of the chemical potential of the polymer molecule between the interior of the pore and the exterior. Thus, a rapid increase in the osmotic pressure outside the pore drives the polymers into pore channels even at the expense of reduced entropy. We present a quantitative analysis of this highly nonlinear partitioning of polymer molecules.

Type
Research Article
Copyright
Copyright © Materials Research Society 1993

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References

[1] Yau, W. W., Kirkland, J. J. and Bly, D. D., in High Performance Liquid Chromatography, Brown, P. R. and Hartwick, R. A., Eds. (John Wiley, New York, 1989), p. 277.Google Scholar
[2] Giddings, J. C., Unified Separation Science (John Wiley, New York, 1991).Google Scholar
[3] Cannell, D. S. and Rondelez, F., Macromolecules 13, 1599 (1980).Google Scholar
[4] Guillot, G., Léger, L. and Rondelez, F., Macromolecules 18, 2531 (1985).Google Scholar
[5] Bohrer, M. P., Patterson, G. D. and Carroll, P. J., Macromolecules 17, 1170 (1984).Google Scholar
[6] Bohrer, M. P., Fetters, L. J., Grizzuti, N., Pearson, D. S. and Tirrell, M. V., Macromolecules 20, 1827 (1987).Google Scholar
[7] Guillot, G., Macromolecules 20, 2600, 2606 (1987).Google Scholar
[8] Davidson, M. G. and Deen, W. M., J. Membr. Sci. 35, 167 (1988).Google Scholar
[9] Davidson, M. G. and Deen, W. M., Macromolecules 21, 3474 (1988).Google Scholar
[10] Bishop, M. T., Langley, K. H. and Karasz, F. E., Phys. Rev. Lett. 57, 1741 (1986), Macromolecules 22, 1220 (1989).Google Scholar
[11] Easwar, N., Langley, K. H. and Karasz, F. E., Macromolecules 23, 738 (1990).Google Scholar
[12] Guo, Y., Langley, K. H. and Karasz, F. E., Macromolecules 23, 2022 (1990).Google Scholar
[13] Guo, Y., Langley, K. H. and Karasz, F. E., Macromolecules 25, 4902 (1992).Google Scholar
[14] Bleha, T., Mlýnek, J. and Berek, D., Polymer. 21, 798 (1980).Google Scholar
[15] Brannon, J. H. and Anderson, J. L., J. Polym. Sci. Polym. Phys. Ed. 20, 857 (1982).Google Scholar
[16] Cifra, P., Bleha, T. and Romanov, A., Polymer 29, 1664 (1988).Google Scholar
[17] Bleha, T., Cifra, P. and Karasz, F. E., Polymer 31, 1321 (1990).Google Scholar
[18] Brochard, F. and de Gennes, P. G., J. Chem. Phys. 67, 52 (1977).Google Scholar
[19] Daoudi, S. and Brochard, F., Macromolecules 11, 751 (1978).Google Scholar
[20] Cloizeaux, J. des and Jannink, G., Polymers in Solution: Their Modelling and Structure (Clarendon Press, Oxford, 1990).Google Scholar
[21] Schmitz, K. S., An Introduction to Dynamic Light Scattering by Macromolecules (Academic Press, San Diego, 1990).Google Scholar
[22] Oono, Y. and Kohmoto, M., J. Chem. Phys. 78, 520 (1983).Google Scholar
[23] Casassa, E. F., J. Polym. Sci. Polym. Lett. Ed. 5, 773 (1967).Google Scholar
[24] Chu, B., Laser Light Scattering (Academic Press, San Diego, 1991).Google Scholar
[25] Provencher, S. W., Makromol. Chem. 180, 201 (1979).Google Scholar
[26] Cloizeaux, J. des, J. Phys. (Paris) 36, 281 (1975).Google Scholar
[27] Daoud, M., Cotton, J. P., Farnoux, B., Jannink, G., Sarma, G., Benoit, H., Duplessix, R., Picot, C. and de Gennes, P. G., Macromolecules 8, 804 (1975).Google Scholar
[28] Ohta, T. and Oono, Y., Phys. Lett. 89A, 460 (1982).Google Scholar
[29] Teraoka, I., Langley, K. H. and Karasz, F. E., Macromolecules, in press.Google Scholar