Diffusion of polystyrene in controlled pore glasses: Transition from the dilute to the semidilute regime

Iwao Teraoka, Kenneth H. Langley, Frank E. Karasz

Research output: Contribution to journalArticle

Abstract

The diffusion of polystyrene molecules inside controlled pore glasses with inert pore walls was investigated by the technique of dynamic light scattering over a wide range of concentrations of dissolved polystyrene in solutions in equilibrium with the porous glasses immersed in them. Index-matching of the solvent to the silica glasses effectively facilitates the acquisition of information on the dynamics of polymer chains inside the pore network without being compromised by multiple scattering of photons. When the solute concentration outside the pore is much smaller than the overlap concentration v*, the apparent diffusion coefficient Dpore of polymers within the pore shows little dependence on concentration, a result indicating the realization of a well-defined dilute regime inside the pore. As the outside concentration increases and approaches vz.ast;, Dpore rapidly increases. This tendency is more pronounced for polystyrene samples that have higher molecular weights and are predicted to have a lower partition coefficient and hence a lower concentration inside the pore. With further increases of concentration beyond v*, Dpore approaches the apparent diffusion coefficient outside the pore. Moreover, Dpore 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 characterized by a correlation length ξ for monomer concentration fluctuations. The value of ξ calculated from Dpore is much smaller than the pore radius. The rapid increase in the diffusion coefficient 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, when the concentration exceeds v*, the osmotic pressure outside the pore increases rapidly and hence the chain tends to be squeezed into a pore even at the expense of reduced entropy. We present a quantitative analysis of this highly nonlinear partitioning of polymer molecules.

Original languageEnglish (US)
Pages (from-to)287-297
Number of pages11
JournalMacromolecules
Volume26
Issue number2
StatePublished - 1993

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Polystyrenes
Glass transition
Polymers
Molecules
Molecular weight
Glass
Multiple scattering
Chemical potential
Dynamic light scattering
Fused silica
Entropy
Photons
Monomers
Chemical analysis

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Diffusion of polystyrene in controlled pore glasses : Transition from the dilute to the semidilute regime. / Teraoka, Iwao; Langley, Kenneth H.; Karasz, Frank E.

In: Macromolecules, Vol. 26, No. 2, 1993, p. 287-297.

Research output: Contribution to journalArticle

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