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31. |
Colloid-induced polymer compression A. R. Denton and M. Schmidt, J. Phys.: Condens. Matt. 14, 12051 (2002). Locate in [bare] [illustrated] list. Get [full paper] as pdf. Abstract. We consider a model mixture of hard colloidal spheres and nonadsorbing polymer chains in a theta solvent. The polymer component is modelled as a polydisperse mixture of effective spheres, mutually noninteracting but excluded from the colloids, with radii that are free to adjust to allow for colloid-induced compression. We investigate the bulk fluid demixing behaviour of this model system using a geometry-based density functional theory that includes the polymer size polydispersity and configurational free energy, obtained from the exact radius-of-gyration distribution for an ideal (random-walk) chain. Free energies are computed by minimizing the free energy functional with respect to the polymer size distribution. With increasing colloid concentration and polymer-to-colloid size ratio, colloidal confinement is found to increasingly compress the polymers. Correspondingly, the demixing fluid binodal shifts, compared to the incompressible-polymer binodal, to higher polymer densities on the colloid-rich branch, stabilizing the mixed phase. [figures] Read the [full paper] as pdf. |