Ap. Chatterjee et Ks. Schweizer, Influence of solvent quality and thermal fluctuations on polymer-mediated depletion interactions, MACROMOLEC, 32(3), 1999, pp. 923-934
Analytic integral equation theory for treating athermal mixtures of hard sp
heres and polymers is extended to study thermal interaction and solvent dua
lity effects in suspensions of infinitely dilute spherical particles in dil
ute and semidilute polymer solutions. Our approach applies to all sphere/ p
olymer size ratios, and polymer-polymer segmental attractive interactions a
re included using both liquid state and Flory-Huggins theory. The effect of
such thermal interactions on the polymer-induced depletion potential betwe
en hard spheres is studied with emphasis on the sphere-sphere second virial
coefficient and the free energy of particle insertion. Strong enhancement
of the purely entropic attractive depletion interaction is found in the pro
ximity of the polymer-solvent critical demixing point. The magnitude of thi
s effect and the distance from the Theta temperature where it becomes impor
tant are sensitive to system specific factors.