Macromolecules, Vol.37, No.23, 8754-8763, 2004
Concentration and solvency effects on the excess amount and surface free energy of a colloidal particle in a solution of nonadsorbing polymer
Analytical expressions are derived for the polymer excess amount and the grand potential (surface free energy) of flat and spherical surfaces immersed in a solution of nonadsorbing polymer chains in the mean-field approximation. We start from a recent mean-field expression for the depletion thickness delta which takes into account not only the effect of the chain length N but also that of the polymer concentration psi(b) and the solvency chi. Simple expressions are obtained for the interfacial properties at a colloidal surface, using both the adsorption method and the osmotic route. For a sphere of radius a, the excess amount can be separated into a planar contribution Gamma = -psi(b)delta and a curvature correction Gamma(c) = -(pi(2)/12)psi(b)delta(c)(2)/alpha, where delta(c) is a "curvature thickness" which is close to (but smaller than) delta. The grand potential has a planar contribution Omega = (2/9)psi(b)/delta and a curvature part Omega(c) = (pi/18)psi(b)/delta. We test the results against numerical lattice computations, taking care that the boundary conditions in the continuum and lattice models are the same. We find good agreement up to a polymer segment volume fraction of 10%, and even for more concentrated solutions our simple model is reasonable. For spherical geometry we propose a new equation for the segment concentration profile which excellently agrees with numerical lattice computations. The results can be used as a starting point for the pair interaction between colloidal particles in a solution containing nonadsorbing chains, which is discussed in the following paper.