Mapping the local osmotic modulus of polymer gels.

Polymer gels undergo volume phase transition in a thermodynamically poor solvent as a result of changes in molecular interactions. The osmotic pressure of gels, both synthetic and biological in nature, induces swelling and imparts the materials with the capacity to resist compressive loads. We have investigated the mechanical and swelling properties of poly(vinyl alcohol) (PVA) gels brought into the unstable state by changing the composition of the solvent. Chemically cross-linked PVA gels were prepared and initially swollen in water at 25 degrees C, and then n-propyl alcohol (nonsolvent) was gradually added to the equilibrium liquid. AFM imaging and force-indentation measurements were made in water/n-propyl alcohol mixtures of different composition. It has been found that the elastic modulus of the gels exhibits simple scaling behavior as a function of the polymer concentration in each solvent mixture over the entire concentration range investigated. The power law exponent n obtained for the concentration dependence of the shear modulus increases from 2.3 (in pure water) to 7.4 (in 35% (v/v) water + 65% (v/v) n-propyl alcohol mixture). In the vicinity of the theta-solvent composition (59% (v/v) water + 41% (v/v) n-propyl alcohol) n approximately 2.9. Shear and osmotic modulus maps of the phase separating gels have been constructed. It is demonstrated that the latter sensitively reflects the changes both in the topography and thermodynamic interactions occurring in the course of volume phase transition.