Studies on mechanical and swelling behavior of polymer networks on the basis of the scaling concept. 6. Gels immersed in polymer solutions

In order to describe the mechanical and swelling behavior of gels immersed in polymer solutions, theoretical considerations based on both classical and scaling theories are discussed and compared with experimental findings. Three situations are studied: (1) the gel is separated from the surrounding solution by a semipermeable membrane; (2) the gel is immersed in the semidilute solution of a chemically identical polymer; (3) the gel is directly immersed in the semidilute solution of a chemically different polymer. An attempt is made to take into account the effect of the penetrating polymer on the elastic modulus and the swelling pressure of the gel. Experimental data referring to chemically cross-linked poly(vinyl alcohol) and poly(vinyl acetate) networks are presented. It was found that the concentration of the free chains inside moderately cross-linked networks may be considerable even for polymers having relatively long chains (27,000 < < M _n < 130,000). Experimental results indicate that the presence of free chains only slightly alters the elastic modulus; however, the swelling pressure is considerably affected by the penetrating polymer. The analysis of mechanical and equilibrium deswelling measurements carried out on several series of gel homologues shows that scaling theory satisfactorily describes the experimental data.