Journal of Chemical Physics, Vol.113, No.17, 7640-7645, 2000
Effects of mechanical stress on the volume phase transition of poly(N-isopropylacrylamide) based polymer gels
The effects of mechanical stress on the volume phase transition of a poly(N-isopropylacrylamide) (PNIPA) gel as well as a copolymer gel composed of N-isopropylacrylamide (NIPA) and sodium acrylate (SA) were investigated in the relatively low stress region. The PNIPA gel without elongational stress showed the behavior close to the second order phase transition. The character of the first order transition became clear under tension, and the transition temperature increased with increasing applied stress. Similar behavior was observed for the NIPA-SA copolymer gel, but the copolymer gel showed the first order transition in the whole stress range investigated. The thermodynamical linear region, where the transition temperature varies linearly with applied stress, was narrower than the mechanical linear region determined by the stress-strain relation of the gels. The change in the transition behavior by the application of the mechanical stress originated chiefly from the volume change in the gels by the applied mechanical stress. It was found that the curve of the transition temperature against applied stress corresponds to the phase boundary between the swollen and collapsed phases for the gels. On the basis of the experimental data, a phenomenological model describing the volume phase transition of the polymer gels is proposed in the frame of the Landau-type free energy expression.