phase instability and molecular kinetics provoked by repeated crossing of the demixing transition of PNIPAM solutions

The demixing process of aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions can occur either via a nucleation and growth process or via spinodal decomposition. The ensuing self-assembly, leading to heterogeneous morphologies within the PNIPAM solution, is codetermined by kinetic processes caused by molecular transport. By subjecting PNIPAM solutions to cyclic changes in temperature leading to repeated crossing of the demixing transition, we are able to assess the importance of kinetics as well as of overheating and supercooling of the phase transition within the metastable range delimited by the binodal and spinodal lines. First indications about the location of these stability limits for the low- and high-temperature phases, separated by about 1.6 K, could be gained by detailed kinetic studies of the refractive index. These investigations are made possible due to the novel technique of temperature-modulated optical refractometry.