Temperature-Triggered Gelation of Aqueous Laponite Dispersions Containing a Cationic Poly(N-isopropyl acrylamide) Graft Copolymer

In this work, temperature-triggered gelation of aqueous laponite dispersions containing a cationic poly(N-isopropylacrylamide) (PNIPAm) graft copolymer was investigated. The copolymer used was PDMA(30)(+)-g-(PNIPAm210)(14) [Liu et al. Langmuir 2008, 24, 7099]. DMA(+) is quarternarized N,N-dimethylaminoethyl methacrylate. The presence of small concentrations of laponite enabled temperature-triggered gel formation to occur at low copolymer concentrations (e.g., 1 wt %). Dynamic rheological measurements of the gels showed that they had storage modulus values of up to 400 Pa when the total solid volume fraction (polymer and laponite) was only about 0.02. The storage modulus was dependent on both the temperature and the composition of the dispersion used for preparation. The key component that provided the temperature-triggered gels with their elasticity was found to be self-assembled nanocomposite (NC) sheets. These NC sheets spontaneously formed at room temperature upon addition of laponite to the copolymer solution. The NC sheets had lateral dimensions on the order of hundreds of micrometers and a thickness of a few micrometers. The NC sheets were present within the temperature-triggered gels and formed elastically effective chains. The NC sheets exhibited temperature-triggered contraction with a contraction onset temperature of 27 degrees C. A conceptual model is proposed to qualitatively explain the relationship between gel elasticity and dispersion composition.