Small-angle neutron scattering and dynamic light scattering have been used to study the thermodynamics of swelling and the associated structure modifications of highly cross-linked temperature-sensitive poly $(N$-isopropylacrylamide) [poly(NIPAM)] microgels in ${\mathrm{D}}_2\mathrm{O}.$ A particle core-shell model is proposed, with the core containing most of the cross-linker molecules. The Flory-Rehner theory, with the inclusion of a concentration dependent Flory solvency parameter, successfully describes the experimental swelling, despite the inhomogeneous character of the particles. Interestingly, the shell evolution with temperature controls the whole particle swelling, exerting an external pressure over the core, which in turn influences its size during the swelling process. Scaling laws for the correlation lengths were found with respect to temperature and polymer concentration. Finally, it has been encountered that for the collapsed microgel states, the particle surface seems to have a fractal character.

• Received 9 April 2002

DOI:https://doi.org/10.1103/PhysRevE.66.051803