On the structure of poly(N-isopropylacrylamide) microgel particles

This investigation presents a study of the internal structure of poly(NIPAM/xBA) microgel particles (NIPAM and BA are N-isopropylacrylamide and N,N′-methylene bisacrylamide, respectively). In this study, x is the wt % of BA used during microgel synthesis. Two values of x were used to prepare the microgels, 1 and 10. The microgel dispersions were investigated using photon correlation spectroscopy (PCS) and small-angle neutron scattering (SANS). These measurements were made as a function of temperature in the range 30-50 °C. Scattering maxima were observed for the microgels when the dispersion temperatures were less than their volume phase transition temperatures. The SANS data were fitted using a model which consisted of Porod and Ornstein-Zernike form factors. The analysis showed that the macroscopic hydrodynamic diameter of the microgel particles and the submicroscopic mesh size of the network are linearly related. This is the first study to demonstrate affine swelling for poly(NIPAM/xBA) microgels. Furthermore, the mesh size does not appear to be strongly affected by x. The data suggest that the swollen particles have a mostly homogeneous structure, although evidence for a thin, low segment density shell is presented. The study confirms that poly(NIPAM/xBA) microgel particles have a core-shell structure. The shell has an average thickness of ∼20 nm for poly(NIPAM/1BA) particles which appears to be independent of temperature over the range studied. The analysis suggests that the particles contained ∼50 vol % water at 50 °C. The molar mass of the poly(NIPAM/1BA) microgel particles was estimated as 6 × 109 g mol-1.