The internal structure of nanometric microgels in water has been studied as a function of temperature, crosslinker content, and level of deuteration. Small-angle neutron scattering from poly(N-isopropylmethacrylamide) (pNIPMAM, volume phase transition ≈ 44 °C) microgel particles of radius well below 100 nm in D2O has been measured. The intensities have been analyzed with a combination of polymer chain scattering and form-free radial monomer volume fraction profiles defined over spherical shells, taking polydispersity in size of the particles determined by AFM into account. A reverse Monte Carlo optimization using a limited number of parameters was developed to obtain smoothly decaying profiles in agreement with the experimentally scattered intensities. Result are compared to the swelling curve of microgel particles in the temperature range from 15 to 55 °C obtained from photon correlation spectroscopy (PCS). In addition to hydrodynamic radii measured by PCS, our analysis provides direct information about internal water content and gradients, the strongly varying steepness of the density profile at the particle-water interface, the total spatial extension of the particles, and the visibility of chains. The model has also been applied to a variation of the crosslinker content, N,N′-methylenebisacrylamide (BIS), from 5 to 15 mol%, providing insight in the impact of chain architecture and crosslinking on water uptake and on the definition of the polymer-water interface. The model can easily be generalized to arbitrary monomer contents and types, in particular mixtures of hydrogenated and deuterated species, paving the way to detailed studies of monomer distributions inside more complex microgels, in particular core-shell particles.

We study the swelling and shrinking behavior of core-shell microgels adsorbed on silicon wafers. In these systems, the core is made of cross-linked poly(N-isopropylmethacrylamide) and the shell consists of cross-linked poly(N-n-propylacrylamide). In suspension, these particles exhibit an extended linear swelling behavior in the temperature interval between the lower critical solution temperatures of the two polymers. Using ellipsometry and atomic force microscopy, we show that this linear response is also observed in the adsorbed state.