Nanoscale mechanics of microgel particles

Microgel particles are highly tuneable materials that are useful for a wide range of industrial applications, such as drug delivery, sensing, nanoactuation, emulsion stabilisation and use as cell substrates. Microgels have also been used as model systems investigating physical phenomena such as crystallization, glass-formation, jamming, ageing and complex flow behaviour. The responsiveness of microgel systems such as poly(N-isopropylacrylamide) (PNIPAm) to external stimuli has been established in fundamental investigations and in applications and recent work has begun to quantify the mechanics of individual particles. However little focus has been placed on determining their internal mechanical properties, which is likely to relate to their nonuniform internal structure. In this work we combine atomic force microscopy, force spectroscopy and dynamic light scattering to mechanically profile the internal structure of microgel particles in the size range of ∼100 nm, which is commonly used both in practical applications and in fundamental studies. Nanoindentation using thermally stable cantilevers allows us to determine the particle moduli and the deformation profiles during particle compression with increasing force, while peak force nanomechanical mapping (PF-QNM) AFM is used to capture high resolution images of the particles' mechanical response. Combining these approaches with dynamic light scattering allows a quantitative profile of the particles' internal elastic response to be determined. Our results provide clear evidence for a radial distribution in particle mechanical response with a softer outer "corona" and a stiffer particle core. We determine the particle moduli in the core and corona, using different force microscopy approaches, and find them to vary systematically both in the core (∼17-50 kPa) and at the outer periphery of the particles (∼3-40 kPa). Importantly, we find that highly crosslinked particles have equivalent moduli across their radial profile, reflecting their significantly lower radial heterogeneity. This ability to accurately and precisely probe microgel radial profiles has clear implications both for fundamental science and for industrial applications.