Elastic modulus distribution in poly(-isopopylacrylamide) and oligo(ethylene glycol methacrylate)-based microgels studied by AFM.

The spatial elastic modulus distribution of microgel networks in presence and absence of bifunctional crosslinkers is studied by AFM. Thermoresponsive poly(N-isopopylacrylamide) (PNIPAM) and poly(2-(2-methoxyethoxy)ethyl methacrylate-co-oligo(ethylene glycol)methacrylate) (P(MEO2MA-co-OEGMA)) microgels are synthesized via precipitation polymerization above their lower critical solution temperature (LCST). High-resolution elastic modulus profiles are acquired using AFM force-indentation mapping of surface-deposited microgels at 25 °C. For both microgel systems, the use of a bifunctional crosslinker leads to a strong elastic modulus gradient with stiff microgel cores and soft networks toward the edge. In absence of a dedicated crosslinker (self-crosslinking), PNIPAM microgels show a homogeneous elastic modulus distribution, whereas self-crosslinked P(MEO2MA-co-OEGMA) microgels still show decreasing elastic moduli from the centre to the edge of the microgels. However, POEGMA microgels without comonomer showed no elastic modulus gradient suggesting that different incorporation rates of MEO2MA and OEGMA result in a radial variation of the polymer segment density. In addition, when varying the molecular weight of OEGMA the overall elastic modulus was affected, possibly due to molecular weight-dependent phase behavior and different reactivity. This shows that quite different microgel architectures can be obtained by the simple "one-pot" precipitation reaction of microgels which may open to new avenues toward advanced applications.