Role of microgel stiffness in particle self-assembly and suspension rheology across the lower consolute solution temperature

Abstract: We synthesize thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) colloidal microgel particles of different stiffnesses by controlling the concentration of crosslinker in a one-pot synthesis method. We employ oscillatory rheology and cryogenic scanning electron microscopy to study the temperature and stiffness-induced mechanical properties and microscopic structures of dense aqueous suspensions of the synthesized PNIPAM microgels. Using Fourier transform infrared (FTIR) spectroscopy, we show that particle hydrophobicity increases with increasing suspension temperature and decreasing particle stiffness. Our zeta potential measurements of soft PNIPAM particles and those of intermediate stiffnesses demonstrate that these particles are electrostatically unstable and prone to aggregation even at temperatures below the lower consolute solution temperature (LCST). In contrast, stiff PNIPAM particles in dilute aqueous suspensions are electrostatically stabilized at all temperatures explored in this study. Interestingly, our frequency and strain amplitude sweep rheology experiments reveal that the linear viscoelastic moduli and yield stresses of all the PNIPAM suspensions increase when the temperature is raised above the LCST. Combining cryogenic scanning electron microscopy (cryo-SEM) and rheology, we demonstrate that dense suspensions of soft PNIPAM microgels show a gel-liquid-gel transition with increase in temperature across the LCST. Suspensions of stiff particles, in contrast, exhibit a glass-glass transition under the same temperature sweep conditions and do not pass through an intermediate liquid state.