Thermal history asymmetry and dissipation in dense colloidal microgel glasses.

HYPOTHESIS: Microstructurally arrested matter, from molecular glasses to soft glassy materials, can retain a memory of their thermal or mechanical (shear) histories. Their history-dependent and nonlinear microstructural recoveries have been studied within the Kovacs framework. The application of temperature ramps of varying magnitudes to dense colloidal suspensions of thermoresponsive, deformable and compressible microgel particles should serve as an effective strategy to probe the nonlinear path-dependent structural recovery of these systems.

EXPERIMENTS: Poly (N-isopropylacrylamide) (PNIPAM) microgel particles were synthesised using the free radical precipitation polymerisation method. Using oscillatory rheology, we studied the relaxations of the viscoelastic moduli of dense PNIPAM suspensions that were heated and cooled at various temperature ramp rates.

FINDINGS: Path-dependent structural recovery was quantified by studying the asymmetric approach of the suspension elastic modulus toward the target temperature during the heating and cooling temperature ramps. The loss modulus peaks, observed at the times of initiation and termination of the temperature ramps, were understood to arise from energy dissipation due to microgel rearrangement events. The heights of the peaks were found to be inversely correlated with the asymmetry in the elastic response. Our work highlights the important role of energy dissipation through microgel rearrangements in eliminating path-dependent asymmetries in the storage moduli of dense PNIPAM suspensions subjected to thermal shocks. By tuning the applied temperature ramp rate and particle packing density, therefore, asymmetric storage modulus relaxations in dense systems can be modulated via adjustments of the accessible free volume.