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We investigate the response of a well-characterized colloidal star glass to large-amplitude oscillatory stress and strain fields. By combining these measurements with dynamic time sweeps we demonstrate the importance of probing both strain- and stress-induced nonlinear rheology of such complex fluids in order to elucidate the yielding and fluidization behavior. We also show that, due to the strong time dependence, it is essential to perform dynamic time sweeps at different strain and stress amplitudes, which result in different departures of the glass cage from its quiescent quasiequilibrium structure. This allows for steady-state responses to be reached and for nonlinear oscillatory responses to be treated properly while also suggesting that yielding is a gradual process. Further, we use a recently published framework for analyzing nonlinear responses to large-amplitude oscillatory shear [Rogers et al., J. Rheol. 55, 435 (2011)], based on the analysis of the whole stress waveforms as a sequence of physic...

We investigate the complex flow behavior of a well-characterized colloidal star glass using linear and nonlinear rheology. The results are integrated into a generic state diagram which specifies the states of the glass for different initial conditions and mechanical histories: viscoelastic liquid and solid, homogeneous shear-thinned solution, and shear-banded material. Aging takes different forms which can be interpreted as kinetic pathways through the state diagram. Shear-banding appears to be an intrinsic mechanical instability which occurs when the solid state of the glass is shear-melted. Our results provide a straightforward methodology to fingerprint the material behavior of soft glassy materials undergoing rheological transitions which can be used as predictive tool to design systems with a desired rheological response.

We use multi-arm star polymers as model soft colloids with tuneable interactions and explore their behaviour in the glassy state. In particular, we perform a systematic rheological study with a well-defined protocol and address aspects of ageing and shear melting of star glasses. Ageing proceeds in two distinct steps: a fast step of O (10 3 s) and a slow step of O (10 4 s). We focus on creep and recovery tests, which reveal a rich, albeit complex response. Although the waiting time, the time between pre-shear (rejuvenation) of the glassy sample and measurement, affects the material’s response, it does not play the same role as in other soft glasses. For stresses below the yield value, the creep curve is divided into three regimes with increasing time: viscoplastic, intermediate steady flow (associated with the first ageing step) and long-time evolving elastic solid. This behaviour reflects the interplay between ageing and shear rejuvenation. The yield behaviour, as investigated with the stress-dependent recoverable strain, indicates a highly nonlinear elastic response intermediate between a low-stress Hookean solid and a high-stress viscoelastic liquid, and exemplifies the distinct characteristics of this class of hairy colloids. It appears that a phenomenological classification of different colloidal glasses based on yielding performance may be possible.

We use time-resolved rheology to elucidate the slow dynamics and aging in highly concentrated suspensions of multiarm star polymers. The linear and nonlinear rheological properties exhibit a terminal regime corresponding to a well-defined maximal relaxation time. Terminal relaxation is driven by arm relaxation which speeds up the escape of stars from their cages. The fact that the system fully relaxes and flows at long times has important consequences. The yield stress only exists in the limited range of frequencies or shear rates where solid-like behavior is observed. Aging is controlled by the total time elapsed after flow cessation and not by the time elapsed from flow cessation to the beginning of the measurement as in other glassy materials. Our results, which demonstrate the importance of particle architecture with respect to glassy dynamics, should be generic for long hairy particles.

We present experimental evidence confirming the recently established rich dynamic state diagram of asymmetric binary mixtures of soft colloidal spheres. These mixtures consist of glassy suspensions of large star polymers to which different small stars are added at varying concentrations. Using rheology and dynamic light scattering measurements along with a simple phenomenological analysis, we show the existence of re-entrance and multiple glassy states, which exhibit distinct features. Cooperative diffusion, as a probe for star arm interpenetration, is proven to be sensitive to the formation of the liquid pockets which signal the melting of the large-star-glass upon addition of small stars. These results provide ample opportunities for tailoring the properties of soft colloidal glasses.