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Slip and flow of hard-sphere colloidal glasses

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 Added by R. Besseling
 Publication date 2008
  fields Physics
and research's language is English




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We study the flow of concentrated hard-sphere colloidal suspensions along smooth, non-stick walls using cone-plate rheometry and simultaneous confocal microscopy. In the glass regime, the global flow shows a transition from Herschel-Bulkley behavior at large shear rate to a characteristic Bingham slip response at small rates, absent for ergodic colloidal fluids. Imaging reveals both the `solid microstructure during full slip and the local nature of the `slip to shear transition. Both the local and global flow are described by a phenomenological model, and the associated Bingham slip parameters exhibit characteristic scaling with size and concentration of the hard spheres.



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We present a comprehensive study of the slip and flow of concentrated colloidal suspensions using cone-plate rheometry and simultaneous confocal imaging. In the colloidal glass regime, for smooth, non-stick walls, the solid nature of the suspension causes a transition in the rheology from Herschel-Bulkley (HB) bulk flow behavior at large stress to a Bingham-like slip behavior at low stress, which is suppressed for sufficient colloid-wall attraction or colloid-scale wall roughness. Visualization shows how the slip-shear transition depends on gap size and the boundary conditions at both walls and that partial slip persist well above the yield stress. A phenomenological model, incorporating the Bingham slip law and HB bulk flow, fully accounts for the behavior. Microscopically, the Bingham law is related to a thin (sub-colloidal) lubrication layer at the wall, giving rise to a characteristic dependence of slip parameters on particle size and concentration. We relate this to the suspensions osmotic pressure and yield stress and also analyze the influence of van der Waals interaction. For the largest concentrations, we observe non-uniform flow around the yield stress, in line with recent work on bulk shear-banding of concentrated pastes. We also describe residual slip in concentrated liquid suspensions, where the vanishing yield stress causes coexistence of (weak) slip and bulk shear flow for all measured rates.
We report results of dynamic light scattering measurements of the coherent intermediate scattering function (ISF) of glasses of hard spheres for several volume fractions and a range of scattering vectors around the primary maximum of the static structure factor. The ISF shows a clear crossover from an initial fast decay to a slower non-stationary decay. Ageing is quantified in several different ways. However, regardless of the method chosen, the perfect aged glass is approached in a power-law fashion. In particular, the coupling between the fast and slow decays, as measured by the degree of stretching of the ISF at the crossover, also decreases algebraically with waiting time. The non-stationarity of this coupling implies that even the fastest detectable processes are themselves non-stationary.
There is growing evidence that the flow of driven amorphous solids is not homogeneous, even if the macroscopic stress is constant across the system. Via event driven molecular dynamics simulations of a hard sphere glass, we provide the first direct evidence for a correlation between the fluctuations of the local volume-fraction and the fluctuations of the local shear rate. Higher shear rates do preferentially occur at regions of lower density and vice versa. The temporal behavior of fluctuations is governed by a characteristic time scale, which, when measured in units of strain, is independent of shear rate in the investigated range. Interestingly, the correlation volume is also roughly constant for the same range of shear rates. A possible connection between these two observations is discussed.
The yielding behaviour of hard sphere glasses under large amplitude oscillatory shear has been studied by probing the interplay of Brownian motion and shear-induced diffusion at varying oscillation frequencies. Stress, structure and dynamics are followed by experimental rheology and Browian Dynamics simulations. Brownian motion assisted cage escape dominates at low frequencies while escape through shear-induced collisions at high ones, both related with a yielding peak in $G^{prime prime}$. At intermediate frequencies a novel, for HS glasses, double peak in $G^{prime prime}$ is revealed reflecting both mechanisms. At high frequencies and strain amplitudes a persistent structural anisotropy causes a stress drop within the cycle after strain reversal, while higher stress harmonics are minimized at certain strain amplitudes indicating an apparent harmonic response.
We report experiments on hard sphere colloidal glasses that reveal a type of shear banding hitherto unobserved in soft glasses. We present a scenario that relates this to an instability arising from shear-concentration coupling, a mechanism previously thought unimportant in this class of materials. Below a characteristic shear rate $dotgamma_c$ we observe increasingly non-linear velocity profiles and strongly localized flows. We attribute this trend to very slight concentration gradients (likely to evade direct detection) arising in the unstable flow regime. A simple model accounts for both the observed increase of $dotgamma_c$ with concentration, and the fluctuations observed in the flow.
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