Nick Koumakis

Two step yielding in attractive colloids: transition from gels to attractive glasses

Steady and oscillatory rheology was utilized to study the mechanical response of colloidal glasses and gels with particular emphasis in their yielding behaviour. We used a suspension of hard sphere colloidal particles with short-range depletion attractions induced by the addition of non-adsorbing linear polymer. While high volume fraction hard sphere glasses exhibit a single yield point due to cage breaking, attraction dominated glasses show a two-step yielding reflecting bond and cage breaking, respectively. Here we investigated the yielding behaviour of frustrated colloid–polymer systems with equal attraction strength and range, varying the particle volume fraction, φ, spanning the region from an attractive glass (φ = 0.6) to a low volume fraction (φ = 0.1) attractive gel. Yielding throughout this range, probed both by oscillatory and steady shear, is found to remain a two step process until very low φs. The first yield strain related with in-cage or inter-cluster bond braking remains constant for φ > 0.3 while the second yield strain, attributed to braking of cages or clusters into smaller constituents, increases as volume fraction is decreased due to enhancement of structural inhomogeneities in the gel. Steady shear tests indicated distinct shear rate regimes: At steady state, low and intermediate shear rates create denser or smaller flowing clusters, whereas high rates may lead to complete break-up into independent particles. When the range of attraction was increased, both yield strains increased scaling with the range of attraction and accompanied structural changes. Finally, ageing leads to an overall strengthening of both the gel and the attractive glass accompanied by an enhancement of the second stress overshoot in steady shear, while the attractive glass also becomes more brittle.

Structure, dynamics, and rheology of colloid-polymer mixtures: From liquids to gels

We investigate the structural, dynamical, and viscoelastic properties of colloid-polymer mixtures at intermediate colloid volume fraction and varying polymer concentrations, thereby tuning the attractive interactions. Within the examined range of polymer concentrations, the samples varied from fluids to gels. In the liquid phase, an increasing correlation length of the density fluctuations when approaching the gelation boundary was observed by static light scattering and microscopy, indicating clustering and formation of space-spanning networks. Simultaneously, the correlation function determined by dynamic light scattering decays completely, indicating the absence of dynamical arrest. Clustering and formation of transient networks when approaching the gelation boundary is supported by significant changes in the viscoelastic properties of the samples. Upon increasing the polymer concentration beyond the gelation boundary, the rheological properties changed qualitatively again, now they are consistent with the formation of colloidal gels. Our experimental results, namely, the location of the gelation boundary as well as the elastic (storage) and viscous (loss) moduli, are compared to different theoretical models. These include consideration of the escape time as well as predictions for the viscoelastic moduli based on scaling relations and mode coupling theories.

Direct comparison of the rheology of model hard and soft particle glasses

The effects of particle softness and the role of the outer shell mechanics on the linear viscoelasticity and yielding behaviour of colloidal glasses are critically assessed using three different model colloidal particles: (i) sterically stabilized PMMA particles with model hard sphere interactions, (ii) core–shell microgels with a deformable PNIPAM outer shell and (iii) ultra-soft star-like micelles with inter-penetrable multi-arms. The volume fraction dependence of the elastic modulus and the yield stress reflects the softness of the effective inter-particle potential. The yield strain exhibits distinct non-monotonic volume fraction dependence for hard spheres below close packing whereas for both soft particles it increases above close packing due to particle softness. Stress overshoots in start-up shear show a common increase with shear rate in all systems. However, the stress overshoots are significantly stronger in star-like micelles due to transient arm entanglements. In relation with that similar stress peaks are detected within the period of the large amplitude oscillatory shear only in star-like micelles. Finally, we discuss the scaling exponents for the G′ and G′′ decrease at large oscillatory strain amplitudes and their relation with steady shear stress.

Effects of shear induced crystallization on the rheology and ageing of hard sphere glasses

The rheological properties of highly concentrated suspensions of hard sphere particles are studied with particular reference to the rheological response of shear induced crystals. Using practically monodisperse hard spheres, we prepare shear induced crystals under oscillatory shear and examine their linear and non-linear mechanical responses in comparison with their glassy counterparts at the same volume fraction. It is evident, that shear induced crystallization causes a significant drop in the elastic and viscous moduli due to structural rearrangements that ease flow. For the same reason the critical (peak of G″) and crossover (overlap of G′ and G″) strain are smaller in the crystal compared to the glass at the same volume fraction. However, when the distance from the maximum packing in each state is taken into account the elastic modulus of the crystal is found to be larger than the glass at the same free volume, suggesting a strengthened material due to long range order. Finally, shear induced crystals counter-intuitively exhibit similar rheological ageing to the glass (with a logarithmic increase of G′), indicating that the shear induced structure is not at thermodynamic equilibrium.

Residual Stresses in Glasses

The history dependence of glasses formed from flow-melted steady states by a sudden cessation of the shear rate γ[over ˙] is studied in colloidal suspensions, by molecular dynamics simulations and by mode-coupling theory. In an ideal glass, stresses relax only partially, leaving behind a finite persistent residual stress. For intermediate times, relaxation curves scale as a function of γ[over ˙]t, even though no flow is present. The macroscopic stress evolution is connected to a length scale of residual liquefaction displayed by microscopic mean-squared displacements. The theory describes this history dependence of glasses sharing the same thermodynamic state variables but differing static properties.

Slip of gels in colloid–polymer mixtures under shear

We investigate the time-dependent rheology and slip behaviour of colloidal gels formed under polymer-induced depletion attraction. The shape of the flow curves at low applied shear rates is suggestive of slip, which we confirm using confocal imaging. Time-dependent linear viscoelastic measurements show an unexpected drop of the elastic modulus below the viscous one after a critical time. We present a dynamic phase diagram characterizing the dependence of slip on polymer concentration and colloid volume fraction. Confocal imaging links slip to the restructuring of clusters with time, which leads to a reduction of the number of contacts between the colloidal network and the rheometer surfaces. Such behaviour is shear rate dependent and correlated to changes in the gel structure, which changed from independent small aggregates at high shear rates to percolated clusters at low shear rates.

Start-up shear of concentrated colloidal hard spheres: Stresses, dynamics, and structure

The transient response of model hard sphere glasses is examined during the application of steady rate start-up shear using Brownian dynamics simulations, experimental rheology and confocal microscopy. With increasing strain, the glass initially exhibits an almost linear elastic stress increase, a stress peak at the yield point and then reaches a constant steady state. The stress overshoot has a nonmonotonic dependence with Peclet number, Pe, and volume fraction, φ, determined by the available free volume and a competition between structural relaxation and shear advection. Examination of the structural properties under shear revealed an increasing anisotropic radial distribution function, g(r), mostly in the velocity-gradient (xy) plane, which decreases after the stress peak with considerable anisotropy remaining in the steady-state. Low rates minimally distort the structure, while high rates show distortion with signatures of transient elongation. As a mechanism of storing energy, particles are trapped within a cage distorted more than Brownian relaxation allows, while at larger strains, stresses are relaxed as particles are forced out of the cage due to advection. Even in the steady state, intermediate super diffusion is observed at high rates and is a signature of the continuous breaking and reformation of cages under shear.

Colloidal gels under shear: Strain rate effects

Attractive colloidal particles are trapped in metastable states such as colloidal gels at high attraction strengths and attractive glasses and high volume fractions. Under shear such states flow via a two step yielding process that relates to bond and cluster or cage breaking. We discuss the way the structural properties and related stress response are affected by the shear rate. At low rates colloidal gels yield during start-up shear essentially in a single step, exhibiting a single stress overshoot due to creation of compact flowing clusters. With increasing shear rate a second stress overshoot, linked with further cluster breaking up to individual particles, is becoming more pronounced. We further present the age dependence of the two step yielding and wall slip effects often taking place during rheological experiments of colloidal gels. The latter is related both with the shear rate dependent gel structure as well as the time evolution of the near wall structure.

Bacteria as living patchy colloids: Phenotypic heterogeneity in surface adhesion

Genetically identical bacteria possess varying numbers of surface-adhering patches. Understanding and controlling the surface adhesion of pathogenic bacteria is of urgent biomedical importance. However, many aspects of this process remain unclear (for example, microscopic details of the initial adhesion and possible variations between individual cells). Using a new high-throughput method, we identify and follow many single cells within a clonal population of Escherichia coli near a glass surface. We find strong phenotypic heterogeneities: A fraction of the cells remain in the free (planktonic) state, whereas others adhere with an adhesion strength that itself exhibits phenotypic heterogeneity. We explain our observations using a patchy colloid model; cells bind with localized, adhesive patches, and the strength of adhesion is determined by the number of patches: Nonadherers have no patches, weak adherers bind with a single patch only, and strong adherers bind via a single or multiple patches. We discuss possible implications of our results for controlling bacterial adhesion in biomedical and other applications.