No Arabic abstract
We introduce a model gel system in which colloidal forces, structure, and rheology are measured by balancing the requirements of rheological and microscopy techniques with those of optical tweezers. Sterically stabilized poly(methyl methacrylate) (PMMA) colloids are suspended in cyclohexane (CH) and cyclohexyl bromide (CHB) with dilute polystyrene serving as a depletion agent. A solvent comprising of 37% weight fraction CH provides sufficient refractive index contrast to enable optical trapping, while maintaining good confocal imaging quality and minimal sedimentation effects on the bulk rheology. At this condition, and at a depletant concentration c = 8.64 mg/mL (c/c* = 0.81), results from optical trapping show that 50% of bonds rupture at 3.3 pN. The linear strain-dependent elastic modulus of the corresponding gel (volume fraction = 0.20) is G = 1.8 Pa, and the mean contact number of the particles in the gel structure is 5.4. These structural and rheological parameters are similar to colloidal gels that are weakly aggregating and cluster-like. Thus, the model gel yields a concomitant characterization of the interparticle forces, microstructure, and bulk rheology in a single experimental system, thereby introducing the simultaneous comparison of these experimental measures to models and simulations.
We use numerical simulations and an athermal quasi-static shear protocol to investigate the yielding of a model colloidal gel. Under increasing deformation, the elastic regime is followed by a significant stiffening before yielding takes place. A space-resolved analysis of deformations and stresses unravel how the complex load curve observed is the result of stress localization and that the yielding can take place by breaking a very small fraction of the network connections. The stiffening corresponds to the stretching of the network chains, unbent and aligned along the direction of maximum extension. It is characterized by a strong localization of tensile stresses, that triggers the breaking of a few network nodes at around 30% of strain. Increasing deformation favors further breaking but also shear-induced bonding, eventually leading to a large-scale reorganization of the gel structure at the yielding. At low enough shear rates, density and velocity profiles display significant spatial inhomogeneity during yielding in agreement with experimental observations.
We identify the sequence of microstructural changes that characterize the evolution of an attractive particulate gel under flow and discuss their implications on macroscopic rheology. Dissipative Particle Dynamics (DPD) is used to monitor shear-driven evolution of a fabric tensor constructed from the ensemble spatial configuration of individual attractive constituents within the gel. By decomposing this tensor into isotropic and non-isotropic components we show that the average coordination number correlates directly with the flow curve of the shear stress vs. shear rate, consistent with theoretical predictions for attractive systems. We show that the evolution in non-isotropic local particle rearrangements are primarily responsible for stress overshoots (strain-hardening) at the inception of steady shear flow and also lead, at larger times and longer scales, to microstructural localization phenomena such as shear banding flow-induced structure formation in the vorticity direction.
We sandwich a colloidal gel between two parallel plates and induce a radial flow by lifting the upper plate at a constant velocity. Two distinct scenarios result from such a tensile test: ($i$) stable flows during which the gel undergoes a tensile deformation without yielding, and ($ii$) unstable flows characterized by the radial growth of air fingers into the gel. We show that the unstable regime occurs beyond a critical energy input, independent of the gels macroscopic yield stress. This implies a local fluidization of the gel at the tip of the growing fingers and results in the most unstable wavelength of the patterns exhibiting the characteristic scalings of the classical viscous fingering instability. Our work provides a quantitative criterion for the onset of fingering in colloidal gels based on a local shear-induced yielding, in agreement with the delayed failure framework.
We investigate the heterogeneous dynamics in a model, where chemical gelation and glass transition interplay, focusing on the dynamical susceptibility. Two independent mechanisms give raise to the correlations, which are manifested in the dynamical susceptibility: one is related to the presence of permanent clusters, while the other is due to the increase of particle crowding as the glass transition is approached. The superposition of these two mechanisms originates a variety of different behaviours. We show that these two mechanisms can be unentangled considering the wave vector dependence of the dynamical susceptibility.
Colloidal particles with strong, short-ranged attractions can form a gel. We simulate this process without and with hydrodynamic interactions (HI), using the lattice-Boltzmann method to account for presence of a thermalized solvent. We show that HI speed up and slow down gelation at low and high volume fractions, respectively. The transition between these two regimes is linked to the existence of a percolating cluster shortly after quenching the system. However, when we compare gels at matched structural age, we find nearly indistinguishable structures with and without HI. Our result explains longstanding, unresolved conflicts in the literature.