Shear thickening in presence of adhesive contact forces: The singularity of cornstarch.

HYPOTHESIS: A number of dense particle suspensions experience a dramatic increase in viscosity with the shear stress, up to a solid-like response. This shear-thickening process is understood as a transition under flow of the nature of the contacts - from lubricated to frictional - between initially repellent particles. Most systems are now assumed to fit in with this scenario, which is questionable. EXPERIMENT: Using an in-house pressure sensor array, we provide a spatio-temporal map of the normal stresses in the flows of two shear-thickening fluids: a stabilized calcium carbonate suspension, known to fit in with the standard scenario, and a cornstarch suspension, which spectacular thickening behavior remains poorly understood. FINDINGS: We evidence in cornstarch a unique, stable heterogeneous structure, which moves in the velocity direction and does not appear in calcium carbonate. Its nature changes from a stress wave to a rolling solid jammed aggregate at high solid fraction and small gap width. The modeling of these heterogenities points to an adhesive force between cornstarch particles at high stress, also evidenced in microscopic measurements. Cornstarch being also attractive at low stress, it stands out of the classical shear-thickening frame, and might be part of a larger family of adhesive and attractive shear-thickening fluids.

Solvents govern rheology and jamming of polymeric bead suspensions.

Despite their apparent simplicity, suspensions of hard spheres in a Newtonian fluid show complex non-Newtonian behaviors and remain poorly understood. Recent works have pointed out the crucial role of interparticle contact forces in these behaviors. Here, we show that the same (polystyrene) particles, when immersed in different Newtonian solvents, show different behaviors at both the microscopic and macroscopic scales. Thanks to interparticle force measurements in each solvent together with rheological measurements, we show how the fine details of the pairwise particle interactions impact the macroscopic behavior. The rheological properties (shear thinning, shear thickening, jamming solid fraction value) of the suspensions, made up of same particles, are shown to depend on the nature of the solvent. Here, we highlight several mechanisms at the particle scale: the swelling of polymeric particles in an organic solvent, the role of colloidal repulsive forces and inertia for particles in a water solution, and the variation of the friction coefficient as a function of the load for particles immersed in silicone oils. Our study provides new quantitative data to test micromechanical models and simulations. It questions the interpretation of previous experimental works. Finally, it shows the need to systematically characterize the interparticle normal and tangential forces when studying a given suspension of hard spheres in a Newtonian fluid.

A mechanism of strain hardening and Bauschinger effect: shear-history-dependent microstructure of elasto-plastic suspensions.

Dispersing solid hard particles in an elasto-plastic material leads to important shear-history dependence of the behavior, namely strain hardening and Bauschinger effect. Strain hardening is observed as the progressive strengthening of a material during its plastic deformation and is usually associated with ductility, a property often sought after in composite materials to postpone fractures and failure. In addition, anisotropic mechanical properties are developed, the material resistance being larger in the direction of the imposed flow, which is referred to as the Bauschinger effect. We show that this is related here to shear-history-dependent particle-pair distribution functions. Roughness and interparticle contacts likely play a major role, as replacing hard particles by non-deformable bubbles modifies the suspension microstructure and suppresses strain hardening. Beyond suspensions, our study provides new insight in the understanding and control of strain hardening and Bauschinger effect in composite materials.

Unexpected Slow Kinetics of Poly(Methacrylic Acid) Phase Separation in the Semi-Dilute Regime.

Poly (methacrylic acid) (PMAA) solutions are known to exhibit a lower critical solution temperature (LCST). A temperature-composition phase diagram of PMAA has been constructed by standard cloud point determination through transmittance measurements, and also by studying the steady states reached under phase separation. This allows us to reconstruct the binodal curve describing the phase behavior of PMAA for both low and high concentration regimes, and to determine accurately the LCST temperature. In a second step, the structures formed following a temperature jump above the cloud point and their evolution in time have been investigated at the nanoscale using small angle neutron scattering (SANS). This approach shows that the formation of phase-separated nanostructures is a slow process, requiring more than 12 h. The formed structures are then shown to depend on the amplitude of the temperature jump above the cloud point. An original mechanism of phase separation is identified in the semi-dilute regime. The growth of micrometric-size droplets with an inner structure displaying the rheological properties of a gel leads to the formation of a percolating network which hinders the influence of gravity. Such a result can explain the slow kinetics of the PMAA LCST transition.

Effect of Solvent on the Mechanical and Structural Properties of N-Alkyldiamide Organogels.

Here, we study organogels prepared thanks to a new organogelator, the N-oleyldiamide molecule, which shows a remarkable propensity to gelify a large scope of solvents, from aprotic to high protic solvents. The solvent plays a key role in the formation and stability of supramolecular self-assemblies. However, the understanding and the control of its effects can be complex as many parameters are a priori involved. This study aims to understand the effect of solvent on the structures of organogels and on their final mechanical properties. Five solvent classes have been selected ranking from low protic to high protic, according to the Hansen H-bond parameter δh. The solvent proticity appears to be one of the main parameters that affect the organogel internal structure and therefore the final rheological properties. For a given organogelator fraction, the terminal elastic modulus measured by oscillatory rheology is observed to increase significantly with the Hansen H-bond solvent parameter δh. Materials of different mechanical properties are then shown to display various structures, which are investigated thanks to cryo-SEM. Besides, wide-angle X-ray scattering (WAXS) has been used to probe the gelator organization at the molecular scale with regard to the solvent nature, to understand the supramolecular self-assembly of this promising molecule.

Competitive Adsorption between a Polymer and Solvents onto Silica.

In polymer nanocomposites, particle-polymer interactions play a key role both in the processing and in the final properties of the obtained materials. Specifically, for silica, because of the surface polarity, surface modification is commonly used to improve the compatibility with apolar polymer matrices in order to prevent agglomeration. In this work, a new way to investigate the polymer-silica affinity and determine dispersibility parameters (HDP) of silica particles in the 3D Hansen space using a solvent approach is proposed. These parameters are estimated from the assessment of the stability of suspensions in a set of organic solvents. Based on the respective locations of the solvent, polymer, and silica representative points in the 3D Hansen space, the adsorption of a given polymer in solution in a given solvent can be predicted. This is shown with the industrial precipitated silica Zeosil 1165MP in combination with polystyrene and polybutadiene. It is shown that silanization of the silica particles decreases the adsorption of polystyrene, even though because of this surface treatment, silica comes closer to polystyrene in the Hansen space. This counter-intuitive effect is rationalized based on the consideration of an adsorption parameter χS computed from the relative locations of the solvent, polymer, and particles in the 3D Hansen space. Basically, this parameter is related to the respective distances of the solvent and polymer representative points to that of the particle in the Hansen space.

Density waves in shear-thickening suspensions.

Shear thickening corresponds to an increase of the viscosity as a function of the shear rate. It is observed in many concentrated suspensions in nature and industry: water or oil saturated sediments, crystal-bearing magma, fresh concrete, silica suspensions, and cornstarch mixtures. Here, we reveal how shear-thickening suspensions flow, shedding light onto as yet non-understood complex dynamics reported in the literature. When shear thickening is important, we show the existence of density fluctuations that appear as periodic waves moving in the direction of flow and breaking azimuthal symmetry. They come with strong normal stress fluctuations of the same periodicity. The flow includes small areas of normal stresses of the order of tens of kilopascals and areas of normal stresses of the order of hundreds of pascals. These stress inhomogeneities could play an important role in the damage caused by thickening fluids in the industry.

Viscous friction of squeezed bubbly liquid layers.

Shear viscosity of bubbly liquids is known to depend on both the gas volume fraction and the capillary number. Here, we study the impact of confinement on their behavior by investigating the viscosity of semi-dilute bubbly liquid layers confined between two plates and characterized by a ratio of the undeformed bubble diameter to the layer thickness equal to or larger than unity. For all the studied confinement ratios, viscosity is shown to be smaller than the viscosity of the suspending liquid for capillary numbers larger than 0.1. Measurements of bubble deformations show that this behavior is related to bubble stretching in the direction of shear induced flow. In the limit of high capillary numbers, viscosity reaches values predicted for unconfined bubbly liquids. On the other hand, our results for smaller capillary numbers, i.e. within the range 0.001-0.1, reveal a non-monotonic variation of the viscosity as a function of the confinement ratio, exhibiting a well-defined maximum value for the ratio close to 1.8. This behavior differs strongly from the reference case of unconfined bubbly liquid, and it is shown to result from both bulk and wall drag forces on the squeezed bubbles.

Transition from Continuous to Discontinuous Shear Thickening: An Excluded-Volume Effect.

In this Letter, we present a new mechanism under the action of which a shear thickening suspension transitions from a continuous to a discontinuous regime. This transition occurs by adding high concentrations of large spheres to a continuous shear thickening suspension. We show that the solid volume fraction of the interstitial shear thickening matrix is locally enhanced due to the presence of large particles and the excluded-volume shells surrounding the large particles, thus leading to a continuous to discontinuous shear thickening transition at the local scale.

Shear thinning in non-Brownian suspensions.

We study the flow of suspensions of non-Brownian particles dispersed into a Newtonian solvent. Combining capillary rheometry and conventional rheometry, we evidence a succession of two shear thinning regimes separated by a shear thickening one. Through X-ray radiography measurements, we show that during each of those regimes, the flow remains homogeneous and does not involve particle migration. Using a quartz-tuning fork based atomic force microscope, we measure the repulsive force profile and the microscopic friction coefficient µ between two particles immersed into the solvent, as a function of normal load. Coupling measurements from those three techniques, we propose that (1) the first shear-thinning regime at low shear rates occurs for a lubricated rheology and can be interpreted as a decrease of the effective volume fraction under increasing particle pressures, due to short-ranged repulsive forces and (2) the second shear thinning regime after the shear-thickening transition occurs for a frictional rheology and can be interpreted as stemming from a decrease of the microscopic friction coefficient at large normal load.

Coupling of elasticity to capillarity in soft aerated materials.

We study the elastic properties of soft solids containing air bubbles. Contrary to standard porous materials, the softness of the matrix allows for a coupling of the matrix elasticity to surface tension forces acting on the bubble surface. Thanks to appropriate experiments on model systems, we demonstrate how the elastic response of the soft porous solid is governed by two dimensionless parameters: the gas volume fraction and a capillary number comparing the elasticity of the matrix with the stiffness of the bubbles. Furthermore, we show that our experimental results are accurately predicted by computations of the shear modulus through a micro-mechanical approach.

Shear thickening and migration in granular suspensions.

We study the emergence of shear thickening in dense suspensions of non-Brownian particles. We combine local velocity and concentration measurements using magnetic resonance imaging with macroscopic rheometry experiments. In steady state, we observe that the material is heterogeneous, and we find that the local rheology presents a continuous transition at low shear rate from a viscous to a shear thickening, Bagnoldian, behavior with shear stresses proportional to the shear rate squared, as predicted by a scaling analysis. We show that the heterogeneity results from an unexpectedly fast migration of grains, which we attribute to the emergence of the Bagnoldian rheology. The migration process is observed to be accompanied by macroscopic transient discontinuous shear thickening, which is consequently not an intrinsic property of granular suspensions.

Yield stress and shear banding in granular suspensions.

We study the emergence of a yield stress in dense suspensions of non-Brownian particles by combining local velocity and concentration measurements using magnetic resonance imaging with macroscopic rheometric experiments. We show that the competition between gravity and viscous stresses is at the origin of the development of a yield stress in these systems at relatively low volume fractions. Moreover, it is accompanied by a shear-banding phenomenon that is the signature of this competition. However, if the system is carefully density matched, no yield stress is encountered until a volume fraction of 62.7 +/- 0.3%.

Influence of shear stress applied during flow stoppage and rest period on the mechanical properties of thixotropic suspensions.

We study the solid mechanical properties of several thixotropic suspensions as a function of the shear stress history applied during their flow stoppage and their aging in their solid state. We show that their elastic modulus and yield stress depend strongly on the shear stress applied during their solid-liquid transition (i.e., during flow stoppage) while applying the same stress only before or only after this transition may induce only second-order effects: there is negligible dependence of the mechanical properties on the preshear history and on the shear stress applied at rest. We also found that the suspensions age with a structuration rate that hardly depends on the stress history. We propose a physical sketch based on the freezing of a microstructure whose anisotropy depends on the stress applied during the liquid-solid transition to explain why the mechanical properties depend strongly on this stress. This sketch points out the role of the internal forces in the colloidal suspensions' behavior. We finally discuss briefly the macroscopic consequences of this phenomenon and show the importance of using a controlled-stress rheometer.