Daniel Bonn

Yield stress and thixotropy: on the difficulty of measuring yield stresses in practice

The yield stress of many yield stress fluids has turned out to be difficult to determine experimentally. This has led to various discussions in the literature about those experimental difficulties, and the usefulness and pertinence of the concept of yield stress fluids. We argue here that most of the difficulties disappear when taking the thixotropy of yield stress fluids into account, and will demonstrate an experimental protocol that allows reproducible data to be obtained for the critical stress necessary for flow of these fluids. As a bonus, we will show that the interplay of yield stress and thixotropy allows one to account for the ubiquitous shear localization observed in these materials. However, due to the thixotropy the yield stress is no longer a material property, since it depends on the (shear) history of the sample.

Controlling droplet deposition with polymer additives

Controlling the impact of drops onto solid surfaces is important for a wide variey of coating and deposition processes—for example, the treatment of plants with herbicides and pesticides requires precise targeting in order to meet stringent toxicological regulations. However, the outer wax-like layer of the leaves is a non-wetting substrate that causes sprayed droplets to rebound; often less than 50% of the initial spray is retained by the plant. Although the impact and subsequent retraction of non-wetting aqueous drops on a hydrophobic surface have been the subjects of extensive experimental and theoretical work, non-newtonian rheological effects have not been considered in any detail. Here we report that, by adding very small amounts of a flexible polymer to the aqueous phase, we can inhibit droplet rebound on a hydrophobic surface and markedly improve deposition without significantly altering the shear viscosity of the solutions. Our results can be understood by taking into account the non-newtonian elongational viscosity, which provides a large resistance to drop retraction after impact, thereby suppressing droplet rebound.

Viscosity bifurcation in thixotropic, yielding fluids

Most concentrated colloidal suspensions such as cement, drilling fluids, paints, muds, etc., have been considered until now thixotropic fluids with a flow curve of an ideal yield stress fluid. We start by showing from inclined plane tests, intended to determine the yield stress, that these systems in fact exhibit peculiar properties. Unlike ideal yield stress fluids, they stop flowing abruptly below a critical stress, and start flowing at a high velocity beyond a critical stress, which in addition increases with the time of preliminary rest. In order to clarify these features we carried out a complete set of rheometrical tests with a model fluid, a bentonite suspension. Our results show that under controlled stress, in some cases after significant flow, there is bifurcation of the behavior towards either stoppage or rapid shear, depending on the relative values of the imposed and critical stresses. As an immediate consequence, we find that no (homogeneous) steady state flows at a shear rate below a critical value can be obtained. These results can be qualitatively predicted by a simple theoretical model that assumes that the viscosity of the material results from the competition between aging and shear rejuvenation, associated to, respectively, the organization or disorganization of the network of particle interactions. This shows that the flow curve in the steady state of concentrated colloidal suspensions and, more generally, of structured fluids, is strongly affected by their thixotropy.Most concentrated colloidal suspensions such as cement, drilling fluids, paints, muds, etc., have been considered until now thixotropic fluids with a flow curve of an ideal yield stress fluid. We start by showing from inclined plane tests, intended to determine the yield stress, that these systems in fact exhibit peculiar properties. Unlike ideal yield stress fluids, they stop flowing abruptly below a critical stress, and start flowing at a high velocity beyond a critical stress, which in addition increases with the time of preliminary rest. In order to clarify these features we carried out a complete set of rheometrical tests with a model fluid, a bentonite suspension. Our results show that under controlled stress, in some cases after significant flow, there is bifurcation of the behavior towards either stoppage or rapid shear, depending on the relative values of the imposed and critical stresses. As an immediate consequence, we find that no (homogeneous) steady state flows at a shear rate below a critic...

An attempt to categorize yield stress fluid behaviour

We propose a new view on yield stress materials. Dense suspensions and many other materials have a yield stress—they flow only if a large enough shear stress is exerted on them. There has been an ongoing debate in the literature on whether true yield stress fluids exist, and even whether the concept is useful. This is mainly due to the experimental difficulties in determining the yield stress. We show that most if not all of these difficulties disappear when a clear distinction is made between two types of yield stress fluids: thixotropic and simple ones. For the former, adequate experimental protocols need to be employed that take into account the time evolution of these materials: ageing and shear rejuvenation. This solves the problem of experimental determination of the yield stress. Also, we show that true yield stress materials indeed exist, and in addition, we account for shear banding that is generically observed in yield stress fluids.

Yield stress fluids slowly yield to analysis

The behavior of a type of complex fluid (exemplified by mayonnaise and concrete) can depend on the samples flow history. We are surrounded in everyday life by yield stress fluids: materials that behave as solids under small stresses but flow like liquids beyond a critical stress. For example, paint must flow under the brush, but remain fixed in a vertical film despite the force of gravity. Food products (such as mayonnaise), other consumer products (such as toothpaste), concrete, and even radioactive nuclear waste sludge exhibit yield stresses. The yield stress may serve to keep particulate fillers from settling, as in many consumer products and gelled propellants, or determine whether bubbles remain trapped in cement. For handling and using these materials, it is paramount to know the stress at which the material starts to flow, but a consensus on the mechanical behavior of these materials is only slowly emerging.

Shear thickening of cornstarch suspensions as a reentrant jamming transition

We study the rheology of cornstarch suspensions, a non-Brownian particle system that exhibits shear thickening. From magnetic resonance imaging velocimetry and classical rheology it follows that as a function of the applied stress the suspension is first solid (yield stress), then liquid, and then solid again when it shear thickens. For the onset of thickening we find that the smaller the gap of the shear cell, the lower the shear rate at which thickening occurs. Shear thickening can then be interpreted as the consequence of dilatancy: the system under flow wants to dilate but instead undergoes a jamming transition because it is confined, as confirmed by measurement of the dilation of the suspension as a function of the shear rate.

Retraction dynamics of aqueous drops upon impact on non-wetting surfaces

We study the impact and subsequent retraction of liquid droplets upon high-speed impact on hydrophobic surfaces. Extensive experiments show that the drop retraction rate is a material constant and does not depend on the impact velocity. We show that on increasing the Ohnesorge number, Oh = η/ √ ρRIγ , the retraction, i.e. dewetting, dynamics crosses from a capillary–inertial regime to a capillary–viscous regime. We rationalize the experimental observations by a simple but robust semi-quantitative model for the solid–liquid contact line dynamics inspired by the standard theories for thin-film dewetting.

Flow of Wet Granular Materials

The transition from frictional to lubricated flows of a dense suspension of non-Brownian particles is studied. The pertinent parameter characterizing this transition is the Leighton number Le=eta(s)gamma / sigma, the ratio of lubrication to frictional forces. Le defines a critical shear rate below which no steady flow without localization exists. In the frictional regime the shear flow is localized. The lubricated regime is not simply viscous: the ratio of shear to normal stresses remains constant and the velocity profile has a universal form in both frictional and lubricated regimes. Finally, a discrepancy between local and global measurements of viscosity is identified, which suggests inhomogeneity of the material under flow.

Wall slip and yielding in pasty materials

We carried out systematic rheometrical tests under controlled stress with smooth and rough parallel disks, along with magnetic resonance imaging (MRI) tests in coaxial cylinder geometry, with foam and a model concentrated emulsion. At low shear stress wall slip appears to occur but the bulk fluid remains static, as proved by the fact that in this regime the apparent shear rate obtained for a given shear stress is inversely proportional to the gap between the disks. At high shear stress data with different surface types and gaps coincide, suggesting that wall slip is negligible in this regime. In parallel, MRI results show that, in contrast with the apparent, simple, yielding behavior observed in usual rheometry, there is an abrupt transition from a finite shear rate to a static one at critical stress. This critical shear rate precisely corresponds to the transition between the two regimes of slip. This suggests that different flow regimes occur with these materials: (1) at low stress, with smooth surfaces a layer of a different material is sheared along the solid surfaces whereas the rest of the fluid does not flow; with rough surfaces there is no flow; (2) beyond a critical stress, for both surface types, the bulk fluid starts to flow but the shear is localized in a thin layer; then the thickness of this layer increases when stress is applied; (3) for both surface types homogeneous flow is obtained only beyond slightly larger stress, which is associated to a critical, apparent shear rate.We carried out systematic rheometrical tests under controlled stress with smooth and rough parallel disks, along with magnetic resonance imaging (MRI) tests in coaxial cylinder geometry, with foam and a model concentrated emulsion. At low shear stress wall slip appears to occur but the bulk fluid remains static, as proved by the fact that in this regime the apparent shear rate obtained for a given shear stress is inversely proportional to the gap between the disks. At high shear stress data with different surface types and gaps coincide, suggesting that wall slip is negligible in this regime. In parallel, MRI results show that, in contrast with the apparent, simple, yielding behavior observed in usual rheometry, there is an abrupt transition from a finite shear rate to a static one at critical stress. This critical shear rate precisely corresponds to the transition between the two regimes of slip. This suggests that different flow regimes occur with these materials: (1) at low stress, with smooth surfaces...

Salt Crystallization during Evaporation: Impact of Interfacial Properties

Salt damage in stone results in part from crystallization of salts during drying. We study the evaporation of aqueous salt solutions and the crystallization growth for sodium sulfate and sodium chloride in model situations: evaporating droplets and evaporation from square capillaries. The results show that the interfacial properties are of key importance for where and how the crystals form. The consequences for the different forms of salt crystallization observed in practice are discussed.