Interfacial Characterization of Ruthenium-Based Amphiphilic Photosensitizers.

Nonreactive surfactant molecules have long been used and characterized for a wide range of applications in industries, life science, and everyday life. Recently, new types of functional amphiphilic molecules have emerged that bear another function, for example, a light-absorbing action, or catalytic properties. However, the surfactant properties of these molecules remain to date essentially unknown. In this context, we investigated here the interfacial activity of photocatalytic surfactants based on a ruthenium(II) tris-bipyridine core, functionalized with two alkyl tails. We realized a systematic characterization of the surfactant properties of these molecules at a water-air interface and studied the effect of the alkyl chain length and of the counterions (hexafluorophosphate or chloride) on these properties. Our data demonstrate that ruthenium surfactants with chloride counteranions form a denser layer at the interface, but their surfactant properties can dramatically deteriorate when the chain length of the alkyl tail increases, leading to simple hydrophobic molecules with poor surfactant properties for the longest chains (C17). These findings pave the way for a better use and understanding of photocatalytic soft interfaces.

Generation and stability of cement soap films.

Foaming a cementitious suspension is a complex process that involves many multiscale chemical, physical and dynamical mechanisms. As a first step, we investigate here experimentally the possibility of withdrawing a single liquid soap film from a suspension of cement. We then determine the film lifetime and if particles are entrained or not. We vary the cement concentration, grain size, rheological properties and withdrawing velocity. We observed that the rheology of the cement paste, characterized through its yield stress, plays a key role in the film formation. We show that an optimum exists, as a low yield stress promotes film creation but is detrimental to the film stability. Another key result is that the rheology alone is not enough to describe film formation: the particle size in the suspension is also crucial, with large particles promoting film creation. Finally, we found that the withdrawing velocity also affects the ability to create films and the possibility to drag particles in them. Experiments performed with a silica suspension for comparison confirm these findings.

Interparticle attraction controls flow heterogeneity in calcite gels.

We couple rheometry and ultrasonic velocimetry to study experimentally the flow behavior of gels of colloidal calcite particles dispersed in water, while tuning the strength of the interparticle attraction through physico-chemistry. We unveil, for the first time in a colloidal gel, a direct connection between attractive interactions and the occurrence of shear bands, as well as stress fluctuations.

Elasticity and yielding of a calcite paste: scaling laws in a dense colloidal suspension.

We address the mechanical characterization of a calcite paste as a model system to investigate the relation between the microstructure and macroscopic behavior of colloidal suspensions. The ultimate goal is to achieve control of the elastic and yielding properties of calcite which will prove valuable in several domains, from paper coating to paint manufacture and eventually in the comprehension and control of the mechanical properties of carbonate rocks. Rheological measurements have been performed on calcite suspensions over a wide range of particle concentrations. The calcite paste exhibits a typical colloidal gel behavior, with an elastic regime and a clear yield strain above which it enters a plastic regime. The yield strain shows a minimum when increasing the solid concentration, connected to a change in the power law scaling of the storage modulus. In the framework of the classical fractal elasticity model for colloidal suspensions proposed by Shih et al. [Phys. Rev. A, 1990, 42, 4772], we interpret this behavior as a switch with the concentration from the strong-link regime to the weak-link regime, which had never been observed so far in one well-defined system without external or chemical forcing.

Yield stress and elasticity influence on surface tension measurements.

We have performed surface tension measurements on carbopol gels of different concentrations and yield stresses. Our setup, based on the force exerted by a capillary bridge on two parallel plates, allows us to measure an apparent surface tension of the complex fluid and to investigate the influence of flow history. More precisely the apparent surface tension measured after stretching the bridge is always higher than after compressing it. The difference between the two values is due to the existence of a yield stress in the fluid. The experimental observations are successfully reproduced with a simple elasto-plastic model. The shape of successive stretching-compression cycles can be described by taking into account the yield stress and the elasticity of the gel. We show that the surface tension γLV of yield stress fluids is the mean of the apparent surface tension values only if the elastic modulus is high compared to the yield stress. This work highlights that measurements of thermodynamic quantities are challenged by the fluid out-of-equilibrium state implied by jamming, even at small scales where the shape of the bridge is driven by surface energy. Therefore setups allowing for deformation in opposite directions are relevant for surface tension measurements on yield stress fluids.

Linear and non-linear wall friction of wet foams.

We study the wall slip of aqueous foams with a high liquid content. We use a set-up where, driven by buoyancy, a foam creeps along an inclined smooth solid wall which is immersed in the foaming solution. This configuration allows the force driving the bubble motion and the bubble confinement in the vicinity of the wall to be tuned independently. First, we consider bubble monolayers with small Bond number Bo < 1 and measure the relation between the friction force F and the bubble velocity V. For bubbles which are so small that they are almost spherical, the friction law F ∝ V is Stokes-like. The analysis shows that the minimal thickness of the lubricating contact between the bubble and the wall is governed by DLVO long-range forces. Our results are the first evidence of this predicted linear friction regime for creeping bubbles. Due to buoyancy, large bubbles flatten against the wall. In this case, dissipation arises because of viscous flow in the dynamic meniscus between the contact film and the spherical part of the bubble. It leads to a non-linear Bretherton-like friction law F ∝ V(2/3), as expected for slipping bubbles with mobile liquid-gas interfaces. The Stokes-like friction dominates for capillary numbers Ca larger than the crossover value Ca* ∼ Bo(3/2). The overall friction force can be expressed as the sum of these two contributions. On this basis, we then study 3D foams close to the jamming transition with osmotic pressures Π small compared to the capillary pressure Pc. We measure the wall shear stress τ as a function of the capillary number, and we evidence two friction regimes that are consistent with those found for the monolayer. Similarly to this latter case, the total shear stress can be expressed as the sum of the Stokes-like friction term τ ∝ Ca and the Bretherton-like one τ ∝ Ca(2/3). However, for a 3D foam, the crossover at a capillary number Ca** between both regimes is governed by the ratio of the osmotic pressure to the capillary pressure, such that Ca** ∼ (Π/Pc)(3/2).

Wave drag on floating bodies.

We measure the deceleration of liquid nitrogen drops floating at the surface of a liquid bath. On water, the friction force is found to be about 10 to 100 times larger than on a solid substrate, which is shown to arise from wave resistance. We investigate the influence of the bath viscosity and show that the dissipation decreases as the viscosity is increased, owing to wave damping. The measured resistance is well predicted by a model imposing a vertical force (i.e., the drop weight) on a finite area, as long as the wake can be considered stationary.

Bubble rearrangement duration in foams near the jamming point.

We investigate the dynamics of bubble rearrangements in coarsening foams, using a time-resolved multiple light scattering technique. We measure the average duration of such events as a function of the foam confinement pressure. Rearrangements slow down as the pressure is decreased toward the jamming point. Our results are explained by a scaling law based on the balance of pressure and Darcy flow, highlighting an analogy between wet foams with mobile interfaces and suspensions of hard grains.

Buckling of viscous filaments of a fluid under compression stresses.

We study the compression of viscous filaments at constant velocity. If slender enough, the filament bends, a viscous analogue of Euler elastic buckling. We measure the characteristic time of this viscous buckling and discuss the link with the elastic critical compression. We show that the analogy only holds in the limit of large capillary numbers. Otherwise capillarity has a stabilizing effect, which suppresses buckling.

Trapping leidenfrost drops with crenelations.

Drops placed on very hot solids levitate on a cushion of their own vapor, as discovered by Leidenfrost. This confers to these drops a remarkable mobility, which makes problematic their control and manipulation. Here we show how crenelated surfaces can be used to increase the friction of Leidenfrost drops by a factor on the order of 100, making them decelerate and be trapped on centimetric distances instead of the usual metric ones. We measure and characterize the friction force as a function of the design of the crenelations.

Simple ions control the elasticity of calcite gels via interparticle forces.

Suspensions of calcite in water are employed in many industrial fields such as paper filling, pharmaceutics or heritage conservation. Whereas organics are generally used to tune the rheological properties of the paste, we also expect simple ions to be able to control the suspension rheology via the interparticle forces. We have thus investigated the impact of calcium, sodium and hydroxide ions on the elasticity of a colloidal gel of nanocalcite. We confront our macroscopic measurements to DLVO interaction potentials, based on chemical speciation and measurements of the zeta potential. Upon addition of calcium hydroxide, we observe a minimum in shear modulus, correlated to a maximum in the DLVO energy barrier, due to two competing effects: Calcium adsorption onto calcite surface rises the zeta potential, while increasing salt concentration induces stronger electrostatic screening. We also demonstrate that the addition of sodium hydroxide completely screens the surface charge and leads to a more rigid paste. A second important result is that carbonation of the calcite suspensions by the atmospheric CO2 leads to a convergent high elasticity of the colloidal gels, whatever their initial value, also well rationalized by DLVO theory and resulting from a decrease in zeta potential.

Laser-speckle-visibility acoustic spectroscopy in soft turbid media.

We image the evolution in space and time of an acoustic wave propagating along the surface of turbid soft matter by shining coherent light on the sample. The wave locally modulates the speckle interference pattern of the backscattered light, which is recorded using a camera. We show both experimentally and theoretically how the temporal and spatial correlations in this pattern can be analyzed to obtain the acoustic wavelength and attenuation length. The technique is validated using shear waves propagating in aqueous foam. It may be applied to other kinds of acoustic waves in different forms of turbid soft matter such as biological tissues, pastes, or concentrated emulsions.

Duration of bubble rearrangements in a coarsening foam probed by time-resolved diffusing-wave spectroscopy: impact of interfacial rigidity.

In aqueous foams, the diffusive gas transfer among neighboring bubbles drives a coarsening process which is accompanied by intermittent rearrangements of the structure. Using time-resolved diffusing-wave spectroscopy, we probe the dynamics of these events as a function of the rigidity of the gas-liquid interfaces, liquid viscosity, bubble size, and confinement pressure. We present in detail two independent techniques for analyzing the light scattering data, from which we extract the rearrangement duration. Our results show that interfacial rheology has a major impact on this duration. In the case of low interfacial rigidity, the rearrangements strongly slow down as the pressure is decreased close to the value zero where the bubble packing unjams. In contrast, if the interfaces are rigid, rearrangement durations are independent of the confinement pressure in the same investigated range. Using scaling arguments, we discuss dissipation mechanisms that may explain the observed dependency of the rearrangement dynamics on foam structure, pressure, and physicochemical solution properties.

Delayed freezing on water repellent materials.

Water drops on hydrophobic microtextured materials sit on a mixture of solid and air. In standard superhydrophobic situations, the drop contacts more air than solid, so that we can think of exploiting the insulating properties of this sublayer. We show here that its presence induces a significant delay in freezing, when depositing water on cold solids. If the substrate is slightly tilted, these drops can thus be removed without freezing and without accumulating on the substrate, a property of obvious practical interest.