Foam coarsening in a yield stress fluid.

Foams coarsen because of pressure differences between bubbles of different sizes. We study the coarsening of quasi-2D foams made from model yield stress fluids: concentrated oil-in-water emulsions. We show that increasing the yield stress of the foamed emulsion continuous phase leads to both slower coarsening and irreversible structural change. The impact of the continuous phase rheology is stronger when the foamed emulsion is wetter or more confined. The bubble growth and organisation both become highly heterogeneous with an excess of small bubbles. We present a model that rationalises the impact of these three parameters by taking into account a resisting pressure required to displace the yield stress fluid around the bubbles.

Hierarchical bubble size distributions in coarsening wet liquid foams.

Coarsening of two-phase systems is crucial for the stability of dense particle packings such as alloys, foams, emulsions, or supersaturated solutions. Mean field theories predict an asymptotic scaling state with a broad particle size distribution. Aqueous foams are good model systems for investigations of coarsening-induced structures, because the continuous liquid as well as the dispersed gas phases are uniform and isotropic. We present coarsening experiments on wet foams, with liquid fractions up to their unjamming point and beyond, that are performed under microgravity to avoid gravitational drainage. As time elapses, a self-similar regime is reached where the normalized bubble size distribution is invariant. Unexpectedly, the distribution features an excess of small roaming bubbles, mobile within the network of jammed larger bubbles. These roaming bubbles are reminiscent of rattlers in granular materials (grains not subjected to contact forces). We identify a critical liquid fraction [Formula: see text], above which the bubble assembly unjams and the two bubble populations merge into a single narrow distribution of bubbly liquids. Unexpectedly, [Formula: see text] is larger than the random close packing fraction of the foam [Formula: see text]. This is because, between [Formula: see text] and [Formula: see text], the large bubbles remain connected due to a weak adhesion between bubbles. We present models that identify the physical mechanisms explaining our observations. We propose a new comprehensive view of the coarsening phenomenon in wet foams. Our results should be applicable to other phase-separating systems and they may also help to control the elaboration of solid foams with hierarchical structures.

Coarsening transitions of wet liquid foams under microgravity conditions.

We report foam coarsening studies which were performed in the International Space Station (ISS) to suppress drainage due to gravity. Foams and bubbly liquids with controlled liquid fractions ϕ between 15 and 50% were investigated to study the transition between bubble growth laws previously reported near the dry limit ϕ → 0 and the dilute limit ϕ → 1 (Ostwald ripening). We determined the coarsening rates for the driest foams and the bubbly liquids, they are in close agreement with theoretical predictions. We observe a sharp cross-over between the respective laws at a critical value ϕ*. At liquid fractions beyond this transition, neighboring bubbles are no longer all in contact, like at a jamming transition. Remarkably ϕ* is significantly larger than the random close packing volume fraction of the bubbles ϕrcp which was determined independently. We attribute the differences between ϕ* and ϕrcp to a weakly adhesive bubble interaction that we have studied in complementary ground-based experiments.

Daisy-shaped liquid bridges in foam-filled granular packings.

HYPOTHESIS: Many applications of liquid foams use them to fill the porosity of various granular media. How is the liquid distributed in such foam-filled systems, in which the geometry of the bubble assembly can be strongly constrained by pore confinement? EXPERIMENTS: We study how the liquid is distributed in a grain packing filled with liquid foam, as a function of both liquid content and bubble-to-grain size ratio. Moreover, Surface Evolver simulations are carried out at the scale of a single bubble confined into a tetrahedral pore. FINDINGS: We reveal that foam-filled granular assemblies exhibit a robust pendular-like regime, which is reminiscent of the pendular regime in unsaturated media. The main difference is that here the liquid bridges are daisy-shaped, i.e. with a liquid core bounded by bubbly petals. A simple theoretical model is proposed to describe the foam liquid bridges between contacting grains. In the case of large bubbles, the model is compared with the Surface Evolver simulation. The model is also applied to the case of wall liquid bridge, which is compared with the experimental observation. Beyond their geometrical characteristics, the presence of these liquid bridges, which can represent almost 25% of the liquid contained in the porosity, makes it possible to imagine a new approach (binder foam-based) to bind granular assemblies and turn them to solid materials.

Influence of the Immune Microenvironment Provided by Implanted Biomaterials on the Biological Properties of Masquelet-Induced Membranes in Rats: Metakaolin as an Alternative Spacer.

Macrophages play a key role in the inflammatory phase of wound repair and foreign body reactions-two important processes in the Masquelet-induced membrane technique for extremity reconstruction. The macrophage response depends largely on the nature of the biomaterials implanted. However, little is known about the influence of the macrophage microenvironment on the osteogenic properties of the induced membrane or subsequent bone regeneration. We used metakaolin, an immunogenic material, as an alternative spacer to standard polymethylmethacrylate (PMMA) in a Masquelet model in rats. Four weeks after implantation, the PMMA- and metakaolin-induced membranes were harvested, and their osteogenic properties and macrophage microenvironments were investigated by histology, immunohistochemistry, mass spectroscopy and gene expression analysis. The metakaolin spacer induced membranes with higher levels of two potent pro-osteogenic factors, transforming growth factor-ß (TGF-ß) and bone morphogenic protein-2 (BMP-2). These alternative membranes thus had greater osteogenic activity, which was accompanied by a significant expansion of the total macrophage population, including both the M1-like and M2-like subtypes. Microcomputed tomographic analysis showed that metakaolin-induced membranes supported bone regeneration more effectively than PMMA-induced membranes through better callus properties (+58%), although this difference was not significant. This study provides the first evidence of the influence of the immune microenvironment on the osteogenic properties of the induced membranes.

Stiffening colloidal gels by solid inclusions.

The elastic properties of a soft matter material can be greatly altered by the presence of solid inclusions whose microscopic properties, such as their size and interactions, can have a dramatic effect. In order to shed light on these effects we use extensive rheology computer simulations to investigate colloidal gels with solid inclusions of different sizes. We show that the elastic properties vary in a highly non-trivial way as a consequence of the interactions between the gel backbone and the inclusions. In particular, we show that the key aspects are the presence of the gel backbone and its mechanical alteration originating from the inclusions. To confirm our observations and their generality, we performed experiments on an emulsion that presents strong analogies with colloidal gels and confirms the trends observed in the simulations.

Wood-Mimicking Bio-Based Biporous Polymeric Materials with Anisotropic Tubular Macropores.

Understanding physical phenomena related to fluid flow transport in plants and especially through wood is still a major challenge for the scientific community. To this end, we have focused our attention on the design of wood-mimicking polymeric architectures through a strategy based on the double porogen templating approach which relies on the use of two distinct types of porogens, namely aligned nylon threads and a porogenic solvent, to produce macro- and nanoporosity levels, respectively. A bio-based phenolic functional monomer, i.e., vanillin methacrylate, was employed to mimic either hard wood or soft wood. Upon free-radical polymerization with a crosslinking agent in the presence of both types of porogenic agents, followed by their removal, biporous materials with anistotropic tubular macropores surrounded by a nanoporous matrix were obtained. They were further fully characterized in terms of porosity and chemical composition via mercury intrusion porosimetry, scanning electron microscopy and X-ray microtomography. It was demonstrated that the two porosity levels could be independently tuned by varying structural parameters. Further, the possibility to chemically modify the pore surface and thus to vary the material surface properties was successfully demonstrated by reductive amination with model compounds via Raman spectroscopy and water contact angle measurements.

Capillary imbibition in open-cell monodisperse foams.

HYPOTHESIS: Although capillary imbibition of solid foams is involved in many industrial applications, general theory for capillary imbibition has never been proved to apply for this specific class of porous materials. EXPERIMENTS: In order to compare accurately experiment and theory we produce solid foam samples with monodisperse pore size distributions and tunable pore volume fraction, and we measure their permeability (Darcy), their capillary pressure and their imbibition rate. FINDINGS: Our findings reveal that the imbibition velocity is qualitatively compatible with the Washburn theory but it is one order of magnitude smaller than the predicted value. This deviation is attributed to the excess time spent by the liquid-gas interface through connections between pores, for which an empirical expression is provided as a function of pore size and solid volume fraction. Our results provide the first step to understand deeply the imbibition process in foams and to predict imbibition rates for various foamed materials.

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.

Synergistic actions of mixed small and large pores for capillary absorption through biporous polymeric materials.

Water absorption in porous media is an important process involved in numerous materials for various applications, such as in the building industry, food processing and bioengineering. Designing new materials with appropriate absorption properties requires an understanding of how absorption behavior depends on both the material's morphology and the properties of the solid matrix, i.e. hydrophilic/hydrophobic nature and swelling/deformation properties. Although the basic principles of imbibition are well-known for simple porous systems, much less is known about absorption in complex porous systems, in particular those containing several coexisting porous phases, such as wood for example. Here, water absorption is studied for model porous organic materials exhibiting several degrees of hydrophobicity and two pore size levels, either as monoporous materials (large or small pores) or as biporous materials (mixed large and small pores). The interconnected biporous structure is designed via a double porogen templating approach using cubic sodium chloride particles as templates for the generation of the larger pore size (250-400 µm) and i-PrOH as a porogenic solvent for the smaller pore size (2-5 µm). While absorption for the small pore material is well described by the classical Washburn theory, the large pore material shows a drastic reduction in the imbibition rate. This behavior is attributed to the slow breakthrough mechanism for the water interface at sharp edge connections between pores. Remarkably, this slow regime is suppressed for the biporous material and the imbibition rate is even higher than the sum of rates obtained for its monoporous counterparts, which highlights the synergistic action of mixed small and large pores.

Gas Marbles: Much Stronger than Liquid Marbles.

Enwrapping liquid droplets with hydrophobic particles allows the manufacture of so-called "liquid marbles" [Aussillous and Quéré Nature (London) 411, 924 (2001); NATUAS0028-083610.1038/35082026Mahadevan Nature (London)411, 895 (2001)NATUAS0028-083610.1038/35082164]. The recent intensive research devoted to liquid marbles is justified by their very unusual physical and chemical properties and by their potential for various applications, from microreactors to water storage, including water pollution sensors [Bormashenko Curr. Opin. Colloid Interface Sci. 16, 266 (2011)COCSFL1359-029410.1016/j.cocis.2010.12.002]. Here we demonstrate that this concept can be successfully applied for encapsulating and protecting small gas pockets within an air environment. Similarly to their liquid counterparts, those new soft-matter objects, that we call "gas marbles," can sustain external forces. We show that gas marbles are surprisingly tenfold stronger than liquid marbles and, more importantly, they can sustain both positive and negative pressure differences. This magnified strength is shown to originate from the strong cohesive nature of the shell. Those interesting properties could be exploited for imprisoning valuable or polluted gases or for designing new aerated materials.

The drainage of foamy granular suspensions.

Foam-based materials are promising micro-structured materials with interesting thermal and acoustical properties. The control of the material morphology requires counteracting all the destabilizing mechanisms during their production, starting with the drainage process, which remains to be understood in the case of the complex fluids that are commonly used to be foamed. Here we perform measurements for the drainage velocity of aqueous foams made with granular suspensions of hydrophilic monodisperse particles and we show that the effect of the particles can be accounted by two parameters: the volume fraction of particles in the suspension (φp) and the confinement parameter (λ), that compares the particle size to the size of passage through constrictions in the foam network. We report data over wide ranges for those two parameters and we identify all the regimes and transitions occurring in the φp-λ diagram. In particular, we highlight a transition which refers to the included/excluded configuration of the particles with respect to the foam network, and makes the drainage velocity evolve from its minimal value (fully included particles) to its maximal one (fully excluded particles). We also determine the conditions (φp,λ) leading to the arrest of the drainage process.

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.

Foam invasion through a single pore.

We investigate experimentally the behavior of liquid foams pumped at a given flow rate through a single pore, in the situation where the pore diameter is smaller than the bubble diameter. Results reveal that foam invasion can be observed only within a restricted range of values for the dimensionless flow rate and the foam liquid fraction. Within this foam invasion regime, the liquid content of invading foams is measured to be three times higher than the initial liquid content. Outside this regime, both gas alone and liquid alone invasion regimes can be observed. The gas invasion regime results from the rupture of foam films during local T1, during bubble rearrangements events induced by foam flow, whereas the liquid invasion regime is allowed by the formation of a stable cluster of jammed bubbles at the pore's opening.

How topological rearrangements and liquid fraction control liquid foam stability.

The stability of foam is investigated experimentally through coalescence events. Instability (coalescence) occurs when the system is submitted to external perturbations (T1) and when the liquid amount in the film network is below a critical value. Microscopically, transient thick films are observed during film rearrangements. Film rupture, with coalescence and eventual collapse of the foam, occurs when the available local liquid amount is too small for transient films to be formed. Similar experiments and results are shown in the two-bubble case.

Forced impregnation of a capillary tube with drop impact.

We experimentally investigate how the impregnation of porous media can be forced using the initial kinetic energy of an impacting drop. We focus on the scale of a single pore--either hydrophilic or hydrophobic--and thus study the impact of a single drop falling on vertical cylindrical capillary tubes. This experimental configuration therefore differs from the impregnation of a porous media because of the finite volume of the drop and its initial kinetic energy. We observe different limit regimes: at low impact velocity, we recover the classical results for impregnation. The liquid does not impregnate the hydrophobic pore while it is totally sucked into the hydrophilic one. At high impact velocities, the drop is broken in two parts: one part spreads at the top of the surface while an isolated slug is trapped within the pore. We determine the critical speeds for these regimes and obtain a full phase-diagram for our observations. We also stress the characteristics of impregnating slugs namely their volume and their motion within the pores.

Foam drainage in the presence of nanoparticle-surfactant mixtures.

The drainage of SiO(2) nanoparticle-cationic surfactant (TTAB) mixtures through calibrated aqueous foams had been studied by combining several approaches on both the macroscopic and the local scale. Macroscopic measurements reveal a strong stabilizing effect arising for nanoparticle concentrations as low as 2 wt % mainly because of a drainage kinetic slow-down dependent on the nanoparticle concentration. We show that the variation of the viscous parameters (bulk viscosity, interfacial viscosity, or both) in the classical theoretical models of foam drainage, mainly developed for aqueous surfactant solutions, does not enable fitting experimental data obtained via steady- or free-drainage strategies for [SiO(2)] > or = 2 wt %. In contrast, the quantitative analysis of the data obtained from front propagation velocities has revealed a drainage regime transition from a node-dominated regime toward a Plateau-border-dominated regime upon nanoparticle concentration increase. Observations performed at the Plateau border scale brought to light the drainage kinetic slow-down process by evidencing that the presence of insoluble aggregates induces traffic jamming and even cork formation for silica concentrations above 2 wt %. Considering these observations, a simple mechanism of aggregate growth and cork formation is proposed. Finally, we analyze the discrepancy between experiments (steady- and free-drainage methods) and theory by pointing out that the hypothesis relative to the foam structure that is usually assumed for both the liquid fraction calculation and the determination via conductivity measurements is strongly modified when large insoluble aggregates are present in the system. In this view, the method based on the liquid fraction determination through the measurement of the front propagation velocity seems to be the most suitable for studying the drainage of colloidal dispersion because of the lower dependence of this approach toward hypothesis on the local geometry of the foam continuous phase.

Quasistatic detachment of a sphere from a liquid interface.

In this paper the problem of removing a spherical particle initially attached to a liquid-gas interface is analytically treated. In particular, the Derjaguin equation for small radii is used to derive a closed-form approximate expression for the work of detachment of the sphere from the interface. Expressions corresponding to the prescribed displacement condition and the applied force condition, which seems to be the relevant condition for the flotation separation process, are presented. A special effort has been made to closely compare analytical results with data obtained through the exact numerical treatment of the detachment process. Results show that proposed expressions are sufficiently accurate to calculate the energy required to detach the sphere from the interface as soon as the sphere radius is small compared to the capillary length. Validity limits are specified.