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We study the efficiency of several Asymmetrical Flow Field-Flow Fractionation (AF4) techniques to investigate the self-associating wheat gluten proteins. We compare the use of a denaturing buffer including sodium dodecyl sulfate (SDS) and a mild chaotropic solvent, water/ethanol, as eluent, on a model gluten sample. Through a thorough analysis of the data obtained from coupled light scattering detectors, and with the identification of molecular composition of the eluted protein, we evidence co-elution events in several conditions. We show that the focus step used in conventional AF4 with the SDS buffer leads to the formation of aggregates that co-elute with monomeric proteins. By contrast, a frit-inlet device enables the fractionation of individual wheat proteins in the SDS buffer. Interestingly conventional AF4, using water/ethanol as eluent, is an effective method for fractionating gluten proteins and their complex dynamic assemblies which involve weak forces and are composed of both monomeric and polymeric proteins.

We study model near-critical polymer gelling systems made of gluten proteins dispersions stabilized at different distances from the gel point. We impose different shear rates and follow the time evolution of the stress. For sufficiently large shear rates, an intermediate stress overshoot is measured before reaching the steady state. We evidence self-similarity of the stress overshoot as a function of the applied shear rate for samples with various distances from the gel point, which is related to the elastic energy stored by the samples, as for dense systems close to the jamming transition. In concordance with the findings for glassy and jammed systems, we also measure that the stress after flow cessation decreases as a power law with time with a characteristic relaxation time that depends on the shear rate previously imposed. These features revealed in non-linear rheology could be the signature of a mesoscopic dynamics, which would depend on the extent of gelation., Comment: 10.1021/acsmacrolett.4c00121

We present a novel dynamic light scattering setup to probe, with time and space resolution, the microscopic dynamics of soft matter systems confined within millimeter-sized spherical drops. By using an ad-hoc optical layout, we tackle the challenges raised by refraction effects due to the unconventional shape of the samples. We first validate the setup by investigating the dynamics of a suspension of Brownian particles. The dynamics measured at different positions in the drop, and hence different scattering angles, are found to be in excellent agreement with those obtained for the same sample in a conventional light scattering setup. We then demonstrate the setup capabilities by investigating a bead made of a polymer hydrogel undergoing swelling. The gel microscopic dynamics exhibit a space dependence that strongly varies with time elapsed since the beginning of swelling. Initially, the dynamics in the periphery of the bead are much faster than in the core, indicative of non-uniform swelling. As the swelling proceeds, the dynamics slow down and become more spatially homogeneous. By comparing the experimental results to numerical and analytical calculations for the dynamics of a homogeneous, purely elastic sphere undergoing swelling, we establish that the mean square displacement of the gel strands deviates from the affine motion inferred from the macroscopic deformation, evolving from fast diffusive-like dynamics at the onset of swelling to slower, yet supradiffusive, rearrangements at later stages.

Soft amorphous materials are viscoelastic solids ubiquitously found around us, from clays and cementitious pastes to emulsions and physical gels encountered in food or biomedical engineering. Under an external deformation, these materials undergo a noteworthy transition from a solid to a liquid state that reshapes the material microstructure. This yielding transition was the main theme of a workshop held from January 9 to 13, 2023 at the Lorentz Center in Leiden. The manuscript presented here offers a critical perspective on the subject, synthesizing insights from the various brainstorming sessions and informal discussions that unfolded during this week of vibrant exchange of ideas. The result of these exchanges takes the form of a series of open questions that represent outstanding experimental, numerical, and theoretical challenges to be tackled in the near future., Comment: 21 pages, 7 figures, perspective on the workshop 'Yield stress and fluidization in brittle and ductile amorphous systems' held from January 9 to 13, 2023 at the Lorentz Center in Leiden

Concentrated colloidal suspensions and emulsions are amorphous soft solids, widespread in technological and industrial applications and studied as model systems in physics and material sciences. They are easily fluidized by applying a mechanical stress, undergoing a yielding transition that still lacks a unified description. Here, we investigate yielding in three classes of repulsive soft solids, using analytical and numerical modelling and experiments probing the microscopic dynamics and mechanical response under oscillatory shear. We find that at the microscopic level yielding consists in a transition between two distinct dynamical states, which we rationalize by proposing a lattice model with dynamical coupling between neighboring sites, leading to a unified state diagram for yielding. Leveraging the analogy with Wan der Waals's phase diagram for real gases, we show that distance from a critical point plays a major role in the emergence of first-order-like vs second-order-like features in yielding, thereby reconciling previously contrasting observations on the nature of the transition., Comment: 23 pages, 5 figures

Understanding the origin of the unique rheological properties of wheat gluten, the protein fraction of wheat grain, is crucial in bread-making processes and questions scientists since polymeric glutenins. To better understand the respective role of the different classes of proteins in the supramolecular structure of gluten and its link to the material properties, we investigate here concentrated dispersions of gluten proteins in water with a fixed total protein concentration but variable composition in gliadin and glutenin. Linear viscoelasticity measurements show a gradual increase of the viscosity of the samples as the glutenin mass content increases from 7 to 66%. While the gliadin-rich samples are microphase-separated viscous fluids, homogeneous and transparent pre-gel and gels are obtained with the replacement of gliadin by glutenin. To unravel the flow properties of the gluten samples, we perform shear start-up experiments at different shear-rates. In accordance with the linear viscoelastic signature, three classes of behaviour are evidenced depending on the protein composition. As samples get depleted in gliadin and enriched in glutenin, distinctive features are measured: (i) viscosity undershoot suggesting droplet elongation for microphase-separated dispersions, (ii) stress overshoot and partial structural relaxation for near-critical pre-gels, and (iii) strain hardening and flow instabilities of gels. We discuss the experimental results by analogy with the behaviour of model systems, including viscoelastic emulsions, branched polymer melts and critical gels, and provide a consistent physical picture of the supramolecular features of the three classes of protein dispersions.

When a drop of fluid hits a small solid target of comparable size, it expands radially until reaching a maximum diameter and subsequently recedes. In this work, we show that the expansion process of liquid sheets is controlled by a combination of shear (on the target) and biaxial extensional (in the air) deformations. We propose an approach toward a rational description of the phenomenon for Newtonian and viscoelastic fluids by evaluating the viscous dissipation due to shear and extensional deformations, yielding a prediction of the maximum expansion factor of the sheet as a function of the relevant viscosity. For Newtonian systems, biaxial extensional and shear viscous dissipation are of the same order of magnitude. On the contrary, for thinning solutions of supramolecular polymers, shear dissipation is negligible compared to biaxial extensional dissipation and the biaxial thinning extensional viscosity is the appropriate quantity to describe the maximum expansion of the sheets. Moreover, we show that the rate-dependent biaxial extensional viscosities deduced from drop impact experiments are in good quantitative agreement with previous experimental data and theoretical predictions for various viscoelastic liquids.

We investigate freely expanding viscoelastic sheets. The sheets are produced by the impact of drops on a quartz plate covered with a thin layer of liquid nitrogen that suppresses shear viscous dissipation as a result of the cold Leidenfrost effect. The time evolution of the sheet is simultaneously recorded from top and side views using high-speed cameras. The investigated viscoelastic fluids are Maxwell fluids, which are characterized by low elastic moduli, and relaxation times that vary over almost two orders of magnitude, thus giving access to a large spectrum of viscoelastic and elastocapillary effects. For the purposes of comparison, Newtonian fluids, with viscosity varying over three orders of magnitude, are also investigated. In this study, $d_{\mathrm{max}}$, the maximal expansion of the sheets, and $t_{\mathrm{max}}$ the time to reach this maximal expansion from the time at impact, are measured as a function of the impact velocity. By using a generalized damped harmonic oscillator model, we rationalize the role of capillarity, bulk elasticity and viscous dissipation in the expansion dynamics of all investigated samples. In the model, the spring constant is a combination of the surface tension and the bulk dynamic elastic modulus. The time-varying damping coefficient is associated to biaxial extensional viscous dissipation and is proportional to the dynamic loss modulus. For all samples, we find that the model reproduces accurately the experimental data for $d_{\mathrm{max}}$ and $t_{\mathrm{max}}$., Comment: Accepted for publication in Soft Matter

We investigate the structure of gluten polymer-like gels in a binary mixture of water/ethanol, $50/50$ v/v, a good solvent for gluten proteins. Gluten comprises two main families of proteins, monomeric gliadins and polymer glutenins. In the semi-dilute regime, scattering experiments highlight two classes of behavior, akin to standard polymer solution and polymer gel, depending on the protein composition. We demonstrate that these two classes are encoded in the structural features of the proteins in very dilute solution, and are correlated with the presence of proteins assemblies of typical size tens of nanometers. The assemblies only exist when the protein mixture is sufficiently enriched in glutenins. They are found directly associated to the presence in the gel of domains enriched in non-exchangeable H-bonds and of size comparable to that of the protein assemblies. The domains are probed in neutron scattering experiments thanks to their unique contrast. We show that the sample visco-elasticity is also directly correlated to the quantity of domains enriched in H-bonds, showing the key role of H-bonds in ruling the visco-elasticity of polymer gluten gels., Comment: accepted for publication in Journal of Physics: Condensed Matter, Special issue on "Glasses and gels: a crossroad of molecular liquids, polymers and colloids"

We investigate the delayed rupture of biopolymer gels under a constant shear load by simultaneous dynamic light scattering and rheology measurements. We unveil the crucial role of normal stresses built up during gelation: all samples that eventually fracture self-weaken during the gelation process, as revealed by a partial relaxation of the normal stress concomitant to a burst of microscopic plastic rearrangements. Upon applying a shear stress, weakened gels exhibit in the creep regime distinctive signatures in their microscopic dynamics, which anticipate macroscopic fracture by up to thousands of seconds. The dynamics in fracturing gels are faster than those of non-fracturing gels and exhibit large spatio-temporal fluctuations. A spatially localized region with significant plasticity eventually nucleates, expands progressively, and finally invades the whole sample triggering macroscopic failure., Comment: accepted for publication in Physical Review Letters

We investigate the linear viscoelasticity of polymer gels produced by the dispersion of gluten proteins in water:ethanol binary mixtures with various ethanol contents, from pure water to 60% v/v ethanol. We show that the complex viscoelasticity of the gels exhibits a time/solvent composition superposition principle, demonstrating the self-similarity of the gels produced in different binary solvents. All gels can be regarded as near critical gels with characteristic rheological parameters, elastic plateau and characteristic relaxation time, which are related one to another, as a consequence of self-similarity, and span several orders of magnitude when changing the solvent composition. Thanks to calorimetry and neutron scattering experiments, we evidencea co-solvency effect with a better solvation of the complex polymer-like chains of the gluten proteins as the amount of ethanol increases. Overall the gel viscoelasticity can be accounted for by a unique characteristic length characterizing the crosslink density of the supramolecular network, which is solvent composition-dependent. On a molecular level, these findings could be interpreted as a transition of the supramolecular interactions, mainly H-bonds, from intra- to interchains, which would be facilitated by the disruption of hydrophobic interactions by ethanol molecules. This work provides new insight for tailoring the gelation process of complex polymer gels., Comment: Macromolecules. In press 2020

We investigate freely expanding liquid sheets made of either simple Newtonian fluids or solutions of high molecular water-soluble polymer chains. A sheet is produced by the impact of a drop on a quartz plate covered with a thin layer of liquid nitrogen that suppresses shear viscous dissipation thanks to an inverse Leidenfrost effect. The sheet expands radially until reaching a maximum diameter and subsequently recedes. Experiments indicate the presence of two expansion regimes: the capillary regime, where the maximum expansion is controlled by surface tension forces and does not depend on the viscosity, and the viscous regime, where the expansion is reduced with increasing viscosity. In the viscous regime, the sheet expansion for polymeric samples is strongly enhanced as compared to that of Newtonian samples with comparable zero-shear viscosity. We show that data for Newtonian and non-Newtonian fluids collapse on a unique master curve where the maximum expansion factor is plotted against the relevant effective biaxial extensional Ohnesorge number that depends on fluid density, surface tension and the biaxial extensional viscosity. For Newtonian fluids, this biaxial extensional viscosity is six times the shear viscosity. By contrast, for the non- Newtonian fluids, a characteristic Weissenberg number-dependent biaxial extensional viscosity is identified, which is in quantitative agreement with experimental and theoretical results reported in the literature for biaxial extensional flows of polymeric liquids., Comment: 10 pages, 9 figures, accepted for publication in Phys. Rev. Fluids

The mechanical properties of soft matter are of great importance in countless applications, in addition of being an active field of academic research. Given the relative ease with which soft materials can be deformed, their non-linear behavior is of particular relevance. Large loads eventually result in material failure. In this Perspective article, we discuss recent work aiming at detecting precursors of failure by scrutinizing the microscopic structure and dynamics of soft systems under various conditions of loading. In particular, we show that the microscopic dynamics is a powerful indicator of the ultimate fate of soft materials, capable of unveiling precursors of failure up to thousands of seconds before any macroscopic sign of weakening., Comment: 12 pages, 7 figures

Material failure is ubiquitous, with implications from geology to everyday life and material science. It often involves sudden, unpredictable events, with little or no macroscopically detectable precursors. A deeper understanding of the microscopic mechanisms eventually leading to failure is clearly required, but experiments remain scarce. Here, we show that the microscopic dynamics of a colloidal gel, a model network-forming system, exhibit dramatic changes that precede its macroscopic failure by thousands of seconds. Using an original setup coupling light scattering and rheology, we simultaneously measure the macroscopic deformation and the microscopic dynamics of the gel, while applying a constant shear stress. We show that the network failure is preceded by qualitative and quantitative changes of the dynamics, from reversible particle displacements to a burst of irreversible plastic rearrangements.

We investigate freely expanding sheets formed by ultrasoft gel beads, and liquid and viscoelastic drops, produced by the impact of the bead or drop on a silicon wafer covered with a thin layer of liquid nitrogen that suppresses viscous dissipation thanks to an inverse Leidenfrost effect. Our experiments show a unified behaviour for the impact dynamics that holds for solids, liquids, and viscoelastic fluids and that we rationalize by properly taking into account elastocapillary effects. In this framework, the classical impact dynamics of solids and liquids as far as viscous dissipation is negligible, appears as the asymptotic limits of a universal theoretical description. A novel material-dependent characteristic velocity that includes both capillary and bulk elasticity emerges from this unified description of the physics of impact., Comment: to appear in PRL

Power law rheology is of widespread occurrence in complex materials that are characterized by the presence of a very broad range of microstructural length and time scales. Although phenomenological models able to reproduce the observed rheological features exist, in general a well-established connection with the microscopic origin of this mechanical behavior is still missing. As a model system, this work focuses on a fractal colloidal gel. We thoroughly characterize the linear power law rheology of the sample and its age dependence. We show that at all sample ages and for a variety of rheological tests the gel linear viscoelasticity is very accurately described by a Fractional Maxwell (FM) model, characterized by a power law behavior. Thanks to a unique set-up that couples small-angle static and dynamic light scattering to rheological measurements, we demonstrate that the power law rheology observed in the linear regime originates from reversible non-affine rearrangements and discuss the possible relationship between the FM model and the microscopic structure of the gel.

We investigate the nucleation and propagation of cracks in self-assembled viscoelastic fluids, which are made of surfactant micelles reversibly linked by telechelic polymers. The morphology of the micelles can be continuously tuned, from spherical to rod-like to wormlike, thus producing transient double networks when the micelles are sufficiently long and entangled, and transient single networks otherwise. For a single network, we show that cracks nucleate when the sample deformation rate involved is comparable to the relaxation time scale of the network. For a double network, by contrast, significant rearrangements of the micelles occur as a crack nucleates and propagates. We show that birefringence develops at the crack tip over a finite length, $\xi$, which corresponds to the length scale over which micelles alignment occur. We find that $\xi$ is larger for slower cracks, suggesting an increase of ductility., Comment: 10 pages, 4 figures

We investigate the dynamics of freely expanding liquid sheets prepared with fluids with different rheological properties, (i) viscous fluids with a zero-shear viscosity $\eta_0$ in the range $(1-1000) \, \mathrm{mPa.s}$ and (ii) viscoelastic Maxwell fluids whose elastic modulus, $G_0$, characteristic relaxation time, $\tau$, and zero-shear viscosity, $\eta_0=G_0 \tau$, can be tuned over several orders of magnitude. The sheets are produced by impacting a drop of fluid on a small cylindrical solid target. For viscoelastic fluids, we show that, when $\tau$ is shorter than the typical lifetime of the sheet ($\sim 10$ ms), the dynamics of the sheet is similar to that of Newtonian viscous liquids with equal zero-shear viscosity. In that case, for little viscous samples ($\eta_0 <\sim 30$ mPa.s), the maximal expansion of the sheet, $d_{\rm{max}}$, is independent of $\eta_0$, whereas for more viscous samples, $d_{\rm{max}}$ decreases as $\eta_0$ increases. We provide a simple model to account for the dependence of the maximal expansion of the sheet with the viscosity that is based on an energy balance between inertia, surface tension and viscous shear dissipation on the solid target, and which accounts well for our experimental data. By contrast, when $\tau$ is longer than the typical lifetime of the sheet, the behavior drastically differs. The sheet expansion is strongly enhanced as compared to that of viscous samples with comparable zero-shear viscosity, but is heterogeneous with the occurrence of cracks, revealing the elastic nature of the viscoelastic fluid., Comment: 10 pages, 9 figures

We study the destabilization mechanism of thin liquid sheets expanding in air and show that dilute oil-in-water emulsion-based sheets disintegrate through the nucleation and growth of holes that perforate the sheet. The velocity and thickness fields of the sheet outside the holes are not perturbed by holes and hole opening follows a Taylor-Culick law. We find that a pre-hole, which widens and thins out the sheet with time, systematically precedes the hole nucleation. The growth dynamics of the pre-hole follows the law theoretically predicted for a liquid spreading on another liquid of higher surface tension due to Marangoni stresses. Classical Marangoni spreading experiments quantitatively corroborate our findings., Comment: Physical Review Letters in press

We investigate how the microstructure of a colloidal polycrystal influences its linear viscoelasticity. We use thermosensitive copolymer micelles that arrange in water in a cubic crystalline lattice, yielding a colloidal polycrystal. The polycrystal is doped with a small amount of nanoparticles, of size comparable to that of the micelles, which behave as impurities and thus partially segregate in the grain boundaries. We show that the shear elastic modulus only depends on the packing of the micelles and does not vary neither with the presence of nanoparticles nor with the crystal microstructure. By contrast, we find that the loss modulus is strongly affected by the presence of nanoparticles. A comparison between rheology data and small-angle neutron scattering data suggests that the loss modulus is dictated by the total amount of nanoparticles in the grain boundaries, which in turn depends on the sample microstructure.

Structuring wheat gluten proteins into gels with tunable mechanical properties would provide more versatility for the production of plant protein-rich food products. Gluten, a strongly elastic protein material insoluble in water, is hardly processable. We use a novel fractionation procedure allowing the isolation from gluten of a water/ethanol soluble protein blend, enriched in glutenin polymers at an unprecedented high ratio (50%). We investigate here the viscoelasticity of suspensions of the protein blend in a water/ethanol (50/50 v/v) solvent, and show that, over a wide range of concentrations, they undergo a spontaneous gelation driven by hydrogen bonding. We successfully rationalize our data using percolation models and relate the viscoelasticity of the gels to their fractal dimension measured by scattering techniques. The gluten gels display self-healing properties and their elastic plateaus cover several decades, from 0.01 to 10000 Pa. In particular very soft gels as compared to standard hydrated gluten can be produced., Comment: Food Hydrocolloids, in press

The collision of a liquid drop against a small target results in the formation of a thin liquid sheet that extends radially until it reaches a maximum diameter. The subsequent retraction is due to the air-liquid surface tension. We have used a time- and space-resolved technique to measure the thickness field of this class of liquid sheet, based on the grey level measurement of the image of a dyed liquid sheet recorded using a fast camera. This method enables a precise measurement of the thickness in the range $(10-450) \, \mathrm{\mu m}$, with a temporal resolution equal to that of the camera. We have measured the evolution with time since impact, $t$, and radial position, $r$, of the thickness, $h(r,t)$, for various drop volumes and impact velocities. Two asymptotic regimes for the expansion of the sheet are evidenced. The scalings of the thickness with $t$ and $r$ measured in the two regimes are those that were predicted in \citet{Rozhkov2004} fort the short-time regime and \citet{Villermaux2011} for the long time regime, but never experimentally measured before. Interestingly, our experimental data also evidence the existence of a maximum of the film thickness $h_{\rm{max}}(r)$ at a radial position $r_{\rm{h_{max}}}(t)$ corresponding to the crossover of these two asymptotic regimes. The maximum moves with a constant velocity of the order of the drop impact velocity, as expected theoretically. Thanks to our visualization technique, we also evidence an azimuthal thickness modulation of the liquid sheets., Comment: accepted for publication in Journal of Fluid Mechanics

The supramolecular organization of wheat gluten proteins is largely unknown due to the intrinsic complexity of this family of proteins and their insolubility in water. We fractionate gluten in a water/ethanol (50/50 v/v) and obtain a protein extract which is depleted in gliadin, the monomeric part of wheat gluten proteins, and enriched in glutenin, the polymeric part of wheat gluten proteins. We investigate the structure of the proteins in the solvent used for extraction over a wide range of concentration, by combining X-ray scattering and multi-angle static and dynamic light scattering. Our data show that, in the ethanol/water mixture, the proteins display features characteristic of flexible polymer chains in a good solvent. In the dilute regime, the protein form very loose structures of characteristic size 150 nm, with an internal dynamics which is quantitatively similar to that of branched polymer coils. In more concentrated regimes, data highlight a hierarchical structure with one characteristic length scale of the order of a few nm, which displays the scaling with concentration expected for a semi-dilute polymer in good solvent, and a fractal arrangement at much larger length scale. This structure is strikingly similar to that of polymeric gels, thus providing some factual knowledge to rationalize the viscoelastic properties of wheat gluten proteins and their assemblies., Comment: to appear in Journal of Physical Chemistry B

We use confocal microscopy and time-resolved light scattering to investigate plasticity in a col- loidal polycrystal, following the evolution of the network of grain boundaries as the sample is submitted to thousands of shear deformation cycles. The grain boundary motion is found to be ballistic, with a velocity distribution function exhibiting non-trivial power law tails. The shear- induced dynamics initially slow down, similarly to the aging of the spontaneous dynamics in glassy materials, but eventually reach a steady state. Surprisingly, the cross-over time between the ini- tial aging regime and the steady state decreases with increasing probed length scale, hinting at a hierarchical organization of the grain boundary dynamics., Comment: main paper + supplementary materials

Fracture processes are ubiquitous in soft materials, even in complex fluids, subjected to stresses. To investigate these processes in a simple geometry, we use a model self-assembled transient gel and study the instability patterns obtained in a radial Hele-Shaw cell when a low viscosity oil pushes the more viscous transient gel. Thanks to an analysis of the morphology of the patterns, we find a discontinuous transition between the standard Saffman-Taylor fingering instability and a fracturing instability as the oil injection rate increases. Our data suggest that the flow properties of the gel ahead of the finger tip controls the transition towards fracturing. By analyzing the displacement field of the gel in the vicinity of the fingers and cracks, we show that in the fingering regime, the oil gently pushes the gel, whereas in the fracturing regime, the crack tears apart the gel, resulting in a strong drop of the gel velocity ahead of the crack tip as compared to the tip velocity. We find a unique behavior for the whole displacement field of a gel around a crack, which is drastically different from that around a finger, and reveals the solid-like behavior of the gel at short time. Our experiments and analysis provide quantitative yet simple tools to unambiguously discriminate a finger from a crack in a visco-elastic material., Comment: to appear in Soft Matter

We use hexagonal mesophases made of oil-swollen surfactant-stabilized tubes arranged on a triangular lattice in water and doped with metallic salts as templates for the radiolytic synthesis of nanostructures. The nanostructures formed in this type of soft matrix are bimetallic palladium-platinum porous nanoballs composed of 3D-connected nanowires, of typical thickness 2.5 nm, forming hexagonal cells. We demonstrate using electron microscopy and small-angle X-ray scattering that the pore size of the nanoballs is directly determined by the diameter of the oil tube of the doped mesophases, which we have varied in a controlled fashion from 10 to 55 nm. Bimetallic nanostructures comprising various proportions of palladium and platinum can be synthesized. Their alloy structure was evidenced by X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, and high-angular dark field scanning transmission electron microscopy experiments. Our templating approach allows therefore the synthesis of bimetallic nanoballs of tunable porosity and composition.

We investigate by scattering techniques the structure of water-based soft composite materials comprising a crystal made of Pluronic block-copolymer micelles arranged in a face-centered cubic lattice and a small amount (at most 2% by volume) of silica nanoparticles, of size comparable to that of the micelles. The copolymer is thermosensitive: it is hydrophilic and fully dissolved in water at low temperature (T ~ 0{\deg}C), and self-assembles into micelles at room temperature, where the block-copolymer is amphiphilic. We use contrast matching small-angle neuron scattering experiments to probe independently the structure of the nanoparticles and that of the polymer. We find that the nanoparticles do not perturb the crystalline order. In addition, a structure peak is measured for the silica nanoparticles dispersed in the polycrystalline samples. This implies that the samples are spatially heterogeneous and comprise, without macroscopic phase separation, silica-poor and silica-rich regions. We show that the nanoparticle concentration in the silica-rich regions is about tenfold the average concentration. These regions are grain boundaries between crystallites, where nanoparticles concentrate, as shown by static light scattering and by light microscopy imaging of the samples. We show that the temperature rate at which the sample is prepared strongly influence the segregation of the nanoparticles in the grain-boundaries., Comment: accepted for publication in Langmuir

We study the crystallization of a colloidal model system in presence of secondary nanoparticles acting as impurities. Using confocal microscopy, we show that the nanoparticles segregate in the grain boundaries of the colloidal polycrystal. We demonstrate that the texture of the polycrystal can be tuned by varying independently the nanoparticle volume fraction and the crystallization rate, and quantify our findings using standard models for the nucleation and growth of crystalline materials. Remarkably, we find that the efficiency of the segregation of the nanoparticles in the grain-boundaries is determined solely by the typical size of the crystalline grains., Comment: accepted for publication in Soft Matter

We study the nonlinear rheology of a novel class of transient networks, made of surfactant micelles of tunable morphology reversibly linked by block copolymers. We couple rheology and time-resolved structural measurements, using synchrotron radiation, to characterize the highly nonlinear viscoelastic regime. We propose the fluctuations of the degree of alignment of the micelles under shear as a probe to identify a fracture process. We show a clear signature of a brittle-to-ductile transition in transient gels, as the morphology of the micelles varies, and provide a parallel between the fracture of solids and the fracture under shear of viscoelastic fluids.

We use light microscopy to investigate the aging dynamics of a glass made of closely packed soft spheres, following a rapid transition from a fluid to a solid-like state. By measuring time-resolved, coarse-grained displacements fields, we identify two classes of dynamical events, corresponding to reversible and irreversible rearrangements, respectively. The reversible events are due to the small, experimentally unavoidable fluctuations of the temperature imposed to the sample, leading to transient thermal expansions and contractions that cause shear deformations. The irreversible events are plastic rearrangements, induced by the repeated shear cycles. We show that the displacement due to the irreversible rearrangements grows linearly with time, both on average and at a local level. The velocity associated with this ballistic motion decreases exponentially with sample age, accounting for the observed slowing down of the dynamics. The displacement field due to the irreversible rearrangements has a vortex-like structure and is spatially correlated over surprisingly long distances., Comment: 10 pages, 7 figures, submitted to PRE

We show quantitatively that tiny amounts of copolymer that decorate a oil/water interfaces can greatly enhance the stability of swollen surfactant hexagonal phases, comprising oil tubes regularly arranged in a water matrix. Such soft composite materials, whose both radius of the tubes and water channel between the tubes can be controlled independently over large ranges, offer a potential interest for the synthesis of mesoporous materials.

We present real-time observations by confocal microscopy of the dynamic behavior of multilamellar vesicles (MLVs), composed of charged synthetic lipids, when put in contact with oppositely charged polyelectrolyte (PE) molecules. We find that the MLVs exhibit astonishing morphological transitions, which result from the discrete and progressive binding of the charged bilayers induced by a high PE concentration gradient. Our physical picture is confirmed by quantitative measurements of the fluorescence intensity as the bilayers bind to each other. The shape transitions lead eventually to the spontaneous formation of hollow capsules, whose thick walls are composed of lipid multilayers condensed with PE molecules. This class of objects may have some (bio)technological applications., Comment: to appear in JACS (2007)

We use time-resolved X-Photon Correlation Spectroscopy to investigate the slow dynamics of colloidal gels made of moderately attractive carbon black particles. We show that the slow dynamics is temporally heterogeneous and quantify its fluctuations by measuring the variance $\chi$ of the instantaneous intensity correlation function. The amplitude of dynamical fluctuations has a non-monotonic dependence on scattering vector $q$, in stark contrast with recent experiments on strongly attractive colloidal gels [Duri and Cipelletti, \textit{Europhys. Lett.} \textbf{76}, 972 (2006)]. We propose a simple scaling argument for the $q$-dependence of fluctuations in glassy systems that rationalizes these findings., Comment: Final version published in PRE

We survey the linear viscoelasticity of a new type of transient network: bridged wormlike micelles, whose structure has been characterized recently [Ramos and Ligoure, (2007)]. This composite material is obtained by adding telechelic copolymers (water-soluble chains with hydrophobic stickers at each extremity) to a solution of entangled wormlike micelles (WM). For comparison, naked WM and WM decorated by amphiphilic copolymers are also investigated. While these latter systems exhibit almost a same single ideal Maxwell behavior, solutions of bridged WM can be described as two Maxwell fluids components blends, characterized by two markedly different characteristic times, t_fast and t_slow, and two elastic moduli, G_fast and G_slow, with G_fast >> G_slow. We show that the slow mode is related to the viscoelasticity of the transient network of entangled WM, and the fast mode to the network of telechelic active chains (i.e. chains that do not form loops but bridge two micelles). The dependence of the viscoelasticity with the surfactant concentration, phi, and the sticker-to-surfactant molar ratio, beta, is discussed. In particular, we show that G_fast is proportional to the number of active chains in the material, phi beta. Simple theoretical expectations allow then to evaluate the bridges/loops ratio for the telechelic polymers.

Creep experiments on polycrystalline surfactant hexagonal columnar phases show a power law regime, followed by a drastic fluidization before reaching a final stationary flow. The scaling of the fluidization time with the shear modulus of the sample and stress applied suggests that the onset of flow involves a bulk reorganization of the material. This is confirmed by X-ray scattering under stress coupled to \textit{in situ} rheology experiments, which show a collective reorientation of all crystallites at the onset of flow. The analogy with the fracture of heterogeneous materials is discussed., Comment: to appear in Phys. Rev. Lett

We study by light microscopy a soft glass consisting of a compact arrangement of polydisperse elastic spheres. We show that its slow and non-stationary dynamics results from the unavoidable small fluctuations of temperature, which induce intermittent local mechanical shear in the sample, because of thermal expansion and contraction. Temperature-induced shear provokes both reversible and irreversible rearrangements whose amplitude decreases with time, leading to an exponential slowing down of the dynamics with sample age., Comment: published in PRL 97, 238301, 2006

Measuring, characterizing and modelling the slow dynamics of glassy soft matter is a great challenge, with an impact that ranges from industrial applications to fundamental issues in modern statistical physics, such as the glass transition and the description of out-of-equilibrium systems. Although our understanding of these phenomena is still far from complete, recent simulations and novel theoretical approaches and experimental methods have shed new light on the dynamics of soft glassy materials. In this paper, we review the work of the last few years, with an emphasis on experiments in four distinct and yet related areas: the existence of two different glass states (attractive and repulsive), the dynamics of systems very far from equilibrium, the effect of an external perturbation on glassy materials, and dynamical heterogeneity.

We study mixtures of charged surfactants, which alone in solution form uni- and multilamellar vesicles, and oppositely charged polyelectrolytes (PEs). The phase behavior is investigated at fixed surfactant concentration as a function of the PE-to-surfactant charge ratio $x$. We find that, for $x>0$, aggregates form. Light microscopy and X-ray scattering experiments show that the isoelectric point plays a crucial role since the morphology and the microscopic structure of the aggregates are different before ($x\leq1$) and after the isoelectric point ($x>1$). To better understand the dynamics for the formation of PE/surfactant complexes, we perform light microscopy experiments where we follow in real-time the effect of a PE solution on one multilamellar vesicle (MLV). We find that the PE induces a peeling of the bilayers of the MLV one by one. The peeling is accompanied by strong shape fluctuations of the MLV and leads ultimately to a pile of small aggregates. This novel phenomenon is analyzed in detail and discussed in terms of PE-induced tension, and pore formation and growth in a surfactant bilayer., Comment: to appear in Langmuir

We investigate by rheology and light scattering the influence of the elastic modulus, $G_0$, on the slow dynamics and the aging of a soft glass. We show that the slow dynamics and the aging can be entirely described by the evolution of an effective viscosity, $\eta_{eff}$, defined as the characteristic time measured in a stress relaxation experiment times $G_0$. At all time, $\eta_{eff}$ is found to be independent of $G_0$, of elastic perturbations, and of the rate at which the sample is quenched in the glassy phase. We propose a simple model that links $\eta_{eff}$ to the internal stress built up at the fluid-to-solid transition.

We use linear rheology and multispeckle dynamic light scattering (MDLS) to investigate the aging of a gel composed of multilamellar vesicles. Light scattering data indicate rearrangement of the gel through an unusual ultraslow ballistic motion. A dramatic slowdown of the dynamics with sample age $t_{w}$ is observed for both rheology and MDLS, the characteristic relaxation time scaling as $t_{w}^{\mu}$. We find the same aging exponent $\mu =0.78$ for both techniques, suggesting that they probe similar physical processes, that is the relaxation of applied or internal stresses for rheology or MDLS, respectively. A simple phenomenological model is developed to account for the observed dynamics., Comment: 8 pages, 4 figures, Submitted to PRL

A positively charged, mixed bilayer vesicle in the presence of negatively charged surfaces (for example, colloidal particles) can spontaneously partition into an adhesion zone of definite area, and another zone that repels additional negative objects. Although the membrane itself has nonnegative charge in the repulsive zone, negative counterions on the interior of the vesicle spontaneously aggregate there, and present a net negative charge to the exterior. Beyond the fundamental result that oppositely charged objects can repel, our mechanism helps explain recent experiments on surfactant vesicles., Comment: Latex using epsfig and afterpage; pdf available at http://www.physics.upenn.edu/~nelson/Mss/repel.pdf