arXiv subjects

Sébastien Manneville

Publications and source records attributed to Sébastien Manneville.

At least 19 recordsLinked to original sources

arXiv2026

Imprinting Macroscopic Fracture during Gelation: A Mechanism for Tuning Colloidal Gels

Colloidal gels form through the sol-gel transition of attractive particle suspensions, where local aggregation leads to a space-spanning network with solid-like properties. Their microstructure and mechanical properties are highly sensitive to external perturbations, which can substantially alter the pathway of network formation. Here, we investigate how nonlinear oscillatory shear affects the sol-gel transition of colloidal silica suspensions. Using large-amplitude oscillatory shear (LAOS), we vary both the strain amplitude and the duration of oscillatory forcing, varying between one and two times the gelation time. We find that sufficiently large strain amplitudes, or prolonged exposure to oscillations in the nonlinear regime, alter irreversibly the gel properties: the storage modulus $G'$ decreases while its frequency dependence remains unchanged. In contrast, the loss modulus $G''$, which decreases monotonically with frequency under quiescent gelation, exhibits an upturn at high frequencies when the gel is formed under strong oscillatory shear. The viscoelastic spectra of gels formed under quiescent conditions are well captured by a fractional Maxwell model, while gels formed under LAOS require an additional fractional element to account for damage-induced dissipation. Rheo-imaging experiments corroborate this interpretation by revealing the growth of cracks in gels formed under LAOS. We further show that these gels display a progressively more ductile nonlinear response for prolonged exposure to LAOS during gelation. These results demonstrate that the interplay between non-linear shear and gelation can permanently imprint a macroscopic fracture pattern into colloidal gels, offering a route to tune their viscoelastic properties.

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arXiv2025

LAOStrain response of carbon black-polymer hydrogels: insights from rheo-TRUSAXS and rheo-electric experiment

Colloid-polymer hydrogels are encountered in various applications, from flow batteries to drug delivery. Here, we investigate hydrogels composed of hydrophobic colloidal soot particles -- carbon black (CB) -- and carboxymethylcellulose (CMC), a food-grade polymer functionalized with hydrophobic groups binding physically to CB. As described in [Legrand et al., Macromolecules 56, 2298-2308 (2023)], CB-CMC hydrogels exist in two flavors: either electrically conductive when featuring a percolated network of CB particles decorated by CMC, or insulating where isolated CB particles act as physical cross-linkers within the CMC matrix. We compare these two types of CB-CMC hydrogels under Large Amplitude Oscillatory Shear (LAOS), combining rheometry with Time-Resolved Ultra-Small-Angle X-ray Scattering (TRUSAXS) and electrical conductivity measurements. Both types of hydrogels exhibit a "type III" yielding scenario, characterized by an overshoot in G'' and a monotonic decrease in G', although the underlying microscopic mechanisms differ markedly. Conductive CB-CMC hydrogels display a yield strain (6%) concomitant with a drop in DC conductivity, indicative of the macroscopic rupture of the percolated CB network at length scales larger than a few microns, beyond USAXS resolution. At larger strain amplitudes, the conductivity of the fluidized sample increases again, exceeding its initial value, consistent with shear-induced formation of a transient, dynamically percolated network of CB clusters. In contrast, insulating CB-CMC hydrogels exhibit a larger yield strain (60%), beyond which the sample flows and the average distance between CB particles decreases. This reorganization is concomitant with a more than tenfold increase in conductivity, although it remains below that of conductive hydrogels at rest.

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arXiv2025

Impact of early-age exposure to power ultrasound on the micromechanical properties of hardened cement paste

Cement paste serves as the universal binder in concrete, formed by mixing water with Ordinary Portland Cement (OPC). In its fresh state, cement paste is a suspension in which the initial particle inventory continuously dissolves, while simultaneously, a growing population of colloidal calcium silica-hydrate (C-S-H) particles forms and progressively builds a percolated structure that densifies and hardens through hydration. Like most colloidal gels, cement paste is sensitive to external stimuli such as mechanical vibrations and temperature variations. Here, we show that power ultrasound (PUS) applied to OPC paste during the very early stages of hydration significantly alters the mechanical properties of the hardened material. Freshly prepared cement pastes are exposed to PUS at varying durations and intensities before curing for 28 days. Micro-indentation testing at the scale of tens of microns reveals that increasing PUS amplitude and prolonged PUS exposure degrade the micro-mechanical properties of hardened cement paste, making it more ductile. This softening behavior evolves continuously with exposure conditions and is consistent with an increase in porosity, likely caused by micro-cracks induced by PUS. This scenario is further supported by micro-scratch testing, which shows higher levels of acoustic emission in PUS-exposed samples. Finally, nano-indentation confirms that the properties of the individual phases composing the hardened paste -- low-density and high-density C-S-H -- remain largely unaffected. These findings offer valuable experimental insights into novel pathways for modifying the mechanical properties of reactive colloidal gels.

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arXiv2025

Anti-thixotropic dynamics in attractive colloidal dispersions: a shear restructuring driven by elastic stresses

Due to rich rheological properties, dispersions of attractive colloidal particles are ubiquitous in industries. Specifically, upon experiencing a sudden reduction in shear rate, these dispersions may exhibit transient behaviors such as thixotropy-where viscosity increases over time-and anti-thixotropy, characterized by an initial viscosity decrease before reaching a steady state. While thixotropy has been described as a competition between structure buildup and disruption, the mechanisms of anti-thixotropy remain poorly understood. Here, we investigate the anti-thixotropic dynamics of carbon black particles dispersed in oil-a system known for exhibiting anti-thixotropy-through flow step-down experiments. Using a multi-technique approach combining rheology with velocimetry and structural characterizations, we show that viscosity decrease results from a decrease in wall slip concomitant to shear-induced structural rearrangements, indicating a transition from a dynamical network of fractal clusters into a network of loosely connected dense agglomerates. Additionally, after a characteristic anti-thixotropic time $τ$, a steady flow is reached. This time $τ$ diverges with increasing shear rate at a critical value corresponding to a Mason number of one, indicating that anti-thixotropy occurs only when colloidal attraction outweighs viscous forces. More precisely, we show that the structural rearrangement underpinning the viscosity decrease is mediated by elastic stresses $σ_e$, such that $τ\propto σ_e^{-3}$. Finally, on long time scales, the steady state is linked to a microstructure with nearly zero yield stress, indicating a loss of flow memory. These findings provide a mechanism for anti-thixotropy and suggest pathways for controlling viscosity and yield stress in attractive colloidal dispersions.

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arXiv2024

Rheological properties of acid-induced carboxymethylcellulose hydrogels

Cellulose ethers represent a class of water-soluble polymers widely utilized across diverse sectors, spanning from healthcare to the construction industry. This experimental study specifically delves into aqueous suspensions of carboxymethylcellulose (CMC), a polymer that undergoes gel formation in acidic environments due to attractive interactions between hydrophobic patches along its molecular chain. We use rheometry to determine the linear viscoelastic properties of both CMC suspensions and acid-induced gels at various temperatures. Then, applying the time-temperature superposition principle, we construct master curves for the viscoelastic spectra, effectively described by fractional models. The horizontal shift factors exhibit an Arrhenius-like temperature dependence, allowing us to extract activation energies compatible with hydrophobic interactions. Furthermore, we show that acid-induced CMC gels are physical gels that display a reversible yielding transition under external shear. In particular, we discuss the influence of pH on the non-linear viscoelastic response under large-amplitude oscillatory shear. Overall, our results offer a comprehensive description of the linear and non-linear rheological properties of a compelling case of physical hydrogel involving hydrophobic interactions.

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arXiv2024

Textural properties of dense granular pastes produced by kneading

The efficiency of supported catalysts depends on the porous microstructure of their solid support, which regulates mass transfer, exposure to the active phase, and mechanical strength. Here, we focus on the manufacturing of a specific type of catalytic support, $γ$-alumina extrudates, by a kneading-extrusion process. In this process, a paste is initially formed by blending and subsequently kneading a boehmite powder, an aluminum oxide hydroxide precursor of $γ$-alumina, with various liquids before undergoing extrusion. The crucial step in this process is the kneading step, which allows control over the textural and mechanical properties of the extrudate. The present experimental study aims to measure the impact of the kneading step on boehmite pastes prepared using a pilot kneader. The pastes are obtained by mixing boehmite powder with an acid and a basic solution in a two-step process known as peptization and neutralization. In this study, kneading is conducted at various mixing speeds and durations while monitoring the torque exerted by the boehmite paste on the kneader blades. Moreover, samples are extracted from the pilot kneader at various stages of the kneading process, and their textural properties are determined by both nitrogen sorption and mercury intrusion porosimetry. Our findings show that, at fixed composition, the textural properties of boehmite pastes are controlled by the overall deformation accumulated during kneading. Conversely, for a fixed accumulated deformation, the pH sets the textural properties. Finally, we identify an empirical control parameter that captures the combined effects of pH and accumulated deformation on the key textural attributes of boehmite pastes. These results set the stage for a systematic design approach of boehmite-based catalyst supports.

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arXiv2024

Acid-induced gelation of carboxymethylcellulose solutions

The present work offers a comprehensive description of the acid-induced gelation of carboxymethylcellulose (CMC), a water-soluble derivative of cellulose broadly used in numerous applications ranging from food packaging to biomedical engineering. Linear viscoelastic properties measured at various pH and CMC contents allow us to build a sol-gel phase diagram, and show that CMC gels exhibit broad power-law viscoelastic spectra that can be rescaled onto a master curve following a time-composition superposition principle. These results demonstrate the microstructural self-similarity of CMC gels, and inspire a mean-field model based on hydrophobic inter-chain association that accounts for the sol-gel boundary over the entire range of CMC content under study. Neutron scattering experiments further confirm this picture and suggest that CMC gels comprise a fibrous network crosslinked by aggregates. Finally, low-field NMR measurements offer an original signature of acid-induced gelation from the solvent perspective. Altogether, these results open avenues for precise manipulation and control of CMC-based hydrogels.

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arXiv2023

Ductile-to-brittle transition and yielding in soft amorphous materials: perspectives and open questions

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.

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arXiv2023

Shear-induced reinforcement in boehmite gels: a rheo-X-ray-scattering study

Boehmite, an aluminum oxide hydroxide $γ$-AlO(OH), is broadly used in the form of particulate dispersions in industrial applications, e.g., for the fabrication of ceramics and catalyst supports or as a binder for extrusion processes. Under acidic conditions, colloidal boehmite dispersions at rest form gels, i.e., space-spanning percolated networks that behave as soft solids at rest, and yet yield and flow like liquids under large enough deformations. Like many other colloidal gels, the solid-like properties of boehmite gels at rest are very sensitive to their previous mechanical history. Our recent work [Sudreau et al., J. Rheol. 66, 91-104 (2022), and Phys. Rev. Material 6, L042601 (2022)] has revealed such \textit{memory effects}, where the shear experienced prior to flow cessation drives the elasticity of boehmite gels: while gels formed following application of a shear rate $\dotγ_{\rm p}$ larger than a critical value $\dotγ_{\rm c}$ are insensitive to shear history, gels formed after application of $\dotγ_{\rm p}<\dotγ_{\rm c}$ display reinforced viscoelastic properties and non-negligible residual stresses. Here, we provide a microstructural scenario for these striking observations by coupling rheometry and small-angle X-ray scattering. Time-resolved measurements for $\dotγ_{\rm p} <\dotγ_{\rm c}$ show that scattering patterns develop an anisotropic shape that persists upon flow cessation, whereas gels exposed to $\dotγ_{\rm p}>\dotγ_{\rm c}$ display isotropic scattering patterns upon flow cessation. Moreover, as the shear rate applied prior to flow cessation is decreased below $\dotγ_{\rm c}$, the level of anisotropy frozen in the sample microstructure grows similarly to the viscoelastic properties, thus providing a direct link between mechanical reinforcement and flow-induced microstructural anisotropy.

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arXiv2022

Dual origin of viscoelasticity in polymer-carbon black hydrogels: a rheometry and electrical spectroscopy study

Nanocomposites formed by mixing nanoparticles and polymers offer a limitless creative space for the design of functional advanced materials with a broad range of applications in materials and biological sciences. Here we focus on aqueous dispersions of hydrophobic colloidal soot particles, namely carbon black (CB) dispersed with a sodium salt of carboxymethylcellulose (CMC), a food additive known as cellulose gum that bears hydrophobic groups, which are liable to bind physically to CB particles. Varying the relative content of CB nanoparticles and cellulose gum allows us to explore a rich phase diagram that includes a gel phase. We investigate this hydrogel using rheometry and electrochemical impedance spectroscopy. CB-CMC hydrogels display two radically different types of mechanical behaviors that are separated by a critical CMC-to-CB mass ratio $r_c$. For $r r_c$ CB-CMC gels display a power-law viscoelastic spectrum that depends strongly on the CMC concentration. These relaxation spectra can be rescaled onto a master curve that exhibits a power-law scaling in the high-frequency limit, with an exponent that follows Zimm theory, showing that CMC plays a key role in the gel viscoelastic properties for $r>r_c$. Our results offer a characterization of CB-CMC dispersions that will be useful for designing nanocomposites based on hydrophobic interactions.

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arXiv2022

Continuum modeling of Soft Glassy Materials under shear

Soft Glassy Materials (SGM) consist in dense amorphous assemblies of colloidal particles of multiple shapes, elasticity, and interactions, which confer upon them solid-like properties at rest. They are ubiquitously encountered in modern engineering, including additive manufacturing, semi-solid flow cells, dip-coating, adhesive locomotion, where they are subjected to complex mechanical histories. Such processes often include a solid-to-liquid transition induced by large enough shear, which results in complex transient phenomena such as non-monotonic stress responses, i.e., stress overshoot, and spatially heterogeneous flows, e.g., shear-banding or brittle failure. In the present article, we propose a pedagogical introduction to a continuum model based on a spatially-resolved fluidity approach that we recently introduced to rationalize shear-induced yielding in SGMs. Our model, which relies upon non-local effects, quantitatively captures salient features associated with such complex flows, including the rate dependence of the stress overshoot, as well as transient shear-banded flows together with nontrivial scaling laws for fluidization times. This approach offers a versatile framework to account for subtle effects, such as avalanche-like phenomena, or the impact of boundary conditions, which we illustrate by including in our model the elasto-hydrodynamic slippage of soft particles compressed against solid surfaces.

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arXiv2022

Interpenetration of fractal clusters drives elasticity in colloidal gels formed upon flow cessation

Colloidal gels are out of equilibrium soft solids composed of attractive Brownian particles that form a space-spanning network at low volume fractions. The elastic properties of these systems result from the network microstructure, which is very sensitive to shear history. Here, we take advantage of such sensitivity to tune the viscoelastic properties of a colloidal gel made of carbon black nanoparticles. Starting from a fluidized state under an applied shear rate $\dot γ_0$, we use an abrupt flow cessation to trigger a liquid-to-solid transition. We observe that the resulting gel is all the more elastic when the shear rate $\dot γ_0$ is low and that the viscoelastic spectra can be mapped on a master curve. Moreover, coupling rheometry to small angle X-ray scattering allows us to show that the gel microstructure is different from gels solely formed by thermal agitation where only two length scales are observed: the dimension of the colloidal and the dimension the fractal aggregates. Competition between shear and thermal energy leads to gels with three characteristic length scales. Such gels structure in a percolated network of fractal clusters that interpenetrate each other. Experiments on gels prepared with various shear histories reveal that cluster interpenetration increases with decreasing values of the shear rate $\dot γ_0$ applied before flow cessation. These observations strongly suggest that cluster interpenetration drives the gel elasticity, which we confirm using a structural model. Our results, which are in stark contrast with previous literature, where gel elasticity was either linked to cluster connectivity or to bending modes, highlight a novel local parameter controlling the macroscopic viscoelastic properties of colloidal gels.

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arXiv2022

Aggregation and disaggregation processes in clusters of particles: simple numerical and theoretical insights of the competition in 2D geometries

Aggregation and disaggregation of clusters of attractive particles under flow are studied from numerical and theoretical points of view. Two-dimensional molecular dynamics simulations of both Couette and Poiseuille flows highlight the growth of the average steady-state cluster size as a power law of the adhesion number, a dimensionless number that quantifies the ratio of attractive forces to shear stress. Such a power-law scaling results from the competition between aggregation and disaggregation processes, as already reported in the literature. Here, we rationalize this behavior through a model based on an energy function, which minimization yields the power-law exponent in terms of the cluster fractal dimension, in good agreement with the present simulations and with previous works.

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arXiv2022

Residual stresses and shear-induced overaging in boehmite gels

Colloidal gels respond like soft solids at rest, whereas they flow like liquids under external shear. Starting from a fluidized state under an applied shear rate $\dotγ_{p}$, abrupt flow cessation triggers a liquid-to-solid transition during which the stress relaxes towards a so-called \textit{residual stress} $σ_{\rm res}$ that tallies a macroscopic signature of previous shear history. Here, we report on the liquid-to-solid transition in gels of boehmite, an aluminum oxide, that shows a remarkable non-monotonic stress relaxation towards a residual stress $σ_{\rm res}(\dotγ_{p})$ characterized by a dual behavior relative to a critical value $\dotγ_{c}$ of the shear rate $\dotγ_{p}$. Following shear at $\dotγ_{p}>\dotγ_{c}$, the gel obtained upon flow cessation is insensitive to shear history, and the residual stress is negligible. However, for $\dotγ_{p}<\dotγ_{c}$, the gel encodes some memory of the shear history, and $σ_{\rm res}$ increases for decreasing shear rate, directly contributing to reinforcing the gel viscoelastic properties. Moreover, we show that both $σ_{\rm res}$ and the gel viscoelastic properties increase logarithmically with the strain accumulated during the shear period preceding flow cessation. Such a shear-induced "overaging" phenomenon bears great potential for tuning the rheological properties of colloidal gels.

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arXiv2021

Shear-induced memory effects in boehmite gels

Colloidal gels are formed by the aggregation of Brownian particles into clusters that are, in turn, part of a space-spanning percolated network. In practice, the microstructure of colloidal gels, which dictates their mechanical properties, strongly depends on the particle concentration and on the nature of their interactions. Yet another critical control parameter is the shear history experienced by the sample, which controls the size and density of the cluster population, via particle aggregation, cluster breakup, and restructuring. Here we investigate the impact of shear history on acid-induced gels of boehmite, an aluminum oxide. We show that following a primary gelation, these gels display a dual response depending on the shear rate $\dotγ_{\rm p}$ used to rejuvenate their microstructure. We identify a critical shear rate $\dotγ_{\rm c}$, above which boehmite gels display a gel-like viscoelastic spectrum upon flow cessation, similar to that obtained following the primary gelation. However, upon flow cessation after shear rejuvenation below $\dotγ_{\rm c}$, boehmite gels display a glassy-like viscoelastic spectrum together with enhanced elastic properties. Moreover, the nonlinear rheological properties of boehmite gels also differ on both sides of $\dotγ_{\rm c}$: weak gels obtained after rejuvenation at $\dotγ_{\rm p}>\dotγ_{\rm c}$ show a yield strain that is constant, independent of $\dotγ_{\rm p}$, whereas strong gels obtained with $\dotγ_{\rm p}<\dotγ_{\rm c}$ display a yield strain that significantly increases with $\dotγ_{\rm p}$. Our results can be interpreted in light of previous literature on shear-induced anisotropy, while we rationalize the critical shear rate in terms of a dimensionless quantity, the Mason number, comparing the strength of the shear flow to the interparticle bond force.

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arXiv2021

Stress Overshoots in Simple Yield Stress Fluids

Soft glassy materials such as mayonnaise, wet clays, or dense microgels display under external shear a solid-to-liquid transition. Such a shear-induced transition is often associated with a non-monotonic stress response, in the form of a stress maximum referred to as "stress overshoot". This ubiquitous phenomenon is characterized by the coordinates of the maximum in terms of stress $σ_\text{M}$ and strain $γ_\text{M}$ that both increase as weak power laws of the applied shear rate. Here we rationalize such power-law scalings using a continuum model that predicts two different regimes in the limit of low and high applied shear rates. The corresponding exponents are directly linked to the steady-state rheology and are both associated with the nucleation and growth dynamics of a fluidized region. Our work offers a consistent framework for predicting the transient response of soft glassy materials upon start-up of shear from the local flow behavior to the global rheological observables.

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arXiv2021

Continuum modelling of shear start-up in soft glassy materials

Yield stress fluids (YSFs) display a dual nature highlighted by the existence of a yield stress such that YSFs are solid below the yield stress, whereas they flow like liquids above it. Under an applied shear rate $\dotγ$, the solid-to-liquid transition is associated with a complex spatiotemporal scenario. Still, the general phenomenology reported in the literature boils down to a simple sequence that can be divided into a short-time response characterized by the so-called "stress overshoot", followed by stress relaxation towards a steady state. Such relaxation can be either long-lasting, which usually involves the growth of a shear band that can be only transient or that may persist at steady-state, or abrupt, in which case the solid-to-liquid transition resembles the failure of a brittle material, involving avalanches. Here we use a continuum model based on a spatially-resolved fluidity approach to rationalize the complete scenario associated with the shear-induced yielding of YSFs. Our model provides a scaling for the coordinates of the stress maximum as a function of $\dotγ$, which shows excellent agreement with experimental and numerical data extracted from the literature. Moreover, our approach shows that such a scaling is intimately linked to the growth dynamics of a fluidized boundary layer in the vicinity of the moving boundary. Yet, such scaling is independent of the fate of that layer, and of the long-term behavior of the YSF. Finally, when including the presence of "long-range" correlations, we show that our model displays a ductile to brittle transition, i.e., the stress overshoot reduces into a sharp stress drop associated with avalanches, which impacts the scaling of the stress maximum with $\dotγ$. Our work offers a unified picture of shear-induced yielding in YSFs, whose complex spatiotemporal dynamics are deeply connected to non-local effects.

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arXiv2021

Mechanics and structure of carbon black gels under high-power ultrasound

Colloidal gels made of carbon black particles dispersed in light mineral oil are "rheo-acoustic" materials, i.e., their mechanical and structural properties can be tuned using high-power ultrasound, sound waves with submicron amplitude and frequency larger than 20~kHz . The effects of high-power ultrasound on the carbon black gel are demonstrated using two experiments: rheology coupled to ultrasound to test for the gel mechanical response and a timeresolved ultra small-angle X-ray scattering experiment (TRUSAXS) coupled to ultrasound to test for structural changes within the gel. We show that high-power ultrasound above a critical amplitude leads to a complex viscoelastic transient response of the gels within a few seconds: a softening of its storage modulus accompanied by a strong overshoot in its loss modulus. Under high-power ultrasound, the gel displays a viscoelastic spectrum with glass-like features and a significant decrease in its yield strain. Those effects are attributed to the formation of intermittent micro-cracks in the bulk of the gel as evidenced by TRUSAXS. Provided that the shear rate is not large enough to fully fluidize the sample, high-power ultrasound also facilitates the flow of the gel, reducing its yield stress as well as increasing the shear-thinning index, thanks again to the formation of micro-cracks.

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