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.
We review continuum elastic models for the transmission of both external forces and internal active cellular forces in biopolymer gels, and relate them to recent experiments. Rather than being exhaustive, we focus on continuum elastic models for small affine deformations and intend to provide a systematic continuum method and some analytical perspectives to the study of force transmissions in biopolymer gels. We start from a very brief review of the nonlinear mechanics of individual biopolymers and a summary of constitutive models for the nonlinear elasticity of biopolymer gels. We next show t…
We present an extensive experimental study of mode-I, steady, slow crack dynamics in gelatin gels. Taking advantage of the sensitivity of the elastic stiffness to gel composition and history we confirm and extend the model for fracture of physical hydrogels which we proposed in a previous paper (Nature Materials, doi:10.1038/nmat1666 (2006)), which attributes decohesion to the viscoplastic pull-out of the network-constituting chains. So, we propose that, in contrast with chemically cross-linked ones, reversible gels fracture without chain scission.
Recent experimental investigations have revealed a non-Maxwellian absorption pattern in the rheological spectra of actin gels, which was interpreted in terms of transient bonds. Here we examine the consequences of reversible crosslinking on the apparent linear spectra of biopolymer solutions theoretically. For a schematic model consisting of a reversibly crosslinked power-law fluid we obtain a simple analytical prediction for the position of the absorption peak, which is backed up by a numerical evaluation of the inelastic glassy wormlike chain model. This establishes bond breaking as a nonlin…
The variational principle of minimum free energy (MFEVP) has been widely used in the study of soft matter statics. MFEVP can be used not only to derive equilibrium equations (including both bulk equations and boundary conditions), but also to develop direct variational methods (such as Ritz method) to find approximate solutions to these equilibrium equations. In this work, we applied these variational methods to study long-range force transmission in nonlinear elastic biopolymer gels. We showed that the slow decay of cell-induced displacements measured experimentally for fibroblast spheroids i…
Hydrogels are widespread soft materials, which can serve a wide range of applications. The control over the viscoelastic properties of the gel is of paramount importance. Ongoing environmental issues have raised the consumer's concern towards the use of more sustainable materials, including hydrogels. However, are greener materials compatible with high functionality? In a safe-by-design approach, this work demonstrates that functional hydrogels with in situ responsivity of their elastic properties by external stimuli can be developed from entirely ``sustainable'' components, a biobased amphiph…
Predicting the time-dependent yielding of colloidal gels under constant stress enables control of their mechanical stability and transport. Using rotational rheometry, we show that the shear rate of colloidal gels during an early stage of deformation known as primary creep can forecast an eventual yielding. Irrespective of whether the gel strain-softens or strain-hardens, the shear rate before failure exhibits a characteristic power-law decrease as a function of time, distinct from the linear viscoelastic response. We model this early-stage behavior as a series of uncorrelated local plastic ev…
When calcium salts are added to an aqueous solution of polysaccharide pectin, ionic cross-links form between pectin chains, giving rise to a gel network in dilute solution. In this work, dynamic light scattering (DLS) is employed to study the microscopic dynamics of the fractal aggregates (flocs) that constitute the gels, while rheological measurements are performed to study the process of gel rupture. As calcium salt concentration is increased, DLS experiments reveal that the polydispersities of the flocs increase simultaneously with the characteristic relaxation times of the gel network. Abo…
We present a Landau type theory for the non-linear elasticity of biopolymer gels with a part of the order parameter describing induced nematic order of fibers in the gel. We attribute the non-linear elastic behavior of these materials to fiber alignment induced by strain. We suggest an application to contact guidance of cell motility in tissue. We compare our theory to simulation of a disordered lattice model for biopolymers. We treat homogeneous deformations such as simple shear, hydrostatic expansion, and simple extension, and obtain good agreement between theory and simulation. We also cons…
We have designed a new experimental setup able to investigate fracture of soft materials at small scales. At high crack velocity, where energy is mostly dissipated through viscoelastic processes, we observe an increasingly large high strain domain in the crack tip vicinity. Taking advantage of our ability to determine where linear elasticity breaks down, we derive a simple prediction for the evolution of the energy release rate with the crack velocity.
When sheared, most elastic solids such as metals, rubbers and polymer hydrogels dilate in the direction perpendicular to the shear plane. This well-known behaviour known as the Poynting effect is characterized by a positive normal stress. Surprisingly, biopolymer gels made of fibrous proteins such as fibrin and collagen, as well as many biological tissues exhibit the opposite effect, contracting under shear and displaying a negative normal stress. Here we show that this anomalous behaviour originates from the open network structure of biopolymer gels, which facilitates interstitial fluid flow …
Following recent X-ray diffraction experiments by Wong, Li, and Safinya on biopolymer gels, we apply Onsager excluded volume theory to a nematic mixture of rigid rods and strong ``$π/2$'' cross-linkers obtaining a long-ranged, highly anisotropic depletion attraction between the linkers. This attraction leads to breakdown of the percolation theory for this class of gels, to breakdown of Onsager's second-order virial method, and to formation of heterogeneities in the form of raft-like ribbons.
Colloidal gels are formed through the aggregation of attractive particles, whose size ranges from 10~nm to a few micrometers, suspended in a liquid. Such gels are ubiquitous in everyday life applications, from food products to paints or construction materials, in particular thanks to their ability to easily "yield", i.e., to turn from a solid to a liquid under the application of a weak external load. Understanding and controlling the mechanical response of colloidal gels is therefore of prime importance. Depending on the details of the system, however, the resulting gel networks present differ…
From soft polymeric gels to hardened cement paste, amorphous solids under constant load exhibit a pronounced time-dependent deformation called creep. The microscopic mechanism of such a phenomenon is poorly understood in amorphous materials and constitutes an even greater challenge in densely packed and chemically reactive granular systems. Both features are prominently present in hydrating cement pastes composed of calcium silicate hydrate (C-S-H) nanoparticles, whose packing density increases as a function of time, while cement hydration is taking place. Performing nano-indentation tests and…
Biomaterials such as protein or polysaccharide gels are known to behave qualitatively as soft solids and to rupture under an external load. Combining optical and ultrasonic imaging to shear rheology we show that the failure scenario of a protein gel is reminiscent of brittle solids: after a primary creep regime characterized by a power-law behavior which exponent is fully accounted for by linear viscoelasticity, fractures nucleate and grow logarithmically perpendicularly to shear, up to the sudden rupture of the gel. A single equation accounting for those two successive processes nicely captur…
Biopolymer gels such as fibrin and collagen networks are known to develop tensile axial stress when subject to torsion. This negative normal stress is opposite to the classical Poynting effect observed for most elastic solids including synthetic polymer gels, where torsion provokes a positive normal stress. As recently shown, this anomalous behavior in fibrin gels depends on the open, porous network structure of biopolymer gels, which facilitates interstitial fluid flow during shear and can be described by a phenomenological two-fluid model with viscous coupling between network and solvent. He…
The stress-induced yielding scenario of colloidal gels is investigated under rough boundary conditions by means of rheometry coupled to local velocity measurements. Under an applied shear stress, the fluidization of gels made of attractive carbon black particles suspended in a mineral oil is shown to involve a previously unreported shear rate response $\dot γ(t)$ characterized by two well-defined and separated timescales $τ_c$ and $τ_f$. First $\dot γ(t)$ decreases as a weak power law strongly reminiscent of the primary creep observed in numerous crystalline and amorphous solids, coined the "A…
We investigate the dynamics of alginate gels, an important class of biopolymer-based viscoelastic materials, by combining mechanical tests and non-conventional, time-resolved light scattering methods. Two relaxation modes are observed upon applying a compressive or shear stress. Dynamic light scattering and diffusive wave spectroscopy measurements reveal that these modes are associated with discontinuous rearrangement events that restructure the gel network via anomalous, non-diffusive microscopic dynamics. We show that these dynamics are due to both thermal activation and internal stress stor…
We report on the interplay between creep and residual stresses in a carbopol microgel. When a constant shear stress $σ$ is applied below the yield stress $σ_\text{y}$, the strain is shown to increase as a power law of time, $γ(t)=γ_0 + (t/τ)^α$, with an exponent $α=0.39\pm 0.04$ that is strongly reminiscent of Andrade creep in hard solids. For applied shear stresses lower than some typical value $σ_\text{c}\simeq 0.2 σ_\text{y}$, the microgel experiences a more complex, anomalous creep behaviour, characterized by an initial decrease of the strain, that we attribute to the existence of residual…
We study the micromechanics of collagen-I gel with the goal of bridging the gap between theory and experiment in the study of biopolymer networks. Three-dimensional images of fluorescently labeled collagen are obtained by confocal microscopy and the network geometry is extracted using a 3d network skeletonization algorithm. Each fiber is modeled as a worm-like-chain that resists stretching and bending, and each cross-link is modeled as torsional spring. The stress-strain curves of networks at three different densities are compared to rheology measurements. The model shows good agreement with e…
The resistance to fracture of reversible biopolymer hydrogels is an important control factor of the cutting/slicing and eating characteristics of food gels. It is also critical for their utilization in tissue engineering, for which mechanical protection of encapsulated components is needed. Its dependence on loading rate and, recently, on the density and strength of cross-links has been investigated. But no attention was paid so far to solvent nor to environment effects. Here we report a systematic study of crack dynamics in gels of gelatin in water/glycerol mixtures. We show on this model sys…
Attractive colloidal gels display a solid-to-fluid transition as shear stresses above the yield stress are applied. This shear-induced transition is involved in virtually any application of colloidal gels. It is also crucial for controlling material properties. Still, in spite of its ubiquity, the yielding transition is far from understood, mainly because rheological measurements are spatially averaged over the whole sample. Here, the instrumentation of creep and oscillatory shear experiments with high-frequency ultrasound opens new routes to observing the local dynamics of opaque attractive c…
Hydrogels behave as viscoelastic soft solids and display a porous microstructure filled with water with typical amounts of 90\%~w/w or more. As such, these materials are highly sensitive to water loss through evaporation, which impacts their mechanical properties. Yet, aside from scattered empirical observations, little is known about the gel drying kinetics for which there is a lack of temporally and spatially resolved measurements. Here we report a benchmark study of the slow drying of agarose gels cast in cylindrical Petri dishes. The weak adhesion of the gel to the lateral wall of the dish…
The internal dynamics of active gels, both in artificial (in-vitro) model systems and inside the cytoskeleton of living cells, has been extensively studied by experiments of recent years. These dynamics are probed using tracer particles embedded in the network of biopolymers together with molecular motors, and distinct non-thermal behavior is observed. We present a theoretical model of the dynamics of a trapped active particle, which allows us to quantify the deviations from equilibrium behavior, using both analytic and numerical calculations. We map the different regimes of dynamics in this s…
Motivated by recent experiments showing that stiff biopolymer gels exhibit highly unusual negative normal elastic stresses, we develop a computational model for stiff polymer networks subject to large strains. In all cases, we find that such networks develop normal stresses that are both negative and of magnitude comparable to the corresponding shear stress. We find that these normal stresses coincide with other nonlinearities in our networks, and specifically with compressive bucking of the individual filaments. Our results suggest that negative normal stresses are a characteristic feature of…
We describe a high-resolution, high-bandwidth technique for determining the local viscoelasticity of soft materials such as polymer gels. Loss and storage shear moduli are determined from the power spectra of thermal fluctuations of embedded micron-sized probe particles, observed with an interferometric microscope. This provides a passive, small-amplitude measurement of rheological properties over a much broader frequency range than previously accessible to microrheology. We study both F-actin biopolymer solutions and polyacrylamide (PAAm) gels, as model semiflexible and flexible systems, resp…
Biogels made of crosslinked polymers such as proteins or polysaccharides behave as porous soft solids and store large amount of solvent. These gels undergo spontaneous aging, called syneresis that consists in the shrinkage of the gel matrix and the progressive expulsion of the solvent. As a result, a biogel originally casted in a container often lose contact with the container sidewalls, and the detachment time is a priori difficult to anticipate since it may occur over variable time spans (from hours to days). Here we report on the syneresis phenomena in agar plates that consist in Petri dish…
Biopolymer networks having a meshwork topology, e.g., extracellular matrix and mucus gels, are ubiquitous. It is an open question to understand how self-propelled agents such as Janus colloidal particles diffuse through such a biopolymer network. Here, we computationally explore this issue in-depth by explicitly modeling three-dimensional biopolymer networks and performing Langevin dynamics simulations of active diffusion of the self-propelled tracers therein. We show that the active tracer performs distinct diffusion dynamics depending on the mesh-to-particle size and Péclet number (Pe). When…
Soft living tissues like cartilage can be considered as biphasic materials comprised of a fibrous complex biopolymer network and a viscous background liquid. Here, we show by a combination of experiment and theoretical analysis that both the hydraulic permeability and the elastic properties of (bio)polymer networks can be determined with simple ramp compression experiments in a commercial rheometer. In our approximate closed-form solution of the poroelastic equations of motion, we find the normal force response during compression as a combination of network stress and fluid pressure. Choosing …
We introduce a novel apparatus designed for stress-controlled rheometers to perform simultaneous rheological and electrical measurements on strongly conductive complex fluids under shear. By means of a non-toxic liquid metal at room temperature, the electrical connection to the rotating shaft is completed with minimal additional mechanical friction, allowing for simultaneous stress measurements as low as 1 Pa. We use the capabilities of this design to perform an extensive set of rheo-electric experiments on gels formulated from attractive carbon black particles, at concentrations ranging from …
In this work, we study the deformation behavior of thin films of various soft glassy materials that are simultaneously subjected to two creep flow fields, rotational shear flow by applying torque and elongational flow by applying normal force. The generic behavior under the combined fields is investigated in different soft glassy materials with diverse microstructure such as: hair gel, emulsion paint, shaving foam and clay suspension. Increase in strength of one stress component while keeping the other constant, not only leads to an expected enhanced deformation in its own direction, but also …
