The competition of depletion attractions and longer-ranged repulsions between colloidal particles in colloid-polymer mixtures leads to the formation of heterogeneous gel-like structures. For instance, gel networks, i.e., states where the colloids arrange in thin strands that span the whole system occur at low packing fractions for attractions that are stronger than those at the binodal line of equilibrium liquid-fluid phase separation. By using Brownian dynamics simulations we explore the formation, structure, and ageing dynamics of gel networks. We determine reduced network that focus on the essential connections in a gel network. We compare the observed properties to those of bulky gels or cluster fluids. Our results demonstrate that both the structure as well as the (often slow) dynamics of the stable or meta-stable heterogenous states in colloid-polymer mixtures possess distinct features on various length and time scales and thus are richly divers.
We combine experiments and simulations to study the link between criticality and gelation in sticky spheres. We employ confocal microscopy to image colloid-polymer mixtures, and Monte Carlo simulations of the square-well (SW) potential as a reference model. To this end, we map our experimental samples onto the SW model. We find excellent structural agreement between experiments and simulations, both for locally favored structures at the single particle level and large-scale fluctuations at criticality. We follow in detail the rapid structural change of the critical fluid when approaching the g…
We report the optical and structural properties of starch films formed on drying droplets of starch solutions on a flat substrate. The starch films formed after drying are circular in shape and have an azimuthally symmetric "M-shaped" height profile along their diameter. These films are found to be semi-crystalline in nature and transparent in visible light. Our experimental results show that these films are optically uniaxial at their center but biaxial away from the center. The variation of birefringence along the radial direction is studied for the films formed after drying droplets with di…
Theory of Sol-Gel Transition in Thermoreversible Gels with due Regard for Fundamental Role of Mesoscopic Cyclization Effects. I. Thermodynamic and Structural Characteristics of Gel Phase
We investigate the collective behavior of suspended thermoresponsive microgels, that expel solvent and subsequently decrease in size upon heating. Using a binary mixture of differently thermoresponsive microgels, we demonstrate how distinctly different gel structures form, depending on the heating profile used. Confocal laser scanning microscopy (CLSM) imaging shows that slow heating ramps yield a core-shell network through sequential gelation, while fast heating ramps yield a random binary network through homo-gelation. Here, secondary particles are shown to aggregate in a monolayer fashion u…
Flexible superparamagnetic filaments are studied under the influence of fast precessing magnetic fields using simulations and a continuum approximation analysis. We find that individual filaments can be made to exert controllable tensile forces along the precession axis. These forces are exploited for microscopic actuation. In bulk, the filaments can be rapidly assembled into different configurations whose material properties depend on the field parameters. The precession frequency affects filament aggregation and conformation by changing the net torques on the filament ends. Using a time-depe…
Univ Lyon, Ens de Lyon, CNRS, Laboratoire de Physique（里昂大学、巴黎高等师范学校里昂分校、法国国家科学研究中心、物理实验室）；Department of Polymer Engineering, IPC, University of Minho（米尼奥大学高分子工程系）
Visualizing shear-induced structures in carbon black gels by tomo-rheoscopy
ENSL, CNRS, Laboratoire de physique（ENS-Lyon, 法国国家科学研究中心, 物理实验室）；Department of Materials, ETH Zürich（苏黎世联邦理工学院材料系）；Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière, UMR5306（里昂第一大学, 法国国家科学研究中心, 光物质研究所）；Swiss Light Source, Paul Scherrer Institut（瑞士光源, 保罗谢尔研究所）；Leibniz Universität Hannover（汉诺威莱布尼茨大学）；International Research Laboratory, French American Center for Theoretical Science, CNRS, KITP, Santa Barbara（国际研究实验室, 法美理论科学中心, 法国国家科学研究中心, 加州大学圣塔芭芭拉分校卡弗里理论物理研究所）
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 …
Our lives are surrounded by a rich assortment of disordered materials. In particular, glasses are well known as dense, amorphous materials, whereas gels exist in low-density, disordered states. Recent progress has provided a significant step forward in understanding the material properties of glasses, such as mechanical, vibrational, and transport properties. In contrast, our understanding of particulate physical gels is still highly limited. Here, using molecular dynamics simulations, we study a simple model of particulate physical gels, the Lennard-Jones (LJ) gels, and provide a comprehensiv…
DNA oligomers with properly designed sequences self-assemble into well defined constructs. Here, we exploit this methodology to produce bulk quantities of tetravalent DNA nanostars (each one composed by 196 nucleotides) and to explore the structural signatures of their aggregation process. We report small-angle neutron scattering experiments focused on the evaluation of both the form factor and the temperature evolution of the scattered intensity at a nano star concentration where the system forms a tetravalent equilibrium gel. We also perform molecular dynamics simulations of one isolated tet…
Thermoreversible hydrogels are commonly prepared by cooling down to ambient temperature, aqueous polymer solutions first brought to a boil. The incubation time of the polymer solution at such a high temperature is traditionally kept to a minimum to minimize its impact on the subsequent gelation. Here we study the effect of a prolonged heating of a 1.5\% w/w agar solution at $T=80^{\circ}$C, well above the gelling temperature. The incubation time $\mathcal{T}$ of the polysaccharide solution is varied from a few hours up to five days. We show that the agar solution ages as the result of both the…
We performed Langevin dynamics simulations of amphiphilic polymers that contain strongly associating stickers connected by long soluble chain segments. We explored the aging of a thermoreversible gel which is crosslinked by aggregates (clusters) of the stickers and observed a dramatic increase of their lifetime with aging. We find that the observed aging is the result of structural reorganization of the network: the number of crosslinks decreases with time as small clusters disintegrate and their stickers are reabsorbed by large clusters that grow and become more stable by forming additional i…
The structural complexity of soft gels is at the origin of a versatile mechanical response that allows for large deformations, controlled elastic recovery and toughness in the same material. A limit to exploiting the potential of such materials is the insufficient fundamental understanding of the microstructural origin of the bulk mechanical properties. Here we investigate the role of the network topology in a model gel through 3D numerical simulations. Our study links the topology of the network organization in space to its non-linear rheological response preceding yielding and damage: our an…
Dynamic Light Scattering (DLS) measurements were performed on colloidal suspensions of Laponite\textsuperscript{\textregistered} at different concentrations in the range $C_\text{w}= (1.5÷3.0)$%. The slowing down of the dynamics induced by aging was monitored by following the temporal evolution of autocorrelation functions at different concentrations towards the gel and glass transition. Exploiting analogies with supercooled liquids approaching their glass transitions, an Angell plot for the structural relaxation times was drawn. Finally, the fragility of Laponite\textsuperscript{\textregister…
Colloidal gels, where nanoscale particles aggregate into an elastic yet fragile network, are at the heart of materials that combine specific optical, electrical and mechanical properties. Tailoring the viscoelastic features of colloidal gels in real-time thanks to an external stimulus currently appears as a major challenge in the design of "smart" soft materials. Here we introduce "rheo-acoustic" gels, a class of materials that are sensitive to ultrasonic vibrations. By using a combination of rheological and structural characterization, we evidence and quantify a strong softening in three wide…
Colloidal particles with strong, short-ranged attractions can form a gel. We simulate this process without and with hydrodynamic interactions (HI), using the lattice-Boltzmann method to account for presence of a thermalized solvent. We show that HI speed up and slow down gelation at low and high volume fractions, respectively. The transition between these two regimes is linked to the existence of a percolating cluster shortly after quenching the system. However, when we compare gels at matched 'structural age', we find nearly indistinguishable structures with and without HI. Our result explain…
We investigate the heterogeneous dynamics in a model, where chemical gelation and glass transition interplay, focusing on the dynamical susceptibility. Two independent mechanisms give raise to the correlations, which are manifested in the dynamical susceptibility: one is related to the presence of permanent clusters, while the other is due to the increase of particle crowding as the glass transition is approached. The superposition of these two mechanisms originates a variety of different behaviours. We show that these two mechanisms can be unentangled considering the wave vector dependence of…
The dynamical arrest of gels is the consequence of a well defined structural phase transition, leading to the formation of a spanning cluster of bonded particles. The dynamical glass transition, instead, is not accompanied by any clear structural signature. Nevertheless, both transitions are characterized by the emergence of dynamical heterogeneities. Reviewing recent results from numerical simulations, we discuss the behavior of dynamical heterogeneities in different systems and show that a clear connection with the structure exists in the case of gels. The emerging picture may be also releva…
Cells and tissues have the remarkable ability to actively generate the forces required to change their shape. This active mechanical behavior is largely mediated by the actin cytoskeleton, a crosslinked network of actin filaments that is contracted by myosin motors. Experiments and active gel theories have established that the length scale over which gel contraction occurs is governed by a balance between molecular motor activity and crosslink density. By contrast, the dynamics that govern the contractile activity of the cytoskeleton remain poorly understood. Here we investigate the microscopi…
Tracking microscopic irreversibility during yielding of a colloidal fractal gel with Rheo-Echo-XPCS
ESRF, The European Synchrotron（欧洲同步辐射光源）；ENSL, CNRS, Laboratoire de Physique（里昂师范学院，法国国家科学研究中心，物理实验室）；C3M, ESPCI Paris, Université PSL, CNRS（C3M，巴黎高等物理化工学院，巴黎文理研究大学，法国国家科学研究中心）；Univ. Grenoble Alpes, CNRS, Grenoble INP, LRP（格勒诺布尔阿尔卑斯大学，法国国家科学研究中心，格勒诺布尔理工学院，L RP）；Department of Polymer Engineering, IPC, University of Minho（米尼奥大学，聚合物工程系，IPC）
External fields can decidedly alter the free energy landscape of soft materials and can be exploited as a powerful tool for the assembly of targeted nanostructures and colloidal materials. Here, we use computer simulations to demonstrate that nonequilibrium internal fields or forces -- forces that are generated by driven components within a system -- in the form of active particles can precisely modulate the dynamical free energy landscape of a model soft material, a colloidal gel. Embedding a small fraction of active particles within a gel can provide a unique pathway for the dynamically frus…
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 siz…
