Colloidal nanocrystal gels can be assembled using a difunctional "linker" molecule to mediate bonding between nanocrystals. The conditions for gelation and the structure of the gel are controlled macroscopically by the linker concentration and microscopically by the linker's molecular characteristics. Here, we demonstrate using a toy model for a colloid-linker mixture that linker flexibility plays a key role in determining both phase behavior and structure of the mixture. We fix the linker length and systematically vary its bending stiffness to span the flexible, semiflexible, and rigid regimes. At fixed linker concentration, flexible-linker and rigid-linker mixtures phase separate at low colloid volume fractions in agreement with predictions of first-order thermodynamic perturbation theory, but the semiflexible-linker mixtures do not. We correlate and attribute this qualitatively different behavior to undesirable "loop" linking motifs that are predicted to be more prevalent for linkers with end-to-end distances commensurate with the locations of chemical bonding sites on the colloids. Linker flexibility also influences the spacing between linked colloids, suggesting strategies to design gels with desired phase behavior, structure, and by extension, structure-dependent properties.
Low-density "equilibrium" gels that consist of a percolated, kinetically arrested network of colloidal particles and are resilient to aging can be fabricated by restricting the number of effective bonds that form between the colloids. Valence-restricted patchy particles have long served as one archetypal example of such materials, but equilibrium gels can also be realized through a synthetically simpler and scalable strategy that introduces a secondary linker, such as a small ditopic molecule, to mediate the bonds between the colloids. Here, we consider the case where the ditopic linker molecu…
Simple models based on isotropic interparticle attractions often fail to capture experimentally observed structures of colloidal gels formed through spinodal decomposition and subsequent arrest: the resulting gels are typically denser and less branched than their experimental counterparts. Here we simulate gels formed from soft particles with directional attractions ("patchy particles"), designed to inhibit lateral particle rearrangement after aggregation. We directly compare simulated structures with experimental colloidal gels made using soft attractive microgel particles, by employing a "sk…
We attempt a classification of different colloidal gels based on colloid-colloid interactions. We discriminate primarily between non-equilibrium and equilibrium routes to gelation, the former case being slaved to thermodynamic phase separation while the latter is individuated in the framework of competing interactions and of patchy colloids. Emphasis is put on recent numerical simulations of colloidal gelation and their connection to experiments. Finally we underline typical signatures of different gel types, to be looked in more details in experiments.
Colloidal gels are a prototypical example of a heterogeneous network solid whose complex properties are governed by thermally-activated dynamics. In this Letter we experimentally establish the connection between the intermittent dynamics of individual particles and their local connectivity. We interpret our experiments with a model that describes single-particle dynamics based on highly cooperative thermal debonding. The model, in quantitative agreement with experiments, provides a microscopic picture for the structural origin of dynamical heterogeneity in colloidal gels and sheds new light on…
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…
Wall adhesion effects during batch sedimentation of strongly flocculated colloidal gels are commonly assumed to be negligible. In this study in-situ measurements of colloidal gel rheology and solids volume fraction distribution suggest the contrary, where significant wall adhesion effects are observed in a 110mm diameter settling column. We develop and validate a mathematical model for the equilibrium stress state in the presence of wall adhesion under both viscoplastic and viscoelastic constitutive models. These formulations highlight fundamental issues regarding the constitutive modeling of …
We study colloidal gels formed by competing electrostatic repulsion and short-range attraction by means of extensive numerical simulations under external shear. We show that, upon varying the repulsion strength, the gel structure and its viscoelastic properties can be largely tuned. In particular, the gel fractal dimension can be either increased or decreased with respect to mechanical equilibrium conditions. Unexpectedly, gels with stronger repulsion, despite being mechanically stiffer, are found to be less viscous with respect to purely attractive ones. We provide a microscopic explanation o…
Colloidal gels formed from small attractive particles are commonly used in formulations to keep larger components in suspension. However, despite extensive work characterizing unfilled gels, little is known about how larger inclusions alter the phase behavior and microstructure of the colloidal system. Here we use numerical simulations to examine how larger `granular' particles can alter the gel transition phase boundaries. We find two distinct regimes depending on both the filler size and native gel structure: a `passive' regime where the filler fits into already-present voids, giving little …
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…
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…
Attractive colloidal gels exhibit solid-like behavior at vanishingly small fractions of solids, owing to ramified space-spanning networks that form due to particle-particle interactions. These networks give the gel its rigidity, and as the attraction between the particles grows, so does the elasticity of the colloidal network formed. The emergence of this rigidity can be described through a mean field approach; nonetheless, fundamental understanding of how rigidity varies in gels of different attraction strengths is lacking. Moreover, recovering an accurate gelation phase diagram based on the …
The elastic properties of a soft matter material can be greatly altered by the presence of solid inclusions whose microscopic properties, such as their size and interactions, can have a dramatic effect. In order to shed light on these effects we use extensive rheology computer simulations to investigate colloidal gels with solid inclusions of different size. We show that the elastic properties vary in a highly non trivial way as consequence of the interactions between the gel backbone and the inclusions. In particular, we show that the key aspects are the presence of the gel backbone and its m…
The liquid-liquid phase separation of a binary solvent can be arrested by colloidal particles trapped at the interface [K. Stratford et al., Science 309, 5744 (2005)]. We show experimentally that the colloidal network so formed can remain stable after fully remixing the liquids, creating a new type of gel in which colloids in a single-phase solvent have locally planar coordination. We argue that this structure is likely maintained by primary-minimum DLVO bonding of our charged colloids, created under strong compression by capillary forces. We present simulation evidence that the combination of…
Shear history plays an important role in determining the linear and nonlinear rheological response of colloidal gels and can be used for tuning their structure and flow properties. Increasing colloidal particle aspect ratio lowers the critical volume fraction for gelation due to an increase of the particle excluded volume. Using a combination of rheology and confocal microscopy we investigate the effect of steady and oscillatory pre-shear history on the structure and rheology of colloidal gels formed by silica spheres and rods of length L and diameter D (L/D = 10) dispersed in 11 M CsCl soluti…
Computer simulations were done of the mean square displacement (MSD) of tracer particles in colloidal gels formed by diffusion or reaction limited aggregation of hard spheres. The diffusion coefficient was found to be determined by the volume fraction accessible to the spherical tracers ($ϕ_a$) independent of the gel structure or the tracer size. In all cases, critical slowing down was observed at $ϕ_a\approx 0.03$ and was characterized by the same scaling laws reported earlier for tracer diffusion in a Lorentz gas. Strong heterogeneity of the MSD was observed at small $ϕ_a$ and was related to…
We examine microstructural and mechanical changes which occur during oscillatory shear flow and reformation after flow cessation of an intermediate volume fraction colloidal gel using rheometry and Brownian Dynamics (BD) simulations. A model depletion colloid-polymer mixture is used, comprising of a hard sphere colloidal suspension with the addition of non-adsorbing linear polymer chains. Results reveal three distinct regimes depending on the strain amplitude of oscillatory shear. Large shear strain amplitudes fully break the structure which results into a more homogenous and stronger gel afte…
We present a detailed numerical study of multi-component colloidal gels interacting sterically and obtained by arrested phase separation. Under deformation, we found that the interplay between the different intertwined networks is key. Increasing the number of component leads to softer solids that can accomodate progressively larger strain before yielding. The simulations highlight how this is the direct consequence of the purely repulsive interactions between the different components, which end up enhancing the linear response of the material. Our work {provides new insight into mechanisms at…
We compare the slow dynamics of irreversible gels, colloidal gels, glasses and spin glasses by analyzing the behavior of the so called non-linear dynamical susceptibility, a quantity usually introduced to quantitatively characterize the dynamical heterogeneities. In glasses this quantity typically grows with the time, reaches a maximum and then decreases at large time, due to the transient nature of dynamical heterogeneities and to the absence of a diverging static correlation length. We have recently shown that in irreversible gels the dynamical susceptibility is instead an increasing functio…
We investigate the thermodynamics and percolation regimes of model binary mixtures of patchy colloidal particles. The particles of each species have three sites of two types, one of which promotes bonding of particles of the same species while the other promotes bonding of different species. We find up to four percolated structures at low temperatures and densities: two gels where only one species percolates, a mixed gel where particles of both species percolate but neither species percolates separately, and a bicontinuous gel where particles of both species percolate separately forming two in…
Locally (re)structuring colloidal gels $\unicode{x2013}$ micron-sized particles forming a connected network with arrested dynamics $\unicode{x2013}$ enables precise tuning of the micromechanical and -rheological properties of the system. A recent experimental study [B. Saint-Michel, G. Petekidis, and V. Garbin, Soft Matter $\boldsymbol{18}$, 2092 (2022)] showed that rapid restructuring can occur by acoustically modulating an embedded microbubble. Here, we perform Brownian dynamics simulations to understand the mechanical effect of an oscillating microbubble on the structure of the embedding co…
Rigidity percolation (RP) occurs when mechanical stability emerges in disordered networks as constraints or components are added. Here we discuss RP with structural correlations, an effect ignored in classical theories albeit relevant to many liquid-to-amorphous-solid transitions, such as colloidal gelation, which are due to attractive interactions and aggregation. Using a lattice model, we show that structural correlations shift RP to lower volume fractions. Through molecular dynamics simulations, we show that increasing attraction in colloidal gelation increases structural correlation and th…
Natural rubber is obtained by processing natural rubber latex, a liquid colloidal suspension that rapidly gels after exudation from the tree. We prepared such gels by acidification, in a large range of particle volume fractions, and investigated their rheological properties. We show that natural rubber latex gels exhibit a unique behavior of irreversible strain hardening: when subjected to a large enough strain, the elastic modulus increases irreversibly. Hardening proceeds over a large range of deformations in such a way that the material maintains an elastic modulus close to, or slightly hig…
The effects of particle roughness and short-ranged non-central forces on colloidal gels are studied using computer simulations in which particles experience a sinusoidal variation in energy as they rotate. The number of minima $n$ and energy scale $K$ are the key parameters; for large $K$ and $n$, particle rotation is strongly hindered, but for small $K$ and $n$ particle rotation is nearly free. A series of systems are simulated and characterized using fractal dimensions, structure factors, coordination number distributions, bond-angle distributions and linear rheology. When particles rotate e…
Gels are low-packing arrested states of matter which are able to support stress. On cooling, limited valence colloidal particles form open networks stabilized by the progressive increase of the interparticle bond lifetime. These gels, named equilibrium gels, are the focus of this review article. Differently from other types of colloidal gels, equilibrium gels do not require an underlying phase separation to form. Oppositely, they form in a region of densities deprived of thermodynamic instabilities. Limited valence equilibrium gels neither coarsen nor age with time.
Repeated loading of a solid leads to microstructural damage that ultimately results in catastrophic material failure. While posing a major threat to the stability of virtually all materials, the microscopic origins of fatigue, especially for soft solids, remain elusive. Here we explore fatigue in colloidal gels as prototypical inhomogeneous soft solids by combining experiments and computer simulations. Our results reveal how mechanical loading leads to irreversible strand stretching, which builds slack into the network that softens the solid at small strains and causes strain hardening at larg…
Interactions between colloidal particles have hitherto usually been fixed by the suspension composition. Recent experimental developments now enable the control of interactions \emph{in-situ}. Here we use Brownian dynamics simulations to investigate the effect of controlling interactions on gelation, by "quenching" the system from an equilibrium fluid to a gel. We find that, contrary to the normal case of an instantaneous quench, where the local structure of the gel is highly disordered, controlled quenching results in a gel with a higher degree of local order. Under sufficiently slow quenchin…
We study experimentally and theoretically the sedimentation of gels made of strongly aggregated colloidal particles, focussing on the long time behavior, when mechanical equilibrium is asymptotically reached. The asymptotic gel height is found to vary linearly with the initial height, a finding in stark contrast with a recent study on similar gels [Manley \textit{et al.} 2005 \textit{Phys. Rev. Lett.} \textbf{94} 218302]. We show that the asymptotic compaction results from the balance between gravity pull, network elasticity, and solid friction between the gel and the container walls. Based on…
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.
Transitions in structural heterogeneity of colloidal depletion gels formed through short-range attractive interactions are correlated with their dynamical arrest. The system is a density and refractive index matched suspension of 0.20 volume fraction poly(methyl methacyrlate) colloids with the non-adsorbing depletant polystyrene added at a size ratio of depletant to colloid of 0.043. As the strength of the short-range attractive interaction is increased, clusters become increasingly structurally heterogeneous, as characterized by number-density fluctuations, and dynamically immobilized, as cha…
We study the sedimentation of colloidal gels by using a combination of light scattering, polarimetry and video imaging. The asymptotic concentration profiles $φ(z,t\rightarrow \infty)$ exhibit remarkable scaling properties: profiles for gels prepared at different initial volume fractions and particle interactions can be superimposed onto a single master curve by using suitable reduced variables. We show theoretically that this behavior stems from a power law dependence of the compressive elastic modulus \textit{vs} $φ$, which we directly test experimentally. The sedimentation kinetics comprise…
Colloidal gels possess a memory of previous shear events, both steady and oscillatory. This memory, embedded in the microstructure, affects the mechanical response of the gel, and therefore enables precise tuning of the material properties under careful preparation. Here we demonstrate how the dynamics of a deformable inclusion, namely a bubble, can be used to locally tune the microstructure of a colloidal gel. We examine two different phenomena of bubble dynamics that apply a local strain to the surrounding material: dissolution due to mass transfer, with a characteristic strain rate of $10^{…
Strong particulate gels are widely believed to behave poroelastically in compression, e.g. in sedimentation, even though they consolidate irreversibly because of the stickiness of the particles. Particulate gels are usually adhesive as well as cohesive and so wall effects are to be expected in general [Michaels & Bolger (1962)]. These are rarely manifest on process engineering scales, although they can be important in the laboratory and with formulated products in small containers. When the assumption of non-linear poroelasticity is combined with the idea that adhesive failure (yield) is britt…
To gain insight into the kinetics of colloidal gel evolution at low particle volume fractions $ϕ$, we utilize differential dynamic microscopy to investigate particle aggregation, geometric percolation, and the subsequent transition to nonergodic dynamics. We report the emergence of unexpectedly rich multiscale dynamics upon the onset of nonergodicity, which separates the wave vectors $q$ into three different regimes. In the high-$q$ domain, the gel exhibits $ϕ$-independent internal vibrations of fractal clusters. The intermediate-$q$ domain is dominated by density fluctuations at the length sc…
We report measurements of the frequency-dependent shear moduli of aging colloidal systems that evolve from a purely low-viscosity liquid to a predominantly elastic glass or gel. Using microrheology, we measure the local complex shear modulus $G^{*}(ω)$ over a very wide range of frequencies (1 Hz- 100 kHz). The combined use of one- and two-particle microrheology allows us to differentiate between colloidal glasses and gels - the glass is homogenous, whereas the colloidal gel shows a considerable degree of heterogeneity on length scales larger than 0.5 micrometer. Despite this characteristic dif…
We extend Wertheim's thermodynamic perturbation theory to derive the association free energy of a multicomponent mixture for which double bonds can form between any two pairs of the molecules' arbitrary number of bonding sites. This generalization reduces in limiting cases to prior theories that restrict double bonding to at most one pair of sites per molecule. We apply the new theory to an associating mixture of colloidal particles ("colloids") and flexible chain molecules ("linkers"). The linkers have two functional end groups, each of which may bond to one of several sites on the colloids. …
Gels in soft-matter systems are an important nonergodic state of matter. We study a colloid-polymer mixture which is quenched by increasing the polymer concentration, from a fluid to a gel. Using confocal microscopy, we study both the static structure and dynamics in three dimensions (3D). Between the dynamically arrested gel and ergodic fluid comprised of isolated particles we find an intermediate 'cluster fluid' state, where the 'bonds' between the colloidal particles have a finite lifetime. The local dynamics are reminiscent of a fluid, while the local structure is almost identical to that …
This paper has been temporarily withdrawn by the authors. We have recently found that noise in the experiments is at the origin of the supposed "back-and-forth" motion which is discussed in the first version of the paper. As a consequence, figs 4 and 5 as well as their discussion are incorrect. Figure 1 and the general trend of fig. 2 are still valid. At this time, we are uncertain whether or not the short time behavior of cI, shown in fig. 3, is affected by measurement noise. We are working on a new version of the paper, using new techniques that allow us to correct for the experimental noise…
Colloidal gels constitute an important class of materials found in many contexts and with a wide range of applications. Yet as matter far from equilibrium, gels exhibit a variety of time-dependent behaviours, which can be perplexing, such as an increase in strength prior to catastrophic failure. Remarkably, such complex phenomena are faithfully captured by an extremely simple model - "sticky spheres". Here we review progress in our understanding of colloidal gels made through the use of real space analysis and particle resolved studies. We consider the challenges of obtaining a suitable experi…
We investigate the slow dynamics in gelling systems by means of MonteCarlo simulations on the cubic lattice of a minimal statistical mechanics model. By opportunely varying some model parameter we are able to describe a crossover from the chemical gelation behaviour to dynamics more typical of colloidal systems. The results suggest a novel connection linking classical gelation, as originally described by Flory, to more recent results on colloidal systems.
We characterize the self-assembly of colloidal particles with surface mobile DNA linkers under kinetically limited valence conditions. For this, we put forward a computer simulation model that captures quantitatively the interplay between the main dynamic processes governing these systems and allows the simulation of the long time scales reached in experiments. The model is validated by direct comparison with available experimental results, showing an overall good agreement that includes measurements of the average effective valence and its probability distribution as a function of the density…
We study the rotational diffusion of aging Laponite suspensions for a wide range of concentrations using depolarized dynamic light scattering. The measured orientational correlation functions undergo an ergodic to non-ergodic transition that is characterized by a concentration-dependent ergodicity-breaking time. We find that the relaxation times associated with rotational degree of freedom as a function of waiting time, when scaled with their ergodicity-breaking time, collapse on two distinct master curves. These master curves are similar to those previously found for the translational dynamic…
Rheological measurements of model colloidal gels reveal that large variations in the shear moduli as colloidal volume-fraction changes are not reflected by simple structural parameters such as the coordination number, which remains almost a constant. We resolve this apparent contradiction by conducting a normal mode analysis of experimentally measured bond networks of the gels. We find that structural heterogeneity of the gels, which leads to floppy modes and a nonaffine-affine crossover as frequency increases, evolves as a function of the volume fraction and is key to understand the frequency…
Restricting the number of attractive physical "bonds" that can form between particles in a fluid suppresses the usual demixing phase transition to very low particle concentrations, allowing for the formation of open, percolated, and homogeneous states, aptly called equilibrium or "empty" gels. Most demonstrations of this concept have directly limited the microscopic particle valence via anisotropic (patchy) attractions; however, an alternative macroscopic valence limitation would be desirable for greater experimental tunability and responsiveness. One possibility, explored in this paper, is to…
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…
The miniaturization of machines towards the micron and nanoscales requires the development of joint-like elements that enable and constrain motion. We present a facile method to create colloidal joints, that is, anisotropic colloidal particles containing surface mobile DNA linkers that control the motion range of bonded particles. We demonstrate quantitatively that we can control the flexibility of these colloidal joints by tuning the DNA linker concentration in the bond area. We show that the colloidal shape controls the range of motion that these colloidal joints enable, due to the finite-si…
Functionalizing colloids with reactive DNA linkers is a versatile way of programming self-assembly. DNA selectivity provides direct control over colloid-colloid interactions allowing the engineering of structures such as complex crystals or gels. However, self-assembly of localized and finite structures remains an open problem with many potential applications. In this work, we present a system in which functionalized surfaces initiate a cascade reaction between linkers leading to self-assembly of crystals with a controllable number of layers. Specifically, we consider colloidal particles funct…
