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Under many conditions, biomolecules and nanoparticles associate by means of attractive bonds, due to hydrophobic attraction. Extracting the microscopic association or dissociation rates from experimental data is complicated by the dissociation events and by the sensitivity of the binding force to temperature ($T$). Here we introduce a theoretical model that combined with light-scattering experiments allows us to quantify these rates and the reversible binding energy as a function of $T$. We apply this method to the reversible aggregation of thermoresponsive polystyrene/poly($N$-isopropylacrylamide) core-shell nanoparticles, as a model system for biomolecules. We find that the binding energy changes sharply with $T$, and relate this remarkable switchable behavior to the hydrophobic-hydrophilic transition of the thermosensitive nanoparticles.

We propose a simple route to analytically evaluate the average coordination of model disordered solids with maximally homogeneous distribution of the particles in space. The model yields the average number of contacts (z) as a function of volume fraction (phi) of a hard-sphere connected system and recovers the critical jamming point of hard spheres (z=6 at phi=0.64). Numerical simulations of Lennard-Jones glasses with a varying attraction range are used to investigate the volume fraction dependence of the average coordination in the presence of attraction. It is observed that upon decreasing phi below 0.6, structural heterogeneity is reflected in values of the coordination number which are higher than those predicted by the model for a statistically homogeneous distribution of particles in space due to the attraction-induced local aggregation. Thus the model can be usefully employed as a quantitative reference to assess the degree of structural heterogeneity in glasses in terms of a directly accessible structural parameter such as the mean number of contacts.

The aggregation of interacting brownian particles in sheared concentrated suspensions is an important issue in colloid and soft matter science per se. Also, it serves as a model to understand biochemical reactions occurring in vivo where both crowding and shear play an important role. We present an effective medium approach within the Smoluchowski equation with shear which allows one to calculate the encounter kinetics through a potential barrier under shear at arbitrary colloid concentrations. Experiments on a model colloidal system in simple shear flow support the validity of the model in the concentration range considered. By generalizing Kramers' rate theory to the presence of shear and collective hydrodynamics, our model explains the significant increase in the shear-induced reaction-limited aggregation kinetics upon increasing the colloid concentration.

We study shear-induced gelation in a microchannel without adding any salt, for a polymer colloid that is fully stable under stagnant conditions. The initial stability is achieved by negative charges from the polymer chain end groups. Then, sulfonate surfactants are added to the system. The surfactant adsorption is characterized by coexistence of domains of gaseous-like noninteracting molecules (G) and condensed patches of interacting molecules (K). It is found that, for a fixed, substantially high shear rate of 1x10(6) 1/s (Peclet number=4.5x10(4)), in the absence of surfactants, the shear-induced gelation of the system does occur, and when the surfactants are added, as the surfactant surface coverage on the particles increases to a certain value, the shear-induced gelation or even small extent of aggregation becomes impossible. We have estimated the Derjaguin-Landau-Verwey-Overbeek (DLVO) interaction energy barrier from the measured zeta-potentials and found that in all the cases the corresponding shear-induced collision energy is orders of magnitude larger than the required energy to overcome the barrier. Thus, one would expect occurrence of gelation for all the systems. This clearly indicates presence of additional non-DLVO interactions, which under very low ionic strength are related to the adsorbed surfactant patches that generate strongly repulsive, short-range hydration force. Moreover, when no gelation but only aggregation occurs after passing through the microchannel, the cluster size distribution exhibits distinct bimodality. The structure of the obtained gels also depends on the surfactant surface coverage.

We evaluate the elasticity of arrested short-ranged attractive colloids by combining an analytically solvable elastic model with a hierarchical arrest scheme into a new approach, which allows to discriminate the microscopic (primary particle-level) from the mesoscopic (cluster-level) contribution to the macroscopic shear modulus. The results quantitatively predict experimental data in a wide range of volume fractions and indicate in which cases the relevant contribution is due to mesoscopic structures. On this basis we propose that different arrested states of short-ranged attractive colloids can be meaningfully distinguished as homogeneous or heterogeneous colloidal glasses in terms of the length-scale which controls their elastic behavior., 3 figures, revised version, to appear in Physical Review Letters

Flow-induced aggregation of colloidal particles leads to aggregates with fairly high fractal dimension (df approximately 2.4-3.0) which are directly responsible for the observed rheological properties of sheared dispersions. We address the problem of the decrease in aggregate size with increasing hydrodynamic stress, as a consequence of breakup, by means of a fracture-mechanics model complemented by experiments in a multipass extensional (laminar) flow device. Evidence is shown that as long as the inner density decay with linear size within the aggregate (due to fractality) is not negligible (as for df approximately 2.4-2.8), this imposes a substantial limitation to the hydrodynamic fragmentation process as compared with nonfractal aggregates (where the critical stress is practically size independent). This is due to the fact that breaking up a fractal object leads to denser fractals which better withstand stress. In turbulent flows, accounting for intermittency introduces just a small deviation with respect to the laminar case, while the model predictions are equally in good agreement with experiments from the literature. Our findings are summarized in a diagram for the breakup exponent (governing the size versus stress scaling) as a function of fractal dimension.

Using a novel approximation scheme within the convective diffusion (two body Smoluchowski) equation framework, we unveil the shear-driven aggregation mechanism at the origin of structure-formation in sheared colloidal systems. The theory, verified against numerics and experiments, explains the induction time followed by explosive (irreversible) rise of viscosity observed in charge-stabilized colloidal and protein systems under steady shear. The Arrhenius-type equation with shear derived here, extending Kramers theory in the presence of shear, is the first analytical result clearly showing the important role of shear-drive in activated-rate processes as they are encountered in soft condensed matter.

The liquid‐like to solid‐like transition (gelation) has been investigated in high turbulent shear flow generated in a microchannel for polymer colloids composed of styrene‐acrylate copolymer particles, fully stabilized by negatively charges from both the polymer chain end groups and adsorbed aliphatic sulfonate surfactant. The main objective is to explore the connection between high shear‐induced gelation and the inhomogeneous state of the adsorbed surfactants on the particle surface, characterized by the coexistence of non‐interactive gaseous molecule and associated condensed cluster patches. The effect of such inhomogeneity on the structure of gels has also been investigated.

The bulk modulus of many amorphous materials, such as metallic glasses, behaves nearly in agreement with the assumption of affine deformation, namely that the atoms are displaced just by the amount prescribed by the applied strain. In contrast, the shear modulus behaves as for nonaffine deformations, with additional displacements due to the structural disorder which induce a marked material softening to shear. The consequence is an anomalously large ratio of the bulk modulus to the shear modulus for disordered materials characterized by dense atomic packing, but not for random networks with point atoms. We explain this phenomenon with a microscopic derivation of the elastic moduli of amorphous solids accounting for the interplay of nonaffinity and short-range particle correlations due to excluded volume. Short-range order is responsible for a reduction of the nonaffinity which is much stronger under compression, where the geometric coupling between nonaffinity and the deformation field is strong, whilst under shear this coupling is weak. Predictions of the Poisson ratio based on this model allow us to rationalize the trends as a function of coordination and atomic packing observed with many amorphous materials.

We show that the slowing-down of diffusion-limited reaction rates in dense liquids can be explained in terms of an effective two-body Smoluchowski framework where many-body correlations are accounted for by means of a nonequilibrium mean-force field. This framework explains recent observations from numerical simulations.

Structural disorder has a dramatic impact on the mechanical response and stability of solids. On the one hand, rigidity percolation shows that the limit of mechanical stability coincides with the emergence of floppy modes. On the other hand, the rigidity of solids is also lowered by nonaffine atomic displacements, i.e. additional motions caused by the disorder on top of the affine displacements dictated by the strain. These two frameworks have offered alternative descriptions of the elasticity of disordered solids with central-force bonds, but the relationship between rigidity percolation and nonaffinity has remained unclear. As such, a unifying theory of real materials, i.e. those with covalent (noncentral) bonds, such as amorphous semiconductors, has been elusive. After briefly reviewing these theories, we present a mean-field argument which attempts to provide the unifying link between rigidity percolation and non-affinity. This framework yields analytical predictions of the shear modulus of covalent amorphous solids with potential applications to amorphous semiconductors and disordered carbon electronic materials.

Colloidal systems that are well stabilized by electrostatic repulsive forces can be activated by intense shear flow and transformed into solid-like gels, without adding any electrolyte. We have experimentally quantified the critical particle volume fraction for such a transition and found that it is a function of primary particle radius and shear rate. In particular, the values of the critical particle volume fraction obtained under different conditions can be represented through a single power-law function of the Breakage Number (Br), which is defined as the ratio between the shearing energy and the interparticle bonding energy. This finding indicates that, instead of shear rate or stress, the correct parameter quantifying the criticality for shear-induced gelation is Br. In addition, it is shown that the clusters formed in the shear aggregation process exhibit fractal scaling with fractal dimension equal to 2.4 ± 0.04, independent of Br (i.e., of the shear stress, the particle size and the interparticle bonding energy). This is similar to the case of quiescent systems where the Brownian motion-induced aggregations, i.e., diffusion-limited and reaction-limited cluster aggregations, lead to clusters with fractal dimension equal to 1.8 ± 0.05 and 2.1 ± 0.05, respectively, which are independent of the particle type and size and the electrolyte concentration. Moreover, the ratio between the radius of gyration of clusters constructing the gel network and the primary particle radius at criticality decreases as Br increases, following a power-law scaling with exponent of −0.31, which is in good agreement with that for breakup of dense fractal clusters of the same fractal dimension in laminar flow.

The stability of a colloidal system composed of styrene-acrylate copolymer particles and potassium stearate (KS) anionic surfactant molecules has been determined in terms of the Fuchs stability ratio, W, as a function of the surfactant concentration, by measuring the initial aggregation kinetics using the small-angle light scattering (SALS) technique. The structure of the particle surface is peculiar, being irregularly patterned, and thus represents a model system to investigate colloidal stability of nonsmooth colloidal particles. From the SALS kinetic experiments, it is found that the stability increases dramatically with KS concentration until the saturation of the available surface occurs. At concentrations higher than the saturation concentration, the W value decreases markedly with KS, as a consequence of attractive depletion forces induced by formation of micelles in the water phase. The adsorption isotherm, determined through the surface tension technique, agrees with the W vs KS behavior, with respect to the onset of saturation and the surface-per-molecule value, and it can be described by the two-step Langmuir isotherm. Static light scattering spectra of the particles at different adsorbed amounts of KS have been fitted by means of the Lorenz-Mie theory and accounting for the experimentally determined particle size distribution. The increase in the particle diameter imputable to KS adsorption is sizable. Stability data measured under high fluid shear in a turbulent capillary (in the absence of any screening salt) fit well into this scenario. However, depletion forces are shown to be noncooperative with turbulent shear in the absence of screening electrolytes.

A theoretical model has been developed which provides analytical expressions for the elastic moduli of disordered isotropic ensembles of spheres interconnected by physical bonds. Young's and shear moduli have been derived assuming an ideal random isotropic network and the radial distribution function for disordered packings of spheres. The interparticle interactions are accounted for in terms of surface forces for the two distinct cases of perfectly rigid spheres and spheres deformable at contact. A theoretical expression is also derived in a similar way for the bulk or compressibility modulus. In this case, an atomistic approach has been followed based on the analogy with noble gas solids and colloidal crystals. Also in this case, disordered spatial distribution of the spheres is described statistically. For the case of colloidal aggregates, a total two-body mean-field interaction potential is used which includes the Born repulsion energy. This latter contribution plays an essential role in determining the compression behavior of systems of particles aggregated in the primary minimum of the potential well and, therefore, must not be neglected. Both the expression of the Young's modulus and that of the compressibility modulus derived in this work are found to be consistent with two distinct sets of experimental data which recently appeared in the literature.

The European physical journal / E 39(4), 44(2016). doi:10.1140/epje/i2016-16044-3, The mechanical response of glasses remains challenging to understand. Recent results indicate that the oscillatory rheology of soft glasses is accompanied by a sharp non-equilibrium transition in the microscopic dynamics. Here, we use simultaneous x-ray scattering and rheology to investigate the reversibility and hysteresis of the sharp symmetry change from anisotropic solid to isotropic liquid dynamics observed in the oscillatory shear of colloidal glasses (D. Denisov, M.T. Dang, B. Struth, A. Zaccone, P. Schall, Sci. Rep. 5 14359 (2015)). We use strain sweeps with increasing and decreasing strain amplitude to show that, in analogy with equilibrium transitions, this sharp symmetry change is reversible and exhibits systematic frequency-dependent hysteresis. Using the non-affine response formalism of amorphous solids, we show that these hysteresis effects arise from frequency-dependent non-affine structural cage rearrangements at large strain. These results consolidate the first-order-like nature of the oscillatory shear transition and quantify related hysteresis effects both via measurements and theoretical modelling., Published by Springer, Berlin

We analyze wave propagation and attenuation in extremely soft, strongly overdamped solids both experimentally and theoretically., The propagation of elastic waves in soft materials plays a crucial role in the spatiotemporal transmission of mechanical signals, e.g., in biological mechanotransduction or in the failure of marginal solids. At high Reynolds numbers Re ≫ 1, inertia dominates and wave propagation is readily observed. However, mechanical cues in soft and biological materials often occur at low Re, where waves are overdamped. Overdamped waves are not only difficult to observe experimentally, also theoretically their description remains incomplete. Here, we present direct measurements of the propagation and attenuation of mechanical signals in colloidal soft solids, induced by an optical trap. We derive an analytical theory for low Re wave propagation and damping, which is in excellent agreement with the experiments. Our results present both a previously unexplored method to characterize damped waves in soft solids and a theoretical framework showing how localized mechanical signals can provoke a remote and delayed response.