Project description:Syneresis, the compaction of a material accompanied by fluid expulsion, is a typical mechanical instability which exists among colloidal gel based materials and that negatively affects the quality of relevant applications. We shed light onto the internal dynamics of model colloidal gels undergoing syneresis using Laser Speckle Imaging (LSI). The resulting dynamical maps capture the distinct differences in spatial and temporal relaxation patterns between colloidal gels comprising solid and liquid particles. This indicates different mechanisms of syneresis between the two systems and highlights the importance of the constituent particles and their mobile or restrictive interfaces in the mechanical relaxation of the colloidal gels during syneresis.
Project description:Colloidal gels are elasto-plastic materials composed of an out-of-equilibrium, self-assembled network of micron-sized (solid) particles suspended in a fluid. Recent work has shown that far-field hydrodynamic interactions do not change gel structure, only the rate at which the network forms and ages. However, during gel formation, the interplay between short-ranged attractions leading to gelation and equally short-ranged hydrodynamic lubrication interactions remains poorly understood. Here, we therefore study gelation using a range of hydrodynamic descriptions: from single-body (Brownian Dynamics), to pairwise (Rotne-Prager-Yamakawa), to (non-)lubrication-corrected many-body (Stokesian Dynamics). We confirm the current understanding informed by simulations accurate in the far-field. Yet, we find that accounting for lubrication can strongly impact structure at low colloid volume fraction. Counterintuitively, strongly dissipative lubrication interactions also accelerate the aging of a gel, irrespective of colloid volume fraction. Both elements can be explained by lubrication forces facilitating collective dynamics and therefore phase-separation. Our findings indicate that despite the computational cost, lubricated hydrodynamic modeling with many-body far-field interactions is needed to accurately capture the evolution of the gel structure.
Project description:Colloidal gels, commonly used as mesoporous intermediates or functional materials, suffer from brittleness, often showing small yield strains on the order of 1% or less for gelled colloidal suspensions. The short-range adhesive forces in most such gels are central forces-combined with the smooth morphology of particles, the resistance to yielding and shear-induced restructuring is limited. In this study, we propose an innovative approach to improve colloidal gels by introducing surface roughness to the particles to change the yield strain, giving rise to non-central interactions. To elucidate the effects of particle roughness on gel properties, we prepared thermoreversible gels made from rough or smooth silica particles using a reliable click-like-chemistry-based surface grafting technique. Rheological and optical characterization revealed that rough particle gels exhibit enhanced toughness and self-healing properties. These remarkable properties can be utilized in various applications, such as xerogel fabrication and high-fidelity extrusion 3D-printing, as we demonstrate in this study.
Project description:Biomedical applications of thermo-responsive (TR) hydrogels require these materials to be biocompatible, non-cytotoxic, and non-immunogenic. Due to serious concerns regarding potential toxicity of poly(N-isopropylacrylamide) (PNIPAm), design of alternative homo- and copolymer gels with controllable swelling properties has recently become a hot topic. This study focuses on equilibrium swelling of five potential candidates to replace PNIPAm in biomedical and biotechnological applications: poly(N-vinylcaprolactam), poly(vinyl methyl ether), poly(N,N-dimethyl amino ethyl methacrylate), and two families of poly(2-oxazoline)s, and poly(oligo(ethylene glycol) methacrylates). To evaluate their water uptake properties and to compare them with those of substituted acrylamide gels, a unified model is developed for equilibrium swelling of TR copolymer gels with various types of swelling diagrams. Depending on the strength of hydrophobic interactions (high, intermediate, and low), the (co)polymers under consideration are split into three groups that reveal different responses at and above the volume phase transition temperature.
Project description:Hydrogels are cross-linked polymer networks swollen in water. The large solvent content enables hydrogels to have unique physical properties and allows them to be used in diverse applications such as tissue engineering, drug delivery, and absorbents. Gel properties are linked to internal dynamics. While bulk gel dynamics have been studied extensively, how gel networks respond locally to deformation has yet to be understood. Here, poly(vinyl alcohol) (PVA) gels have been stretched to study the effects of deformation on gel dynamics parallel and perpendicular to the stretching direction using dynamic small angle light scattering (DSALS). The implementation of DSALS is described and compared to traditional DLS for PVA gels with different crosslink densities, ranging from 0.75-2%. Despite the orders of magnitude difference in the scattering vector, q, range of the techniques, the dynamics match, and the apparent elastic diffusion coefficient, DA increases linearly with the crosslink density for unstretched gels at a constant 2 wt% concentration. We observe that the elastic motion depends on the direction of stretch, decreasing perpendicular to stretching and increasing at parallel direction. Using DSALS can therefore be an effective tool to evaluate local hydrogel response to deformation.
Project description:Locally (re)structuring colloidal gels - micron-sized particles forming a connected network with arrested dynamics - can enable 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, 2022, 18, 2092] showed that local ordering can be rapidly induced by acoustically modulating an embedded microbubble. Here, we perform Brownian dynamics simulations to understand the mechanical effect of an oscillating microbubble on the next-to-bubble structure of the embedding colloidal gel. Our simulations reveal hexagonal-close-packed structures over a range that is comparable to the amplitude of the oscillations. However, we were unable to reproduce the unexpectedly long-ranged modification of the gel structure - dozens of amplitudes - observed in experiment. This suggests including long-ranged effects, such as fluid flow, should be considered in future computational work.
Project description:Amongst colloidal gels, those designed by the assembly of anisotropic colloidal particles tend to form fibrillar gels and are attracting interest as artificial cell growth environments since they have a structure reminiscent of biological extracellular matrices. Their properties can be tuned by controlling the size, shape, and rigidity of the nanoparticles used during their formation. Herein, the relationship between the physical and mechanical properties of the nanocolloidal building blocks and the properties of the resulting gels is investigated. Thermoresponsive particles with different aspect ratios and controlled rigidity were prepared, and the gelation and the properties of the resulting gels were studied. The results show how the aspect ratio and rigidity of polymer colloids tune the properties of the gels. An increase in the aspect ratio of the nanocolloid used led to a sol-gel transition observed at lower particle concentration, but an increase in the rigidity of the nanocolloids delayed the sol-gel transition to higher concentration. However, at a constant concentration, increases in the anisotropy produced gels with higher modulus and lower yield strain. Similarly, an increase in rigidity of the colloids increased the modulus and reduced the yield strain of the resulting gels.
Project description:Endothelial morphogenesis into capillary networks is dependent on the matrix morphology and mechanical properties. In current 3D gels, these two matrix features are interdependent and their distinct roles in endothelial organization are not known. Thus, it is important to decouple these parameters in the matrix design. Colloidal gels can be engineered to regulate the microstructural morphology and mechanics in an independent manner because colloidal gels are formed by the aggregation of particles into a self-similar 3D network. In this work, gelatin based colloidal gels with distinct mechanomorphology were developed by engineering the electrostatic interaction mediated aggregation of particles. By altering the mode of aggregation, colloidal gels showed either compact dense microstructure or tenuous strand-like networks, and the matrix stiffness was controlled independently by varying the particle fraction. Endothelial Cell (EC) networks were favored in tenuous strand-like microstructure through increased cell-matrix and cell-cell interactions, while compact dense microstructure inhibited the networks. For a given microstructure, as the gel stiffness was increased, the extent of EC network was reduced. This result demonstrates that 3D matrix morphology and mechanics provide distinct signals in a bidirectional manner during EC network formation. Colloidal gels can be used to interrogate the angiogenic responses of ECs and can be developed as a biomaterial for vascularization.
Project description:Collections of interacting active particles, self-propelling or not, have shown remarkable phenomena including the emergence of dynamic patterns across different length scales, from animal groups to vibrated grains, microtubules, bacteria, and chemical- or field-driven colloids. Burgeoning experimental and simulation activities are now exploring the possibility of realizing solid and stable structures from passive elements that are assembled by a few active dopants. Here we show that such an elusive task may be accomplished by using a small amount of apolar dopants, namely synthetic active but not self-propelling units. We use blue light to rapidly assemble 2D colloidal clusters and gels via nonequilibrium diffusiophoresis, where microscopic hematite dockers form long-living interstitial bonds that strongly glue passive silica microspheres. By varying the relative fraction of doping, we uncover a rich phase diagram including ordered and disordered clusters, space-filling gels, and bicontinuous structures formed by filamentary dockers percolating through a solid network of silica spheres. We characterize the slow relaxation and dynamic arrest of the different phases via correlation and scattering functions. Our findings provide a pathway toward the rapid engineering of mesoscopic gels and clusters via active colloidal doping.
Project description:Malleable biomaterials such as Herschel-Bulkley (H-B) fluids possess shear responsive rheological properties and are capable of self-assembly and viscoelastic recovery following mechanical disruption (e.g., surgical placement via injection or spreading). This study demonstrated that the addition of moderate molecular weight glycosaminoglycans (GAGs) such as chondroitin sulfate (CS) (Mw = 15-30 kDa) and hyaluronic acid (HA) (Mw = 20-41 kDa) can be used to modify several rheological properties including consistency index (K), flow-behavior index (n), and yield stress (?y) of submicrometer hydroxyapatite (HAP) (Davg ? 200 nm) colloidal gels. GAG-HAP colloidal mixtures exhibited substantial polymer-particle synergism, likely due to "bridging" flocculation, which led to a synergistic increase in consistency index (KGAG-HAP ? KGAG + KHAP) without compromising shear-thinning behavior (n < 1) of the gel. In addition, GAG-HAP colloids containing high concentrations of HAP (60-80% w/v) exhibited substantial yield stress (?y ? 100 Pa) and viscoelastic recovery properties (G'recovery ? 64%). While rheological differences were observed between CS-HAP and HA-HAP colloidal gels, both CS and HA represent feasible options for future studies involving bone defect filling. Overall, this study identified mixture regions where rheological properties in CS-HAP and HA-HAP colloidal gels aligned with desired properties to facilitate surgical placement in non-load-bearing tissue-filling applications such as calvarial defects.