Colloidal solids (COLIS) is a state-of-the-art light scattering setup developed for experiments onboard the International Space Station (ISS). COLIS allows for probing the structure and dynamics of soft matter systems on a wide range of length scales, from a few nm to tens of microns, and on time scales from 100 ns to tens of hours. In addition to conventional static and dynamic light scattering, COLIS includes depolarized dynamic light scattering, a small-angle camera, photon correlation imaging, and optical manipulation of thermosensitive samples through an auxiliary near-infrared laser beam, thereby providing a unique platform for probing soft matter systems.
View Article and Find Full Text PDFThe Brownian dynamics of a colloidal particle is consistently modified by the presence in the solvent of other particles of comparable size, whose effects on the particle diffusion coefficient cannot be attributed to a change of the effective solvent viscosity. So far, despite their impact on subjects ranging from microrheology to phoretic transport in crowded environments, a detailed experimental survey of these effects is still lacking. By exploiting the peculiar properties of fluorinated colloidal particle, we have performed an extensive dynamic light scattering (DLS) investigation of short-time self-diffusion in binary colloidal mixtures, focusing on systems where one of the two species (the "tracer" particles) is very diluted compared to the other one (the "host" particles).
View Article and Find Full Text PDFSelf-assembling peptides (SAPs) have been increasingly studied as hydrogel-former gelators because they can create biocompatible environments. A common strategy to trigger gelation, is to use a pH variation, but most methods result in a change in pH that is too rapid, leading to gels with hardly reproducible properties. Here, we use the urea-urease reaction to tune gel properties, by a slow and uniform pH increase.
View Article and Find Full Text PDFThe weak absorption of a laser beam generates in a fluid an inhomogeneous refractive index profile acting as a negative lens. This self-effect on beam propagation, known as Thermal Lensing (TL), is extensively exploited in sensitive spectroscopic techniques, and in several all-optical methods for the assessment of thermo-optical properties of simple and complex fluids. Using the Lorentz-Lorenz equation, we show that the TL signal is directly proportional to the sample thermal expansivity α, a feature allowing minute density changes to be detected with high sensitivity in a tiny sample volume, using a simple optical scheme.
View Article and Find Full Text PDFWe investigate the rheo-mechanical properties of Mebiol Gel®, a thermosensitive gel-forming polymer extensively used as a medium for cellular culture, using passive microrheology made either by standard dynamic light scattering or by photon correlation imaging. In the dilute limit, Mebiol displays a Newtonian behavior with an effective viscosity that decreases with temperature, consistent with a peculiar aggregation mechanism characterized by an increase of the molecular weight with a simultaneous reduction of the aggregate size. By increasing concentration and approaching gelation, both the storage and loss moduli show a nonmonotonic dependence with temperature, with a pronounced maximum around T ≃ 28-30 °C, the value above which, in the dilute limit, the individual Mebiol chains are fully compacted.
View Article and Find Full Text PDFThe fundamental understanding of the gelation kinetics, stress relaxation and temporal evolution in colloidal filamentous gels is central to many aspects of soft and biological matter, yet a complete description of the inherent complex dynamics of these systems is still missing. By means of photon correlation imaging (PCI), we studied the gelation of amyloid fibril solutions, chosen as a model filamentous colloid with immediate significance to biology and nanotechnology, upon passage of ions through a semi-permeable membrane. We observed a linear-in-time evolution of the gelation front and rich rearrangement dynamics of the gels, the magnitude and the spatial propagation of which depend on how effectively electrostatic interactions are screened by different ionic strengths.
View Article and Find Full Text PDFThe fast setting of gels originating from an arrested phase separation leads to solid structures that incorporate a substantial amount of frozen-in stresses. Using a colloidal system made of particles whose interactions can accurately be tuned with temperature and exploiting Photon Correlation Imaging (PCI), an optical correlation technique blending the powers of scattering and imaging, we show that the relaxation of these internal stresses, which occurs through a cascade of microscopic restructuring events, is strongly influenced by the thermal history of the sample. By changing with a temperature jump the interparticle interactions in an already set gel, we specifically show that gels formed by a deep quench within the coexistence region store a lot of residual stress.
View Article and Find Full Text PDFThe achievement of a homogeneous dispersion of nanoparticles is of paramount importance in supporting their technological application. In wet processing, stable dispersions were largely obtained via surfactant or surface functionalization: although effective, the use of dispersant can alter, or even impair, the functional properties of the resulting nanostructured systems. Herein, we report a novel integrated modeling and experimental approach to obtain stable ZrO nanoparticle (NP) dispersions at native dimensions (about 5 nm) in homogeneous ternary mixtures of solvents (i.
View Article and Find Full Text PDFWe experimentally investigate the gravitational-driven motion of a heavy object inside a vertical 2D assembly of identical, plastic cylinders arranged in a regular, triangular lattice. The bottom of the assembly is in contact with a rough plate whose horizontal, sinusoidal motion induces the formation of shear bands in the granular solid, aligned with the edges of the lattice. The intruder sinks when the width of the shear band is as large as its size and halts once the regular configuration of the grains is recovered.
View Article and Find Full Text PDFRelaxation of internal stresses through a cascade of microscopic restructuring events is the hallmark of many materials, ranging from amorphous solids like glasses and gels to geological structures subjected to a persistent external load. By means of photon correlation imaging, a recently developed technique that blends the powers of scattering and imaging, we provide a spatially and temporally resolved survey of the restructuring and aging processes that spontaneously occur in physical gels originating from an arrested phase separation. We show that the temporal dynamics is characterized by an intermittent sequence of spatially localized "microquakes" that eventually lead to global rearrangements occurring at a rate that scales with the gel age.
View Article and Find Full Text PDFDue to its exquisite sensitivity to interfacial properties, thermophoresis, i.e., particle motion driven by thermal gradients, can provide novel, exclusive, and often surprising information on the structural properties of colloidal or macromolecular fluids and on particle/solvent interactions at the nanoscale.
View Article and Find Full Text PDFJ Phys Condens Matter
January 2018
We have investigated the stationary sedimentation profiles of colloidal gels obtained by an arrested phase-separation process driven by depletion forces, which have been compressed either by natural gravity or by a centrifugal acceleration ranging between 6g and 2300g. Our measurements show that the gel rheological properties display a drastic change when the gel particle volume fraction exceeds a value [Formula: see text], which barely depends on the strength of the interparticle attractive forces that consolidate the network. In particular, the gel compressive yield stress [Formula: see text], which increases as [Formula: see text] for [Formula: see text], displays a diverging behaviour for [Formula: see text], with an asymptotic value that is close to the random close packing value for hard spheres.
View Article and Find Full Text PDFWe propose a new method to produce fluorinated nanoparticles (NPs) based on ab initio reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization without the use of toxic surfactants. NP size, surface charge, and chemistry can be controlled via the adoption of different macromolecular transfer agents produced via RAFT polymerization of amphiphilic monomers. Thanks to this versatility, interparticle interactions can be easily tuned by changing solvent composition and temperature.
View Article and Find Full Text PDFDense suspensions of motile bacteria, possibly including the human gut microbiome, exhibit collective dynamics akin to those observed in classic, high Reynolds number turbulence with important implications for chemical and biological transport, yet this analogy has remained primarily qualitative. Here, we present experiments in which a dense suspension of Bacillus subtilis bacteria was flowed through microchannels and the velocity statistics of the flowing suspension were quantified using a recently developed velocimetry technique coupled with vortex identification methods. Observations revealed a robust intermittency phenomenon, whereby the average velocity profile of the suspension fluctuated between a plug-like flow and a parabolic flow profile.
View Article and Find Full Text PDFBy experimenting on model colloids where depletion forces can be carefully tuned and quantified, we show that attractive interactions consistently "promote" particle settling, so much that the sedimentation velocity of a moderately concentrated dispersion can even exceed its single-particle value. At larger particle volume fraction ϕ, however, hydrodynamic hindrance eventually takes over. Hence, v(ϕ) actually displays a nonmonotonic trend that may threaten the stability of the settling front to thermal perturbations.
View Article and Find Full Text PDFWe re-examine the classical problem of irreversible colloid aggregation, showing that the application of Digital Fourier Imaging (DFI), a class of optical correlation methods that combine the power of light scattering and imaging, allows one to pick out novel useful evidence concerning the restructuring processes taking place in a strong colloidal gel. In particular, the spatially-resolved displacement fields provided by DFI strongly suggest that the temporally-intermittent local rearrangements taking place in the course of gel ageing are characterized by very long-ranged spatial correlations.
View Article and Find Full Text PDFJ Phys Condens Matter
November 2014
Pectin is a natural biopolymer that forms, in the presence of divalent cations, ionic-bound gels typifying a large class of biological gels stabilized by non-covalent cross-links. We investigate and compare the kinetics of formation and aging of pectin gels obtained either through external gelation via perfusion of free Ca(2+) ions, or by internal gelation due to the supply of the same ions from the dissolution of CaCO3 nanoparticles. The microscopic dynamics obtained with photon correlation imaging, a novel optical technique that allows obtaining the microscopic dynamics of the sample while retaining the spatial resolution of imaging techniques, is contrasted with macroscopic rheological measurements at constant strain.
View Article and Find Full Text PDFBy exploiting photon correlation imaging and ghost particle velocimetry, two novel optical correlation techniques particularly suited to the investigation of the microscopic dynamics of spatially heterogeneous samples, we investigate the settling and restructuring dynamics of colloidal gels generated by short-ranged depletion interactions. Three distinct regions can be clearly set apart within the liquid-liquid coexistence region of the phase diagram where gel formation is observed. When depletion forces are barely sufficient to drive the system within the metastable region, an initial disordered gel hosts the rapid nucleation of crystallites, which stress the gel structure until it fully collapses, leading to the formation of a macroscopic colloidal crystal.
View Article and Find Full Text PDFWe describe and test a new approach to particle velocimetry, based on imaging and cross correlating the scattering speckle pattern generated on a near-field plane by flowing tracers with a size far below the diffraction limit, which allows reconstructing the velocity pattern in microfluidic channels without perturbing the flow. As a matter of fact, adding tracers is not even strictly required, provided that the sample displays sufficiently refractive-index fluctuations. For instance, phase separation in liquid mixtures in the presence of shear is suitable to be directly investigated by this "ghost particle velocimetry" technique, which just requires a microscope with standard lamp illumination equipped with a low-cost digital camera.
View Article and Find Full Text PDFGravity or ultracentrifuge settling of colloidal particles and macromolecules usually involves several disperse species, either because natural and industrial colloids display a large size polydispersity, or because additives are put in on purpose to allow for density-based fractionation of the suspension. Such 'macromolecular crowding', however, may have surprising effects on sedimentation, for it strongly affects the buoyant force felt by a settling particle. Here we show that, as a matter of fact, the standard Archimedes' principle is just a limiting law, valid only for mesoscopic particles settling in a molecular fluid, and we obtain a fully general expression for the actual buoyancy force providing a microscopic basis to the general thermodynamic analysis of sedimentation in multi-component mixtures.
View Article and Find Full Text PDFThe buoyancy concept is critically re-examined for applications to dispersions of nano-particles, such as colloids, proteins, or macromolecules. It is shown that when the size of the buoyant particle is not too different (say, at most a factor of ten) from the size of the dispersed particles, new intriguing phenomena emerge, leading to the violation of the Archimedes' principle. The resulting buoyancy force depends not only on the volume of the particle and on the mass density of the dispersion, but also on the relative size of the particles, on their geometry, and on the interactions between the buoyant particle and the fluid.
View Article and Find Full Text PDFWe study the sedimentation of colloidal gels by using a combination of light scattering, polarimetry and video imaging. The asymptotic concentration profiles (z,t → ∞) 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 versus , which we directly test experimentally.
View Article and Find Full Text PDFJ Phys Condens Matter
July 2012
Sedimentation has played a key role in the development of colloid science. In fact, it is because of the celebrated experiments by Perrin, yielding a concrete demonstration of molecular reality and giving strong support to Einstein's theory of Brownian motion, that colloids enter the realm of basic physics. Subsequent investigations have shown that a lot more can be learnt both from sedimentation equilibrium and from particle settling dynamics.
View Article and Find Full Text PDFDepletion interactions in correlated fluids are investigated both theoretically and experimentally. A formally exact derivation of a general expression for depletion interactions is presented and then specialized to the case of critical correlations in the depletant by employing a long wavelength approximate analysis. A scaling expression is obtained in the critical region, suggesting a close connection to the critical Casimir effect.
View Article and Find Full Text PDFWe use a combination of original light scattering techniques and particles with unique optical properties to investigate the behavior of suspensions of attractive colloids under gravitational stress, following over time the concentration profile, the velocity profile, and the microscopic dynamics. During the compression regime, the sedimentation velocity grows nearly linearly with height, implying that the gel settling may be fully described by a (time-dependent) strain rate. We find that the microscopic dynamics exhibit remarkable scaling properties when time is normalized by the strain rate, showing that the gel microscopic restructuring is dominated by its macroscopic deformation.
View Article and Find Full Text PDF