arXiv subjects

S. U. Egelhaaf

Publications and source records attributed to S. U. Egelhaaf.

At least 19 recordsLinked to original sources

arXiv2018

Microliter viscometry using a bright-field microscope: $η$-DDM

Passive microrheology exploits the Brownian motion of colloidal tracer particles. From the mean-squared displacement (MSD) of the tracers, the bulk rheological and viscometric properties of the host medium can be inferred. Here, the MSD is determined by applying Differential Dynamic Microscopy (DDM). Compared to other microscopy techniques, DDM avoids particle tracking but provides parameters commonly acquired in light scattering experiments. Based on the spatial Fourier transform of image differences, the intermediate scattering function and subsequently the MSD is calculated. Then the usual microrheology procedure and the empirical Cox-Merz rule yield the steady-shear viscosity. This method, $η$-DDM, is tested and illustrated using three different systems: Newtonian fluids (glycerol-water mixtures), colloidal suspensions (protein samples) and a viscoelastic polymer solution (aqueous poly(ethylene oxide) solution). These tests show that common lab equipment, namely a bright-field optical microscope, can be used as a convenient and reliable microliter viscometer. Because $η$-DDM requires much smaller sample volumes than classical rheometry, only about a microliter, it is particularly useful for biological and soft matter systems.

cond-mat.soft↗

arXiv2017

Stress-strain relations in bulk metallic glasses and colloidal dispersions

A comparison is made between the nonlinear rheological response of bulk metallic glass formers and of colloidal dispersions. Stress-strain curves measured after switch-on of constant deformation rates are analyzed quantitatively using a schematic model of mode coupling theory generalized to homogeneous and incompressible flows. A mapping between metallic and dispersion rheology is possible when stresses are rescaled by an entropic scale, accumulated strains by geometrical factors, and rates by the intrinsic relaxation time. Exploiting this similarity and the possibility to directly observe individual colloidal particles, we investigate the structural distortions in the colloidal system using confocal microscopy. The distortions exhibit the (from elasticity theory) expected quadrupolar but also a strong isotropic component.

cond-mat.soft↗

arXiv2017

Triple junction at the triple point resolved on the individual particle level

At the triple point of a repulsive screened Coulomb system, a face-centered-cubic (fcc) crystal, a body-centered-cubic (bcc) crystal and a fluid phase coexist. At their intersection, these three phases form a liquid groove, the triple junction. Using confocal microscopy, we resolve the triple junction on a single particle level in a model system of charged PMMA colloids in a nonpolar solvent. The groove is found to be extremely deep and the incommensurate solid-solid interface to be very broad. Thermal fluctuations hence appear to dominate the solid-solid interface. This indicates a very low interfacial energy. The fcc-bcc interfacial energy is quantitatively determined based on Young's equation and, indeed, it is only about 1.3 times higher than the fcc-fluid interfacial energy close to the triple point.

cond-mat.soft↗

arXiv2017

Start-up Shear of Concentrated Colloidal Hard Spheres: Stresses, Dynamics and Structure

The transient response of model hard sphere glasses is examined during the application of steady rate start-up shear using Brownian Dynamics (BD) simulations, experimental rheology and confocal microscopy. With increasing strain the glass initially exhibits an almost linear elastic stress increase, a stress peak at the yield point and then reaches a constant steady state. The stress overshoot has a non-monotonic dependence with Peclet number, Pe, and volume fraction, ϕ, determined by the available free volume and a competition between structural relaxation and shear advection. Examination of the structural properties under shear revealed an increasing anisotropic radial distribution function, g(r), mostly in the velocity - gradient (xy) plane, which decreases after the stress peak with considerable anisotropy remaining in the steady-state. Low rates minimally distort the structure, while high rates show distortion with signatures of transient elongation. As a mechanism of storing energy, particles are trapped within a cage distorted more than Brownian relaxation allows, while at larger strains, stresses are relaxed as particles are forced out of the cage due to advection. Even in the steady state, intermediate super diffusion is observed at high rates and is a signature of the continuous breaking and reformation of cages under shear.

cond-mat.soft↗

arXiv2016

Colloids Exposed to Random Potential Energy Landscapes: from Particle Number Density to Particle-Potential and Particle-Particle Interactions

Colloidal particles were exposed to a random potential energy landscape (rPEL) that has been created optically via a speckle pattern. The mean particle density as well as the potential roughness, i.e. the disorder strength, were varied. The local probability density of the particles as well as its main characteristics were determined. For the first time, the disorder-averaged pair density correlation function and an analogue of the Edwards-Anderson order parameter, which quantifies the correlation of the mean local density among disorder realisations, were measured experimentally and shown to be consistent with replica liquid state theory results.

cond-mat.soft↗

arXiv2016

Experimental creation and characterization of random potential energy landscapes exploiting speckle patterns

The concept of potential energy landscapes is applied in many areas of science. We experimentally realize a random potential energy landscape (rPEL) to which colloids are exposed. This is achieved exploiting the interaction of matter with light. The optical set-up is based on a special diffuser, which creates a top-hat beam containing a speckle pattern. This is imposed on colloids. The effect of the speckle pattern on the colloids can be described by a rPEL. The speckle pattern as well as the rPEL are quantitatively characterized. The distributions of both, intensity and potential energy values, can be approximated by Gamma distributions. They can be tuned from exponential to approximately Gaussian with variable standard deviation, which determines the contrast of the speckles and the roughness of the rPEL. Moreover, the characteristic length scales, e.g. the speckle size, can be controlled. By rotating the diffuser, furthermore, a flat potential can be created and hence only radiation pressure exerted on the particles.

physics.optics↗

arXiv2015

Creep and flow of glasses: strain response linked to the spatial distribution of dynamical heterogeneities

Mechanical properties are of central importance to materials sciences, in particular if they depend on external stimuli. Here we investigate the rheological response of amorphous solids, namely col- loidal glasses, to external forces. Using confocal microscopy and computer simulations, we establish a quantitative link between the macroscopic creep response and the microscopic single-particle dy- namics. We observe dynamical heterogeneities, namely regions of enhanced mobility, which remain localized in the creep regime, but grow for applied stresses leading to steady flow. These different behaviors are also reflected in the average particle dynamics, quantified by the mean squared dis- placement of the individual particles, and the fraction of active regions. Both microscopic quantities are found to be proportional to the macroscopic strain, despite the non-equilibrium and non-linear conditions during creep and the transient regime prior to steady flow.

cond-mat.soft↗

arXiv2013

Colloids in light fields: particle dynamics in random and periodic energy landscapes

The dynamics of colloidal particles in potential energy landscapes have mainly been investigated theoretically. In contrast, here we discuss the experimental realization of potential energy landscapes with the help of light fields and the observation of the particle dynamics by video microscopy. The experimentally observed dynamics in periodic and random potentials are compared to simulation and theoretical results in terms of, e.g. the mean-squared displacement, the time-dependent diffusion coefficient or the non-Gaussian parameter. The dynamics are initially diffusive followed by intermediate subdiffusive behaviour which again becomes diffusive at long times. How pronounced and extended the different regimes are, depends on the specific conditions, in particular the shape of the potential as well as its roughness or amplitude but also the particle concentration. Here we focus on dilute systems, but the dynamics of interacting systems in external potentials, and thus the interplay between particle-particle and particle-potential interactions, is also mentioned briefly. Furthermore, the observed dynamics of dilute systems resemble the dynamics of concentrated systems close to their glass transition, with which it is compared. The effect of certain potential energy landscapes on the dynamics of individual particles appears similar to the effect of interparticle interactions in the absence of an external potential.

cond-mat.soft↗

arXiv2013

Yielding of binary colloidal glasses

The rheological response, in particular the non-linear response, to oscillatory shear is experimentally investigated in colloidal glasses. The glasses are highly concentrated binary hard-sphere mixtures with relatively large size disparities. For a size ratio of 0.2, a strong reduction of the normalized elastic moduli, the yield strain and stress and, for some samples, even melting of the glass to a fluid is observed upon addition of the second species. This is attributed to the more efficient packing, as indicated by the shift of random close packing to larger total volume fractions. This leads to an increase in free volume which favours cage deformations and hence a loosening of the cage. Cage deformations are also favoured by the structural heterogeneity introduced by the second species. For a limited parameter range, we furthermore found indications of two-step yielding, as has been reported previously for attractive glasses. In samples containing spheres with more comparable sizes, namely a size ratio of 0.38, the cage seems less distorted and structural heterogeneities on larger length scales seem to become important. The limited structural changes are reflected in only a small reduction of the moduli, yield strain and stress.

cond-mat.soft↗

arXiv2013

Residual Stresses in Glasses

The history dependence of the glasses formed from flow-melted steady states by a sudden cessation of the shear rate $\dotγ$ is studied in colloidal suspensions, by molecular dynamics simulations, and mode-coupling theory. In an ideal glass, stresses relax only partially, leaving behind a finite persistent residual stress. For intermediate times, relaxation curves scale as a function of $\dotγt$, even though no flow is present. The macroscopic stress evolution is connected to a length scale of residual liquefaction displayed by microscopic mean-squared displacements. The theory describes this history dependence of glasses sharing the same thermodynamic state variables, but differing static properties.

cond-mat.soft↗

arXiv2008

Rheology, Structure and Dynamics of Colloid-Polymer Mixtures: from Liquids to Gels

We investigated the viscoelastic properties of colloid-polymer mixtures at intermediate colloid volume fraction and varying polymer concentrations, thereby tuning the attractive interactions. Within the examined range of polymer concentrations, the samples ranged from fluids to gels. Already in the liquid phase the viscoelastic properties significantly changed when approaching the gelation boundary, indicating the formation of clusters and transient networks. This is supported by an increasing correlation length of the density fluctuations, observed by static light scattering and microscopy. At the same time, the correlation function determined by dynamic light scattering completely decays, indicating the absence of dynamical arrest. Upon increasing the polymer concentration beyond the gelation boundary, the rheological properties changed qualitatively again, now they are consistent with the formation of colloidal gels. Our experimental results, namely the location of the gelation boundary as well as the elastic (storage) and viscous (loss) moduli, are compared to different theoretical models. These include consideration of the escape time as well as predictions for the viscoelastic moduli based on scaling relations and Mode Coupling Theories (MCT).

cond-mat.soft↗

arXiv2008

From Equilibrium to Steady State: The Transient Dynamics of Colloidal Liquids under Shear

We investigate stresses and particle motion during the start up of flow in a colloidal dispersion close to arrest into a glassy state. A combination of molecular dynamics simulation, mode coupling theory and confocal microscopy experiment is used to investigate the origins of the widely observed stress overshoot and (previously not reported) super-diffusive motion in the transient dynamics. A link between the macro-rheological stress versus strain curves and the microscopic particle motion is established. Negative correlations in the transient auto-correlation function of the potential stresses are found responsible for both phenomena, and arise even for homogeneous flows and almost Gaussian particle displacements.

cond-mat.soft↗

arXiv2006

Fluid-bicontinuous emulsions stabilized by colloidal particles

Using controlled spinodal decomposition, we have created a fluid-bicontinuous structure stabilized by colloidal particles. We present confocal microscopy studies of these structures and their variation with kinetic pathway. Our studies reveal a rigid multilayer of colloidal particles jammed at the interface which prevents the liquids demixing for many hours. The arrangement of two-fluid domains, interpenetrating on the meso-scale, could be useful as a microreaction medium.

cond-mat.soft↗

arXiv2004

Structure of strongly interacting polyelectrolyte diblock copolymer micelles

The structure of spherical micelles of the diblock poly(styrene-block-acrylic acid) [PS-b-PA] copolymer in water was investigated up to concentrations where the polyelectrolyte coronal layers have to shrink and/or interpenetrate in order to accommodate the micelles in the increasingly crowded volume. We obtained the partial structure factors pertaining to the core and corona density correlations with small angle neutron scattering (SANS) and contrast matching in the water. The counterion structure factor was obtained with small angle X-ray scattering (SAXS) with a synchrotron radiation source. Furthermore, we have measured the flow curves and dynamic visco-elastic moduli. The functionality of the micelles is fixed with a 9 nm diameter PS core and a corona formed by around 100 PA arms. As shown by the SAXS intensities, the counterions are distributed in the coronal layer with the same density profile as the corona forming segments. Irrespective ionic strength and micelle charge, the corona shrinks with increasing packing fraction. At high charge and minimal screening conditions, the polyelectrolyte chains remain almost fully stretched and they interdigitate once the volume fraction exceeds the critical value 0.53+/-0.02. Interpenetration of the polyelectrolyte brushes also controls the fluid rheology: the viscosity increases by 3 orders of magnitude and the parallel frequency scaling behavior of the dynamic moduli suggests the formation of a physical gel. In excess salt, the coronal layers are less extended and they do not interpenetrate in the present concentration range.

cond-mat.soft↗

arXiv2004

Do Spherical Polyelectrolyte Brushes Interdigitate?

The structure of spherical micelles of the diblock copolymer poly(styrene-block-acrylic acid) in water was investigated with small angle neutron scattering (SANS) and contrast matching. We have monitored inter-micelle correlation and the extension of the polyelectrolyte chains in the coronal layer through the overlap concentration. Irrespective of ionic strength, the corona shrinks with increasing packing fraction. Furthermore, at high charge and minimal screening conditions, the corona layers interpenetrate once the volume fraction exceeds the critical value 0.53.

cond-mat.soft↗

arXiv2003

Non-equilibrium behavior of lysozyme solutions: beads, clusters and gels

Observation of salt-induced aggregation of lysozyme at pH = 4.5, 22$^{\circ}$C by optical microscopy revealed four regimes: bicontinuous texture, `beads', large aggregates, and transient gelation. The interaction of a metastable liquid-liquid binodal and an ergodic to non-ergodic transition boundary inside the equilibrium crystallization region can explain our findings. Lysozyme data at -2$^{\circ}$C, as well as many literature results, are consistent with the relative movement of these boundaries.

cond-mat.soft↗

arXiv2003

Protein crystallization in confined geometries

We studied the crystallization of a globular protein, lysozyme, in the cubic phase of the lipid monoolein. The solubility of lysozyme in salt solution decreased by a factor of $\sim 4$ when confined in cubic phase. Calculations and Monte Carlo simulations show that this can be explained by the {\it confinement} of lysozyme molecules to the narrow water cells in the cubic phase.

cond-mat.soft↗

arXiv2003

Glasses in hard spheres with short-range attraction

We report a detailed experimental study of the structure and dynamics of glassy states in hard spheres with short-range attraction. The system is a suspension of nearly-hard-sphere colloidal particles and non-adsorbing linear polymer which induces a depletion attraction between the particles. Observation of crystallization reveals a re-entrant glass transition. Static light scattering shows a continuous change in the static structure factors upon increasing attraction. Dynamic light scattering results, which cover 11 orders of magnitude in time, are consistent with the existence of two distinct kinds of glasses, those dominated by inter-particle repulsion and caging, and those dominated by attraction. Samples close to the `A3 point' predicted by mode coupling theory for such systems show very slow, logarithmic dynamics.

cond-mat.soft↗