Showing papers by "Peter Schurtenberger published in 2021"

Self-diffusion of nonspherical particles fundamentally conflicts with effective sphere models

Abstract: Modeling diffusion of nonspherical particles presents an unsolved and considerable challenge, despite its importance for the understanding of crowding effects in biology, food technology and formulation science. A common approach in experiment and simulation is to map nonspherical objects on effective spheres to subsequently use the established predictions for spheres to approximate phenomena for nonspherical particles. Using numerical evaluation of the hydrodynamic mobility tensor, we show that this so-called effective sphere model fundamentally fails to represent the self-diffusion in solutions of ellipsoids as well as rod-like assemblies of spherical beads. The effective sphere model drastically overestimates the slowing down of self-diffusion down to volume fractions below 0.01. Furthermore, even the linear term relevant at lower volume fraction is inaccurate, linked to a fundamental misconception of effective sphere models. To overcome the severe problems related with the use of effective sphere models, we suggest a protocol to predict the short-time self-diffusion of rod-like systems, based on simulations with hydrodynamic interactions that become feasible even for more complex molecules as the essential observable shows a negligible system-size effect.

Structure and dynamics of dense colloidal ellipsoids at the nearest-neighbor length scale

Abstract: Anisotropic particles are known to exhibit a richer and more complex phase behavior in comparison to their spherical counterpart. While the majority of the existing studies address structural properties, the dynamic behavior of anisotropic particles is a relatively lesser explored avenue. Using multispeckle ultra-small-angle x-ray photon correlation spectroscopy (USA-XPCS), we have carried out a systematic investigation of the structural and dynamic properties of colloidal ellipsoids at the nearest-neighbor length scale. The USA-XPCS measurements have allowed us to probe, as a function of the volume fraction, the q-dependent effective structure factor, Seff(q), along with the effective long time diffusion coefficient, Deff(q), for this anisotropic system. Our results indicate a scaling behavior of Deff(q) with 1/Seff(q) from which we have estimated the effective amplitude function Aeff(q), which can be directly related to the effective hydrodynamic function Heff(q). Aeff(q) shows a similar q dependence to that of S(q). Our investigation also allows for the precise determination of the volume fraction corresponding to the arrest transition.

Anisotropic dynamics of magnetic colloidal cubes studied by x-ray photon correlation spectroscopy

Abstract: Herein we present our results on the investigation of the influence of external magnetic fields on the anisotropic collective dynamics of core/shell colloidal cubes having a hematite core and silica shell. Owing to the hematite cores, these micrometer-sized particles possess permanent dipole moments, which are at an angle with respect to the long diagonal of the cubes. As a result, they self-assemble into chains, which subsequently sediment to form higher-order structures. Using multispeckle ultrasmall-angle x-ray photon correlation spectroscopy, the anisotropic dynamics within these structures at the nearest-neighbor length scale was probed. The relaxation of the intermediate scattering function follows a compressed exponential behavior along all the different directions with respect to the external field---parallel, perpendicular, and at an angle $\ensuremath{\approx}{45}^{\ensuremath{\circ}}$---indicating hyperdiffusive behavior. We believe that the inhomogeneous distribution of stress points originating from the interplay of external field-induced (both gravitational and magnetic) alignment of the chains are responsible for the anomalous dynamics. The effective diffusion coefficients along and at $\ensuremath{\approx}{45}^{\ensuremath{\circ}}$ angle exhibit mild de Gennes narrowing, which is not very common for hyperdiffusive dynamics. We rationalize our observations by considering a superposition of diffusive and stress-induced ballistic processes and argue that depending on the azimuthal direction the relative contribution from these two processes changes.

ArGSLab: A tool for analyzing experimental or simulated particle networks

Abstract: Microscopy and particle-based simulations are both powerful techniques to study aggregated particulate matter such as colloidal gels. The data provided by these techniques often contains information on a wide array of length scales, but structural analysis methods typically focus on the local particle arrangement, even though the data also contains information about the particle network on the mesoscopic length scale. In this paper, we present a MATLAB software package for quantifying mesoscopic network structures in colloidal samples. ArGSLab (Arrested and Gelated Structures Laboratory) extracts a network backbone from the input data, which is in turn transformed into a set of nodes and links for graph theory-based analysis. The routines can process both image stacks from microscopy as well as explicit coordinate data, and thus allows quantitative comparison between simulations and experiments. ArGSLab furthermore enables the accurate analysis of microscopy data where, e.g., an extended point spread function prohibits the resolution of individual particles. We demonstrate the resulting output for example datasets from both microscopy and simulation of colloidal gels, in order to showcase the capability of ArGSLab to quantitatively analyze data from various sources. The freely available software package can be used either with a provided graphical user interface or directly as a MATLAB script.

On the role of softness in ionic microgel interactions.

Abstract: Thermoresponsive microgels are a popular model system to study phase transitions in soft matter, because temperature directly controls their volume fraction. Ionic microgels are additionally pH-responsive and possess a rich phase diagram. Although effective interaction potentials between microgel particles have been proposed, these have never been fully tested, leading to a gap in our understanding of the link between single-particle and collective properties. To help resolve this gap, four sets of ionic microgels with varying crosslinker density were synthesised and characterised using light scattering techniques and confocal microscopy. The resultant structural and dynamical information was used to investigate how particle softness affects the phase behaviour of ionic microgels and to validate the proposed interaction potential. We find that the architecture of the microgel plays a marked role in its phase behaviour. Rather than the ionic charges, it is the dangling ends which drive phase transitions and interactions at low concentration. Comparison to theory underlines the need for a refined theoretical model which takes into consideration these close-contact interactions.

ArGSLab: a tool for analyzing experimental or simulated particle networks.

Abstract: Microscopy and particle-based simulations are both powerful techniques to study aggregated particulate matter such as colloidal gels. The data provided by these techniques often contains information on a wide array of length scales, but structural analysis methods typically focus on the local particle arrangement, even though the data also contains information about the particle network on the mesoscopic length scale. In this paper, we present a MATLAB software package for quantifying mesoscopic network structures in colloidal samples. ArGSLab (Arrested and Gelated Structures Laboratory) extracts a network backbone from the input data, which is in turn transformed into a set of nodes and links for graph theory-based analysis. The routines can process both image stacks from microscopy as well as explicit coordinate data, and thus allows quantitative comparison between simulations and experiments. ArGSLab furthermore enables the accurate analysis of microscopy data where, e.g., an extended point spread function prohibits the resolution of individual particles. We demonstrate the resulting output for example datasets from both microscopy and simulation of colloidal gels, in order to showcase the capability of ArGSLab to quantitatively analyze data from various sources. The freely available software package can be used either with a provided graphical user interface or directly as a MATLAB script.