Fabian Westermeier

Structure and short-time dynamics in concentrated suspensions of charged colloids

We report a comprehensive joint experimental-theoretical study of the equilibrium pair-structure and short-time diffusion in aqueous suspensions of highly charged poly-acrylate (PA) spheres in the colloidal fluid phase. Low-polydispersity PA sphere systems with two different hard-core radii, R(0) = 542 and 1117 Å, are explored over a wide range of concentrations and salinities using static and dynamic light scattering (DLS), small angle x-ray scattering, and x-ray photon correlation spectroscopy (XPCS). The measured static and dynamic scattering functions are analyzed using state-of-the-art theoretical methods. For all samples, the measured static structure factor, S(Q), is in good agreement with results by an analytical integral equation method for particles interacting by a repulsive screened Coulomb plus hard-core pair potential. In our DLS and XPCS measurements, we have determined the short-time diffusion function D(Q) = D(0) H(Q)∕S(Q), comprising the free diffusion coefficient D(0) and the hydrodynamic function H(Q). The latter is calculated analytically using a self-part corrected version of the δγ-scheme by Beenakker and Mazur which accounts approximately for many-body hydrodynamic interactions (HIs). Except for low-salinity systems at the highest investigated volume fraction φ ≈ 0.32, the theoretical predictions for H(Q) are in excellent agreement with the experimental data. In particular, the increase in the collective diffusion coefficient D(c) = D(Q → 0), and the decrease of the self-diffusion coefficient, D(s) = D(Q → ∞), with increasing φ is well described. In accord with the theoretical prediction, the peak value, H(Q(m)), of H(Q) relates to the nearest neighbor cage size ∼2π∕Q(m), for which concentration scaling relations are discussed. The peak values H(Q(m)) are globally bound from below by the corresponding neutral hard-spheres peak values, and from above by the limiting peak values for low-salinity charge-stabilized systems. HIs usually slow short-time diffusion on colloidal length scales, except for the cage diffusion coefficient, D(cge) = D(Q(m)), in dilute low-salinity systems where a speed up of the system dynamics and corresponding peak values of H(Q(m)) > 1 are observed experimentally and theoretically.

Fast two-dimensional detection for X-ray photon correlation spectroscopy using the PILATUS detector.

The first X-ray photon correlation spectroscopy experiments using the fast single-photon-counting detector PILATUS (Paul Scherrer Institut, Switzerland) have been performed. The short readout time of this detector permits access to intensity autocorrelation functions describing dynamics in the millisecond range that are difficult to access with charge-coupled device detectors with typical readout times of several seconds. Showing no readout noise the PILATUS detector enables measurements of samples that either display fast dynamics or possess only low scattering power with an unprecedented signal-to-noise ratio.

Performance tests of an AGIPD 0.4 assembly at the beamline P10 of PETRA III

The Adaptive Gain Integrating Pixel Detector (AGIPD) is a novel detector system, currently under development by a collaboration of DESY, the Paul Scherrer Institute in Switzerland, the University of Hamburg and the University of Bonn, and is primarily designed for use at the European XFEL. To verify key features of this detector, an AGIPD 0.4 test chip assembly was tested at the P10 beamline of the PETRA III synchrotron at DESY. The test chip successfully imaged both the direct synchrotron beam and single 7.05 keV photons at the same time, demonstrating the large dynamic range required for XFEL experiments. X-ray scattering measurements from a test sample agree with standard measurements and show the chips capability of observing dynamics at the microsecond time scale.

Colloidal crystallite suspensions studied by high pressure small angle x-ray scattering

We report on high pressure small angle x-ray scattering on suspensions of colloidal crystallites in water. The crystallites made out of charge-stabilized poly-acrylate particles exhibit a complex pressure dependence which is based on the specific pressure properties of the suspending medium water. The dominant effect is a compression of the crystallites caused by the compression of the water. In addition, we find indications that also the electrostatic properties of the system, i.e. the particle charge and the dissociation of ions, might play a role for the pressure dependence of the samples. The data further suggest that crystallites in a metastable state induced by shear-induced melting can relax to a similar structural state upon the application of pressure and dilution with water. X-ray cross correlation analysis of the two-dimensional scattering patterns indicates a pressure-dependent increase of the orientational order of the crystallites correlated with growth of these in the suspension. This study underlines the potential of pressure as a very relevant parameter to understand colloidal crystallite systems in aqueous suspension.

Structure and dynamics of glassy charged colloids studied with coherent small angle X-ray scattering

Coherent small angle X-ray scattering methods have been used to investigate the structure and dynamics of charged colloidal systems with different volume concentration. The static structure factor indicates that the degree of ordering depends on both the electrostatic interactions and the volume fraction. All systems showed a compressed exponential form of the dynamic structure factor. The Q-dependence of the relaxation time τ hints towards ballistic motion of the colloidal particles in the glassy state. For the sample with the highest volume fraction we observe an influence of the static structure factor on the relaxation rate of the particles indicating a caging effect also for the ballistic type of motion.

Brownian and advective dynamics in microflow studied by coherent X-ray scattering experiments

Combining microfluidics with coherent X-ray illumination offers the possibility to not only measure the structure but also the dynamics of flowing samples in a single-scattering experiment. Here, the power of this combination is demonstrated by studying the advective and Brownian dynamics of colloidal suspensions in microflow of different geometries. Using an experimental setup with a fast two-dimensional detector and performing X-ray correlation spectroscopy by calculating two-dimensional maps of the intensity auto-correlation functions, it was possible to evaluate the sample structure and furthermore to characterize the detailed flow behavior, including flow geometry, main flow directions, advective flow velocities and diffusive dynamics. By scanning a microfocused X-ray beam over a microfluidic device, the anisotropic auto-correlation functions of driven colloidal suspensions in straight, curved and constricted microchannels were mapped with the spatial resolution of the X-ray beam. This method has not only a huge potential for studying flow patterns in complex fluids but also to generally characterize anisotropic dynamics in materials.