Tina Autenrieth

X-ray cross correlation analysis uncovers hidden local symmetries in disordered matter.

We explore the different local symmetries in colloidal glasses beyond the standard pair correlation analysis. Using our newly developed X-ray cross correlation analysis (XCCA) concept together with brilliant coherent X-ray sources, we have been able to access and classify the otherwise hidden local order within disorder. The emerging local symmetries are coupled to distinct momentum transfer (Q) values, which do not coincide with the maxima of the amorphous structure factor. Four-, 6-, 10- and, most prevalently, 5-fold symmetries are observed. The observation of dynamical evolution of these symmetries forms a connection to dynamical heterogeneities in glasses, which is far beyond conventional diffraction analysis. The XCCA concept opens up a fascinating view into the world of disorder and will definitely allow, with the advent of free electron X-ray lasers, an accurate and systematic experimental characterization of the structure of the liquid and glass states.

Core shell particles consisting of cobalt ferrite and silica as model ferrofluids [CoFe2O4–SiO2 core shell particles]

Abstract Nearly monodisperse core shell particles consisting of a magnetic core of cobalt ferrite (CoFe 2 O 4 ) and a shell of silica (SiO 2 ) are prepared via a modified Stober synthesis. The core shell structure is confirmed by TEM, the size distribution of the whole particles was determined by means of photon correlation spectroscopy and small angle X-ray scattering. Due to charged surface groups of the silica shells and the magnetic moments of the cores, these particles interact both via a screened Coulomb potential and via a magnetic dipole potential. If stray ions are removed in the presence of a mixed bed ion exchanger, the electrostatic repulsion induces colloidal crystallisation. The lattice constant is influenced by the interaction with a magnetic field gradient, indicated by a blue shift of the Laue spots towards increasing field gradient.

Measuring temporal speckle correlations at ultrafast x-ray sources

We present a new method to extract the intermediate scattering function from series of coherent diffraction patterns taken with 2D detectors. Our approach is based on analyzing speckle patterns in terms of photon statistics. We show that the information obtained is equivalent to the conventional technique of calculating the intensity autocorrelation function. Our approach represents a route for correlation spectroscopy on ultrafast timescales at X-ray free-electron laser sources.

Highly charged inorganic-organic colloidal core-shell particles.

Highly defined, hybrid inorganic-organic colloidal core-shell particles consisting of a silica core and a shell of fluorinated acrylate are prepared in a two-step route. The core-shell structure of the particles is investigated by means of small-angle X-ray scattering (SAXS). Because of highly acidic sulfonic acid surface groups resulting from the radical initiator sodium peroxodisulfate at the organic shell, long-range electrostatic interactions lead to the formation of liquidlike mesostructures. Increasing the effective interaction by reducing the next-neighbor distances induces a freezing of the liquidlike structures, i.e., a transition to crystalline and glassy structures. Because of the high electron density in the core and the fluorinated polymer shell, these particles are strong X-ray scatterers. In combination with the large number of effective charges and the outstanding monodispersity, these core-shell particles are a promising model system for the investigation of the glass transition by photon correlation spectroscopy employing coherent X-rays.

Spatially Resolved Investigation of Solution Cast Nanoparticle Films by X-ray Scattering and Multidimensional Data Set Classification

A combinatorial high-throughput approach is used to investigate a solution cast gradient consisting of colloidal gold nanoparticles on top of a silicon substrate by means of a X-ray nanobeam. Classification algorithms are used to reveal and visualize structural transitions from a frozen colloidal solution to a well-defined nanostructure. Prominent length scales on the order of 100 nm are observed. A periodic change in the nanostructure along the gradient is explained by a simplified stick-slip model.

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.

Field induced anisotropy of charged magnetic colloids: A rescaled mean spherical approximation study

The liquidlike structure of colloidal suspensions with both electrostatic and magnetic interactions is investigated by means of small angle x-ray scattering (SAXS) dependent on an external magnetic field. For weak magnetic interactions, without external field, the magnetic dipoles are randomly oriented. Under this condition, isotropic structures are observed. In an external field, however, the magnetic momenta arrange parallel to the external field and induce anisotropic liquidlike structures. For weak magnetic interactions, the structure factor can be described within the framework of the rescaled mean spherical approximation. Due to the high experimental accuracy of synchrotron SAXS, from the anisotropic distortion of liquidlike structures, interparticle forces smaller than 10(-15) N can easily be detected.

Structure and dynamics of electrostatically interacting magnetic nanoparticles in suspension

We investigate the structure and dynamics of charge-stabilized CoFe(2)O(4)-SiO(2) core-shell magnetic nanoparticles in suspensions. Small angle x-ray scattering and x-ray photon correlation spectroscopy allow us to analyze the intraparticle (core-shell) and interparticle structure of the suspension, as well as their dynamic and hydrodynamic behavior. Due to the weak magnetic interactions, the liquidlike structure is governed by screened Coulomb interactions. The hydrodynamic interactions of the measured systems are significantly stronger than predicted by current theories.

Dynamics in dense suspensions of charge-stabilized colloidal particles

Abstract.The dynamic behavior of charge-stabilized colloidal particles in suspension was studied by photon correlation spectroscopy with coherent X-rays (XPCS). The short-time diffusion coefficient, D(Q) , was measured for volume concentrations φ ⩽ 0.18 and compared to the free particle diffusion constant D0 and the static structure factor S(Q) . The data show that indirect, hydrodynamic interactions are relevant for the system and hydrodynamic functions were derived. The results are in striking contrast to the predictions of the PA (pairwise-additive approximation) model, but show features typical for a hard-sphere system. The observed mobility is however considerably smaller than the one of a respective hard-sphere system. The hydrodynamic functions can be modelled quantitatively if one allows for an increased effective viscosity relative to the hard-sphere case.

Structure and dynamics of charged magnetic colloids

By coating cobalt ferrite nanoparticles with a silica shell, the polydispersity of the resulting core–shell particles can be reduced. Hereby, opposite to the case for conventional ferrofluids, self-organization to liquid-like and even crystalline structures in aqueous media is enabled. The resulting structures mainly originate from the predominant electrostatic repulsion of colloidal macroions bearing charged groups at the surface of the silica shell. Due to the small magnetic moment of the cobalt ferrite cores, however, these structures can be influenced by external magnetic fields or field gradients. While field gradients act as a magnetic trap for these particles, homogeneous fields induce an aligning of the magnetic momenta. Hereby a decrease of symmetry from spherical to cylindrical symmetry of the structures appearing can be observed. Due to collective phenomena, even interactions significantly smaller than the thermal energy can induce clearly observable structural distortions. Even in the absence of an external field, suspensions of such magnetic particles show an unexpected slow diffusion caused by hydrodynamic interactions.