Stephan V. Roth

Small-angle options of the upgraded ultrasmall-angle x-ray scattering beamline BW4 at HASYLAB

We present the upgrade and present status of the ultrasmall-angle x-ray scattering (USAXS) beamline BW4 at the Hamburg Synchrotronstrahlungslabor. In order to extend the accessible scattering vector range, new small-angle setups have been established, making use of the high flux and small divergence of BW4. In standard transmission geometry using a beam size of B=400×400μm2 (horizontal×vertical), typical small-angle resolution ranges from dmax=90to650nm, depending on sample-to-detector distance. Additionally a new microfocus option has been established. This microfocus option allows reducing the sample size by one order of magnitude. Using parabolic beryllium compound refractive lenses, a new standard beam size of B=65×35μm2 (horizontal×vertical) can be provided. The μ-SAXS resolution is as high as dmax=150nm. Using μ-SAXS in combination with grazing incidence (μ-GISAXS) on a standard noble metal gradient multilayer, we prove the feasibility of μ-GISAXS experiments at a second generation source.

Hydrodynamic alignment and assembly of nanofibrils resulting in strong cellulose filaments.

Cellulose nanofibrils can be obtained from trees and have considerable potential as a building block for biobased materials. In order to achieve good properties of these materials, the nanostructure must be controlled. Here we present a process combining hydrodynamic alignment with a dispersion–gel transition that produces homogeneous and smooth filaments from a low-concentration dispersion of cellulose nanofibrils in water. The preferential fibril orientation along the filament direction can be controlled by the process parameters. The specific ultimate strength is considerably higher than previously reported filaments made of cellulose nanofibrils. The strength is even in line with the strongest cellulose pulp fibres extracted from wood with the same degree of fibril alignment. Successful nanoscale alignment before gelation demands a proper separation of the timescales involved. Somewhat surprisingly, the device must not be too small if this is to be achieved.

P03, the microfocus and nanofocus X-ray scattering (MiNaXS) beamline of the PETRA III storage ring: the microfocus endstation

The MiNaXS (P03) beamline of the new third-generation synchrotron radiation source PETRA III (DESY, Germany) has been designed to perform small-, ultra-small- and wide-angle X-ray scattering in both transmission and grazing-incidence geometries. The high photon flux available at the beamline enables time-resolved investigations of kinetic phenomena with a time resolution below 100 ms. The microfocus endstation started user operation in May 2011.

In Situ GISAXS Study of Gold Film Growth on Conducting Polymer Films

The growth of a thin gold film on a conducting polymer surface from nucleation to formation of a continuous layer with a thickness of several nanometers is investigated in situ with grazing incidence small-angle X-ray scattering (GISAXS). Time resolution is achieved by performing the experiment in cycles of gold deposition on poly(N-vinylcarbazole) (PVK) and subsequently recording the GISAXS data. The 2D GISAXS patterns are simulated, and morphological parameters of the gold film on PVK such as the cluster size, shape, and correlation distance are extracted. For the quantitative description of the cluster size evolution, scaling laws are applied. The time evolution of the cluster morphology is explained with a growth model, suggesting a cluster growth proceeding in four steps, each dominated by a characteristic kinetic process: nucleation, lateral growth, coarsening, and vertical growth. A very limited amount of 6.5 wt % gold is observed to be incorporated inside a 1.2-nm-thick enrichment layer in the PVK film.

A Direct Evidence of Morphological Degradation on a Nanometer Scale in Polymer Solar Cells

In situ measurement of a polymer solar cell using micro grazing incidence small angle X-ray scattering (μGISAXS) and current-voltage tracking is demonstrated. While measuring electric characteristics under illumination, morphological changes are probed by μGISAXS. The X-ray beam (green) impinges on the photo active layer with a shallow angle and scatters on a 2d detector. Degradation is explained by the ongoing nanomorphological changes observed.

Self-assembled gradient nanoparticle-polymer multilayers investigated by an advanced characterization method: microbeam grazing incidence x-ray scattering

We investigated a gradient of nanometer-sized, self-assembled gold clusters on top of a thin polymer film. Using an advanced characterization method for gradient surfaces and thin films, the characteristic change in cluster height is detected. Our unprecedented approach combining a powerful thin-film characterization method with a micrometer-sized x-ray beam enhances the spatial resolution used thus far by two orders of magnitude. We show that this advanced concept allows for a nondestructive and contact-free reconstruction of the three-dimensional structure and morphology of the nanocluster gradient layer. Despite its change in thickness, the individual clusters’ in-plane shape and distance remains constant.

Hierarchically Structured Titania Films Prepared by Polymer/Colloidal Templating

Hierarchically structured titania films for application in hybrid solar cells are prepared by combining microsphere templating and sol-gel chemistry with an amphiphilic diblock copolymer as a structure-directing agent. The films have a functional structure on three size scales: (1) on the micrometer scale a holelike structure for reduction of light reflection, (2) on an intermediate scale macropores for surface roughening and improved infiltration of a hole transport material, and (3) on a nanometer scale a mesoporous structure for charge generation. Poly(dimethyl siloxane)-block-methyl methacrylate poly(ethylene oxide) (PDMS-b-MA(PEO)) is used as a structure-directing agent for the preparation of the mesopore structure, and poly(methyl methacrylate) (PMMA) microspheres act as a template for the micrometer-scale structure. The structure on all levels is modified by the method of polymer extraction as well as by the addition of PMMA particles to the sol-gel solution. Calcination results in structures with increased size and a higher degree of order than extraction with acetic acid. With addition of PMMA a microstructure is created and the size of the mesopores is reduced. Already moderate microstructuring results in a strong decrease in film reflectivity; a minimum reflectivity value of less than 0.1 is obtained by acetic acid treatment and subsequent calcination.

Mapping the local nanostructure inside a specimen by tomographic small-angle x-ray scattering

Small-angle x-ray scattering is combined with scanning microtomography to reconstruct the small-angle diffraction pattern in the direction of the tomographic rotation axis at each location on a virtual section through a specimen. These data yield information about the local nanoscale structure of the sample. With rotational symmetry present in the diffraction patterns, e.g., for isotropic or fiber-textured scatterers, the full reciprocal space information in the small-angle scattering regime can be reconstructed at each location inside the specimen. The method is illustrated investigating a polymer rod made by injection molding.

Anisotropic particles align perpendicular to the flow direction in narrow microchannels

The flow orientation of anisotropic particles through narrow channels is of importance in many fields, ranging from the spinning and molding of fibers to the flow of cells and proteins through thin capillaries. It is commonly assumed that anisotropic particles align parallel to the flow direction. When flowing through narrowed channel sections, one expects the increased flow rate to improve the parallel alignment. Here, we show by microfocus synchrotron X-ray scattering and polarized optical microscopy that anisotropic colloidal particles align perpendicular to the flow direction after passing a narrow channel section. We find this to be a general behavior of anisotropic colloids, which is also observed for disk-like particles. This perpendicular particle alignment is stable, extending downstream throughout the remaining part of the channel. We show by microparticle image velocimetry that the particle reorientation in the expansion zone after a narrow channel section occurs in a region with considerable extensional flow. This extensional flow is promoted by shear thinning, a typical property of complex fluids. Our discovery has important consequences when considering the flow orientation of polymers, micelles, fibers, proteins, or cells through narrow channels, pipes, or capillary sections. An immediate consequence for the production of fibers is the necessity for realignment by extension in the flow direction. For fibrous proteins, reorientation and stable plug flow are likely mechanisms for protein coagulation.

A customizable software for fast reduction and analysis of large X‐ray scattering data sets: applications of the new DPDAK package to small‐angle X‐ray scattering and grazing‐incidence small‐angle X‐ray scattering

DPDAK is a software for simple and fast on- and offline reduction and analysis of X-ray scattering data. It is an open-source software with a plug-in structure allowing tailored extensions.