Scanning Small-angle X-ray Scattering Research Articles

Time-resolved structure investigation with small angle X-ray scattering using scanning techniques

Due to the availability of high-brilliance X-rays at synchrotron radiation facilities, small angle X-ray scattering (SAXS) measurements have become feasible for new sample environments, like microfluidics or aerosol systems. The combination of continuous flow methods and SAXS with spatial scanning enables in situ measurements of time-resolved structures at the nanoscale important for reactions kinetics and material synthesis and processing. In this review we present the latest achievements in terms of scanning SAXS along continuous flow mixing devices reducing the limit of time resolution at the microsecond range. This led to the determination of early stages of biological reactions like protein folding, and to gain insight into chemical reaction kinetics like nanoparticles formation. We also describe the coupling of scanning SAXS with aerosol generators, which is the only way to study the mechanisms for the self-assembly and aggregation of nanomaterials via the aerosol route. We finally give a brief outlook, as the potentiality of these techniques has not been fully exploited, leaving the possibility for further improvements in time resolution and sample consumption, for example with the new X-ray sources like Free Electron Lasers.

Scanning small-angle X-ray scattering analysis of the size and organization of the mineral nanoparticles in fluorotic bone using a stack of cards model

A model describing the size and arrangement of mineral particles in bone tissues is used to analyse the results of a scanning small-angle X-ray scattering (SAXS) experiment on a pathological bone biopsy. The overall description assumes that the nanometre-sized mineral platelets are arranged in a parallel fashion with possible fluctuations in their relative position, orientation and thickness. This method is tested on a thin sample section obtained from the biopsy of an osteoporotic patient treated with a high cumulative dose of NaF. The mineralization pattern of fluorotic bone is known to exhibit significant differences as compared to healthy bone in terms of density, particle size and organization. This is the first attempt to provide quantitative indicators of the degree of regularity in the packing of the mineral platelets in human pathological bone. Using scanning SAXS with a synchrotron microbeam of 15 µm allows discrimination between pathological and healthy bone at the tissue level. Additionally, the benefits of this method are discussed with respect to the accuracy of particle size determination using SAXS.

Collagen imaged by Coherent X-ray Diffraction: towards a complementary tool to conventional scanning SAXS

Third generation x-ray sources offer unique possibilities for exploiting coherence in the study of materials. New insights in the structure and dynamics of soft condensed matter and biological samples can be obtained by coherent x-ray diffraction (CXD). However, the experimental procedures for applying these methods to collagen tissues are still under development. We present here an investigation for the optimal procedure in order to obtain high quality CXD data from collagen tissues. Sample handling and preparation and adequate coherence defining apertures are among the more relevant factors to take into account. The impact of the results is also discussed, in particular in comparison with the information that can be extracted from conventional scanning small angle x-ray scattering (SAXS). Images of collagen tissues obtained by CXD reconstructions will give additional information about the local structure with higher resolution and will complement scanning SAXS images.

Characterization of the Orientation Parameters Around Crack Tips in Unfilled and Nanofilled Poly(propylene) Using in‐situ Synchrotron Small and Wide Angle Scanning Scattering Techniques

AbstractThe fracturing behavior of polymers and polymeric composites is of great interest in the scientific and application community. Especially in the case of silicate‐layered nanocomposites the influence of fillers on the fracturing behavior is still fairly unclear. Fractures of semicrystalline polymers are accompanied by various processes of which shearing and cavitations are the most common ones. Nanocomposite deformation due to the delamination of fillers seems to be the most practical way leading to fractures with relatively low strains. With the method of scanning small angle X‐ray scattering (SAXS) and wide angle X‐ray diffraction (WAXD) it is possible to combine information on the structural details with the position on the sample, with the actual position resolution of the investigation being defined by the size of the X‐ray beam used to scan the sample. By means of the application of synchrotron radiation it is nowadays possible to adjust the actual beam size to the dimensions of the region of interest, which is why it is an adequate tool for studying the deformation region near a crack tip.In a native polypropylene sample, the fracturing process was accompanied by shear yielding as well as lamellae fragmentation and reorienting. In the highly deformed material near the crack tip fibrillated material could be found. However, in the polymeric nanocomposites (PNC) shearing, lamellae fragmentation, and fibrillation were hindered by the filler due to which the material did not have so much freedom to dissipate energy and fractures occurred much earlier. In this paper the comparison of a PNC and its native polymer is to provide an overview of the different deformation mechanism and the structural details around the crack tip.

Nanostructure of the neurocentral growth plate: Insight from scanning small angle X-ray scattering, atomic force microscopy and scanning electron microscopy

In this study, the experimental techniques scanning electron microscopy (SEM) including energy-dispersive X-ray analysis, atomic force microscopy (AFM) and scanning small angle X-ray scattering (SAXS) have been exploited to characterize the organization of large molecules and nanocrystallites in and around the neurocentral growth plate (NGP) of a pig vertebrae L4. The techniques offer unique complementary information on the nano- to micrometer length scale and provide new insight in the changes in the matrix structure during endochondral bone formation. AFM and SEM imaging of the NGP reveal a fibrous network likely to consist of collagen type II and proteoglycans. High-resolution AFM imaging shows that the fibers have a diameter of approximately 100 nm and periodic features along the fibers with a periodicity of 50–70 nm. This is consistent with the SAXS analysis that yields a cross-sectional diameter of the fibers in the range of 90 to 112 nm and a predominant orientation in the longitudinal direction of the NGP. Furthermore, we find inhomogeneities around 7 nm in the NGP by SAXS analysis. Moving towards the bone in the direction perpendicular to the growth plate, a systematic change in apparent thickness is observed, while the large-scale structural features remain constant. In the region of bone, the apparent thickness equals the mean mineral thickness and increases from 2 nm to approximately 3.5 nm as a function distance from the NGP. The mineral particles are organized as plates in a rather compact network structure. We have demonstrated that SEM, AFM and SAXS are valuable tools for the investigation of the organization of large molecules and nanocrystallites in the NGP and adjacent trabecular bone. Our findings will be an important basis for future work into identifying the defects on nanometer length scale responsible for idiopathic scoliosis and other growth-plate-related diseases.

Mineralized microstructure of calcified avian tendons: a scanning small angle X-ray scattering study.

The micrometer level spatial distribution of the size, shape, and orientation of mineral crystallites in the calcifying matrix of tendons near the edge of the mineralizing front was investigated by scanning small angle X-ray scattering using synchrotron X-ray radiation. Using a special microbeam arrangement enabling 20 microm beam resolution and short measurement times, linear diffraction scans were made on sections from the normally calcifying tendons (tibialis cranialis) from the domestic turkey, which calcify in the distal to proximal direction. A change in shape and arrangement of mineral crystals was observed within the first 200 microm of the mineralization front, and the mineral crystal distribution was highly anisotropic with crystals aligned parallel to the fiber axis. In a cross-section of the tendon cut at right angles to the fiber axis, the orientation distribution of crystals was not azimuthally symmetric, and showed a small but nonzero anisotropy and a continuous change in mean orientation angle across the width of the tendon cross-section.

Scanning small angle X-ray scattering analysis of human bone sections.

Scanning small-angle X-ray scattering (scanning SAXS) was applied for the first time on bone to compare results from SAXS directly with those from other position-sensitive methods, such as light and polarized light microscopy, back-scattered electron imaging, and radiographic imaging. Since scanning SAXS is a nondestructive method of investigation, images from all these techniques could be obtained from the same bone sections. Thus, it could be shown that both the collagen and the mineral crystals were predominantly aligned parallel to the trabeculae and, therefore, to principle stress directions. Moreover, the mean crystal thickness as determined by scanning SAXS was found to be different at various positions inside the trabecular and cortical structure. Finally, it could be shown that scanning SAXS is suitable for detecting local changes in bone material, e.g., due to fluoride treatment.

Micro x-ray small-angle scattering with synchrotron radiation

Three small-angle scattering cameras based on mirror/monochromator optics, a circular Bragg-Fresnel (BF) lens, and a microcollimation system combined with a double-focusing mirror have been tested for microfocusing applications. In order to reach a focal spot less than or equal to 10 μm. a microcollimation system provides a flexible solution for medium-resolution applications. When using a glass capillary as a collimation system, a minimum s-value of 5·10−2 nm−1 was attained. Scanning small-angle x-ray scattering (SAXS) patterns from a poly(tetramethyl-p-silphenylene)-siloxane spherulite and a 40-μm polyethyl-eneterephthalate fiber were obtained in a few seconds per pattern with a 4 μm diameter beam at a wavelength of λ = 0.095 nm.