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At least 361 records · Page 20

Component Particle Structure in Heterogeneous Disordered Ensembles Extracted from High-Throughput Fluctuation X-Ray Scattering

The ring angular correlation function is a characteristic feature determined by the particle structure. Averaging over a large number of ring angular correlation functions calculated from x-ray diffraction patterns will cancel out the cross correlations between different particles and converge to the autocorrelation functions of single particles. Applied on heterogeneous disordered ensembles, the retrieved function is a linear combination of a single-particle autocorrelation function multiplied by the molar ratios in a heterogeneous system. Using this relation, the ring angular correlation functions of the individual component particles in the heterogeneous system can be retrieved through the high throughput fluctuation x-ray scattering technique. This method is demonstrated with a simulated heterogeneous system composed of nanorods, nanoprism, and nanorice.

Fluctuation X-ray Scattering, high throughput, Het↗

Correlating dynamic microstructure to observed color in electrophoretic displays via in situ small-angle x-ray scattering

Electrophoretic deposition (EPD) is an industrially relevant and scalable technique used to form particle deposits from colloidal suspensions. Highly concentrated particle suspensions generally prevent real-time in situ microscopy observations which limit the characterization of EPD films to ex situ, or postprocessed, laboratory techniques. For dynamic systems, such as tunable amorphous photonic crystals (APCs), only reversible deposits are formed during the EPD process. Since reversible deposits cannot be characterized with standard ex situ methods, the particle-particle and particle-field interactions that govern the displayed color and crystallinity of these systems are not well understood. In this paper, we present in situ small-angle x-ray scattering and UV-Vis techniques for measuring both the structural and optical response of an APC under applied electric fields. Furthermore, we also develop a computational model based on colloidal interactions to explain the observed change in the interparticle spacing of APCs due to the applied electric field which correlates to displayed color. Ultimately, this work provides a new in situ characterization method that could be expanded for other dynamic, tunable colloidal systems.

36 MATERIALS SCIENCE↗

Noninvasive Synchrotron-Based X-ray Raman Scattering Discriminates Carbonaceous Compounds in Ancient and Historical Materials [ In situ synchrotron-based X-Ray Raman scattering discriminates carbonaceous compounds in ancient and historical materials]

Carbon compounds are ubiquitous and occur in a diversity of chemical forms in many systems including ancient and historic materials ranging from cultural heritage to paleontology. Determining their speciation cannot only provide unique information on their origin but may also elucidate degradation processes. Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge (280–350 eV) is a very powerful method to probe carbon speciation. However, the short penetration depth of soft X-rays imposes stringent constraints on sample type, preparation, and analytical environment. A hard X-ray probe such as X-ray Raman scattering (XRS) can overcome many of these difficulties. Here we report the use of XRS at ~6 keV incident energy to collect carbon K-edge XANES data and probe the speciation of organic carbon in several specimens relevant to cultural heritage and natural history. This methodology enables the measurement to be done in a nondestructive way, in air, and provides information that is not compromised by surface contamination by ensuring that the dominant signal contribution is from the bulk of the probed material. Using the backscattering geometry at large photon momentum transfer maximizes the XRS signal at the given X-ray energy and enhances nondipole contributions compared to conventional XANES, thereby augmenting the speciation sensitivity. The capabilities and limitations of the technique are discussed. As a result, we show that despite its small cross section, for a range of systems the XRS method can provide satisfactory signals at realistic experimental conditions. XRS constitutes a powerful complement to FT-IR, Raman, and conventional XANES spectroscopy, overcoming some of the limitations of these techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reductive Dissolution Mechanisms at the Hematite-Electrolyte Interface Probed by In Situ X-ray Scattering

The electron-catalyzed dissolution and reprecipitation of iron (oxyhydr)oxides constitute critical steps in natural geochemical iron cycling. However, the atomic-scale mechanisms of reductive dissolution and oxidative precipitation of Fe2+ remain poorly understood because they are difficult to directly experimentally probe. Using in situ synchrotron X-ray scattering and a novel electrochemical cell, we interrogate the interfacial structure between the hematite (?-Fe2O3) (11 ¯02) surface and acidic aqueous solution (5 mM Na2SO4, pH 4.0) under controlled electrochemical potential from open circuit to cathodic bias as the reductive dissolution potential is approached and then exceeded. The crystalline order of the surface improves under mild reducing conditions, and the surface Fe stoichiometry changes with cathodic bias. After significant reductive dissolution occurs and cathodic bias is removed, dissolved Fe is re-deposited, forming a disordered interface. Unlike at circumneutral pH, water layers at the hematite interface with acidic solution are poorly ordered, likely due to the adsorption of sulfate from the electrolyte. These results provide a novel atomic-scale view into the behavior of reducible transition metal oxide surfaces under fluctuating (electro)chemical conditions.

McBriarty, Martin E.↗

Bulk Metallic Glass-like Scattering Signal in Small Metallic Nanoparticles

The atomic structure of Ni-Pd nanoparticles has been studied using atomic pair distribution function (PDF) analysis of X-ray total scattering data and with transmission electron microscopy (TEM). Larger nanoparticles have PDFs corresponding to the bulk face-centered cubic packing. However, the smallest nanoparticles have PDFs that strongly resemble those obtained from bulk metallic glasses (BMGs). In fact, by simply scaling the distance axis by the mean metallic radius, the curves may be collapsed onto each other and onto the PDF from a metallic glass sample. In common with a wide range of BMG materials, the intermediate range order may be fit with a damped single-frequency sine wave. When viewed in high-resolution TEM, these nanoparticles exhibit atomic fringes typical of those seen in small metallic clusters with icosahedral or decahedral order. These two seemingly contradictory results are reconciled by calculating the PDFs of models of icosahedra that would be consistent with the fringes seen in TEM. These model PDFs resemble the measured ones when significant atom-position disorder is introduced, drawing together the two diverse fields of metallic nanoparticles and BMGs and supporting the view that BMGs may contain significant icosahedral or decahedral order.

Doan-Nguyen, VVT↗

Space- and time-resolved small angle X-ray scattering to probe assembly of silver nanocrystal superlattices

Abstract The structure of nanocrystal superlattices has been extensively studied and well documented, however, their assembly process is poorly understood. In this work, we demonstrate an in situ space- and time-resolved small angle X-ray scattering measurement that we use to probe the assembly of silver nanocrystal superlattices driven by electric fields. The electric field creates a nanocrystal flux to the surface, providing a systematic means to vary the nanocrystal concentration near the electrode and thereby to initiate nucleation and growth of superlattices in several minutes. Using this approach, we measure the space- and time-resolved concentration and polydispersity gradients during deposition and show how they affect the superlattice constant and degree of order. We find that the field induces a size-selection effect that can reduce the polydispersity near the substrate by 21% leading to better quality crystals and resulting in field strength-dependent superlattice lattice constants.

36 MATERIALS SCIENCE↗