Critical fluctuations in liquid-liquid extraction organic phases controlled by extractant and diluent molecular structure.

Extractant aggregation in liquid-liquid extraction organic phases impacts extraction energetics and is related to the deleterious efficiency-limiting liquid-liquid phase transition known as third phase formation. Using small angle X-ray scattering, we find that structural heterogeneities across a wide range of compositions in binary mixtures of malonamide extractants and alkane diluents are well described by Ornstein-Zernike scattering. This suggests that structure in these simplified organic phases originates from the critical point associated with the liquid-liquid phase transition.

Advancing Chemical Separations: Unraveling the Structure and Dynamics of Phase Splitting in Liquid-Liquid Extraction.

Liquid-liquid extraction (LLE), the go-to process for a variety of chemical separations, is limited by spontaneous organic phase splitting upon sufficient solute loading, called third phase formation. In this study we explore the applicability of critical phenomena theory to gain insight into this deleterious phase behavior with the goal of improving separations efficiency and minimizing waste. A series of samples representative of rare earth purification were constructed to include each of one light and one heavy lanthanide (cerium and lutetium) paired with one of two common malonamide extractants (DMDOHEMA and DMDBTDMA).

Nonuniform Flow Dynamics Probed by Nanosecond X-Ray Speckle Visibility Spectroscopy.

We report observations of nanosecond nonuniform colloidal dynamics in a free flowing liquid jet using ultrafast x-ray speckle visibility spectroscopy. Utilizing a nanosecond double-bunch mode, the Linac Coherent Light Source free electron laser produced pairs of femtosecond coherent hard x-ray pulses. By exploring anisotropy in the visibility of summed speckle patterns which relates to the correlation functions, we evaluate not only the average particle flow rate in a colloidal nanoparticle jet, but also the nonuniform flow field within.

Mesostructuring in Liquid-Liquid Extraction Organic Phases Originating from Critical Points.

Organic phase structure plays an important role in solute extraction energetics and phase behavior of liquid-liquid extraction (LLE) systems. For a binary extractant (amphiphile)/solvent mixture of relevance to LLE, we find that the organic phase mesostructuring is consistent with extractant concentration fluctuations as the compositional isotherm traverses the Widom line above its liquid-liquid critical point. This reveals a different mechanism for the well-documented heterogeneities in LLE organic phases that are typically attributed to micellization.

In situ microbeam surface X-ray scattering reveals alternating step kinetics during crystal growth.

The stacking sequence of hexagonal close-packed and related crystals typically results in steps on vicinal {0001} surfaces that have alternating A and B structures with different growth kinetics. However, because it is difficult to experimentally identify which step has the A or B structure, it has not been possible to determine which has faster adatom attachment kinetics. Here we show that in situ microbeam surface X-ray scattering can determine whether A or B steps have faster kinetics under specific growth conditions.

Instrument for in situ hard x-ray nanobeam characterization during epitaxial crystallization and materials transformations.

Solid-phase epitaxy (SPE) and other three-dimensional epitaxial crystallization processes pose challenging structural and chemical characterization problems. The concentration of defects, the spatial distribution of elastic strain, and the chemical state of ions each vary with nanoscale characteristic length scales and depend sensitively on the gas environment and elastic boundary conditions during growth. The lateral or three-dimensional propagation of crystalline interfaces in SPE has nanoscale or submicrometer characteristic distances during typical crystallization times.

Nanoscale Critical Phenomena in a Complex Fluid Studied by X-Ray Photon Correlation Spectroscopy.

The advent of high-speed x-ray photon correlation spectroscopy now allows the study of critical phenomena in fluids to much smaller length scales and over a wider range of temperatures than is possible with dynamic light scattering. We present an x-ray photon correlation spectroscopy study of critical fluctuation dynamics in a complex fluid typical of those used in liquid-liquid extraction (LLE) of ions, dodecane-DMDBTDMA with extracted aqueous Ce(NO_{3})_{3}. We observe good agreement with both static and dynamic scaling without the need for significant noncritical background corrections.

Double-pulse speckle contrast correlations with near Fourier transform limited free-electron laser light using hard X-ray split-and-delay.

The ability to deliver two coherent X-ray pulses with precise time-delays ranging from a few femtoseconds to nanoseconds enables critical capabilities of probing ultra-fast phenomena in condensed matter systems at X-ray free electron laser (FEL) sources. Recent progress made in the hard X-ray split-and-delay optics developments now brings a very promising prospect for resolving atomic-scale motions that were not accessible by previous time-resolved techniques. Here, we report on characterizing the spatial and temporal coherence properties of the hard X-ray FEL beam after propagating through split-and-delay optics.

Characterization of the X-ray coherence properties of an undulator beamline at the Advanced Photon Source.

In anticipation of the increased use of coherent X-ray methods and the need to upgrade beamlines to match improved source quality, here the coherence properties of the X-rays delivered by beamline 12ID-D at the Advanced Photon Source have been characterized. The measured X-ray divergence, beam size, brightness and coherent flux at energies up to 26 keV are compared with the calculated values from the undulator source, and the effects of beamline optics such as a mirror, monochromator and compound refractive lenses are evaluated. Diffraction patterns from slits as a function of slit width are analyzed using wave propagation theory to obtain the beam divergence and thus coherence length.

Towards ultrafast dynamics with split-pulse X-ray photon correlation spectroscopy at free electron laser sources.

One of the important challenges in condensed matter science is to understand ultrafast, atomic-scale fluctuations that dictate dynamic processes in equilibrium and non-equilibrium materials. Here, we report an important step towards reaching that goal by using a state-of-the-art perfect crystal based split-and-delay system, capable of splitting individual X-ray pulses and introducing femtosecond to nanosecond time delays. We show the results of an ultrafast hard X-ray photon correlation spectroscopy experiment at LCLS where split X-ray pulses were used to measure the dynamics of gold nanoparticles suspended in hexane.

Measuring Three-Dimensional Strain and Structural Defects in a Single InGaAs Nanowire Using Coherent X-ray Multiangle Bragg Projection Ptychography.

III-As nanowires are candidates for near-infrared light emitters and detectors that can be directly integrated onto silicon. However, nanoscale to microscale variations in structure, composition, and strain within a given nanowire, as well as variations between nanowires, pose challenges to correlating microstructure with device performance. In this work, we utilize coherent nanofocused X-rays to characterize stacking defects and strain in a single InGaAs nanowire supported on Si.

Bragg Coherent Diffractive Imaging of Zinc Oxide Acoustic Phonons at Picosecond Timescales.

Mesoscale thermal transport is of fundamental interest and practical importance in materials such as thermoelectrics. Coherent lattice vibrations (acoustic phonons) govern thermal transport in crystalline solids and are affected by the shape, size, and defect density in nanoscale materials. The advent of hard x-ray free electron lasers (XFELs) capable of producing ultrafast x-ray pulses has significantly impacted the understanding of acoustic phonons by enabling their direct study with x-rays.

Bragg coherent diffractive imaging of single-grain defect dynamics in polycrystalline films.

Polycrystalline material properties depend on the distribution and interactions of their crystalline grains. In particular, grain boundaries and defects are crucial in determining their response to external stimuli. A long-standing challenge is thus to observe individual grains, defects, and strain dynamics inside functional materials.

Kinetic Monte Carlo simulations of GaN homoepitaxy on c- and m-plane surfaces.

The surface orientation can have profound effects on the atomic-scale processes of crystal growth and is essential to such technologies as GaN-based light-emitting diodes and high-power electronics. We investigate the dependence of homoepitaxial growth mechanisms on the surface orientation of a hexagonal crystal using kinetic Monte Carlo simulations. To model GaN metal-organic vapor phase epitaxy, in which N species are supplied in excess, only Ga atoms on a hexagonal close-packed (HCP) lattice are considered.

An instrument for in situ coherent x-ray studies of metal-organic vapor phase epitaxy of III-nitrides.

We describe an instrument that exploits the ongoing revolution in synchrotron sources, optics, and detectors to enable in situ studies of metal-organic vapor phase epitaxy (MOVPE) growth of III-nitride materials using coherent x-ray methods. The system includes high-resolution positioning of the sample and detector including full rotations, an x-ray transparent chamber wall for incident and diffracted beam access over a wide angular range, and minimal thermal sample motion, giving the sub-micron positional stability and reproducibility needed for coherent x-ray studies. The instrument enables surface x-ray photon correlation spectroscopy, microbeam diffraction, and coherent diffraction imaging of atomic-scale surface and film structure and dynamics during growth, to provide fundamental understanding of MOVPE processes.

Stability Limits and Defect Dynamics in Ag Nanoparticles Probed by Bragg Coherent Diffractive Imaging.

Dissolution is critical to nanomaterial stability, especially for partially dealloyed nanoparticle catalysts. Unfortunately, highly active catalysts are often not stable in their reactive environments, preventing widespread application. Thus, focusing on the structure-stability relationship at the nanoscale is crucial and will likely play an important role in meeting grand challenges.

Three-dimensional imaging of dislocation dynamics during the hydriding phase transformation.

Crystallographic imperfections significantly alter material properties and their response to external stimuli, including solute-induced phase transformations. Despite recent progress in imaging defects using electron and X-ray techniques, in situ three-dimensional imaging of defect dynamics remains challenging. Here, we use Bragg coherent diffractive imaging to image defects during the hydriding phase transformation of palladium nanocrystals.

A liquid jet setup for x-ray scattering experiments on complex liquids at free-electron laser sources.

In this paper we describe a setup for x-ray scattering experiments on complex fluids using a liquid jet. The setup supports Small and Wide Angle X-ray Scattering (SAXS/WAXS) geometries. The jet is formed by a gas-dynamic virtual nozzle (GDVN) allowing for diameters ranging between 1 μm and 20 μm at a jet length of several hundred μm.

Single shot speckle and coherence analysis of the hard X-ray free electron laser LCLS.

The single shot based coherence properties of hard x-ray pulses from the Linac Coherent Light Source (LCLS) were measured by analyzing coherent diffraction patterns from nano-particles and gold nanopowder. The intensity histogram of the small angle x-ray scattering ring from nano-particles reveals the fully transversely coherent nature of the LCLS beam with a number of transverse mode 〈Ms〉 = 1.1.

Imaging local polarization in ferroelectric thin films by coherent x-ray Bragg projection ptychography.

We used x-ray Bragg projection ptychography (BPP) to map spatial variations of ferroelectric polarization in thin film PbTiO3, which exhibited a striped nanoscale domain pattern on a high-miscut (001) SrTiO3 substrate. By converting the reconstructed BPP phase image to picometer-scale ionic displacements in the polar unit cell, a quantitative polarization map was made that was consistent with other characterization. The spatial resolution of 5.

Oxidation of PtNi nanoparticles studied by a scanning X-ray fluorescence microscope with multi-layer Laue lenses.

We report a study of the oxidation process of individual PtNi nanoparticles (NPs) conducted with a novel scanning multi-layer Laue lens X-ray microscope. The elemental maps reveal that alloyed PtNi NPs were transformed into Pt/NiO core-shell NPs by thermal oxidation. The observations furthermore indicate that a coalescence of Pt/NiO core-shell NPs occurred during oxidation.