Surface-mediated formation of Pu(IV) nanoparticles at the muscovite-electrolyte interface.

The formation of Pu(IV)-oxo-nanoparticles from Pu(III) solutions by a surface-enhanced redox/polymerization reaction at the muscovite (001) basal plane is reported, with a continuous increase in plutonium coverage observed in situ over several hours. The sorbed Pu extends >70 Å from the surface with a maximum concentration at 10.5 Å and a total coverage of >9 Pu atoms per unit cell area of muscovite (0.77 µg Pu/cm(2)) (determined independently by in situ resonant anomalous X-ray reflectivity and by ex-situ alpha-spectrometry). The presence of discrete nanoparticles is confirmed by high resolution atomic force microscopy. We propose that the formation of these Pu(IV) nanoparticles from an otherwise stable Pu(III) solution can be explained by the combination of a highly concentrated interfacial Pu-ion species, the Pu(III)-Pu(IV) redox equilibrium, and the strong proclivity of tetravalent Pu to hydrolyze and form polymeric species. These results are the first direct observation of such behavior of plutonium on a naturally occurring mineral, providing insights into understanding the environmental transport of plutonium and other contaminants capable of similar redox/polymerization reactions.

Interfacial bonding and structure of Bi2Te3 topological insulator films on Si(111) determined by surface x-ray scattering.

Interfacial topological states are a key element of interest for topological insulator thin films, and their properties can depend sensitively on the atomic bonding configuration. We employ in situ nonresonant and resonant surface x-ray scattering to study the interfacial and internal structure of a prototypical topological film system: Bi2Te3 grown on Si(111). The results reveal a Te-dominated buffer layer, a large interfacial spacing, and a slightly relaxed and partially strained bottom quintuple layer of an otherwise properly stacked bulklike Bi2Te3 film. The presence of the buffer layer indicates a nontrivial process of interface formation and a mechanism for electronic decoupling between the topological film and the Si(111) substrate.

Adsorption of plutonium oxide nanoparticles.

Adsorption of monodisperse cubic plutonium oxide nanoparticles ("Pu-NP", [Pu(38)O(56)Cl(x)(H(2)O)(y)]((40-x)+), with a fluorite-related lattice, approximately 1 nm in edge size) to the muscovite (001) basal plane from aqueous solutions was observed in situ (in 100 mM NaCl background electrolyte at pH 2.6). Uptake capacity of the surface quantified by α-spectrometry was 0.92 µg Pu/cm(2), corresponding to 10.8 Pu per unit cell area (A(UC)). This amount is significantly larger than that of Pu(4+) needed for satisfying the negative surface charge (0.25 Pu(4+) for 1 e(-)/A(UC)). The adsorbed Pu-NPs cover 17% of the surface area, determined by X-ray reflectivity (XR). This correlates to one Pu-NP for every 14 unit cells of muscovite, suggesting that each particle compensates the charge of the unit cells onto which it adsorbs as well as those in its direct proximity. Structural investigation by resonant anomalous X-ray reflectivity distinguished two different sorption states of Pu-NPs on the surface at two different regimes of distance from the surface. A fraction of Pu is distributed within 11 Å from the surface. The distribution width matches the Pu-NP size, indicating that this species represents Pu-NPs adsorbed directly on the surface. Beyond the first layer, an additional fraction of sorbed Pu was observed to extend more broadly up to more than 100 Å from the surface. This distribution is interpreted as resulting from "stacking" or aggregation of the nanoparticles driven by sorption and accumulation of Pu-NPs at the interface although these Pu-NPs do not aggregate in the solution. These results are the first in situ observation of the interaction of nanoparticles with a charged mineral-water interface yielding information important to understanding the environmental transport of Pu and other nanophase inorganic species.

A new x-ray interface and surface scattering environmental cell design for in situ studies of radioactive and atmosphere-sensitive samples.

We present a novel design of a purpose-built, portable sample cell for in situ x-ray scattering experiments of radioactive or atmosphere sensitive samples. The cell has a modular design that includes two independent layers of containment that are used simultaneously to isolate the sensitive samples. Both layers of containment can be flushed with an inert gas, thus serving a double purpose as containment of radiological material (either as a solid sample or as a liquid phase) and in separating reactive samples from the ambient atmosphere. A remote controlled solution flow system is integrated into the containment system that allows sorption experiments to be performed on the diffractometer. The cell's design is discussed in detail and we demonstrate the cell's performance by presenting first results of crystal truncation rod measurements. The results were obtained from muscovite mica single crystals reacted with 1 mM solutions of Th(IV) with 0.1 M NaCl background electrolyte. Data were obtained in specular as well as off-specular geometry.

Direct and quantitative comparison of pixelated density profiles with high-resolution X-ray reflectivity data.

A method for comparing pixelated density profiles (e.g. obtained from molecular dynamics or other computational techniques) with experimental X-ray reflectivity data both directly and quantitatively is described. The conditions under which such a comparison can be made quantitatively (e.g. with errors <1%) are determined theoretically by comparing calculated structure factors for an intrinsic continuous density profile with those obtained from density profiles that have been binned into regular spatial increments. The accuracy of the X-ray reflectivity calculations for binned density profiles is defined in terms of the inter-relationships between resolution of the X-ray reflectivity data (i.e. its range in momentum transfer), the chosen bin size and the width of the intrinsic density profile. These factors play a similar role in the application of any structure-factor calculations that involve the use of pixelated density profiles, such as those obtained from iterative phasing algorithms for inverting structures from X-ray reflectivity and coherent diffraction imaging data. Finally, it is shown how simulations of a quartz-water interface can be embedded into an exact description of the `bulk' phases (including the substrate crystal and the fluid water, below and above the actual interface) to quantitatively reproduce the experimental reflectivity data of a solid-liquid interface.

Image contrast in X-ray reflection interface microscopy: comparison of data with model calculations and simulations.

The contrast mechanism for imaging molecular-scale features on solid surfaces is described for X-ray reflection interface microscopy (XRIM) through comparison of experimental images with model calculations and simulated measurements. Images of elementary steps show that image contrast is controlled by changes in the incident angle of the X-ray beam with respect to the sample surface. Systematic changes in the magnitude and sign of image contrast are asymmetric for angular deviations of the sample from the specular reflection condition. No changes in image contrast are observed when defocusing the condenser or objective lenses. These data are explained with model structure-factor calculations that reproduce all of the qualitative features observed in the experimental data. These results provide new insights into the image contrast mechanism, including contrast reversal as a function of incident angle, the sensitivity of image contrast to step direction (i.e. up versus down), and the ability to maximize image contrast at almost any scattering condition defined by the vertical momentum transfer, Q(z). The full surface topography can then, in principle, be recovered by a series of images as a function of incident angle at fixed momentum transfer. Inclusion of relevant experimental details shows that the image contrast magnitude is controlled by the intersection of the reciprocal-space resolution function (i.e. controlled by numerical aperture of the condenser and objective lenses) and the spatially resolved interfacial structure factor of the object being imaged. Together these factors reduce the nominal contrast for a step near the specular reflection condition to a value similar to that observed experimentally. This formalism demonstrates that the XRIM images derive from limited aperture contrast, and explains how non-zero image contrast can be obtained when imaging a pure phase object corresponding to the interfacial topography.

On the use of CCD area detectors for high-resolution specular X-ray reflectivity.

The use and application of charge coupled device (CCD) area detectors for high-resolution specular X-ray reflectivity is discussed. Direct comparison of high-resolution specular X-ray reflectivity data measured with CCD area detectors and traditional X-ray scintillator ('point') detectors demonstrates that the use of CCD detectors leads to a substantial (approximately 30-fold) reduction in data acquisition rates because of the elimination of the need to scan the sample to distinguish signal from background. The angular resolution with a CCD detector is also improved by a factor of approximately 3. The ability to probe the large dynamic range inherent to high-resolution X-ray reflectivity data in the specular reflection geometry was demonstrated with measurements of the orthoclase (001)- and alpha-Al2O3 (012)-water interfaces, with measured reflectivity signals varying by a factor of approximately 10(6) without the use of any beam attenuators. Statistical errors in the reflectivity signal are also derived and directly compared with the repeatability of the measurements.

Zn2+ and Sr2+ adsorption at the TiO2 (110)-electrolyte interface: influence of ionic strength, coverage, and anions.

The X-ray standing wave technique was used to probe the sensitivity of Zn2+ and Sr2+ ion adsorption to changes in both the adsorbed ion coverage and the background electrolyte species and concentrations at the rutile (alpha-TiO2) (110)-aqueous interface. Measurements were made with various background electrolytes (NaCl, NaTr, RbCl, NaBr) at concentrations as high as 1 m. The results demonstrate that Zn2+ and Sr2+ reside primarily in the condensed layer and that the ion heights above the Ti-O surface plane are insensitive to ionic strength and the choice of background electrolyte (with <0.1 A changes over the full compositional range). The lack of any specific anion coadsorption upon probing with Br-, coupled with the insensitivity of Zn2+ and Sr2+ cation heights to changes in the background electrolyte, implies that anions do not play a significant role in the adsorption of these divalent metal ions to the rutile (110) surface. Absolute ion coverage measurements for Zn2+ and Sr2+ show a maximum Stern-layer coverage of approximately 0.5 monolayer, with no significant variation in height as a function of Stern-layer coverage. These observations are discussed in the context of Gouy-Chapman-Stern models of the electrical double layer developed from macroscopic sorption and pH-titration studies of rutile powder suspensions. Direct comparison between these experimental observations and the MUltiSIte Complexation (MUSIC) model predictions of cation surface coverage as a function of ionic strength revealed good agreement between measured and predicted surface coverages with no adjustable parameters.

Ion adsorption at the rutile-water interface: linking molecular and macroscopic properties.

A comprehensive picture of the interface between aqueous solutions and the (110) surface of rutile (alpha-TiO2) is being developed by combining molecular-scale and macroscopic approaches, including experimental measurements, quantum calculations, molecular simulations, and Gouy-Chapman-Stern models. In situ X-ray reflectivity and X-ray standing-wave measurements are used to define the atomic arrangement of adsorbed ions, the coordination of interfacial water molecules, and substrate surface termination and structure. Ab initio calculations and molecular dynamics simulations, validated through direct comparison with the X-ray results, are used to predict ion distributions not measured experimentally. Potentiometric titration and ion adsorption results for rutile powders having predominant (110) surface expression provide macroscopic constraints of electrical double layer (EDL) properties (e.g., proton release) which are evaluated by comparison with a three-layer EDL model including surface oxygen proton affinities calculated using ab initio bond lengths and partial charges. These results allow a direct correlation of the three-dimensional, crystallographically controlled arrangements of various species (H2O, Na+, Rb+, Ca2+, Sr2+, Zn2+, Y3+, Nd3+) with macroscopic observables (H+ release, metal uptake, zeta potential) and thermodynamic/electrostatic constraints. All cations are found to be adsorbed as "inner sphere" species bonded directly to surface oxygen atoms, while the specific binding geometries and reaction stoichiometries are dependent on ionic radius. Ternary surface complexes of sorbed cations with electrolyte anions are not observed. Finally, surface oxygen proton affinities computed using the MUSIC model are improved by incorporation of ab initio bond lengths and hydrogen bonding information derived from MD simulations. This multitechnique and multiscale approach demonstrates the compatibility of bond-valence models of surface oxygen proton affinities and Stern-based models of the EDL structure, with the actual molecular interfacial distributions observed experimentally, revealing new insight into EDL properties including specific binding sites and hydration states of sorbed ions, interfacial solvent properties (structure, diffusivity, dielectric constant), surface protonation and hydrolysis, and the effect of solution ionic strength.

Reliability of stabilised commercial dynamometers for measuring hip abduction strength: a pilot study.

BACKGROUND: Reliable quantification of hip abductor strength in a clinical setting is challenging. OBJECTIVES: To examine the intrarater and interrater reliability of three commonly used commercial dynamometers in the measurement of hip abduction. METHODS: Supine gravity minimised measures of unilateral hip abduction strength were recorded in 10 women (mean (SD) age 23.5 (1.9) years) using three different commercially available dynameters. Measurements were repeated over a three day period with a different device used on each day. RESULTS: Intrarater reliability ranged from 0.880 to 0.958 across the three devices, and measures of interrater reliability ranged from 0.899 to 0.948. CONCLUSION: Commercially available dynamometers can be used to quantify hip abduction strength with good to excellent reliability. A previously undescribed method of quantifying hip abduction strength in a clinical setting using readily available instrumentation is presented.

Fourier-expansion solution of atom distributions in a crystal using X-ray standing waves.

Term-by-term Fourier-expansion series, each made up of components having element-specific phases and amplitudes acquired with x-ray standing wave measurements on successive orders of Bragg reflections, are used to reconstruct impurity atom distributions in muscovite mica with respect to the (001) lattice without a priori assumptions on their structures.

Molecular-scale density oscillations in water adjacent to a mica surface.

High-resolution specular x-ray reflectivity of the mica(001)-water interface under ambient conditions reveals oscillations in water oxygen density in the surface-normal direction, giving evidence of interfacial water ordering. The spacings between neighboring water layers in the near-surface, strongly oscillatory region are 2.5(2)-2.7(2) A, approximately the size of the water molecule. The density oscillations extend to about 10 A above the surface and do not strictly maintain a solvent-size periodicity as that in interfacial liquid metal and hard-sphere molecular liquids. We interpret this oscillatory density profile of the interfacial water as due to the "hard-wall" effect of the molecularly smooth mica surface.

Electrical Double-Layer Structure at the Rutile-Water Interface as Observed in Situ with Small-Period X-Ray Standing Waves.

X-Ray standing wave (XSW) measurements were made of Rb and Sr adsorbed from aqueous solutions at the rutile (110)-water interface. These experiments were performed to address the extent to which direct measurements of electrical double-layer structure are possible. The experimental results show that the Bragg XSW technique, using small-period standing waves generated by Bragg diffraction from the substrate, can precisely measure ion locations within the condensed layer and the in situ partitioning of ions between the condensed and diffuse layers. Differences in condensed layer ion positions were observed for Sr ions (measured in situ) as compared with Rb ions (in situ) and also for Sr ions (ex situ). An additional constraint on the ex situ Sr site geometry was provided by polarization-dependent surface EXAFS measurements. Such measurements can provide important constraints for the development and verification of electrical double-layer theory especially as applied to ion adsorption at the solid-water interface. Copyright 2000 Academic Press.

Biomimetic Pathways for Assembling Inorganic Thin Films

Living organisms construct various forms of laminated nanocomposites through directed nucleation and growth of inorganics at self-assembled organic templates at temperatures below 100°C and in aqueous solutions. Recent research has focused on the use of functionalized organic surfaces to form continuous thin films of single-phase ceramics. Continuous thin films of mesostructured silicates have also been formed on hydrophobic and hydrophilic surfaces through a two-step mechanism. First, under acidic conditions, surfactant micellar structures are self-assembled at the solid/liquid interface, and second, inorganic precursors condense to form an inorganic-organic nanocomposite. Epitaxial coordination of adsorbed surfactant tubules is observed on mica and graphite substrates, whereas a random arrangement is observed on amorphous silica. The ability to process ceramic-organic nanocomposite films by these methods provides new technological opportunities.

Self-Assembly of n-Alkyl Thiols as Disulfides on Au(111).

A grazing incidence x-ray diffraction study of CH(3)(CH(2))(9)SH self-assembled on the (111) surface of gold revealed a disulfide head group structure, which provides a context in which to understand the structure and self-assembly process of this widely studied system. The structure consists of a nearly hexagonal two-dimensional arrangement of the hydrocarbon chains with a dimerization of the sulfur head groups (accommodated through a gauche bond), resulting in a S-S spacing of 2.2 angstroms. These results demonstrate the importance of internal molecular degrees of freedom in the templating of "soft" organic materials on inorganic substrates.