Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. ...

Stanford Synchrotron Radiation Lightsource

We describe two women with early onset breast cancer (at ages 31 and 38) who were found to have common variable immunodeficiency (CVID). Both women had a history of frequent and unusual bacterial infections. The incidence of breast cancer in young women and of CVID are both low, and the coincident diagnosis in two patients from a relatively small population base suggests the possibility of a pathophysiologic or causal relationship.

Common variable immunodeficiency and breast cancer.

Development of synchrotron techniques for the determination of the structure of disordered, amorphous and surface materials has exploded over the past 20 years owing to the increasing availability of high-flux synchrotron radiation and the continuing development of increasingly powerful synchrotron techniques. These techniques are available to materials scientists who are not necessarily synchrotron scientists through interaction with effective user communities that exist at synchrotrons such as the Stanford Synchrotron Radiation Laboratory. In this article the application of multiple synchrotron characterization techniques to two classes of materials defined as 'surface compounds' is reviewed. One class of surface compounds are materials like MoS(2-x)C(x) that are widely used petroleum catalysts, used to improve the environmental properties of transportation fuels. These compounds may be viewed as 'sulfide-supported carbides' in their catalytically active states. The second class of 'surface compounds' are the 'Maya blue' pigments that are based on technology created by the ancient Maya. These compounds are organic/inorganic 'surface complexes' consisting of the dye indigo and palygorskite, common clay. The identification of both surface compounds relies on the application of synchrotron techniques as described here.

Synchrotron and simulations techniques applied to problems in materials science: catalysts and Azul Maya pigments.

"The PDA as a Reference Tool: The Libraries' Role in Enhancing Nursing Education" is a pilot project funded by the University of Massachusetts President's Office Information Technology Council through their Professional Development Grant program in 2004. The project's goal is to offer faculty and students in nursing programs at two University of Massachusetts campuses access to an array of medical reference information, such as handbooks, dictionaries, calculators, and diagnostic tools, on small handheld computers called personal digital assistants. Through exposure to the variety of information resources in this digital format, participants can discover and explore these resources at no personal financial cost. Participants borrow handhelds from the University Library's circulation desks. The libraries provide support in routine resynchronizing of handhelds to update information. This report will discuss how the projects were administered, what we learned about what did and did not work, the problems and solutions, and where we hope to go from here.

The PDA as a reference tool: libraries' role in enhancing nursing education.

The aim of this study is to characterize rituximab-induced interstitial lung disease (R-ILD). The information on all reported cases of R-ILD was reviewed. This analysis focused on patient characteristics, underlying disease, rituximab dosing schedule, and R-ILD characteristic-like symptoms, diagnosis, treatment, and outcomes. Sixteen cases of R-ILD, including our two cases, have been reported in the literature. Commonalities include older age, clinical presentation, computerized tomography findings, pulmonary function tests, and biopsy findings. Therapy included corticosteroids and broad spectrum antibiotics. Prognosis has been variable. Patients who worsen despite corticosteroids have a poor outcome. The pathogenesis of R-ILD is largely unknown. Potential explanations for R-ILD may include the induction and release of cytotoxic substances. R-ILD is a rare but potentially fatal pulmonary toxicity due to rituximab. R-ILD should be considered in patients who present with dyspnea, fever, and cough, and there is no clear evidence of infection. Prompt diagnosis and treatment with corticosteroids is essential.

Rituximab-induced interstitial lung disease.

Funding from the University of Massachusetts president's office allowed two campuses of the University of Massachusetts system to offer nursing faculty and students PDAs containing medical/nursing databases for use during their clinical rotations. A study was designed to explore student's attitudes toward the use of PDAs in a clinical setting and to determine if the manner in which the technology was introduced affected the formation of these attitudes. During the fall and spring semesters of 2005 to 2006, both sites used and evaluated the effectiveness of PDAs at the point of care, but the clinical course, faculty experience with PDAs, and method and stage of introduction varied on each campus. The University library acted as the public point of access for borrowing and technical support of the PDAs. All students were asked to complete a 21-question survey that collected quantitative and qualitative data about their attitudes toward the use of PDAs at their clinical agency. Results of questionnaires relating to students attitudes to the PDA as a learning tool showed that there were differences in the student's perceptions and acceptance of the PDA as a learning tool. The results from the analysis of the data and suggestions for the possible reasons for the differences are explored.

Evaluating students' attitudes to using PDAs in nursing clinicals at two schools.

The stability of biogenic uraninite with respect to oxidation is seminal to the success of in situ bioreduction strategies for remediation of subsurface U(VI) contamination. The properties and hence stability of uraninite are dependent on its size, structure, and composition. In this study, the local-, intermediate-, and long-range molecular-scale structure of nanoscale uraninite produced by Shewanella oneidensis strain MR-1 was investigated using EXAFS, SR-based powder diffraction and TEM. The uraninite products were found to be structurally homologous with stoichiometric U02 under all conditions considered. Significantly, there was no evidence for lattice strain of the biogenic uraninite nanoparticles. The fresh nanoparticles were found to exhibit a well-ordered interior core of diameter ca. 1.3 nm and an outer region of thickness ca approximately 0.6 nm in which the structure is locally distorted. The lack of nanoparticle strain and structural homology with stoichiometric U02 suggests that established thermodynamic parameters for the latter material are an appropriate starting point to model the behavior of nanobiogenic uraninite. The detailed structural analysis in this study provides an essential foundation for subsequent investigations of environmental samples.

Structure of biogenic uraninite produced by Shewanella oneidensis strain MR-1.

The efficacy of a site remediation strategy involving the stimulaton of microbial U(VI) reduction hinges in part upon the long-term stability of the product, biogenic uraninite, toward environmental oxidants. Geological sedimentary uraninites (nominal formula UO2) reportedly contain abundant cation impurities that enhance their resistance to oxidation. By analogy, incorporation of common groundwater solutes into biogenic uraninite could also impart stability-enhancing properties. Mn(II) is a common groundwater cation, which has a favorable ionic radiusfor substitution reactions. The structure and reactivity of Mn(II)-reacted biogenic uraninite are investigated in this study. Up to 4.4 weight percent Mn(II) was found to be structurally bound in biogenic uraninite. This Mn(II) incorporation was associated with decreasing uraninite particle size and structural order. Importantly, the equilibrium solubility of Mn-reacted uraninite was halved relative to unreacted uraninite, demonstrating changes in thermodynamic properties, while the dissolution rate was up to 38-fold lower than that of unreacted biogenic uraninite. We conclude that structuralincorporation of Mn(II) into uraninite has an important stabilizing effect leading to the prediction that other groundwater solutes may similarly stabilize biogenic uraninite.

Effect of Mn(II) on the structure and reactivity of biogenic uraninite.

While the product of microbial uranium reduction is often reported to be "UO(2)", a comprehensive characterization including stoichiometry and unit cell determination is available for only one Shewanella species. Here, we compare the products of batch uranyl reduction by a collection of dissimilatory metal- and sulfate-reducing bacteria of the genera Shewanella, Geobacter, Anaeromyxobacter, and Desulfovibrio under similar laboratory conditions. Our results demonstrate that U(VI) bioreduction by this assortment of commonly studied, environmentally relevant bacteria leads to the precipitation of uraninite with an approximate composition of UO(2.0), regardless of phylogenetic or metabolic diversity. Coupled analyses, including electron microscopy, X-ray absorption spectroscopy, and powder diffraction, confirm that structurally and chemically analogous uraninite solids are produced. These biogenic uraninites have particle diameters of about 2-3 nm and lattice constants consistent with UO(2.0) and exhibit a high degree of intermediate-range order. Results indicate that phylogenetic and metabolic variability within delta- and gamma-proteobacteria has little effect on biouraninite structure or crystal size under the investigated conditions.

Structural similarities between biogenic uraninites produced by phylogenetically and metabolically diverse bacteria.

The ability to probe morphology and phase distribution in complex systems at multiple length scales unravels the interplay of nano- and micrometer-scale factors at the origin of macroscopic behavior. While different electron- and X-ray-based imaging techniques can be combined with spectroscopy at high resolutions, owing to experimental time limitations the resulting fields of view are too small to be representative of a composite sample. Here a new X-ray imaging set-up is proposed, combining full-field transmission X-ray microscopy (TXM) with X-ray absorption near-edge structure (XANES) spectroscopy to follow two-dimensional and three-dimensional morphological and chemical changes in large volumes at high resolution (tens of nanometers). TXM XANES imaging offers chemical speciation at the nanoscale in thick samples (>20 µm) with minimal preparation requirements. Further, its high throughput allows the analysis of large areas (up to millimeters) in minutes to a few hours. Proof of concept is provided using battery electrodes, although its versatility will lead to impact in a number of diverse research fields.

Three-dimensional imaging of chemical phase transformations at the nanoscale with full-field transmission X-ray microscopy.

Reductive bioremediation is currently being explored as a possible strategy for uranium-contaminated aquifers such as the Old Rifle site (Colorado). The stability of U(IV) phases under oxidizing conditions is key to the performance of this procedure. An in situ method was developed to study oxidative dissolution of biogenic uraninite (UO₂), a desirable U(VI) bioreduction product, in the Old Rifle, CO, aquifer under different variable oxygen conditions. Overall uranium loss rates were 50-100 times slower than laboratory rates. After accounting for molecular diffusion through the sample holders, a reactive transport model using laboratory dissolution rates was able to predict overall uranium loss. The presence of biomass further retarded diffusion and oxidation rates. These results confirm the importance of diffusion in controlling in-aquifer U(IV) oxidation rates. Upon retrieval, uraninite was found to be free of U(VI), indicating dissolution occurred via oxidation and removal of surface atoms. Interaction of groundwater solutes such as Ca²⁺ or silicate with uraninite surfaces also may retard in-aquifer U loss rates. These results indicate that the prolonged stability of U(IV) species in aquifers is strongly influenced by permeability, the presence of bacterial cells and cell exudates, and groundwater geochemistry.

Oxidative Dissolution of Biogenic Uraninite in Groundwater at Old Rifle, CO.

Chemical and structural heterogeneity and the resulting interaction of coexisting phases can lead to extraordinary behaviours in oxides, as observed in piezoelectric materials at morphotropic phase boundaries and relaxor ferroelectrics. However, such phenomena are rare in metallic alloys. Here we show that, by tuning the presence of structural heterogeneity in textured Co(1-x)Fe(x) thin films, effective magnetostriction λ(eff) as large as 260 p.p.m. can be achieved at low-saturation field of ~10 mT. Assuming λ(100) is the dominant component, this number translates to an upper limit of magnetostriction of λ(100)≈5λ(eff) >1,000 p.p.m. Microstructural analyses of Co(1-x)Fe(x) films indicate that maximal magnetostriction occurs at compositions near the (fcc+bcc)/bcc phase boundary and originates from precipitation of an equilibrium Co-rich fcc phase embedded in a Fe-rich bcc matrix. The results indicate that the recently proposed heterogeneous magnetostriction mechanism can be used to guide exploration of compounds with unusual magnetoelastic properties.

Giant magnetostriction in annealed Co(1-x)Fe(x) thin-films.

Determination of the heterogeneous distribution of metals in alloy/battery/catalyst and biological materials is critical to fully characterize and/or evaluate the functionality of the materials. Using synchrotron-based transmission x-ray microscopy (TXM), it is now feasible to perform nanoscale-resolution imaging over a wide X-ray energy range covering the absorption edges of many elements; combining elemental sensitive imaging with determination of sample morphology. We present an efficient and reliable methodology to perform 3D elemental sensitive imaging with excellent sample penetration (tens of microns) using hard X-ray TXM. A sample of an Al-Si piston alloy is used to demonstrate the capability of the proposed method.

Apurva Mehta

Stanford Synchrotron Radiation Lightsource

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques