51 research outputs found
Jahn-Teller-driven Phase Segregation in MnCoO Spinel Thin Films
Transition metal spinel oxides comprised of Earth-abundant Mn and Co have
long been explored for their use in catalytic reactions and energy storage.
However, understanding of functional properties can be challenging due to
differences in sample preparation and the ultimate structural properties of the
materials. Epitaxial thin film synthesis provides a novel means of producing
precisely-controlled materials to explore the variations reported in the
literature. In this work, MnCoO samples from x = 0 to x =
1.28 were synthesized through molecular beam epitaxy and characterized to
develop a material properties map as a function of stoichiometry. Films were
characterized via in situ X-ray photoelectron spectroscopy, X-ray diffraction,
scanning transmission electron microscopy, and polarized K-edge X-ray
absorption spectroscopy. Mn cations within this range were found to be
octahedrally coordinated, in line with an inverse spinel structure. Samples
largely show mixed Mn and Mn character with evidence of phase
segregation tendencies with increasing Mn content and increasing Mn
formal charge. Phase segregation may occur due to structural incompatibility
between cubic and tetragonal crystal structures associated with Mn and
Jahn-Teller active Mn octahedra, respectively. Our results help to
explain the reported differences across samples in these promising materials
for renewable energy technologies.Comment: 25 pages, 8 figures; Supplemental info and figures, 9 page
Plutonium Migration during the Leaching of Cemented Radioactive Waste Sludges
One of the most challenging components of the UK nuclear legacy is Magnox sludge, arising from the corrosion of Mg alloy-clad irradiated metallic U fuel that has been stored in high pH ponds. The sludges mainly comprise Mg hydroxide and carbonate phases, contaminated with fission products and actinides, including Pu. Cementation and deep geological disposal is one option for the long-term management of this material, but there is a need to understand how Pu may be leached from the waste, if it is exposed to groundwater. Here, we show that cemented Mg(OH)2 powder prepared with Pu(IV)aq is altered on contact with water to produce a visibly altered ‘leached zone’, which penetrates several hundred microns into the sample. In turn, this zone shows slow leaching of Pu, with long-term leaching rates between 1.8–4.4 × 10−5% of total Pu per day. Synchrotron micro-focus X-ray fluorescence mapping identified decreased Pu concentration within the ‘leached zone’. A comparison of micro-focus X-ray absorption spectroscopy (µ-XAS) spectra collected across both leached and unleached samples showed little variation, and indicated that Pu was present in a similar oxidation state and coordination environment. Fitting of the XANES spectra between single oxidation state standards and EXAFS modeling showed that Pu was present as a mixture of Pu(IV) and Pu(V). The change in Pu oxidation from the stock solution suggests that partial Pu oxidation occurred during sample ageing. Similarity in the XAS spectra from all samples, with different local chemistries, indicated that the Pu oxidation state was not perturbed by macro-scale variations in cement chemistry, surface oxidation, sample aging, or the leaching treatment. These experiments have demonstrated the potential for leaching of Pu from cementitious waste forms, and its underlying significance requires further investigation
Antimony-Doped Tin(II) Sulfide Thin Films
Thin-film solar cells made from earth-abundant, inexpensive, and nontoxic materials are needed to replace the current technologies whose widespread use is limited by their use of scarce, costly, and toxic elements. Tin monosulfide (SnS) is a promising candidate for making absorber layers in scalable, inexpensive, and nontoxic solar cells. SnS has always been observed to be a p-type semiconductor. Doping SnS to form an n-type semiconductor would permit the construction of solar cells with p-n homojunctions. This paper reports doping SnS films with antimony, a potential n-type dopant. Small amounts of antimony (1%) were found to greatly increase the electrical resistance of the SnS. The resulting intrinsic SnS(Sb) films could be used for the insulating layer in a p-i-n design for solar cells. Higher concentrations (5%) of antimony did not convert the SnS(Sb) to low-resistivity n-type conductivity, but instead the films retain such a high resistance that the conductivity type could not be determined. Extended X-ray absorption fine structure analysis reveals that the highly doped films contain precipitates of a secondary phase that has chemical bonds characteristic of metallic antimony, rather than the antimony–sulfur bonds found in films with lower concentrations of antimony.United States. Dept. of Energy. Sunshot Initiative (Contract DE-EE0005329)National Science Foundation (U.S.) (Grant CBET-1032955
Plutonium Migration during the Leaching of Cemented Radioactive Waste Sludges
One of the most challenging components of the UK nuclear legacy is Magnox sludge, arising from the corrosion of Mg alloy-clad irradiated metallic U fuel that has been stored in high pH ponds. The sludges mainly comprise Mg hydroxide and carbonate phases, contaminated with fission products and actinides, including Pu. Cementation and deep geological disposal is one option for the long-term management of this material, but there is a need to understand how Pu may be leached from the waste, if it is exposed to groundwater. Here, we show that cemented Mg(OH)2 powder prepared with Pu(IV)aq is altered on contact with water to produce a visibly altered ‘leached zone’, which penetrates several hundred microns into the sample. In turn, this zone shows slow leaching of Pu, with long-term leaching rates between 1.8–4.4 × 10−5% of total Pu per day. Synchrotron micro-focus X-ray fluorescence mapping identified decreased Pu concentration within the ‘leached zone’. A comparison of micro-focus X-ray absorption spectroscopy (µ-XAS) spectra collected across both leached and unleached samples showed little variation, and indicated that Pu was present in a similar oxidation state and coordination environment. Fitting of the XANES spectra between single oxidation state standards and EXAFS modeling showed that Pu was present as a mixture of Pu(IV) and Pu(V). The change in Pu oxidation from the stock solution suggests that partial Pu oxidation occurred during sample ageing. Similarity in the XAS spectra from all samples, with different local chemistries, indicated that the Pu oxidation state was not perturbed by macro-scale variations in cement chemistry, surface oxidation, sample aging, or the leaching treatment. These experiments have demonstrated the potential for leaching of Pu from cementitious waste forms, and its underlying significance requires further investigation
VAST: An ASKAP Survey for Variables and Slow Transients
The Australian Square Kilometre Array Pathfinder (ASKAP) will give us an
unprecedented opportunity to investigate the transient sky at radio
wavelengths. In this paper we present VAST, an ASKAP survey for Variables and
Slow Transients. VAST will exploit the wide-field survey capabilities of ASKAP
to enable the discovery and investigation of variable and transient phenomena
from the local to the cosmological, including flare stars, intermittent
pulsars, X-ray binaries, magnetars, extreme scattering events, interstellar
scintillation, radio supernovae and orphan afterglows of gamma ray bursts. In
addition, it will allow us to probe unexplored regions of parameter space where
new classes of transient sources may be detected. In this paper we review the
known radio transient and variable populations and the current results from
blind radio surveys. We outline a comprehensive program based on a multi-tiered
survey strategy to characterise the radio transient sky through detection and
monitoring of transient and variable sources on the ASKAP imaging timescales of
five seconds and greater. We also present an analysis of the expected source
populations that we will be able to detect with VAST.Comment: 29 pages, 8 figures. Submitted for publication in Pub. Astron. Soc.
Australi
An IGF-I promoter polymorphism modifies the relationships between birth weight and risk factors for cardiovascular disease and diabetes at age 36
OBJECTIVE: To investigate whether IGF-I promoter polymorphism was associated with birth weight and risk factors for cardiovascular disease (CVD) and type 2 diabetes (T2DM), and whether the birth weight – risk factor relationship was the same for each genotype. DESIGN AND PARTICIPANTS: 264 subjects (mean age 36 years) had data available on birth weight, IGF-I promoter polymorphism genotype, CVD and T2DM risk factors. Student's t-test and regression analyses were applied to analyse differences in birth weight and differences in the birth weight – risk factors relationship between the genotypes. RESULTS: Male variant carriers (VCs) of the IGF-I promoter polymorphism had a 0.2 kg lower birth weight than men with the wild type allele (p = 0.009). Of the risk factors for CVD and T2DM, solely LDL concentration was associated with the genotype for the polymorphism. Most birth weight – risk factor relationships were stronger in the VC subjects; among others the birth weight – systolic blood pressure relationship: 1 kg lower birth weight was related to an 8.0 mmHg higher systolic blood pressure CONCLUSION: The polymorphism in the promoter region of the IGF-I gene is related to birth weight in men only, and to LDL concentration only. Furthermore, the genotype for this polymorphism modified the relationships between birth weight and the risk factors, especially for systolic and diastolic blood pressure
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