Neutronic performance characteristics of different LEU fuels in a proposed NIST research reactor.

As a potential replacement for the National Bureau Standards Reactor (NBSR) at the U.S. National Institute of Standards and Technology (NIST), a conceptual design of a new reactor with a horizontally-split core has recently been studied using low-enriched uranium (LEU) silicide dispersion (U3Si2/Al) fuel. In this paper, the neutronics calculations of the proposed NIST reactor with other two low-enriched U-Mo fuels (U-10Mo monolithic fuel and U-7Mo/Al dispersion fuel) were performed, and the results were compared to that of the U3Si2/Al fuel, with the objective of identifying the best fuel candidate for the reactor cycle length and maximum cold neutron production. To make consistent comparisons, fuel inventories for multi-cycle equilibrium cores were produced for each fuel based on a 30 d reactor cycle at 20 MW thermal power. With its very high uranium density, the potential to load more uranium in the core with U-10Mo monolithic fuel was explored with test cases using an alternate fuel management scheme, a higher power level (30 MW), or a longer cycle (45 d). The research results indicate similar neutronics performance characteristics of the three LEU fuel options in the proposed NIST reactor with the same power level. However, the ability to load more fuel in the reactor with the U-10Mo option allows additional flexibility in the reactor design and could lead to other optimizations that maximize cold neutron production.

Benchmarking the Energy Intensity of Small Water Resource Recovery Facilities.

To enable small communities to benchmark the energy efficiency of their water resource recovery facilities (also known as wastewater treatment facilities), multiple linear regression models of electric and overall energy intensity (kWh/m3) were created using data from Nebraska and Pennsylvania. Key variables found to be significant include: facility type, supplemental energy usage for sludge treatment, average flow, percent design flow, climate controlled floor area, effluent NH3-N, and influent CBOD5. The results show that energy use models for small systems differ from those for large facilities and that regulatory changes can affect energy usage. Step changes in the data for facilities that changed operators highlight the importance of operational decisions on energy efficiency for small facilities serving fewer than 10,000 people. Differences were observed between the models of data from specific states. Although these models may not include all factors that account for variability in energy use, they can provide a reference benchmark for small WRRFs.

Crystallization kinetics of cerium oxide nanoparticles formed by spontaneous, room-temperature hydrolysis of cerium(iv) ammonium nitrate in light and heavy water.

A stable sol of cerium oxide nanoparticles forms spontaneously when cerium(iv) ammonium nitrate (CAN) is dissolved in room-temperature water at mM concentrations. Electron microscopy experiments reveal the formation of highly crystalline cerium oxide particles several nm in diameter and suggest that they are formed from amorphous particles that are similar in size. Under the low pH conditions of the experiments, the nanoparticles form a stable dispersion and show no evidence of aggregation, even many months after synthesis. The absence of particles large enough to scatter light significantly makes it possible to observe the crystallization kinetics through dramatic changes in the UV-visible absorption spectra that occur during solution aging. Measurements show that the cerium oxide nanocrystals are formed roughly an order of magnitude more slowly in D2O than in H2O solution. This large solvent kinetic isotope effect (kH/kD ∼ 10), which is reported here for the first time for the crystallization of a solid metal oxide phase, indicates a rate-determining proton transfer reaction, which is assigned to the conversion of hydroxy to oxo bridges. In D2O solution, the absorption per mole of cerium ions increases by over 400% at 290 nm as the weakly absorbing precursor phase is transformed into nanocrystalline cerium oxide. An isosbestic point is detected at 368 nm, and the absorption spectra can be modeled throughout aging by the sum of spectra of just two interconverting species. Preliminary ultrafast transient absorption experiments confirm that the optical properties of the amorphous precursors differ greatly from those of the final, nanocrystalline phase. Crystallization of CeO2 from CAN in water has much in common with the crystallization of iron oxides from iron(iii) salts, including the importance of non-classical nucleation and growth pathways. It is an outstanding system for studying the poorly understood events that cause molecularly solvated ions to self-assemble into nanocrystals, following hydrolysis. At the same time, the strong susceptibility of CAN to spontaneously form CeO2 nanocrystals under the mildest of reaction conditions indicates that caution is needed when working with this common sacrificial oxidant.

A Small Spot, Inert Gas, Ion Milling Process as a Complementary Technique to Focused Ion Beam Specimen Preparation.

This paper reports on the substantial improvement of specimen quality by use of a low voltage (0.05 to ~1 keV), small diameter (~1 µm), argon ion beam following initial preparation using conventional broad-beam ion milling or focused ion beam. The specimens show significant reductions in the amorphous layer thickness and implanted artifacts. The targeted ion milling controls the specimen thickness according to the needs of advanced aberration-corrected and/or analytical transmission electron microscopy applications.

Identifying and imaging polymer functionality at high spatial resolution with core-loss EELS.

Electron energy loss spectroscopy (EELS) is a proven tool for probing materials chemistry at high spatial resolution. Core-loss EELS fine structure should allow measurement of local polymer chemistry. For organic materials, sensitivity to radiolysis is expected to limit the resolution achievable with EELS: but core-loss EELS has proven difficult at any resolution, yielding inconsistent spectra that compare unfavorably with theoretically analogous x-ray absorption spectra. Many of the previously identified shortcomings should not be limiting factors on modern equipment. This study establishes that EELS can generate identifiable carbon K-edge spectra for a range of common polymer types and chemistry, and demonstrates fine structure features matching prior x-ray absorption spectra. EELS fine structure features broaden intuitively with the instrument's energy resolution, and beam-induced features are readily differentiated by collecting spectra at a series of doses. The results are demonstrated with spectrum images of a model polymer blend, and used to estimate practical pixel sizes that can be used for mapping core-loss EELS as a function of electron dose.

Manipulating acoustic and plasmonic modes in gold nanostars.

In this contribution experimental evidence of plasmonic edge modes and acoustic breathing modes in gold nanostars (AuNSs) is reported. AuNSs are synthesized by a surfactant-free, one-step wet-chemistry method. Optical extinction measurements of AuNSs confirm the presence of localized surface plasmon resonances (LSPRs), while electron energy-loss spectroscopy (EELS) using a scanning transmission electron microscope (STEM) shows the spatial distribution of LSPRs and reveals the presence of acoustic breathing modes. Plasmonic hot-spots generated at the pinnacle of the sharp spikes, due to the optically active dipolar edge mode, allow significant intensity enhancement of local fields and hot-electron injection, and are thus useful for size detection of small protein molecules. The breathing modes observed away from the apices of the nanostars are identified as stimulated dark modes - they have an acoustic nature - and likely originate from the confinement of the surface plasmon by the geometrical boundaries of a nanostructure. The presence of both types of modes is verified by numerical simulations. Both these modes offer the possibility of designing nanoplasmonic antennas based on AuNSs, which can provide information on both mass and polarizability of biomolecules using a two-step molecular detection process.

Heterodimeric Plasmonic Nanogaps for Biosensing.

We report the study of heterodimeric plasmonic nanogaps created between gold nanostar (AuNS) tips and gold nanospheres. The selective binding is realized by properly functionalizing the two nanostructures; in particular, the hot electrons injected at the nanostar tips trigger a regio-specific chemical link with the functionalized nanospheres. AuNSs were synthesized in a simple, one-step, surfactant-free, high-yield wet-chemistry method. The high aspect ratio of the sharp nanostar tip collects and concentrates intense electromagnetic fields in ultrasmall surfaces with small curvature radius. The extremities of these surface tips become plasmonic hot spots, allowing significant intensity enhancement of local fields and hot-electron injection. Electron energy-loss spectroscopy (EELS) was performed to spatially map local plasmonic modes of the nanostar. The presence of different kinds of modes at different position of these nanostars makes them one of the most efficient, unique, and smart plasmonic antennas. These modes are harnessed to mediate the formation of heterodimers (nanostar-nanosphere) through hot-electron-induced chemical modification of the tip. For an AuNS-nanosphere heterodimeric gap, the intensity enhancement factor in the hot-spot region was determined to be 106, which is an order of magnitude greater than the single nanostar tip. The intense local electric field within the nanogap results in ultra-high sensitivity for the presence of bioanalytes captured in that region. In case of a single BSA molecule (66.5 KDa), the sensitivity was evaluated to be about 1940 nm/RIU for a single AuNS, but was 5800 nm/RIU for the AuNS-nanosphere heterodimer. This indicates that this heterodimeric nanostructure can be used as an ultrasensitive plasmonic biosensor to detect single protein molecules or nucleic acid fragments of lower molecular weight with high specificity.

Multimodal Evidence of Mesostructured Calcium Fatty Acid Deposits in Human Hair and Their Role on Hair Properties.

We provide the first conclusive evidence for the presence of exogenous calcium fatty acid deposits, which not only form in-between the cuticle layers in the lipid-rich cell membrane complex, but also grow to dimensions large enough to cause the structure to bulge, thereby impacting the optical and mechanical properties of the hair fiber. The composition and phase of these deposits were probed using a multimodal analytical approach with spatially resolved techniques including synchrotron micro X-ray fluorescence coupled with X-ray scattering, focused ion beam (FIB)-scanning electron microscopy (SEM), scanning transmission electron microscopy, X-ray energy dispersive spectroscopy, and Fourier transform infrared and Raman imaging where the collective analysis is consistent with a meso-phase composed of calcium C16/C18 saturated fatty acids from natural sources such as sebum. X-ray microtomography and serial "slice and view" FIB/SEM both reveal the location and volumetric shape of the deposits.

rBPI(10-193) is secreted by CHO cells and retains the activity of rBPI21.

rBPI23, a recombinant N-terminal fragment of human bactericidal/permeability-increasing protein (BPI), kills Gram-negative bacteria and neutralizes endotoxin. rBPI21, a variant in which cysteine 132 is changed to alanine, retains the activities of rBPI23. Analysis of certain purified rBPI21 preparations revealed that some of the molecules had lost nine amino acids from the amino terminus. To explore the effect of this modification on structure and activity, we cloned and expressed a variant of rBPI21, designated rBPI(10-193), which lacks the first nine amino acids. A monoclonal antibody believed to recognize the amino terminus of rBPI21 cross-reacted with rBPI21, but not with rBPI(10-193) or full length recombinant BPI (rBPI). These results demonstrated that the antibody recognizes the first nine amino acids of rBPI21 and that this region of the holoprotein (rBPI) is inaccessible to the antibody (as suggested by the known 3-D structure). Purified rBPI(10-193) and rBPI21 were similarly potent in in vitro assays measuring bactericidal, endotoxin binding and neutralization activities. In a mouse model of lethal bacteremia, rBPI(10-193) and rBPI21 were similarly potent whereas in a mouse endotoxin challenge model, rBPI(10-193) appeared to be at least 2-fold more potent than rBPI21. In conscious rats, a rapid bolus dose of 40 mg/kg of rBPI21 caused a significant transient decrease in blood pressure while the same dose of rBPI(10-193) caused no blood pressure decrease. We conclude from these studies that the first nine amino acids of rBPI21 are not essential for the anti-infective and endotoxin-neutralizing activities of BPI.

Computational Studies of Nido-8-Vertex Boranes, Carboranes, Heteroboranes, and the Lewis Base Adduct nido-B(8)H(10)L.

An extensive investigation of boranes, carboranes, and heteroboranes falling into the nido-8-vertex electron-count class has been carried out using ab initio methods. The results of this study indicate a nido six-membered open face geometry, ni-8, is usually the preferred configuration over a nido five-membered open face geometry, ni-8. In only two systems, B(8)H(9)(3)(-) and OB(7)H(7)(2)(-), is a ni-8 geometry calculated to be of lowest energy. Attempts to test empirical carbon placement rules along with the skeletal bridge and endo-hydrogen location preferences were also evaluated. The results indicate the nido-8-vertex family is not ideally suited for the application of these empirical rules alone. This is probably due to the open face of these clusters not having homogeneous vertexes and/or not being "rigid". The ab initio/IGLO/NMR method was applied to the disputed B(8)H(10).L and C(4)B(4)H(8) systems. The known nido-B(8)H(10).NEt(3) was found to have a ni-8 geometry with a fluxional bridge hydrogen. The calculations confirmed that the known alkylated derivatives of the nido-C(4)B(4)H(8) carboranes have ni-8 configurations in solution. In an investigation of B(8)H(12), a previously unreported isomer of C(2) symmetry was found which high-level G2MP2 calculations indicate is only 1.6 kcal/mol higher in energy than the lowest energy C(s)() symmetry isomer. This C(2) symmetry isomer is likely the higher energy intermediate in the degenerate interconversion of B(8)H(12) into its mirror image. The transition state for the conversion of the C(s)() to the C(2) symmetry isomer has C(1) symmetry with a barrier of 2.1 kcal/mol at the MP2/6-31G level of ab initio theory.

Ab Initio/IGLO/NMR Investigation of nido-C(4)B(7)H(11) Configurations: Structural Assignment of the Three Known Isomers and Reconfirmation of Empirical Carbon Placement Patterns.

The ab initio/IGLO/NMR method has been successfully applied to establish the structures of the three known isomers of nido-C(4)B(7)H(11). The method confirms the previously proposed structure, nido-7,8,9,10-C(4)B(7)H(11), 1a, as one of the three known isomers. Of four candidates considered for the second isomer, one of the previously proposed structures, nido-1,7,8,10-C(4)B(7)H(11), 2b, is selected. Of four candidates considered for the third isomer, structure nido-2,7,9,10-C(4)B(7)H(11), 3b, which had not been previously proposed, is established. The relative order of stability is 1a > 2b > 3b. A comparison of the relative energies of the nine cage structures considered in this study shows that, in complete agreement with previous empirically determined patterns, the most stable structures are those in which the carbons occupy low coordinate sites. This preference is more important than avoiding carbon-carbon connections.

HUBBLE SPACE TELESCOPE FAR ULTRAVIOLET SPECTROSCOPY OF THE RECURRENT NOVA T PYXIDIS.

With six recorded nova outbursts, the prototypical recurrent nova T Pyxidis (T Pyx) is the ideal cataclysmic variable system to assess the net change of the white dwarf mass within a nova cycle. Recent estimates of the mass ejected in the 2011 outburst ranged from a few ~10-5M⊙ to 3.3 × 10-4M⊙, and assuming a mass accretion rate of 10-8-10-7M⊙ yr-1 for 44 yr, it has been concluded that the white dwarf in T Pyx is actually losing mass. Using NLTE disk modeling spectra to fit our recently obtained Hubble Space Telescope COS and STIS spectra, we find a mass accretion rate of up to two orders of magnitude larger than previously estimated. Our larger mass accretion rate is due mainly to the newly derived distance of T Pyx (4.8 kpc, larger than the previous 3.5 kpc estimate), our derived reddening of E(B - V) = 0.35 (based on combined IUE and GALEX spectra), and NLTE disk modeling (compared to blackbody and raw flux estimates in earlier works). We find that for most values of the reddening (0.25 ≤ E(B-V) ≤ 0.50) and white dwarf mass (0.70 M⊙ ≤ Mwd ≤ 1.35 M⊙) the accreted mass is larger than the ejected mass. Only for a low reddening (~0.25 and smaller) combined with a large white dwarf mass (0.9 M⊙ and larger) is the ejected mass larger than the accreted one. However, the best results are obtained for a larger value of reddening.

Nature of the interfaces between the constituent phases in the high entropy alloy CoCrCuFeNiAl.

The interfaces between the phase separated regions in the dendritic grains of laser-deposited samples of the high entropy alloy CoCrCuFeNiAl have been studied using aberration-corrected analytical (scanning) transmission electron microscopy ((S)TEM). The compositional variations have been determined using energy dispersive x-ray spectroscopy (EDS) in (S)TEM. It was found that between B2, consisting mainly of Al, Ni, Co, and Fe, and disordered bcc phase, consisting mainly of Cr and Fe, there is a transition region, approximately 1.5 nm in width, over which the chemical composition changes from the B2 to that of the bcc phase. The crystal structure of this interfacial region is also B2, but with very different sublattice occupancy than that of the adjacent B2 compound. The structural aspects of the interface between the ordered B2 phase and the disordered bcc phase have been characterized using high angle annular dark-field (HAADF) imaging in STEM. It has been determined that the interfaces are essentially coherent, with the lattice parameters of the two B2 regions and the disordered bcc phase being more or less the same, the uncertainty arising from possible relaxations from the proximity of the surfaces of the thin foils used in imaging of the microstructures. Direct observations show that there is a planar continuity between all three constituent phases.

Data dependent systems technique: a methodology with an application to human systems.

The objective of this paper is to introduce the application of Data Dependent Systems (DDS) methodology to the field of ergonomics. Many current techniques in ergonomics utilize static models, which can have significant limitations. DDS is a stochastic modelling and analysis technique that can be used to capture the dynamics of a system through quantitative analysis of the available data. DDS has been successfully applied to the analysis of manufacturing processes and the surfaces generated by those processes. In this research, DDS was used to analyse time-based hand-skin temperature data for the evaluation of two types of glove liners to be used underneath latex gloves. DDS was able to capture the differences between the two glove liners and the two subjects. The implications of the results and the potential of the DDS methodology are discussed.