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Synthesis, Characterization, and Testing of High-Lithium-Density Composite Breeders

Solid tritium breeder materials must first and foremost have sufficiently high concentrations of lithium to enable a plant-scale tritium breeding ratio greater than 1:1. However, in addition to lithium content, such breeder materials must also meet other performance metrics including high tritium release rates, thermal conductivities, and irradiation damage tolerance. Perhaps most importantly, tritium breeders must maintain their mechanical integrity during reactor operation so as to avoid degradation which can jeopardize the functionality of the tritium breeder blanket module, which in most designs takes the form of a pebble bed geometry. Unfortunately, the mechanical robustness of most lithium-bearing ceramics under investigation for fusion applications is often inversely related to the lithium atom density. For example, a material such as lithium oxide (Li2O), which has one of the highest lithium atom densities, has a much lower mechanical splitting strength than lithium metatitanate (Li2TiO3), though Li2TiO3 has less than half the lithium atom density of Li2O. This work seeks to provide an alternative to monolithic ceramic tritium breeders, in the form of metal-reinforced composite tritium breeders. Specifically, composite tritium breeders have been synthesized combining Li2O with various ferrous metal reinforcements via electric field assisted sintering (EFAS), also known as spark plasma sintering (SPS). As the metal reinforcement content is increased, metallic networks are observed, via electron microscopy and X-ray computed tomography, to form throughout the composite material. Through destructive mechanical testing, even dilute metal reinforcement loading enables drastic mechanical strength improvements over pure Li2O while higher loadings give rise to quasi-ductile behavior and higher ultimate strengths than Li2TiO3 – while still maintaining a higher density of lithium atoms than Li2TiO3 and many other breeder candidates. In addition to microstructural characterization and mechanical testing, thermal property measurements and hydrogen permeability testing are underway to further assess the suitability of such composites for fusion reactor applications.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Chemical and isotopic evolution of flowback fluids from the Utica Gas Shale Play, Eastern Ohio USA

For this work, hydraulic fracturing flowback fluids were collected from two Utica/Point Pleasant well pads in eastern Ohio. One site was in the wet gas zone (UPPW), while the site ~50 km south consisted of four wells on the same pad in the dry gas zone (UPPS). Samples of input fluids also were collected before and during hydraulic fracturing. Flowback fluids are Na-Ca-Cl brines with total dissolved salt (TDS) concentrations that increase over several months from ~100 to 200 g/L. The slightly higher TDS of the dry gas fluids are in part due to recycled flowback used as input fluids, and in part due to lower volume of water used in hydraulic fracturing. Concentrations of most major ions (Ca 2+ , Mg 2+ , Na + , Sr2 + , Fe, Mn, Cl – , Br – ) are similar for the five wells sampled, although small but systematic changes occur in the major element ratios over time. Most notably, an increase in the Sr/Cl ratio corresponds to an increase in the 87 Sr/ 86 Sr ratio in the fluids, suggesting interactions with a more radiogenic Sr source in the subsurface. Dissolved Ba concentrations and Ra activities were different between the two sites, reflecting a high SO 4 2– fluid used at the UPPW site, and water-rock reactions occurring during hydraulic fracturing at the UPPS site. Water oxygen (δ 18 O) and hydrogen (δD) isotopes for input fluids used in the UPPW4 well and fresh water used for the UPPS wells fall on the Global Meteoric waterline (GMWL). Flowback fluids from both sites are relatively enriched in δ 18 O and δD compared to the input, but do not appear to follow a simple mixing trend, suggesting reaction and isotopic exchange with carbonates and fractionation due to imbibition in the rock. Cl isotopes, δ 37 Cl in the FP fluids varied from ~ –0.43 to +0.13‰, the largest variation was observed in the earlier stages of flowback, while in the later stages δ 37 Cl exhibited a small but systematic increase over time, suggesting diffusion control of isotopic composition. Some of the trace species measured (dissolved Fe, Mn, thiosulfate and organic acids) do not follow the same trends as the major ions, suggesting contributions from input fluids, or microbially mediated reactions are exerting control on their concentrations. Input water chemistry exerts an important control on the Sr and Ba concentrations in flowback water. High SO 4 2– in the input fluids used for hydraulically fracturing the wet gas well leads to precipitation of barite-celestite in flowback fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An analysis of the reflection spectrum of Jupiter from 1500 A to 1740 A

The Jovian reflection spectrum was modeled to determine the mixing ratios of C2H2, the upper limits to mixing ratios of C2H4, C4H2, and NH3, to detect the amount of dust in the stratosphere, and to measure the intensity of the H2 Lyman band dayglow emission. Data were gathered by the IUE spacecraft in the wavelength regions 1500 A to 1740 A, concentrating in the 10 mbar pressure region. Detailed Jupiter model parameters are provided. The mixing ratios of C2H2, C2H6, and C4H2 were found to be near 10 to the -7th, 6.6 x 10 to the -6th, and 2.9 x 10 to the -10th, respectively. Comparisons made with the Voyager 1 and 2 data indicated that the scale height of C2H2 in the 150-10 mbar region is double that of the bulk atmosphere. The data are significant for photochemical modeling of the upper Jovian atmosphere.

Gladstone, G. R.↗

Highly conducting ZnSe films by reactive magnetron sputtering

This paper presents the results of an effort to deposit high-conductivity ZnSe on glass and conducting SnO2-coated glass substrates by reactive magnetron sputter deposition, using pure metal sputter targets of Zn and dopants such as In, Ga, and Al. Clear yellow ZnSe films were successfully obtained. By using substrate temperatures as low as 150 C, cosputtered dopants, and sputter parameters and H2Se injection rates which maximize the Zn-to-Se ratio in the films, ZnSe bulk resistivities have been lowered by up to seven orders of magnitude, reaching values as low as 20 ohm cm. The most effective dopant to data has been In, cosputtered with Zn in amounts leading to In atomic concentrations as high as 1.4 percent. Atomic-absorption measurements show an average 49.9/48.9 ratio of Zn to Se.

Nouhi, A.↗

Highly sensitive 2D X-ray absorption spectroscopy via physics informed machine learning

Abstract Improving the spatial and spectral resolution of 2D X-ray near-edge absorption structure (XANES) has been a decade-long pursuit to probe local chemical reactions at the nanoscale. However, the poor signal-to-noise ratio in the measured images poses significant challenges in quantitative analysis, especially when the element of interest is at a low concentration. In this work, we developed a post-imaging processing method using deep neural network to reliably improve the signal-to-noise ratio in the XANES images. The proposed neural network model could be trained to adapt to new datasets by incorporating the physical features inherent in the latent space of the XANES images and self-supervised to detect new features in the images and achieve self-consistency. Two examples are presented in this work to illustrate the model’s robustness in determining the valence states of Ni and Co in the LiNi x Mn y Co 1-x-y O 2 systems with high confidence.

36 MATERIALS SCIENCE↗

High-Temperature Heat Transfer Fluid Circulator for Concentrating Solar Power Systems

A high temperature Heat Transfer Fluid circulator compressor with wide turn down ratio aerodynamic performance was designed, fabricated and tested for application with high pressure super Critical CO2 fluid capable of temperatures and pressures to >750°C and 25 MPa respectively. The modular system decoupled the drive motor system from an independent compressor shaft to provide thermal isolation between the high temperature compressor shaft and the lower temperature capable motor elements. While the thermal management approach appears to be viable there are potential losses in the secondary cooling flows that need to be taken into account and fine-tuned during operation in order to achieve desired overall system efficiencies. The system was also shown to be viable and dynamically stable throughout the entire operating speed range, thereby validating the overall system configuration and structural design approach used. Finally, while it was not possible to achieve specific PTC-10 test points, the compressor performance tests provide sufficient data to indicate that the compressor has the ability to achieve the required performance in practice. The two key factors affecting compressor design and cost are the maximum expected temperature and pressure. The maximum allowable temperatures for current state-of-the-art (SOA) motor driven compressor technology is limited to of approximately 150-200°C, but inlet temperatures >750 °C may be encountered. While the optimal efficiency of compression is in the transcritical region, some concepts require inlet pressures to 225 bar.

14 SOLAR ENERGY↗

Evolution of Gases and Particles from a Savanna Fire in South Africa

Airborne measurements of particles and gases fiom a 1000-ha savanna fire in South Africa are presented. These measurements represent the most extensive data set reported on the aging of biomass smoke. The measurements include total concentrations of particles (CN), particle sizes, particulate organic carbon and black carbon, light-scattering coefficients, downwelling UV fluxes, and mixing ratios for 42 trace gases and 7 particulate species. The ratios of excess nitrate, ozone, and gaseous acetic acid to excess CO increased significantly as the smoke aged over approximately 40-45 min, indicating that these species were formed by photochemistry in the plume. For 17 other species, the excess mixing ratio normalized by the excess mixing ratio of CO decreased significantly with ' smoke age. The relative rates of decrease for a number of chemical species imply that the average OH concentration in the plume was approximately 1.7 x l0(exp 7) molecules /cubic centimeter. Excess CN, normalized by excess CO, decreased rapidly during the first approximately 5 min of aging, probably due to coagulation, and then increased, probably due to gas-to-particle conversion. The CO-normalized concentrations of particles < 1.5 microns in diameter decreased, and particles >1.5 micron diameter increased, with smoke age. The spectral depletion of solar radiation by the smoke is depicted. The downwelling UV flux near the vertical center of the plume was about two-thirds of that near the top of the plume.

Hobbs, Peter V.↗

Comparison of near-background concentrations of Argon-37 and Xenon-133 in the Atmosphere

Radioisotopes of noble gases xenon and argon can be important indicators of underground nuclear explosions. The Comprehensive Nuclear-Test-Ban Treaty (CTBT) includes monitoring capabilities to identify potential nuclear explosions conducted in violation of the CTBT. This monitoring currently focuses on measurement of the xenon isotopes 133Xe, 135Xe, 131mXe and 133mXe. However, it is predicted that within 100 days of an underground nuclear explosion (UNE) 37Ar would be released to the atmosphere at higher concentrations than xenon isotopes (Haas et al. 2010) and with a higher signal to background ratio, depending on the radioxenon background levels. Therefore, inclusion of 37Ar measurement capabilities at atmospheric International Monitoring System (IMS) stations may represent an improvement in the capability to detect a nuclear explosion. At an IMS station, it could be difficult to determine what constitutes an elevated concentration as a result of an UNE without first understanding the expected range of background concentrations. This work describes our analysis of atmospheric samples for 37Ar to evaluate the range of background concentrations. Samples were collected at multiple locations, with approximately half coming from a sampler co-located with an IMS xenon monitoring station (RN75). The range of 37Ar concentrations measured in atmospheric air samples was relatively narrow; for samples considered detectable, the minimum and maximum measured concentrations were 0.56 and 2.3 mBq/m3, respectively. Comparison of 37Ar and 133Xe concentrations measured at the IMS station indicated some correlation between the measured concentrations. The results presented here demonstrate the capability to detect background concentrations of 37Ar in atmospheric air and provide a basis for potential implementation of 37Ar monitoring at IMS stations.

Fritz, Brad G.↗

Gas sampling method for determining pollutant concentrations in the flame zone of two swirl-can combustor modules

A gas sampling probe and traversing mechanism were developed to obtain detailed measurements of gaseous pollutant concentrations in the primary and mixing regions of combustors in order to better understand how pollutants are formed. The gas sampling probe was actuated by a three-degree-of-freedom traversing mechanism and the samples obtained were analyzed by an on-line gas analysis system. The pollutants in the flame zone of two different swirl-can combustor modules were measured at an inlet-air temperature of 590 K, pressure of 6 atmospheres, and reference velocities of 23 and 30 meters per second at a fuel-air ratio of 0.02. Typical results show large spatial gradients in the gaseous pollutant concentration close to the swirl-can module. Average concentrations of unburned hydrocarbons and carbon monoxide decrease rapidly in the downstream wake regions of each module. By careful and detailed probing, the effect of various module design features on pollutant formation can be assessed. The techniques presently developed seem adequate to obtain the desired information.

Duerr, R. A.↗

Influence of manganese abundances on iron and arsenic solubility in rice paddy soils

Arsenic (As) mobilization in rice paddy soils under fluctuating redox conditions is influenced by the biogeochemical cycling of redox sensitive elements such as iron (Fe) and manganese (Mn). Arsenic mobility in paddy soils is highly variable, and the influence of Mn abundances and Mn/Fe ratios on As mobility in these soils have received little attention. In this contribution, we developed a complementary set of field and laboratory experiments designed to evaluate the impact of Mn on interconnected Fe and As solubilization in rice paddy soils experiencing wetting-drying cycles through controlled irrigation. Porewater monitoring and synchrotron-based imaging and spectroscopy of thin sections prepared from an Arkansas paddy soil confirmed that As release was primarily governed by reductive dissolution of Fe (oxy)hydroxide phases. Experiments with laboratory soil microcosms amended with the synthetic nanocrystalline Mn oxide, δ-MnO 2 , showed that higher initial Mn/Fe inhibited Fe and As mobilization into porewater relative to unamended soil by up to 95% and 45%, respectively. Geochemical modeling suggests that pH increases driven by microbial MnO 2 reduction, in conjunction with microbial Fe- and sulfate-reduction in carbonate-rich porewater, enhanced the precipitation of siderite (FeCO 3(s) ), mackinawite (FeS (s) ), and potentially a Mn(II) arsenate phase. These secondary mineral phases likely played a greater role in controlling As solubilization than the role of Mn as a redox buffer regulating the redox conditions in the flooded soils. Field and laboratory experiments showed that alternate wetting and drying approaches with a single dry-down can be effective at reducing dissolved As concentrations in porewater through the oxidation of Fe. Differences in soil Mn/Fe ratios had no clear impact on the effectiveness of dry-downs as a strategy to reduce As mobilization.

54 ENVIRONMENTAL SCIENCES↗

The rate coefficient for the reaction NO2 + NO3 yielding NO + NO2 + O2 from 273 to 313 K

The ratio of rate constants for the reaction NO3 + NO yielding 2 NO2 (k3) and the reaction NO2 + NO3 yielding NO + NO2 + O2 (k4) were determined by measuring of NO and NO2 concentrations of NO and NO2 in an N2O5/NO2/N2 mixture over the temperature range 273-313 K. The measured ratio was found to be expressed by the equation k3/k4 = 387 exp(-1375/T). The results are consistent with those of Hammer et al. (1986).

Cantrell, Chris A.↗

Studies on cosmogenic nuclides in meteorites with regard to an application as potential depth indicators

Measurements of stable and radioactive spallation products in meteorites allow to investigate their histories, especially with respect to the exposure to galactic cosmic ray particles and the pre-atmospheric size of the object. While the concentrations of spallation products lead to the determination of exposure and terrestrial ages, production rate ratios are characteristic for the location of the sample in the meteorite. So, one of the aims of this investigation on meteorites is to obtain depth indicators from suitable pairs of cosmogenic nuclides. Because of the different depth profiles for nuclide productions it is necessary to determine the concentrations of a larger number of spallation products in aliquots of a single small sample. Such same sample measurements of Be-10 and light noble gases were performed on 15 ordinary chondrites (7 H- and 8 L-chondrites. Be-10 was determined by accelerator mass spectrometry and the noble gases were measured by static mass spectrometry. The results are summarized and discussed.

Sarafin, R.↗

An estimate of the influence of sediment concentration and type on remote sensing penetration depth for various coastal waters

Under the assumptions of collimated light, a homogenous water column, zero molecular scattering, and constant ratio of volume scattering function to scattering coefficient, estimates of the remote sensing depth parameter, Z90, are made for various coastal waters at 540 nm. Calculations indicate that sediment concentration and type have a strong influence on remote sensing depth when concentrations are below 5 mg/theta. Above 5 mg/theta, the absorption coefficient of the sediments becomes large in comparison to that of water, causing Z90 values to be less than 2 m with only small differences between various sediment types.

Whitlock, C. H.↗

Mobilization of mercury from contaminated creekbank soils

The industrial use of mercury (Hg) led to the contamination of numerous watersheds worldwide, including the East Fork Poplar Creek (EFPC) in Tennessee, USA. Mercury can accumulate in creek banks and floodplain soils and is mobilized into downstream environments due to erosion from precipitation and flooding. Here, this study aimed to evaluate the geochemical conditions contributing to the release of Hg from contaminated soils in this watershed. Bank soil samples from the EFPC watershed with total Hg concentrations ranging from 27.2 to 1,425 mg·kg −1 were used in a series of batch experiments with artificial creek water at a solid-to-solution ratio of 1:30 to assess Hg release. Additional experiments examined Hg release across different soil size fractions and solid-to-solution ratios, as well as the effect of dissolved organic matter and time on Hg mobilization. Mercury release ranged from 0.011 to 0.17% of the total soil Hg and is correlated with total Hg concentrations. Variations in release among size fractions suggested heterogeneous distribution of labile Hg species. Results indicated two distinct solubility regimes depending on solid-to-solution ratios. Dissolved organic matter enhanced Hg release, and time-dependent experiments showed that changes in mercury speciation could decrease dissolved Hg concentrations over time. Identifying conditions that promote Hg mobilization from contaminated soils improves our understanding of Hg fluxes into downstream environments. Key factors influencing mercury release include soil characteristics, water chemistry, and temporal changes in mercury speciation.

54 ENVIRONMENTAL SCIENCES↗

Some things we can infer about the Moon from the Composition of the Apollo 16 Regolith

Characteristics of the regolith of Cayley plains as sampled at the Apollo 16 lunar landing site are reviewed and new compositional data are presented for samples of less than 1 mm fines ('soils') and 1-2 mm regolith particles. As a means of determining which of the many primary (igneous) and secondary (crystalline breccias) lithologic components that have been identified in the soil are volumetrically important and providing an estimate of their relative abundances, more than 3 x 10(exp 6) combinations of components representing nearly every lithology that has been observed in the Apollo 16 regolith were systematically tested to determine which combinations best account for the composition of the soils. Conclusions drawn from the modeling include the following. At the site, mature soil from the Cayley plains consists of 64.5% +/- 2.7% components representing 'prebasin' materials: anorthosites, feldspathic breccias, and a small amount (2.6% +/- 1.5% of total soil) of nonmare, mafic plutonic rocks, mostly gabbronorites. On average, these components are highly feldspathic, with average concentrations of 3l-32% Al2O3 and 2-3% FeO and a molar Mg/(Mg+Fe) ratio of O.68. The remaining 36% of the regolith is syn- and postbasin material: 28.8% +/- 2.4% mafic impact-melt breccias (MIMBS, i.e., 'LKFM' and 'VHA basalts') created at the time of basin formation, 6.0% +/- 1.4% mare-derived material (impact and volcanic glass, crystalline basalt) with an average TiO2 concentration of 2.4%, and 1% postbasin meteoritic material. The MIMBs are the principal (80-90%) carrier of incompatible trace elements (rare earths, Th, etc.) and the carrier of about one-half of the siderophile elements and elements associated with mafic mineral phases (Fe, Mg, Mn, Cr, Sc). Most (71 %) of the Fe in the present regolith derives from syn- and postbasin sources (MIMBS, mare-derived material, and meteorites). Thus, although the bulk composition of the Apollo 16 regolith is nominally that of noritic anorthosite, the noritic part (the MIMBs) and anorthositic parts (the prebasin components) are largely unrelated.

Korotev, Randy L.↗

Carbon and silicon background impurity control in undoped GaN layers grown with trimethylgallium and triethylgallium via metalorganic chemical vapor deposition

The unintentional impurity incorporation in GaN epitaxial layers impacts the electrical conductivity and optical properties of the films grown by metalorganic chemical vapor deposition (MOCVD). It is critical to control impurity-related states for device structure development. The aim of this work is to contribute to the understanding of the reasons for the presence of certain background impurities. In this paper, the unintentional impurity incorporation of carbon, hydrogen, oxygen, and silicon in undoped (u-) GaN films grown by low-pressure MOCVD were studied. Background impurity concentrations were evaluated by secondary ion mass spectroscopy (SIMS) to optimize growth parameters including V/III ratio, growth temperature (T g ), growth pressure (P g ), and gallium (Ga) precursors of trimethylgallium (TMG) or triethylgallium (TEG). Unintentional [C] and [Si] incorporations are found to be highly dependent on the growth parameters. Further, for the same growth conditions, u-GaN films grown with a TEG precursor exhibited a lower background concentration of C compared to that of GaN grown with TMG. However, the lowest background [C] achieved was grown with TMG using optimized conditions and exhibited [C]<4×10 15 cm -3 which was at the detection limit of the SIMS measurement. These results were measured for a u-GaN layer grown with TMG at 200 Torr, 1030°C, and a V/III of 3700. The lowest background [Si] of 4×10 15 cm -3 was achieved by growing with TMG at 200 Torr, 1000°C, and V/III of 650.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Notch Sensitivity of Woven Ceramic Matrix Composites Under Tensile Loading: An Experimental, Analytical, and Finite Element Study

The stress concentrations associated with circular notches and subjected to uniform tensile loading in woven ceramic matrix composites (CMCs) have been investigated for high-efficient turbine engine applications. The CMC's were composed of Nicalon silicon carbide woven fabric in SiNC matrix manufactured through polymer impregnation process (PIP). Several combinations of hole diameter/plate width ratios and ply orientations were considered in this study. In the first part, the stress concentrations were calculated measuring strain distributions surrounding the hole using strain gages at different locations of the specimens during the initial portion of the stress-strain curve before any microdamage developed. The stress concentration was also calculated analytically using Lekhnitskii's solution for orthotropic plates. A finite-width correction factor for anisotropic and orthotropic composite plate was considered. The stress distributions surrounding the circular hole of a CMC's plate were further studied using finite element analysis. Both solid and shell elements were considered. The experimental results were compared with both the analytical and finite element solutions. Extensive optical and scanning electron microscopic examinations were carried out for identifying the fracture behavior and failure mechanisms of both the notched and notched specimens. The stress concentration factors (SCF) determined by analytical method overpredicted the experimental results. But the numerical solution underpredicted the experimental SCF. Stress concentration factors are shown to increase with enlarged hole size and the effects of ply orientations on stress concentration factors are observed to be negligible. In all the cases, the crack initiated at the notch edge and propagated along the width towards the edge of the specimens.

Haque, A.↗

Probing electronic and dielectric properties of ultrathin Ga 2 O 3 /Al 2 O 3 atomic layer stacks made with in vacuo atomic layer deposition

Ultrathin (1–4 nm) films of wide-bandgap semiconductors are important to many applications in microelectronics, and the film properties can be sensitively affected by defects especially at the substrate/film interface. Motivated by this, an in vacuo atomic layer deposition (ALD) was developed for the synthesis of ultrathin films of Ga 2 O 3 /Al 2 O 3 atomic layer stacks (ALSs) on Al electrodes. It is found that the Ga 2 O 3 /Al 2 O 3 ALS can form an interface with the Al electrode with negligible interfacial defects under the optimal ALD condition whether the starting atomic layer is Ga 2 O 3 or Al 2 O 3 . Such an interface is the key to achieving an optimal and tunable electronic structure and dielectric properties in Ga 2 O 3 /Al 2 O 3 ALS ultrathin films. In situ scanning tunneling spectroscopy confirms that the electronic structure of Ga 2 O 3 /Al 2 O 3 ALS can have tunable bandgaps (E g ) between ~2.0 eV for 100% Ga 2 O 3 and ~3.4 eV for 100% Al 2 O 3 . With variable ratios of Ga:Al, the measured E g exhibits significant non-linearity, agreeing with the density functional theory simulation, and tunable carrier concentration. Furthermore, the dielectric constant of ultrathin Ga 2 O 3 /Al 2 O 3 ALS capacitors is tunable through the variation in the ratio of the constituent Ga 2 O 3 and Al 2 O 3 atomic layer numbers from 9.83 for 100% Ga 2 O 3 to 8.28 for 100% Al 2 O 3 . The high ε leads to excellent effective oxide thickness ~1.7–2.1 nm for the ultrathin Ga 2 O 3 /Al 2 O 3 ALS, which is comparable to that of high-K dielectric materials.

36 MATERIALS SCIENCE↗