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Nucleation and growth behaviors of hydriding and dehydriding reactions of Mg2Ni

Highlights: • Preparation of Mg{sub 2}Ni by sintering under Ar in a stainless steel crucible at 823 K. • Application of Johnson-Mehl equation for the nucleation and growth mechanism. • Reverse dependences on temperature of initial hydriding rate and quantity of H absorbed for 60 min. • Hydriding and dehydriding reactions progressed by a nucleation and growth mechanism. - Abstract: Mg{sub 2}Ni has drawn attention due to its high reaction rates, good reversibility, and possibility to be applied as a negative electrode in the Ni-MH (metal hydride) batteries. Mg{sub 2}Ni samples were prepared by sintering under Ar in a stainless-steel crucible at 823 K. Johnson-Mehl equation for nucleation and growth mechanism was applied to the behaviors of hydriding and dehydriding reactions of Mg{sub 2}Ni. At 571 K under 30 bar H{sub 2}, the activation of the Mg{sub 2}Ni sample was completed at the number of cycles of three (n = 3). At n = 3, hydrided fractions of the sample were 0.51 (1.92 wt% H) at 0.50 min and 0.90 (3.38 wt% H) at 2.00 min. Reverse temperature dependences of the initial hydriding rate and the quantity of hydrogen absorbed for 60 min appeared from 571 K to 620 K. Hydriding and dehydriding reactions progressed by the nucleation and growth mechanism and could be expressed by the Johnson-Mehl equation.

36 MATERIALS SCIENCE↗

Sol-Gel synthesis of MgO-SiO2 glass compositions having stable liquid-liquid immiscibility

MgO-SiO2 glasses containing up to 15 mol % MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol % MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol % MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol %) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

Bansal, Narottam P.↗

Measurement of Residual Stresses in Different Thicknesses of Laser Shock Peened Aluminium Alloy Samples

This study focused on depth-resolved residual stress results determined with a number of complementary techniques on Laser Shock Peening (LSP) treated aluminium alloy 7075-T651 samples with different thicknesses (6 mm and 1.6 mm). Samples were prepared from a single commercially produced rolled plate that was then treated with LSP. Residual stresses were measured using Laboratory X-Ray Diffraction (LXRD), Incremental Hole Drilling (IHD), Neutron Diffraction (ND) and Synchrotron XRD (SXRD). The LSP treatment resulted in the establishment of compressive residual stresses that varied rapidly in the near surface region. The compressive stresses extended up to 1.5 mm in depth in the 6 mm thick sample. Some surface stress relaxation was observed in the first 25 μm, but substantially large stresses existed at 50 mu m. Finally, this investigation strongly motivated why residual stress profiles should be obtained using a variety of techniques.

36 MATERIALS SCIENCE↗

Sol-gel synthesis of magnesium oxide-silicon dioxide glass compositions

MgO-SiO2 glasses containing up to 15 mol pct MgO, which could not have been prepared by the conventional glass melting method due to the presence of stable liquid-liquid immiscibility, were synthesized by the sol-gel technique. Clear and transparent gels were obtained from the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) and magnesium nitrate hexahydrate when the water/TEOS mole ratio was four or more. The gelling time decreased with increase in magnesium content, water/TEOS ratio, and reaction temperature. Magnesium nitrate hexahydrate crystallized out of the gels containing 15 and 20 mol pct MgO on slow drying. This problem was partially alleviated by drying the gels quickly at higher temperatures. Monolithic gel samples were prepared using glycerol as the drying control additive. The gels were subjected to various thermal treatments and characterized by several methods. No organic groups could be detected in the glasses after heat treatments to approx. 800 C, but trace amounts of hydroxyl groups were still present. No crystalline phase was found from X-ray diffraction in the gel samples to approx. 890 C. At higher temperatures, alpha quartz precipitated out as the crystalline phase in gels containing up to 10 mol pct MgO. The overall activation energy for gel formation in 10MgO-90SiO2 (mol pct) system for water/TEOS mole ratio of 7.5 was calculated to be 58.7 kJ/mol.

Bansal, Narottam P.↗

Industrialization of Hydrogen Getter for Nuclear Waste Transportation Application - 18189

The hydrogen risk generated by radiolysis of organic compounds during a nuclear waste transport is a major issue. The use of irreversible getters is considered to limit this risk. We previously worked on MnO{sub 2}/Ag{sub 2}O getter, in order to better understand the trapping phenomenon and to ensure its reliability. We demonstrated that chemisorption of hydrogen, which is required for its application, has been shown by using several characterization techniques. Proton insertion mechanism in MnO{sub 2} has been elucidated by pair distribution function analysis. Gamma irradiation up to 4 MGy has been performed on MnO{sub 2}/Ag{sub 2}O hydrogen getter and shown that chemical and crystallographic properties are not influenced under gamma irradiation. After those fundamentals studies, industrialization of MnO{sub 2}/Ag{sub 2}O getter preparation has been studied in order to have available getter materials for industrial applications with large amounts of MnO{sub 2}/Ag{sub 2}O powder. The preparation of hydrogen getter at laboratory scale consists of mixing commercial powders with various chemical treatments (grounding, moistening, sonication and drying). The industrialization strategy consists of preparing firstly on a laboratory scale and then increasing the getter preparation up to several kilograms. At each preparation step, hydrogen trapping experiments are performed to confirm the expected performance of getter materials. Several characterizations techniques have been performed (X-Ray Diffraction, Specific Surface Area...) to analyse the properties of the getter and have shown that no impact of upscale preparation is evidenced. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

B/PS bulges in DESI Legacy edge-on galaxies – I. Sample building

ABSTRACT We present the biggest up-to-date sample of edge-on galaxies with boxy/peanut-shaped (B/PS) bulges and X-structures. The sample was prepared using images from the Dark Energy Spectroscopic Instrument (DESI) Legacy catalogue and contains about 2000 galaxies. To find suitable candidates in catalogue, we made the assumption that the residues (original images minus model) of galaxies with B/PS bulges should exhibit a characteristic X-shape. Galaxies with such features were selected by eye and then used as input data for a neural network training, which was applied to a bigger sample of edge-on galaxies. Using the available data and the photometric models from the literature, we investigated the observational and statistical properties of the sample created. Comparing the B/D ratios for galaxies with and without B/PS bulges, we found that the B/D ratio for galaxies from our sample is statistically higher, with typical values in the range ≈0.2–0.5 depending on the decomposition procedure. We studied how the opening angles φ of the X-structure and the length of its rays are distributed in the formed sample and found them to be consistent with previous measurements and predictions from N-body models, e.g. $\varphi \gtrsim 25{^\circ }$, but measured here for a much larger number of galaxies. We found a sharp increase in the B/PS bulge fraction for stellar masses log M⋆ ≳ 10.4, but for edge-on galaxies, which complements the results of previous works. The sample can be used in future work to test various bar models and their relationship with B/PS bulges, as well as to study their stability and evolution.

79 ASTRONOMY AND ASTROPHYSICS↗

The influence of humic acid and colloidal silica on the sorption of U(VI) onto SRS Sediments Collected from the F/H Area - 15499

Between 1955 and 1988, the F/H Area Seepage Basins located in the center of SRS received approximately 6,814,000 m{sup 3} of acidic waste solutions containing radionuclides and dissolved metals. Uranium (VI) is a key contaminant of concern in groundwater associated with the basins. The pump-and-treat water treatment unit designed and built in 1997 to remove metals and radionuclides eventually became less effective, prompting research for new remedial alternatives. The pump-and-treat system was discontinued in 2004, replaced with a funnel-and-gate system in which base solutions are injected at the gates to raise pH. To take advantage of the potential formation of uranium silicate minerals, Florida International University - Applied Research Center (FIU-ARC), in collaboration with Savannah River National Laboratory (SRNL), is conducting an investigation into a base containing sodium silicate to evaluate whether these solutions have sufficient alkalinity to correct the acidic nature of the aquifer sediments. The research was extended to investigate if U(VI) is bound to colloidal silica and if any synergy exists between humic acid (HA) and colloidal Si that would influence the removal of uranium. Humic substances (HS) are a major component of soil organic matter and are known for their abilities to influence the migration behavior and fate of heavy metals. Studies showed that HA function as an important ion exchange and metal-complexing ligand, carrying a large number of functional groups with high complexing capacity that can greatly affect the mobility behavior of actinides in natural systems. The study investigates if there are any synergistic interactions between U(VI) ions, humic acid and colloidal silica under oxidized conditions and studies the influence of HA and Si on the sorption of U(VI) onto sediments collected from the F/H Area. The experiments also evaluated the effects of different environmental variables such as pH, presence of U(VI) and varying concentrations of HA on the sorption behavior of U(VI) in multi-component batch systems in the pH range between 3 and 8. Several background sediment samples were collected at SRS from archived cores obtained during installation of the well FSB 91C and used for preparation of triplicate samples. The experimental matrix was set up as follows: - Batch 1: Si (3.5 mM) + U (VI) (0.5 ppm) (no sediments and no HA); - Batch 2: Si (3.5 mM) + U (VI) (0.5 ppm) + HA (10 ppm) (no sediments); - Batch 3: U (VI) (0.5 ppm) + HA (10 ppm) (no Si and no sediments); - Batch 4: Sediments + Si (3.5 mM) + U (VI) (0.5 ppm) (no HA); - Batch 5: Sediments + Si (3.5 mM) + U (VI) (0.5 ppm) + HA; - Batch 6: Sediments + U (VI) (0.5 ppm) + HA, (no Si); - Batch 7: Sediments + U (VI) (0.5 ppm) (no Si and no HA). All samples were prepared in triplicate 50-mL conical tubes. All control and experimental tubes were vortexed and kept on a shaker for 24 h at 100 rpm and room temperature. Results showed that the sediment-bearing batches typically exceeded the performance of non-sediment batches. Results showed that the sorption of U(VI) onto sediments was influenced by the pH and the presence of HA. At low pH 3, the addition of HA slightly enhances U(VI) sorption compared to the HA-free samples. This result is consistent with other studies; in the acidic pH range, the addition of HA slightly enhances U(VI) sorption relative to the HA-free system. Conversely, in the pH range of 4 to 7, the sorption of U(VI) on Si was reduced in the presence of HA in comparison to the system without HA. In subsequent experiments the concentration of HA will be increased to 50 ppm. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

FY23 Update: Aerosol Sampling for the Canister Deposition Field Demonstration

This report describes the results of preliminary testing of aerosol monitoring equipment that will be used to continuously monitor the aerosol source term for the multi-year Canister Deposition Field Demonstration (CDFD). These data are required inputs for the development and validation of models for the deposition of dust and potentially corrosive salts on the surface of spent nuclear fuel (SNF) dry storage canisters. Surface salt loads correlate with the extent of corrosion damage on a metal surface, and potentially to the likelihood and timing of initiation of stress corrosion cracks. Aerosols will be monitored at the CDFD site using three instruments. A Dekati ® ELPI+ cascade impactor will be used for real-time monitoring of aerosol particle sizes. It will also collect dust in 14 size bins on impactor targets that can be chemically analyzed to determine the soluble salts present as a function of particle size. However, this instrument can only measure dried aerosols, with a diameter of <10 µm. The second instrument is a Topas laser particle size spectrometer, which provides real-time monitoring of aerosol particle sizes up to ~40 µm in size. It monitors both the ambient (potentially deliquesced) aerosol particle size distributions required for the dust deposition models and the distributions of the equivalent dried particles, allowing correlation with the Dekati ® data. However, it does not discriminate between inert dust particles and salt aerosols, and it does not retain samples of the different particle sizes for later analysis. The third instrument that will monitor aerosols at the CDFD site is a Clean Air Status and Trends Network (CASTNET) tower, which uses a multiple canister system to collect weekly samples for analysis to total suspended aerosol particle compositions and atmospheric gas concentrations. This status report describes work in FY23 to develop the capabilities for using these tools. In two training exercises, the cascade impactor and laser particle sizer were deployed in two different testing environments, one indoor and one outdoor. For the cascade impactor, the tests provided opportunities for the operators to familiarize themselves with impactor substrate preparation, and post-test sample removal and analysis. For the laser particle sizer, the tests were used to evaluate different instrument parameters, to determine the most appropriate settings for capturing transient events. Data and samples were collected for weeks to months for each test, and the results are presented here. In addition to the preliminary testing, contracts were developed with WSP Analytical Labs for sample preparation and analysis of the cascade impactor samples. The impactor tower from outdoor test was delivered to WSP and used to train the staff there in disassembly, sample extraction, sample analysis, and tower reassembly with new target substrates. These are tasks that WSP will be performing routinely for the CDFD project. The CASTNET system cannot be purchased or tested until an actual site has been selected for the CDFD test. Work for this FY has been restricted to preparation of contracts for purchasing the CASTNET tower, and for sample analysis, once the tower is in operation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Effect of cobalt doping on structural, optical and dielectric properties of TiO{sub 2}

A diluted magnetic semiconductor (DMS) Co-doped TiO{sub 2} is studied here for dielectric properties. Undoped and Co-doped TiO{sub 2} samples were prepared by sol-gel method. The formation of anatase phase has been investigated by X-ray diffraction (XRD). UV-Vis absorption spectra show that the incorporation of Co into the TiO{sub 2} lattice leads to redshift in the optical response, as well as lowering the band gap energy. The defect oriented emissions were seen from photoluminescence (PL) study. The dielectric properties of pure and Co-doped TiO{sub 2} samples were studied in the frequency range of 10 Hz to 10 MHz at different temperatures. Doped sample exhibit low dielectric constant when compared with host system. Both dielectric constant and ac conductivity increases with temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Survey of probable micrometer-sized Earth-orbital debris fragments in the NASA-JSC cosmic dust sample collection

A program to collect extraterrestrial dust samples from the stratosphere using impactors mounted on NASA U-2 and WB-57F aircraft is discussed. Sample collection, preparation, and analysis techniques are described and the particle types found are reviewed. Preliminary examination of the particles indicates that they represent not only extraterrestrial material, but some fraction of terrestrial contamination from both natural and manmade sources. This examination involves a combination of optical microscopy, scanning electron microscopy (SEM) and qualitative bulk elemental analysis using an energy-dispersive X-ray spectrometer (EDS) to characterize each particle. The cosmic dust collection contains samples of at least three classes of material that may present some hazard to extended spacecraft operations in near-Earth orbit: (1) micrometeorites/cosmic dust, (2) aluminum oxide spheres, and (3) alloy spherules and fragments.

Clanton, U. S.↗

Wettability variation and its impact on CO 2 storage capacity at the Wyoming CarbonSAFE storage hub: An experimental approach

Meeting global and national net zero carbon emission targets will require geologic carbon disposal. The U.S. Department of Energy (DOE) has accordingly funded significant research in this area, including the Wyoming CarbonSAFE project at Dry Fork Station (DFS) in Campbell County, Wyoming. This work studied wettability on micro- and macro-scales, CO 2 storage potential, and the correlation between the two to support the Wyoming CarbonSAFE project’s subsurface assessment. During the study, a target formation’s wettability was found to affect how much CO 2 can be stored in a given formation. Here, in this study, representative rock samples were selected from the target storage formations— Lakota, Hulett, and Minnelusa—based on the heterogeneity of the lithology, permeability, and porosity of the respective formations. The rock samples are all fine-grained sandstone with variable cementation and bedding structure, including different scales of laminated bedding. The porosity and permeability vary within the range of 9.0–14.3% and 0.1–28.9 mD, respectively. These rock samples were prepared for the micro-scale wettability (contact angle measurement), macro-scale wettability (wettability index derived from unsteady-state flow characterization for the core plugs), and CO 2 storage evaluation. The macro-scale experiments suggested that wettability appeared to dominate the CO 2 storage potential performance during the drainage process, where less water-wet behavior promoted higher CO 2 storage potential. The micro-scale wettability tests showed that the rock samples at the studied reservoir conditions behaved water-wet and became more water-wet as pressure increased. This kind of wettability change discourages further CO 2 storage potential yet benefits the CO 2 residual trapping as the CO 2 injection proceeds for the studied area. The results allow the recommendation of the best reservoir candidate for storage based on wettability that affects CO 2 storage. The work presented in this study provides valuable insights into wettability’s effect on the CO 2 storage capacity and wettability’s importance when identifying the optimal CO 2 storage formation to meet the project’s goals.

58 GEOSCIENCES↗

Pre-Flight Characterization of Samples for the MISSE-7 Spacesuit Fabric Exposure Experiment

A series of six sample spacesuit pressure garment assembly (PGA) fabric samples were prepared for the Materials International Space Station Experiment 7 (MISSE-7) flight experiment to test the effects of damage by lunar dust on the susceptibility of the fabrics to radiation damage. These included pristine Apollo-era fluorinated ethylene-propylene (FEP) fabric, Apollo-era FEP fabric that had been abraded with JSC-1A lunar simulant, and a piece of Alan Bean s Apollo 12 PGA sectioned from near the left knee. Also included was a sample of pristine orthofabric, and orthofabric that had been abraded to two different levels with JSC-1A. The samples were characterized using optical microscopy, field emission scanning electron microscopy, and atomic force microscopy. Two sets of six samples were then loaded in space environment exposure hardware, one of which was stored as control samples. The other set was affixed to the MISSE-7 experiment package, and will be mounted on the International Space Station, and exposed to the wake-side low Earth orbit environment. It will be retrieved after an exposure of approximately 12 months, and returned for post flight analysis.

Gaier, James R.↗

Fracture toughness of schist, amphibolite, and rhyolite from the Sanford Underground Research Facility (SURF), Lead, South Dakota

The Cracked Chevron Notched Brazilian Disc (CCNBD) method was selected for Mode I fracture toughness tests on Poorman schist, Yates amphibolite, and rhyolite dikes from the EGS Collab site at the SURF in Lead, South Dakota. The effects of lithology, anisotropy, and loading rate were investigated. Fracture toughness was greatest in amphibolite, with schist and rhyolite having similar toughness values ($K$ amphibolite > $K$ rhyolite ≈ $K$ schist ). The effects of anisotropy on fracture toughness were investigated in the foliated schist samples. Schist samples were prepared in three geometries (divider, arrester, and short transverse) which controlled how the fracture would propagate relative to foliations. The divider geometry was strongest and short transverse geometry was the weakest ($K$ divider > $K$ arrester > $K$ shorttransverse ). Fracture toughness was observed to decrease with decreasing loading rate. Optical and SEM microscopy revealed that for the short transverse geometry, fractures tended to propagate along grain boundaries, whereas in arrester and divider geometries fractures tended to propagate through grains. In foliated samples, the tortuosity of the fracture observed in thin section was greater in arrester and divider geometries than in short transverse geometries.

58 GEOSCIENCES↗

Research study for gel precursors as glass and ceramic starting materials for space processing applications research

The development of techniques for the preparation of glass and ceramic starting materials that will result in homogeneous glasses or ceramic products when melted and cooled in a containerless environment is described. Metal-organic starting materials were used to make compounds or mixtures which were then decomposed by hydrolysis reactions to the corresponding oxides. The sodium tungstate system was chosen as a model for a glass with a relatively low melting temperature. The alkoxide tungstates also have interesting optical properties. For all the compositions studied, comparison samples were prepared from inorganic starting materials and submitted to the same analyses.

Downs, R. L.↗

Effect of roll hot press temperature on crystallite size of PVDF film

Fabrication PVDF films have been made using Hot Roll Press. Preparation of samples carried out for nine different temperatures. This condition is carried out to see the effect of Roll Hot Press temperature on the size of the crystallite of PVDF films. To obtain the diffraction pattern of sample characterization is performed using X-Ray Diffraction. Furthermore, from the diffraction pattern is obtained, the calculation to determine the crystallite size of the sample by using the Scherrer equation. From the experimental results and the calculation of crystallite sizes obtained for the samples with temperature 130 °C up to 170 °C respectively increased from 7.2 nm up to 20.54 nm. These results show that increasing temperatures will also increase the size of the crystallite of the sample. This happens because with the increasing temperature causes the higher the degree of crystallization of PVDF film sample is formed, so that the crystallite size also increases. This condition indicates that the specific volume or size of the crystals depends on the magnitude of the temperature as it has been studied by Nakagawa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of the effective anisotropy constant of CoFe{sub 2}O{sub 4} nanoparticles through the T-dependence of the coercive field

We present a systematic study of the coercive field of CoFe{sub 2}O{sub 4}–SiO{sub 2} nanocomposites. The samples were prepared via the sol-gel method by using the Tetraethyl Orthosilicate as starting reagent. Results of X-ray diffraction, transmission electron microscopy, and X-ray fluorescence confirm the dispersion of the magnetic nanoparticles inside the silica matrix. In addition, the shift in the maximum of Zero-Field-Cooled curves observed by varying the weight ratio of CoFe{sub 2}O{sub 4} nanoparticles to the precursor of silica is consistent with the increasing of average interparticle distances. Because our samples present a particle size distribution, we have used a generalized model which takes account such parameter to fit the experimental data of coercive field extracted from the magnetization curves as a function of applied field. Unlike most of the coercive field results reported in the literature for this material, the use of this model provided a successful description of the temperature dependence of the coercive field of CoFe{sub 2}O{sub 4} nanoparticles in a wide temperature range. Surprisingly, we have observed the decreasing of the nanoparticles anisotropy constant in comparison to the bulk value expected for the material. We believe that this can be interpreted as due to both the migration of the Co{sup 2+} from octahedral to tetrahedral sites.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Microstructural Study of Micron-Sized Craters Simulating Stardust Impacts in Aluminum 1100 Targets

Various microscopic techniques were used to characterize experimental micro- craters in aluminium foils to prepare for the comprehensive analysis of the cometary and interstellar particle impacts in aluminium foils to be returned by the Stardust mission. First, SEM (Scanning Electron Microscopy) and EDS (Energy Dispersive X-ray Spectroscopy) were used to study the morphology of the impact craters and the bulk composition of the residues left by soda-lime glass impactors. A more detailed structural and compositional study of impactor remnants was then performed using TEM (Transmission Electron Microscopy), EDS, and electron diffraction methods. The TEM samples were prepared by Focused Ion Beam (FIB) methods. This technique proved to be especially valuable in studying impact crater residues and impact crater morphology. Finally, we also showed that InfraRed microscopy (IR) can be a quick and reliable tool for such investigations. The combination of all of these tools enables a complete microscopic characterization of the craters.

Leroux, Hugues↗