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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Fundamental Studies of Tritium Formation and Diffusivity in Pure and Defective Zircaloy-4 Getters

Zirconium (Zr) and its alloys are used as fuel cladding in nuclear reactors. These materials have their low absorption cross-section for thermal neutrons and have good mechanical and thermal properties. In addition, they are used as tritium getters in tritium-producing burnable absorber rods (TPBARs), in the form of nickel-plated Zircaloy-4 tubes. To produce 3 H, the breading blankets such as lithium aluminate are irradiated in pressurized water. 3 H produced in this process is captured by the getter and 3 H reacts chemically with Zr to form metal hydride (ZrTx). The precipitation of metal hydride results in not only the volume increase and hydrogen embrittlement of zircaloy but also changes in getter’s chemical properties. This degrades the getter’s performance. Therefore, understanding the behavior of 3 H (such as diffusion and solubility) in zircaloy is important to understand getter performance.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Raman Spectroscopy Based On-Line, Real-Time Monitoring to Reduce Composition Uncertainties: Enhanced sensitivity through optimization of Raman Parameters

Optical spectroscopy-based on-line monitoring of Hanford processing streams can enable real-time characterization of chemical composition of process streams and batches, ultimately enabling and enhancing process control. It can provide immediate feedback on process conditions and has the potential to reduce the needed number of grab sample collections, thereby reducing times and costs associated with laboratory processing. Here we discuss the utilization of Raman spectroscopy to quantify multiple target analytes that are common within Hanford tanks and waste processing streams. Analytes include: nitrate, nitrite, carbonate, chromate, sulfate, phosphate, hydroxide, oxalate, ammonia, and aluminate. Most notably in this work, Raman applications to low-concentration streams are explored and optimized. Raman instrument specifications are compared; specifically, the impact of utilizing three different Raman excitation wavelengths, 405, 532, and 671 nm, is discussed. Also, Raman data collection parameters such as collection time and spectral averaging are measured and discussed. Finally, optical libraries of chemical targets were collected using optimized collection parameters and chemometric models were built to automate quantification of chemical targets. These models were validated through application to simulants and real Hanford process samples. Chemometric models performed well on both training and validation sets, suggesting these approaches can be successfully applied to on-line and real-time monitoring of low concentration Hanford processing streams. The use of the combine Raman wave lengths with the enhanced chemometric models for the low concentration streams significantly improved the chemical detection levels and significantly reduced uncertainties of those measurements.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

TCF - Sustainable Well Cement for Geothermal, Thermal Recovery, and Carbon Storage wells

Primary cementing is the most important operation performed on a subterranean well. Cement, placed in the annulus between the casing and the formations, serves as a hydraulic seal preventing fluids and gas migrations, protecting steel casing from corrosion, and supporting the well structure. Poor cementing jobs can be directly responsible for wells not reaching their full capacity, casing corrosion, compromised well integrity and, in the worst-case scenarios, well collapse. Geothermal, thermal recovery, and carbon storage wells offer environments that are especially difficult for cements to survive while the required lifespan of these wells can be years. In these wells currently used cements cannot provide durable well integrity, and new solutions are necessary. The necessity of stabilizing the electric grid, increasing its flexibility, and providing energy on demand will further expand the market of durable cement solutions for applications in high-temperature underground reservoir thermal energy storage wells (HT RTES). The design challenges of special cement systems for such wells originate from chemistry limitations of currently used well cements, aggressive environments, temperature and repeated shock conditions associated with them, and very weak formations that are not uncommon in these wells. During the last 70 years the most common systems for thermal-well construction have been Ordinary Portland Cement (OPC) (absolute majority of the wells), silica-lime system, and high aluminum cement-containing formulations. The major issues of calcium-silicate hydrates, that form during the hydration of OPC resulting in hardened material, are their poor chemical resistance to acids due to the calcium interactions with acid anions followed by its eventual dissolution, even in mild acids, such as carbonic acid from CO 2 dissolution, and inadequate bonding to the steel causing serious casing corrosion problems (Sugama & Pyatina, 2019). Performance of OPC-based cement may be significantly improved with organic additives; however, those are limited by their temperature stability. An alternative to calcium-silicate cement was developed by BNL and commercialized by Halliburton as ThermaLock TM cement. Calcium-aluminate-phosphate-based chemistry of the material allowed overcoming acid-resistance problems of OPC, especially in CO 2 -rich geothermal environments. In 2012-2015, building upon this experience, BNL developed Thermal Shock Resistant Cement (TSRC) with the support of Geothermal Technology Office (GTO) of DOE. TSRC has high-temperature stable chemistry, superior properties of cement-metal casing bond and corrosion protection (4-times better than currently used OPC-based formulation), significantly outperforms common well-cements in thermal-shock tests, has self-healing properties, and like ThermaLock TM is CO 2 resistant incorporating carbonate ions into stable hydrates (Gill et al., 2012).

15 GEOTHERMAL ENERGY↗
DOE OSTI2026

Findings from Large Bench-Scale Testing of Denitration Electrolyzers for the EDCGe Project

This report highlights the key findings and outcomes relevant to the processability of waste supernatant at Hanford using a denitration electrolyzer. The Electrosynthesis Company issued a Phase 1 report to the Savannah River National Laboratory (SRNL), summarizing the evaluation of large bench-scale denitration electrolyzers to support the electrochemical denitration and caustic generation (EDCGe) project. The Electrosynthesis Company’s report (attached as Appendix A) provides insights into the initial steps required to implement an electrolyzer system at Hanford. Phase 1 experiments focused on validating the denitration electrolyzer’s performance, operating parameters, and reaction products. The robustness of the electrochemical denitration process was demonstrated by two electrolyzer flow cell systems (a 100 cm 2 ElectroCell MP and a 150 cm 2 NESI NS01 cell), both of which achieved significant nitrate and nitrite removal (>50%) with a current efficiency of ~95% for both systems. Higher current densities (500 mA cm –2 ) improved nitrate and nitrite removal rates compared to lower current densities (333 mA cm –2 ), while maintaining a current efficiency of ~94%. The NS01 cell achieved a nitrate species removal rate of ~0.41 mol h –1 at 5 kA m –2 (equiv. to 500 mA cm –2 ). The primary reaction product was ammonia (NH 3 ), constituting 78.3–91.6% of the products (excluding OH – formation). NH 3 was predominantly retained in the catholyte liquid phase rather than being off-gassed. Additionally, the NS01 cell reported an NH 3 generation rate of ~0.36 mol h –1 at 5 kA m –2 . Other gas formation included ~7% N 2 , ~7% H 2 , and trace amounts of N 2 O. The estimated power requirement (extrapolated from the 0.015 m 2 cell data) for a full-scale denitration electrolyzer is approximated to be ~1.6 MW (DC-only) to treat 50% of nitrate and nitrite in a waste stream and generates ~2.1 kmol h –1 of NH 3 with an initial concentration of 4 M NO 3 – /NO 2 – at 300 gal h –1 . Simulated waste containing aluminate, carbonate, oxalate, and halogens exhibited no adverse effects on denitration performance. A preliminary experiment comparing alkaline anolyte (5 M NaOH) with a nickel based anode to acidic media (2 M H 2 SO 4 ) with a DSA-O 2 anode showed a lower operating voltage and generated less H 2 than the acid media. Maintaining a stable 5 M OH – concentration in the anolyte through periodic additions of caustic did not significantly impact denitration performance. This operational mode will be required for long-term experiments. All the experiments demonstrated that electrochemical denitration is a promising approach for treating nitrate and nitrite in simulated waste streams, achieving significant conversion and robustness across varying experimental conditions and electrochemical cell configurations. Lastly, the ability to generate a nearly pure NH 3 stream may prove advantageous for processing at other locations within the Hanford site.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

FY24 Task 4: Studies of Phosphate and Fluoride Solubility for Dissolution of High Phosphate Tank Waste

Knowledge gaps have been identified in phosphate solubility in almost every single- and multi-component system, and particularly for aluminate in phosphate/hydroxide, where uncertainties in predicted values of aluminum solubility are greater than 50%. Solubility data of multicomponent, aqueous electrolytes containing sodium hydroxide, sodium fluoride, sodium phosphate, sodium nitrite, sodium nitrate, and dissolved gibbsite are also sparse. For example, for solutions of (i) sodium nitrate and sodium phosphate, data are only available at 30 and 50 °C, and for (ii) dissolved gibbsite in sodium hydroxide and sodium phosphate, only two data points are available at 20 and 40 °C. There is no data available on mixtures of sodium hydroxide, sodium phosphate, sodium fluoride, and dissolved gibbsite. These knowledge gaps were identified in a technical review of waste solubility data and the impact of dilution on solution stabilities and will be addressed in this work to predict aluminum hydroxide and sodium phosphate solubility in multicomponent electrolytes upon dilution, and upon variation of temperature. Results will provide the technical basis to develop accurate models for (i) gibbsite solubility and mass transfer of aluminum between solid and liquid forms following the sluicing of sludge and saltcake with water; and (ii) further blending of these suspensions with bismuth from bismuth phosphate waste, and zirconium and uranium left from the fuel decladding. This work will be essential to developing a disposition path for retrieval solutions from bismuth phosphate wastes. This effort would also support sludge washing to further reduce phosphate concentration if that process were to be added back to the flowsheet in the future.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Non-Stoichiometric High Entropy Spinel Oxides as Regenerable Catalysts for Methane Dry Reforming

In this work, novel high entropy oxides were developed and applied as catalysts in the methane dry reforming reaction. Catalytic results show high activity and regenerable structure of the high entropy oxides but degradation of simple nickel aluminate spinels commonly applied to this reaction. A proof-of-concept experiment demonstrated heating of the high entropy oxide catalyst to reaction relevant temperatures using concentrating solar power equipment.

Riva, Andrew↗
DOE OSTI2024

Summary of Structural Alloy Compatibility in Supercritical CO2 at 450°-800°C

Supercritical CO2 (sCO2) is of interest as a working fluid for several concepts including the direct- fired Allam cycle as a low-emission fossil energy power cycle. Over the past 10 years, laboratory exposures at 300 bar sCO2 have found reasonably good compatibility for Ni-based alloys at <800°C, including an assessment of the sCO2 impact on room temperature mechanical properties after 750°C exposures. However, initial screening tests at 1 and 20 bar CO2 at 900°-1100°C showed poor compatibility for Ni-based alloys. In an open cycle, the introduction of 1%O2 and 0.1- 0.25%H2O impurities at 300 bar increased the reaction rates ≥2X at 750°C. At lower temperatures, steels are susceptible to C ingress and embrittlement. Creep-strength enhanced ferritic steels may be limited to <550°C and conventional stainless steels to <600°C. Two strategies to increase those temperatures are higher Ni and Cr alloying additions and Al- or Cr-rich coatings. Alloy 709 (Fe- 20Cr-25Ni) shows some promising results at 650°C in sCO2 but reaction rates were accelerated with the addition of O2 and H2O impurities. Pack aluminized and chromized Gr.91 (Fe-9Cr-1Mo) and type 316H stainless steel show some promise at 600°-650°C but further coating optimization is needed.

Pint, Bruce↗
DOE OSTI2021

Multiphysics and Multiscale Modeling of Coupled Transport of Chloride Ions in Concrete

Chloride ions (Cl−)-induced corrosion is one of the main degradation mechanisms in reinforced concrete (RC) structures. In most situations, the degradation initiates with the transport of Cl− from the surface of the concrete towards the reinforcing steel. The accumulation of Cl− at the steel-concrete interface could initiate reinforcement corrosion once a threshold Cl− concentration is achieved. An accurate numerical model of the Cl− transport in concrete is required to predict the corrosion initiation in RC structures. However, existing numerical models lack a representation of the heterogenous concrete microstructure resulting from the varying environmental conditions and the indirect effect of time dependent temperature and relative humidity (RH) on the water adsorption and Cl− binding isotherms. In this study, a numerical model is developed to study the coupled transport of Cl− with heat, RH and oxygen (O2) into the concrete. The modeling of the concrete microstructure is performed using the Virtual Cement and Concrete Testing Laboratory (VCCTL) code developed by the U.S. National Institute of Standards and Technology (NIST). The concept of equivalent maturation time is utilized to eliminate the limitation of simulating concrete microstructure using VCCTL in specific environmental conditions such as adiabatic. Thus, a time-dependent concrete microstructure, which depends on the hydration reactions coupled with the temperature and RH of the environment, is achieved to study the Cl− transport. Additionally, Cl− binding isotherms, which are a function of the pH of the concrete pore solution, Cl− concentration, and weight fraction of mono-sulfate aluminate (AFm) and calcium-silicate-hydrate (C-S-H), obtained from an experimental study by the same authors are utilized to account for the Cl− binding of cement hydration products. The temperature dependent RH diffusion was considered to account for the transport of Cl− with moisture transport. The temperature and RH diffusion in the concrete domain, composite theory, and Cl− binding and water adsorption isotherms are used in combination, to estimate the ensuing Cl− diffusion field within the concrete. The coupled transport process of heat, RH, Cl−, and O2 is implemented in the Multiphysics Object-Oriented Simulation Environment (MOOSE) developed by the U.S. Idaho National Laboratory (INL). The model was verified and validated using data from multiple experimental studies with different concrete mixture proportions, curing durations, and environmental conditions. Additionally, a sensitivity analysis was performed to identify that the water-to-cement (w/c) ratio, the exposure duration, the boundary conditions: temperature, RH, surface Cl− concentration, Cl− diffusion coefficient in the capillary water, and the critical RH are the important parameters that govern the Cl− transport in RC structures. In a case study, the capabilities of the developed numerical model are demonstrated by studying the complex 2D diffusion of Cl− in a RC beam located in two different climatic regions: warm and humid weather in Galveston, Texas, and cold and dry weather in North Minnesota, Minnesota, subjected to time varying temperature, RH, and surface Cl− concentrations.

composite theory↗
DOE OSTI2021

Hydrophobic Lightweight Cement with Thermal Shock Resistance and Thermal Insulating Properties for Energy-Storage Geothermal Well Systems

This study assessed the possibility of using polymethylhydrosiloxane (PMHS)-treated fly ash cenospheres (FCS) for formulating a thermally insulating and thermal shock (TS)-resistant cementitious blend with calcium aluminate cement. To prevent FCS degradation in an alkaline cement environment at high temperatures, the cenospheres were pre-treated with sodium metasilicate to form silanol and aluminol groups on their surface. These groups participated in a dehydrogenation reaction with the functional ≡Si–H groups within PMHS with the formation of siloxane oxygen-linked M-FCS (M: Al or Si). At high hydrothermal temperatures of 175 and 250 °C, some Si–O–Si and SiCH 3 bonds ruptured, causing depolymerization of the polymer at the FCS surface and hydroxylation of the raptured sites with the formation of silanol groups. Repolymerization through self-condensation between the silanol groups followed, resulting in the transformation of siloxane to low crosslinked silicon-like polymer as a repolymerization-induced product (RIP) without carbon. The RIP provided adequate protection of FCS from pozzolanic reactions (PR), which was confirmed by the decline in zeolites as the products of PR of FCS. Cements with PMHS-treated FCS withstood both hydrothermal and thermal temperature of 250 °C in TS tests, and they also showed improved compressive strength, toughness, and water repellency as well as decreased thermal conductivity. The lubricating properties of PMHS increased the fluidity of lightweight slurries.

15 GEOTHERMAL ENERGY↗
DOE OSTI2022

Mechanical Activation and Cation Site Disorder in MgAl 2 O 4

The synthesis and crystallographic site occupancy were investigated for MgAl 2 O 4 with and without mechanical activation of the precursor powders. Heating to 1200 °C or higher resulted in the formation of a single spinel phase regardless of whether the powders were mechanically activated or not. Neutron diffraction analysis was used to determine cation site occupancy and revealed that mechanical activation resulted in a lower degree of cation site inversion compared to the nonactivated materials, which indicated that the powders were closer to thermodynamic equilibrium. This is the first study to characterize the effects of mechanical activation on crystallographic site occupancy in magnesium aluminate spinel using neutron diffraction.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structure and Stability of Iron Fluoride at High Pressure–Temperature and Implication for a New Reservoir of Fluorine in the Deep Earth

Fluorine (F) is the most abundant halogen in the bulk silicate Earth. F plays an important role in geochemical and biological systems, but its abundance and distribution in the terrestrial mantle are still unclear. Recent studies suggested that F reservoirs in the deep mantle are potentially hosted in terrestrial oxide minerals, especially in aluminous bridgmanite. However, the knowledge about the formation and stability field of fluoride in the Earth’s interior is rare. In this study, we combine in situ laser-heated diamond anvil cell, synchrotron X-ray diffraction, and first-principles structure search to show that a new tetragonal structure of FeF 3 is stable at pressures of 78–130 GPa and temperatures up to ~1900 K. Simulation predicted the tetragonal phase takes a much denser structure due to the rotation of FeF 6 octahedral units. The equations of states of tetragonal FeF3 are determined by experiment and verified by simulation. Our results indicate that FeF 3 can be a potential key phase for storing F in the Earth’s lower mantle and may explain some mantle-derived magma with high F concentration.

58 GEOSCIENCES↗
NASA NTRS1967

Inexpensive cryogenic insulation replaces vacuum jacketed line

Commercially available aluminized Mylar, cork and fiber glass form a multilayered sealed system and provide rugged and economical field installed insulation for cryogenic /liquid nitrogen or oxygen/ pipe lines in an exposed environment.

Fuchs, C. E.↗
NASA NTRS1968

Panelized high performance multilayer insulation

Multilayer insulation coverings with low conductivity foam spacers are interleaved with quarter mil aluminized polymer film radiation shields to cover flight type liquid hydrogen tankage of space vehicles with a removable, structurally compatible, lightweight, high performance cryogenic insulation capable of surviving extended space mission environments.

Burkley, R. A.↗