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DOE OSTI2020

Major element composition controls rare earth element solubility during leaching of coal fly ash and coal by-products

Coal combustion ash and pre-combustion coal refuse are currently under consideration as potential sources of rare earth elements. One of the early steps in recovering REEs from coal by-products is often acid leaching, which can result in low pH leachates with complex aqueous chemistry. The aim of this work was to understand the connection between REE solubility, pH, and major elemental components of leachates for coal by-products. To accomplish this, we investigated the effects of solids concentration (i.e., pulp density) and pH adjustment on REE solubility in acid leachates of coal fly ashes from the Powder River Basin (PRB) and Appalachian Basin in the United States, and a coal processing refuse from the Southwestern U.S. For PRB ashes, the concentrations of soluble REEs generally increased with increasing pulp density; however, at pulp density values above 80–100 g/L, the soluble REE concentrations in the leachates were markedly lower. Similarly, the soluble concentrations of other major solutes (Fe, Al, Si) that leached from PRB fly ashes were also non-linear with pulp density. These major elements tended to reach maximum concentration values at 60–70 g/L pulp density. In contrast, for the Appalachian fly ashes and the coal by-product, soluble concentrations of REE and major elements in leachates increased linearly with pulp density. Chemical equilibria calculations of mineral saturation indices indicated that trends in soluble REE concentrations could be explained by saturation conditions for Fe and Al-(hydr)oxides and possibly sulfate minerals, but not lanthanide hydroxides. Furthermore, pH adjustment of the acid leachates showed that REEs and many major solutes were removed from solution at pH values above 4.5, also consistent with Fe- and Al-(hydr)oxide precipitation. These results highlight the importance of understanding the chemical composition of leachates when designing REE recovery processes for low-grade geologic feedstocks and that precipitation of hydr(oxide) or sulfate minerals of major elements rather than discreet formation of REE mineral phases could be used for process optimization.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2024

Bioblendstocks to Optimize Mixing Controlled Compression Ignition (MCCI) Engines

In this project, a team of researchers from the University of Massachusetts Lowell, the University of Maine, and Mainstream Engineering developed an integrated process for the product of bioblendstocks to optimize mixing controlled compression ignition (MCCI) engines. The objective was to improve the energy density, sooting propensity, and cetane number of base diesel fuel while maintaining cold weather behavior. The process converts woody biomass (e.g. sawmill residues) into bio-oil through selective fast pyrolysis; the bio-oil is then selectively upgraded to form selectively oxygenated, minimally-branched hydrocarbons using non-noble metal catalysts in combination with metal-catalyzed hydrogenation. Advanced predictive models, in conjunction with existing property databases, and experimental testing are used to evaluate overall bioblendstock properties and their impact on base diesel fuel. An iterative, targeted upgrading approach was implemented to optimize the proposed bioblendstock’s properties. Assessment methodologies included techno-economic analysis, life-cycle assessment, property testing, and engine testing. Ultimately, the project team successfully produced a viable bioblendstock while identifying critical process points related to scale-up efforts. It was found that producing pyrolysis oils at 500 degrees C and with pine particle sizes of 1-2 mm led to bio-oil with a higher yield (of approximately 45 wt%) and rich amounts of aromatic alcohols. The resultant pyrolysis oil was then upgraded using a sequence of mild hydrotreating, followed by catalytic etherification and esterification, followed by another final mild hydrotreating to produce a blendstock containing saturated species with a limited, but non-zero, amount of oxygen. The aromatic alcohols produced by pyrolysis were especially helpful in this regard, as the resulting bicycloethers and derivatives exhibited high cetane numbers. While most bulk properties of the bioblendstock met or exceeded targeted thresholds, viscosity and cloud point notably fell outside the expected range; this could be addressed by blending limits and/or through the use of additives that are commonplace in current refinding practices. Identification of a bioblendstock that can be produced economically at scale while improving the performance and emissions characteristics of internal combustion engines positively affects the economy by boosting domestic fuel production and the environment by decreasing harmful emissions and increasing efficiency.

09 BIOMASS FUELS↗

NASA NTRS2021

Experimental and Computational Investigation of Flow Boiling in Microgravity

This study explores use of Computational Fluid Dynamics (CFD) to predict near-saturated flow boiling of FC-72 in microgravity. The computational method employs transient analysis to predict detailed interfacial behavior and heat transfer characteristics along a rectangular channel heated along two opposite walls. Predicted results are validated against experimental temperature measurements and high-speed video images captured during a series of parabolic aircraft maneuvers for three sets of operating conditions which include variations of both mass velocity and wall heat flux. The computational method is based on the multi-phase volume of fluid (VOF) model, which is combined with appropriate phase change and turbulence models, and accounts for both shear-lift force on bubbles and conjugate heat transfer along the heating walls. A key advantage of the CFD method is ability to capture details that are very difficult to measure experimentally, including detailed spatial variations of bubble shape, void fraction, mixture fluid temperature, liquid velocity, and vapor velocity, results for which are presented for each of the three test cases. Different flow regimes predicted along the heated length exhibit a number of dominant mechanisms including bubble nucleation, bubble growth, coalescence, vapor blankets, interfacial waviness, and residual liquid sub-layer, all of which agree well with experiment. Vapor velocity is shown to increase appreciably along the heated length because of increased void fraction, while liquid velocity experiences large fluctuations. Non-equilibrium effects are accentuated with increasing mass velocity, contributing minor deviations of fluid temperature from simulations compared to those predicted by the analytical method. Predicted wall temperature is fairly uniform in the middle of the heated length but increases in the entrance region, due to sensible heat transfer in the subcooled liquid, and decreases toward the exit, mostly because of flow acceleration resulting from increased void fraction.

two-phase cooling; flow boiling; CFD; microgravity↗

NASA NTRS2014

Current Ground Test Options for Nuclear Thermal Propulsion (NTP)

About 20 different NTP engines/ reactors were tested from 1959 to 1972 as part of the Rover and Nuclear Engine for Rocket Vehicle Application (NERVA) program. Most were tested in open air at test cell A or test cell C, at the Nevada Test Site (NTS). Even after serious engine breakdowns of the reactor (e.g., Phoebus 1A), the test cells were cleaned up for other engine tests. The engine test stand (ETS) was made for high altitude (approximately 1 psia) testing of an NTP engine with a flight configuration, but still had the exhaust released to open air. The Rover/NERVA program became aware of new environmental regulations which would prohibit the release of any significant quantity of radioactive particulates and noble gases into the open air. The nuclear furnace (NF-1) was the last reactor tested before the program was cancelled in 1973, but successfully demonstrated a scrubber concept on how to filter the NTP exhaust. The NF-1 was demonstrated in the summer of 1972. The NF-1 used a 44MW reactor and operated each run for approximately 90 minutes. The system cooled the hot hydrogen exhaust from the engine with a water spray before entering a particle filter. The exhaust then passed through a series of heat exchangers and water separators to help remove water from the exhaust and further reduce the exhaust temperatures. The exhaust was next prepared for the charcoal trap by passing through a dryer and effluent cooler to bring exhaust temperatures close to liquid nitrogen. At those low temperatures, most of the noble gases (e.g., Xe and Kr made from fission products) get captured in the charcoal trap. The filtered hydrogen is finally passed through a flare stack and released to the air. The concept was overall successful but did show a La plating on some surfaces and had multiple recommendations for improvement. The most recent detailed study on the NTP scrubber concept was performed by the ARES Corporation in 2006. The concept is based on a 50,000 lbf thrust engine (approximately 1 GW) with a maximum burn time of 1 hour. The concept utilized lessons learned from NF-1. The strategy breaks down the exhaust into parallel paths to allow flexibility with engine size and mass flow of exhaust. Similar to NF-1, the exhaust is slowed down, cooled, filtered of particulates, filtered of noble gases, and then the clean hydrogen is flared to open air. Another concept proposed by Steve Howe (currently Director of the Center for Space Nuclear Research) to simplify the NTP exhaust filtering is to run the hydrogen exhaust into boreholes underground to filter the exhaust. The two borehole site locations proposed are at the NTS and at the Idaho National Laboratory (INL). At NTS, the boreholes are 8' diameter and 1200' deep. The permeability of hydrogen through the soil and its buoyancy will allow it to rise up through the soil and allow the filtering of noble gases and radioactive particulates. The exhaust needs to be cooled to 600C before entering the borehole to avoid soil glazing. Preliminary analysis shows a small buildup of back pressure with time which depends on permeability. Noble gases entering the borehole walls deep can take a long time before reaching the surface. Other factors affecting permeability include borehole pressure, water saturation, and turbulence. Also, a possible need to pump out contaminated water collected at the bottom of the borehole. At INL, the borehole concept is slightly different. The underground borehole has openings to the soil at special depths which have impermeable interbeds above the water table and below the surface to allow the exhaust to travel horizontal between the impermeable layers. Preliminary results indicate better permeability than at NTS. The last option is total containment of the exhaust during the test run. The concept involves slowing down the flow to subsonic in a water cooled diffuser. The hydrogen is burned off in an oxygen rich afterburner with the only products being steam, oxygen, and some noble gases. A heat exchanger and water spray pulls heat from the steam and lowers the temperature for condensation. The optimum ratio between the two is being investigated, with a goal to minimize the total volume of the water hold tanks. A water tank farm collects the contaminated water. The amount of water produced from burning the hydrogen is approximately 100,000 gallons (not including cooling water) for a 25k lbf engine operating for 50 minutes. Residual gases (e.g., oxygen and some noble gases) can be captured at cryogenic levels with a liquid nitrogen cooled dewar. After a few weeks post-test, the radiation levels can drop to more favorable levels before slowly draining each capture tank and using existing filters. With today's environmental regulations, the NTP exhaust is filtered to meet 10 mrem/year exposure to the general public (at a DOE site) or 100 mrem/year (via NRC when tested elsewhere), when natural background radiation exposure to the general public is 300- 600 mrem per year. The current society feels more comfortable with filtering even lower to as low as reasonably achievable (ALARA).

Gerrish, Harold P., Jr.↗

DOE OSTI2026

Localization and functional exploration of leiomodin-2’s C-terminal binding sites

Striated muscle contraction occurs through interactions between overlapping myosin-based thick and actin-based thin filaments within the sarcomere. For effective contraction to occur, the length of the thin filament must be maintained to allow for sufficient overlap with the thick filament. The proteins leiomodin and tropomodulin compete for binding at the pointed end of thin filaments to regulate their length, utilizing their homologous N-terminal actin and tropomyosin binding sites. Leiomodin also has a region called the C-terminal extension, absent in tropomodulin. In this region, the cardiac isoform (leiomodin-2) contains additional actin-binding sites that enable it to bind along the sides of thin filaments in a Ca2+-dependent manner. Here, using nuclear magnetic resonance spectroscopy, we localize the regions of the C-terminal extension that contain residues involved in thin filament side-binding. Using co-sedimentation assays, we reveal that these regions can independently bind thin filaments and discover that the poly-proline region plays a role as a linker, maintaining an adequate distance between two of the regions required for effective interaction to occur. In addition to its role in side-binding, we provide direct evidence that the poly-proline region interacts with profilin and propose a new mechanism by which leiomodin-2 may assist in the polymerization of profilin-bound actin at thin filament pointed ends.

ACTIN-BINDING PROTEINS↗

NASA NTRSDate not supplied

Mitigation of Silver Ion Loss from Solution by Polymer Coating of Metal Surfaces, Part IV

Ionic silver (Ag+) biocide is a leading candidate to provide residual microbial control in spacecraft potable water systems, but suffers from rapid concentration loss due to interactions with the metallic storage containers and tubing. One approach to resolve this problem is the coating of metal surfaces with an inert barrier film. In previous reports, we have described our investigations addressing Ag+ loss mitigation and adhesion performance of parylene barrier coatings on coupons of several metal alloys and 316Ltubing under static immersion. In such conditions, parylene-C and -AF4 coatings have shown excellent Ag+loss mitigation and mixed long-term adhesion performance, depending on parylene species and substrate surface chemistry/structure. In Part IV of this series, we report on our work to investigate the performance of parylene-C barrier coatings, under more challenging and realistic conditions, in order to evaluate potential suitability for use. The resilience and associated Ag+ loss with Parylene-C coating on½” (12.7 mm)316L tubing and fittings under medium-term immersion and repeated fitting dis/reassembly were investigated. Potential mechanical challenges to barrier coatings in spacecraft potable water systems were investigated, with two main focuses being identified: liquid flow/pressure cycling in tubing and cyclic operation of bellows in positive-expulsion storage tanks. Two corresponding testbeds for experimental characterization of coating performance were developed. In the Flow/Pressure Testbed System, Ag+ solution will be pumped through internally coated 316L tubing, with optional pressure cycling. In the Bellows Tank Testbed System, an internally coated edge-welded 316L bellows containing Ag+ solution will be cyclically extended and compressed, analogous to the operation of bellows tanks used for potable water storage and delivery on the International Space Station. The design and operation of these testbeds are described. Finally, the Ag+ adsorption and saturation behaviors of Kalrez and Viton, for potential use as seal materials in fittings and other connections, were characterized in limited experiments.

mitigation↗

DOE OSTI2021

Modeling and Measuring the Stress Distribution in Soft Magnetic Cores due to Epoxy Impregnation and Curing

Understanding the effects of viscoelastic relaxation of stresses is critical in electric motor and inductor applications, where the magnetic material is fully or partially comprised of an amorphous phase and impregnated in an epoxy. Magnetic Amorphous Nanocomposites (MANCs) are a class of recently developed high-frequency magnetic materials that exhibit low magnetic hysteresis, high saturation flux density and very low AC magnetic losses. MANCs are formed as long, thin ribbons, a shape factor that minimizes eddy current-induced self-heating. This feature, in addition to their 1 GPa strength, and makes them attractive candidates for high-speed, high-power density, electric motors. MANCs are used in the form of tape-wound cores (TWCs). During the manufacturing process, the cores are impregnated with liquid epoxy between each layer of ribbon. Validated knowledge of the stresses imposed by the manufacturing process and during operation is necessary to understand motor performance limitations with respect to strength. Magnetostriction, the strain imposed by reversal of the magnetic field, also affects performance. When the epoxy cures, it contracts volumetrically by 8%, imposing radial and circumferential stresses that vary along the radial direction. To date, these stresses have received little attention in the literature. Here, we model the stress distribution throughout a TWC due to epoxy curing. Strain gauge measurements reported here indicate substantially lower tangential strain than model values, which is beneficial and which we attribute to viscoelastic relaxation of the epoxy layers. We will incorporate a constitutive model of this viscoelastic relaxation, and conduct more detailed strain measurements to understand how this takes

24 POWER TRANSMISSION AND DISTRIBUTION↗

NASA NTRS2013

Analysis of Water Recovery Rate from the Heat Melt Compactor

Human space missions generate trash with a substantial amount of plastic (20% or greater by mass). The trash also contains water trapped in food residue and paper products and other trash items. The Heat Melt Compactor (HMC) under development by NASA Ames Research Center (ARC) compresses the waste, dries it to recover water and melts the plastic to encapsulate the compressed trash. The resulting waste disk or puck represents an approximately ten-fold reduction in the volume of the initial trash loaded into the HMC. In the current design concept being pursued, the trash is compressed by a piston after it is loaded into the trash chamber. The piston face, the side walls of the waste processing chamber and the end surface in contact with the waste can be heated to evaporate the water and to melt the plastic. Water is recovered by the HMC in two phases. The first is a pre-process compaction without heat or with the heaters initially turned on but before the waste heats up. Tests have shown that during this step some liquid water may be expelled from the chamber. This water is believed to be free water (i.e., not bound with or absorbed in other waste constituents) that is present in the trash. This phase is herein termed Phase A of the water recovery process. During HMC operations, it is desired that liquid water recovery in Phase A be eliminated or minimized so that water-vapor processing equipment (e.g., condensers) downstream of the HMC are not fouled by liquid water and its constituents (i.e., suspended or dissolved matter) exiting the HMC. The primary water recovery process takes place next where the trash is further compacted while the heated surfaces reach their set temperatures for this step. This step will be referred to herein as Phase B of the water recovery process. During this step the waste chamber may be exposed to different selected pressures such as ambient, low pressure (e.g., 0.2 atm), or vacuum. The objective for this step is to remove both bound and any remaining free water in the trash by evaporation. The temperature settings of the heated surfaces are usually kept above the saturation temperature of water but below the melting temperature of the plastic in the waste during this step to avoid any encapsulation of wet trash which would reduce the amount of recovered water by blocking the vapor escape. In this paper, we analyze the water recovery rate during Phase B where the trash is heated and water leaves the waste chamber as vapor, for operation of the HMC in reduced gravity. We pursue a quasi-one-dimensional model with and without sidewall heating to determine the water recovery rate and the trash drying time. The influences of the trash thermal properties, the amount of water loading, and the distribution of the water in the trash on the water recovery rates are determined.

Heat Melt Compactor↗

DOE OSTI2023

Impact of biochar amendments on soil water and plant uptake dynamics under different cropping systems

Abstract Application of biochar amendments in agricultural systems has received much attention in recent years. In this study, we assess the 5‐year impacts of biochar application on soil water and plant interactions for an irrigated fresh market tomato ( Solanum lycopersicum ) and a rainfed pasture ( Poaceae ) cropping system. In particular, we focus on three varieties of locally produced biochar from agricultural waste materials—almond shell, walnut shell, and almond pruning residues that are pyrolyzed using a mobile pyrolysis unit. We used the soil hydrological model HYDRUS‐1D to explicitly track seasonal and annual soil water fluxes through changes in water retention, drainage, evaporation, and plant water uptake under biochar application. Modeling results show that the application of biochar at 5% increased soil water availability within the top 20 cm for a rainfed system, irrespective of biochar amendment type. This is clearly indicative of higher plant water uptake and greater water use efficiency (WUE) under biochar application. In contrast, a similar biochar amendment for the irrigated system did not affect WUE, instead reducing seasonal soil evaporation loss and thereby reducing irrigation demand. In both cropping systems, year‐to‐year variability in precipitation significantly impacted the total amount of water saved under biochar application with certain amendments retaining more water than others. Given that biochar application increased water retention irrespective of cropping systems, we further used a simple approach to determine yield trade‐off, if any, between control and biochar treatments. Our economic balance clearly demonstrates that the water saved by amending soil with biochar does not offset the yield disparity if compensated with carbon credits and therefore, application of biochar should be actively considered for both its direct and indirect benefits to potential greenhouse gas mitigation (e.g., diverting orchard waste from open burning), water savings, and soil health.

54 ENVIRONMENTAL SCIENCES↗