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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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Six-step chemical processing method extracts minute quantities of transplutonium elements found in rock debris following a nuclear detonation. The process consists of dissolution of rock, feed preparation, liquid-liquid extraction, final purification of transplutonium elements and plutonium, and separation of the transplutonium elements.
Oscillations of supported liquid drops are the subject of wide scientific interest, with applications in areas as diverse as liquid-liquid extraction, synthesis of ceramic powders, growing of pure crystals in low gravity, and measurement of dynamic surface tension. In this research, axisymmetric forced oscillations of arbitrary amplitude of viscous liquid drops of fixed volume which are pendant from or sessile on a rod with a fixed or moving contact line and surrounded by an inviscid ambient gas are induced by moving the rod in the vertical direction sinusiodally in time. In this paper, a preliminary report is made on the computational analysis of the oscillations of supported drops that have 'clean' interfaces and whose contact lines remain fixed throughout their motions. The relative importance of forcing to damping can be increased by either increasing the amplitude of rod motion A or Reynolds number Re. It is shown that as the ratio of forcing to damping rises, for drops starting from an initial rest state a sharp increase in deformation can occur when they are forced to oscillate in the vicinity of their resonance frequencies, indicating the incipience of hysteresis. However, it is also shown that the existence of a second stable limit cycle and the occurrence of hysteresis can be observed if the drop is subjected to a so-called frequency sweep, where the forcing frequency is first increased and then decreased over a suitable range. Because the change in drop deformation response is abrupt in the vicinity of the forcing frequencies where hysteresis occurs, it should be possible to exploit the phenomenon to accurately measure the viscosity and surface tension of the drop liquid.
Rare earth elements (REEs), especially heavy rare earth elements such as dysprosium (Dy), have gained immense attention globally due to their widespread use in many state-of-the-art technologies. Consequently, demand for REEs is increasing rapidly in comparison to their supply. Recycling of REEs from end-of-life (EoL) electronic waste (e-waste) can help to mitigate the increasing gap between the demand and supply of REEs. This study reports the separation and recovery of high-purity Dy from various feedstocks such as scrap permanent magnets (SPMs), electric vehicle (EV) magnets, and mixed rare earth oxides (REOs) using an economically viable and scalable membrane solvent extraction (MSX) process. First, the optimized conditions (organic phase composition and feed solution acid concentration) for the separation of Dy from light REEs such as neodymium (Nd) and praseodymium (Pr) were evaluated using liquid–liquid extraction. Thereafter, a multistage MSX process was developed to separate high purity (>99.5 wt %) Dy from Nd and Pr using Cyanex 572, a cationic extractant. Using feedstocks with varying initial compositions, the MSX process obtained 100% pure Dy with 63–96% Dy recovery in three to six stages with a maximum extraction rate of 2.9 g m–2 h –1 . Purity of the recovered Dy was confirmed via additional characterization such as scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. This novel MSX process holds immense potential for industry deployment for the separation of heavy and light rare REEs from a wide range of e-waste.
Process support materials' compatibility with cleaning processes is critical to ensure final hardware cleanliness and that performance requirements are met. Previous discovery of potential contaminants in process materials shows the need for incoming materials testing and establishment of a process materials database. The Contamination Control Team of the Materials, Processes, and Manufacturing (MP&M) Department at Marshall Space Flight Center (MSFC) has initiated the development of such an infrared (IR) database, called the MSFC Process Materials IR database, of the common process support materials used at MSFC. These process support materials include solvents, wiper cloths, gloves, bagging materials, etc. Testing includes evaluation of the potential of gloves, wiper cloths, and other items to transfer contamination to handled articles in the absence of solvent exposure, and the potential for solvent exposure to induce material degradation. This Technical Memorandum (TM) summarizes the initial testing completed through December 2002. It is anticipated that additional testing will be conducted with updates provided in future TMs.Materials were analyzed using two different IR techniques: (1) Dry transference and (2) liquid extraction testing. The first of these techniques utilized the Nicolet Magna 750 IR spectrometer outfitted with a horizontal attenuated total reflectance (HATR) crystal accessory. The region from 650 to 4,000 wave numbers was analyzed, and 50 scans were performed per IR spectrum. A dry transference test was conducted by applying each sample with hand pressure to the HATR crystal to first obtain a spectrum of the parent material. The material was then removed from the HATR crystal and analyzed to determine the presence of any residues. If volatile, liquid samples were examined both prior to and following evaporation.The second technique was to perform an extraction test with each sample in five different solvents.Once the scans were complete for both the dry transference and the extraction tests, the residue from each scan was interpreted.
Polycyclic aromatic hydrocarbons (PAHs) are robust and abundant molecules in extraterrestrial environments. They are found ubiquitously in the interstellar medium and have been identified in extracts of meteorites collected on Earth. PAHs are important target molecules for planetary exploration missions that investigate the organic inventory of planets, moons and small bodies. This study is part of an interdisciplinary preparation phase to search for organic molecules and life on Mars. We have investigated PAH compounds in desert soils to determine their composition, distribution and stability. Soil samples (Mars analogue soils) were collected at desert areas of Utah in the vicinity of the Mars Desert Research Station (MDRS), in the Arequipa region in Peru and from the Jutland region of Denmark. The aim of this study was to optimize the solid-phase microextraction (SPME) method for fast screening and determination of PAHs in soil samples. This method minimizes sample handling and preserves the chemical integrity of the sample. Complementary liquid extraction was used to obtain information on five- and six-ring PAH compounds. The measured concentrations of PAHs are, in general, very low, ranging from 1 to 60 ng g(sup -1). The texture of soils is mostly sandy loam with few samples being 100% silt. Collected soils are moderately basic with pH values of 8-9 except for the Salten Skov soil, which is slightly acidic. Although the diverse and variable microbial populations of the samples at the sample sites might have affected the levels and variety of PAHs detected, SPME appears to be a rapid, viable field sampling technique with implications for use on planetary missions.
Reductive catalytic fractionation (RCF) is a promising method to extract and depolymerize lignin from biomass, and bench-scale studies have enabled considerable progress in the past decade. RCF experiments are typically conducted in pressurized batch reactors with volumes ranging between 50 and 1000 mL, limiting the throughput of these experiments to one to six reactions per day for an individual researcher. Here, we report a high-throughput RCF (HTP-RCF) method in which batch RCF reactions are conducted in 1 mL wells machined directly into Hastelloy reactor plates. The plate reactors can seal high pressures produced by organic solvents by vertically stacking multiple reactor plates, leading to a compact and modular system capable of performing 240 reactions per experiment. Using this setup, we screened solvent mixtures and catalyst loadings for hydrogen-free RCF using 50 mg poplar and 0.5 mL reaction solvent. The system of 1:1 isopropanol/methanol showed optimal monomer yields and selectivity to 4-propyl substituted monomers, and validation reactions using 75 mL batch reactors produced identical monomer yields. To accommodate the low material loadings, we then developed a workup procedure for parallel filtration, washing, and drying of samples and a 1H nuclear magnetic resonance spectroscopy method to measure the RCF oil yield without performing liquid-liquid extraction. As a demonstration of this experimental pipeline, 50 unique switchgrass samples were screened in RCF reactions in the HTP-RCF system, revealing a wide range of monomer yields (21-36%), S/G ratios (0.41-0.93), and oil yields (40-75%). These results were successfully validated by repeating RCF reactions in 75 mL batch reactors for a subset of samples. We anticipate that this approach can be used to rapidly screen substrates, catalysts, and reaction conditions in high-pressure batch reactions with higher throughput than standard batch reactors.
The separation of 241 Am, 244 Cm and 249 Cf from rare earth elements using LN resin and lactate buffer solutions with diethylenetriaminepentaacetic acid is described with numerous columns studies. The elutions are based on TALSPEAK liquid–liquid extraction chemistry, and provide high yield (> 90%), rapid, simple separations of the trivalent actinides from the lanthanides, which is often challenging due to similarities in chemical behavior among the trivalent f-block elements. Further, all three actinides can be separated from rare earth elements, including from massless fission product samples and samples with small amounts (~ 1–5 mg) of stable lanthanides. Separations with no detectable overlap between the actinide and lanthanide elutions is possible with massless samples, and in samples with mass high separation factors can be achieved (Am/Eu: 171; Am/La: 10 6 ).
A fundamental understanding of coordination chemistry across the lanthanide series is essential for explaining the chemical behavior of rare-earth metals in complex liquid–liquid extraction processes. Probing the exact bonding between the extractant and the metal is sometimes done through the synthesis of solid-state compounds that can serve as models for metal speciation in solution. In the case of diglycolamide (DGA), a commonly used neutral diamide extractant, extensive studies identify the stepwise formation of 1:1 [Ln(DGA)(H 2 O) 6 ] 3+ , 1:2 [Ln(DGA) 2 (H 2 O) 3 ] 3+ , and 1:3 [Ln(DGA) 3 ] 3+ complexes in solution. The crystallographic reports, however, exclusively show a 1:3 [Ln(DGA) 3 ] 3+ moiety in the solid state, while the structures of 1:1 and 1:2 complexes are yet to be isolated and comprehensively studied. In this work, we report the synthesis and characterization of three new families of stoichiometric N,N,N′,N’ -tetramethyldiglycolamide (TMDGA) compounds: [Ln(TMDGA)(H 2 O) 5 Cl]Cl 2 ·2H 2 O, [Ln(TMDGA) 2 (H 2 O) 3 ]Cl 3 ·3H 2 O, and [Ln(TMDGA) 3 ]Cl 3 ·7H 2 O, where Ln = Nd, Eu, Gd, with Ln:TMDGA ratios of 1:1, 1:2, and 1:3, respectively. Further, the compounds have been analyzed using vibrational spectroscopy (both Raman and FT-IR), as well as variable temperature fluorescence spectroscopy. A spectrophotometric titration of Eu(III) was performed to confirm the presence of the [Eu(TMDGA) n ] 3+ ( n = 1, 2, and 3) species in solution and to compare the individual solid-state emission spectra to their respective analogues in solution.
Understanding complex, multistep chemical reactions at the molecular level is a major challenge whose solution would greatly benefit the design and optimization of numerous chemical processes. The separation of rare-earth (4f) and actinide (5f) elements is an example where improving our chemical understanding is important for designing and optimizing new chemistries, even with a limited number of observations. Here, in this work, we leverage data-driven artificial intelligence and machine-learning approaches to develop kinetic reaction networks that describe the liquid–liquid extraction mechanism of uranium using N,N-di-2-ethylhexyl-isobutyramide (DEHiBA). Specifically, we compare and contrast the properties of two classes of models: (1) purely data-driven models that are regularized using chemistry-agnostic, L1 regression and (2) chemistry-informed models that are regularized using relative reaction energies provided by quantum mechanical calculations. We observe that purely data-driven models are unbiased, simple, and accurate in their predictions of experimental measurements when provided with sufficient data but are difficult to fully constrain and interpret. In contrast, chemistry-informed models exhibit significantly improved chemical interpretability and consistency, providing a detailed description of the separation process while achieving high accuracy through ensemble averaging. Overall, the dominant species predicted to be extracted into the organic phase is UO 2 (NO 3 ) 2 (DEHiBA) 2 , agreeing with experimental slope analysis, thermodynamic modeling, EXAFS, and crystal structures. This work demonstrates that leveraging the fundamental structure of the problem can lead to efficient learning schemes that provide both accurate predictions and chemical insights at a low computational cost.
Common separation techniques, such as liquid− liquid extraction, are usually used for extractions and purifications due to their industrial scalability and affordability. However, these well-established practices are hindered by low selectivity and challenges in recovering solutes and solvents. Deep eutectic solvents (DES), a fairly new type of solvent, have the potential to overcome these issues. DESs are binary mixtures whose physical properties can be tuned by selecting the appropriate precursors to facilitate and/or enhance processes such as extraction. A promising DES for selective separations is formed when lauric acid (LA) is mixed with N-methylacetamide (NMA). This LA-NMA DES has a heterogeneous microscopic structure that can solvate compounds with completely different polarities. This study explores how forming an organized structure on the mesoscale affects the solubility of nonpolar solutes in nonionic DESs. To this end, the molecular and mesoscale structures and their effect on the solubility and solvation properties are evaluated for the LA-NMA DES and two new DESs with slight chemical variations in their precursors. It is observed that the organization of the nonpolar DES domains and, consequently, of their interfaces directly relates to the solubility of nonpolar compounds. Specifically, correctly selecting the DES precursors that form organized nonpolar domains leads to an organized interface in which the nonpolar solutes are solvated, thereby increasing the solubility. Additionally, enhanced dissolution power was observed in a completely different DES with mesoscale order in its molecular structure and composed of menthol and lauric acid. The latter result further validates the proposed tunability of the DES dissolution power through organized interfaces, extending it beyond a specific DES family and opening the possibility of new extraction-tailored designer solvents.
Reductive catalytic fractionation (RCF) can produce high yields of aromatic monomers from lignin in native biomass. Quantification of these aromatic monomers is a well-known but demanding task, in part due to the lack of commercially available standards. Here, we demonstrate 1 H NMR spectroscopy as a complementary method to rapidly quantify aromatic monomer concentrations in RCF oils. The method exhibited good agreement with measurements from ultrahigh pressure liquid chromatography (UHPLC) for 96 RCF oils with varying monomer selectivity, with average absolute deviations of individual monomer yields between 0.5 and 1.1 wt % (relative 11–17%) and R 2 values above 0.9 compared to conventional UHPLC quantification. Quantification of S-type monomers, including for 4-ethylsyringol and 4-propenylsyringol, was generally reliable. The validity of G-type monomer quantifications depended on reaction selectivity due to overlap between peaks of 4-ethylguaiacol and 4-(3-hydroxypropyl)-guaiacol. The method could be applied on crude RCF oils without needing to perform the liquid–liquid extraction typically done for RCF reactions, thereby providing a convenient way to quantify lignin extraction and aromatic monomer yield. Overall, 1 H NMR spectroscopy can serve as a rapid primary quantification or secondary validation method for RCF monomer yield and selectivity measurements.
We report the first example of a polyoxometalate (POM) compound containing californium. Using a Wells–Dawson POM ligand, K 17 Cf(P 2 W 17 O 61 ) 2 ·2H 2 O was synthesized and characterized. Californium is the heaviest element ever crystalized with a POM. Significant solubility differences among the POM's f-element complexes were observed, enabling selective precipitation with separation factors rivaling liquid–liquid extraction.
The Kennedy and O’Hagan (KOH) calibration framework uses coupled Gaussian processes (GPs) to meta-model an expensive simulator (first GP), tune its “knobs” (calibration inputs) to best match observations from a real physical/field experiment and correct for any modeling bias (second GP) when predicting under new field conditions (design inputs). There are well-established methods for placement of design inputs for data-efficient planning of a simulation campaign in isolation, that is, without field data: space-filling, or via criterion like minimum integrated mean-squared prediction error (IMSPE). Analogues within the coupled GP KOH framework are mostly absent from the literature. Here, in this study, we derive a closed form IMSPE criterion for sequentially acquiring new simulator data for KOH. We illustrate how acquisitions space-fill in design space, but concentrate in calibration space. Closed form IMSPE precipitates a closed-form gradient for efficient numerical optimization. We demonstrate that our KOH-IMSPE strategy leads to a more efficient simulation campaign on benchmark problems, and conclude with a showcase on an application to equilibrium concentrations of rare earth elements for a liquid–liquid extraction reaction.
In many bioprocesses, maximum achievable titers are limited below economically viable levels by toxic accumulation of the primary end-product. To combat end-product inhibition, a variety of in situ product removal technologies have been developed to selectively remove or partition toxic bioproducts, thereby prolonging fermentation and improving overall process efficiency. Use of an in situ organic overlay to partition toxic hydrophobic products is a commonly employed approach, but this technique occupies valuable space in the fermentor, imposes replacement costs for unrecovered solvent, and increases downstream separation due to formation of stable emulsions. In addition, for many volatile hydrophobic products produced under aerobic conditions—including medium-chain alcohols, esters, monoterpenes, and other aviation fuel precursors—a significant fraction of the product is volatilized to the fermentor off-gas and must be recovered separately to maximize product yield. To address these challenges, we explore the viability of leveraging existing aeration energy to fully strip and recover volatile products from the fermentor off-gas. We compare two strategies of in situ product removal—liquid–liquid extraction and direct recovery from fermentation off-gas—for the production and recovery of intermediates used to generate isoprene and DMCO (1,4-dimethylcyclooctane), a high-performance jet fuel. We evaluate product toxicity, solvent toxicity, solvent partitioning, and the impact of aeration and internal overlay configurations on product volatilization rates. We then optimize product recovery from fermentor off-gas via condensation in chilled solvent, achieving 84% capture efficiency. In addition to greatly simplifying downstream processing, relying on aeration for product volatilization in the absence of an internal overlay enables continuous removal of toxic fermentation products up to maximum isoprenol titers of 20.4 g/L, the highest reported to date.
Industrial demand for rare earth elements (REEs) has surged over the past three decades due to their unique properties that support sustainable energy and new technologies. Separating individual REEs is challenging and hazardous, typically done through liquid-liquid extraction. There is an urgent need for environmentally friendly and efficient separation technologies for REEs. Porous materials offer promising advances for sustainable REE separation via ion-selective capture. We hypothesize that REE separation can be efficiently achieved in reactive nanopores, such as Zr(IV) and Cr(III) metal-organic frameworks (MOFs), through surface functionalization. By integrating material synthesis, interfacial chemistry experiments, theory, computation, and machine learning, we gained insights into the chemical factors controlling REE speciation and their competitive adsorption on MOFs. Our findings show that these materials’ selectivity can be tuned by surface functionalization. The machine learning component addressed ion-specific diffusion based on MOF topology and chemistry.
The long-term objective of this project is to develop new, more energy-efficient and environmentally benign separations of the rare earth elements. The current approaches to separate the rare earth elements employ liquid-liquid extraction methods, using a biphasic mixture of aqueous and organic solvents containing different metal-binding agents. Although a significant amount of work has been carried out to develop new organic-phase extractants, significantly less has been executed for the design of aqueous complexants. Our approach to achieve better rare earth separations is to modify and optimize these aqueous complexants for achieving different rare earth-binding properties. Once synthesized, these new complexants were evaluated for more environmentally friendly and energy-efficient separations of the rare earth elements.
The CELSS (controlled ecological life support system) resource recovery system, which is a waste processing system, uses aerobic and anaerobic bioreactors to recover plants nutrients and secondary foods from the inedible biomass. The anaerobic degradation of the inedible biomass by means of culture of rumen bacteria,generates organic compounds such as volatile fatty acids (acetic, propionic, butyric, VFA) and ammonia. The presence of VFA in the bioreactor medium at fairly low concentrations decreases the microbial population's metabolic reactions due to end-product inhibition. Technologies to remove VFA continuously from the bioreactor are of high interest. Several candidate technologies were analyzed, such as organic solvent liquid-liquid extraction, adsorption and/or ion exchange, dialysis, electrodialysis, and pressure driven membrane separation processes. The proposed technique for the on-line removal of VFA from the anaerobic bioreactor was a nanofiltration membrane recycle bioreactor. In order to establish the nanofiltration process performance variables before coupling it to the bioreactor, a series of experiments were carried out using a 10,000 MWCO tubular ceramic membrane module. The variables studied were the bioreactor slurry permeation characteristics, such as, the permeate flux, VFA and the nutrient removal rates as a function of applied transmembrane pressure, fluid recirculation velocity, suspended matter concentration, and process operating time. Results indicate that the permeate flux, VFA and nutrients removal rates are directly proportional to the fluid recirculation velocity in the range between 0.6 to 1.0 m/s, applied pressure when these are low than 1.5 bar, and inversely proportional to the total suspended solids concentration in the range between 23,466 to 34,880. At applied pressure higher than 1.5 bar the flux is not more linearly dependent due to concentration polarization and fouling effects over the membrange surface. It was also found that the permeate flux declines rapidly during the first 5 to 8 hours, and then levels off with a diminishing rate of flux decay.
Contamination of potable water supplies with halogenated phenols in concentrations of 2-10 parts per billion (ppb) produces objectionable tastes and odors capable of influencing consumer acceptability. Routine analysis by the distillation/ 4-aminoantipyrine method is limited by lack of sensitivity and subject to interference by aryl amines. This has been overcome by developing a continuous liquid-liquid extraction system to selectively isolate phenols and eliminate major interfering substances. Stable reagents have been formulated to reduce blank color and extend sensitivity. Equipment suitable for analysis of phenols at the 1 ppb level or less in 20 minutes is described.