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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Electron Glass Phase with Resilient Zhang-Rice Singlets in LiCu 3 ⁢O 3

LiCu 3 ⁢O 3 is an antiferromagnetic mixed valence cuprate where trilayers of edge-sharing Cu(II)O (3⁢d 9 ) are sandwiched in between planes of Cu(I) (3⁢d 10 ) ions, with Li stochastically substituting Cu(II). Angle-resolved photoemission spectroscopy (ARPES) and density functional theory reveal two insulating electronic subsystems that are segregated in spite of sharing common oxygen atoms: a Cu d z 2 /O p z derived valence band (VB) dispersing on the Cu(I) plane, and a Cu 3⁢d x 2 -y 2 /O 2⁢p x,y derived Zhang-Rice singlet (ZRS) band dispersing on the Cu(II)O planes. First-principle analysis shows the Li substitution to stabilize the insulating ground state, but only if antiferromagnetic correlations are present. Li further induces substitutional disorder and a 2D electron glass behavior in charge transport, reflected in a large 530 meV Coulomb gap and a linear suppression of VB spectral weight at E F that is observed by ARPES. Surprisingly, the disorder leaves the Cu(II)-derived ZRS largely unaffected. Finally, this indicates a local segregation of Li and Cu atoms onto the two separate corner-sharing Cu⁡(II)⁢O 2 sub-lattices of the edge-sharing Cu(II)O planes, and highlights the ubiquitous resilience of the entangled two hole ZRS entity against impurity scattering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

System Regulates the Water Contents of Fuel-Cell Streams

An assembly of devices provides for both humidification of the reactant gas streams of a fuel cell and removal of the product water (the water generated by operation of the fuel cell). The assembly includes externally-sensing forward-pressure regulators that supply reactant gases (fuel and oxygen) at variable pressures to ejector reactant pumps. The ejector supply pressures depend on the consumption flows. The ejectors develop differential pressures approximately proportional to the consumption flow rates at constant system pressure and with constant flow restriction between the mixer-outlet and suction ports of the ejectors. For removal of product water from the circulating oxygen stream, the assembly includes a water/gas separator that contains hydrophobic and hydrophilic membranes. The water separator imposes an approximately constant flow restriction, regardless of the quality of the two-phase flow that enters it from the fuel cell. The gas leaving the water separator is nearly 100 percent humid. This gas is returned to the inlet of the fuel cell along with a quantity of dry incoming oxygen, via the oxygen ejector, thereby providing some humidification.

Vasquez, Arturo↗
DOE OSTI2022

Kinetics and evolution of solid-state metal dealloying in thin films with multimodal analysis

Thin-film solid-state metal dealloying (thin-film SSMD) is an emerging technique that uses self-organization to design nanostructured thin films. The resulting 3D bicontinuous nanostructures are promising for a wide range of applications, such as catalysis and energy storage. In this work, we prepared thin films by SSMD using Ti-Cu as the parent alloy and Mg as the solvent. Using a multimodal approach, we combined synchrotron X-ray spectroscopy, diffraction, and high-resolution electron-based spectroscopy and imaging to study their morphological, structural, and chemical evolution. The processing-structure relationship was analyzed as a function of parent alloy composition and dealloying temperature and time. Morphological transitions from globular, to lamellar, to bicontinuous structures, in conjunction with a ligament size evolution, were identified as functions of the parent alloy composition. The dealloying rate increased with increasing concentration of interdiffusing elements (dissolving component) in the parent alloy. The parting limit, a dealloying compositional threshold, was systematically analyzed and determined to be 30%–40%. The order of crystalline phase formation is CuMg 2 , Cu 2 Mg, and Ti; the Ti phase first shows self-reorganization during dealloying, separate from the crystallization process. The coarsening in thin-film SSMD was identified and not entirely self-similar; in addition to the increase of ligament size over time, the formation of larger globular ligaments were also observed. This work furthers our fundamental understanding of thin-film SSMD and nanostructured thin-film design, where the thermodynamic and kinetic effects differ from the bulk counterparts. The fact that dealloying and diffusion outpaces the crystallization and new phase formation also offers opportunities to utilize thin-film SSMD in certain alloy systems in which deleterious intermetallic phases need to be suppressed, that may not be possible in the bulk geometry.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Discovery of charge density wave in a kagome lattice antiferromagnet

A hallmark of strongly correlated quantum materials is the rich phase diagram resulting from competing and intertwined phases with nearly degenerate ground state energies. A well-known example is the copper oxides, where a charge density wave (CDW) is ordered well above and strongly coupled to the magnetic order to form spin-charge separated stripes that compete with superconductivity. Recently, such rich phase diagrams have also been revealed in correlated topological materials. In two-dimensional kagome lattice metals consisting of corner-sharing triangles, the geometry of the lattice can produce flat bands with localized electrons, non-trivial topology, chiral magnetic order, superconductivity and CDW order. While CDW has been found in weakly electron correlated nonmagnetic AV 3 Sb 5 (A = K, Rb, Cs), it has not yet been observed in correlated magnetic ordered kagome lattice metals. Here we report the discovery of CDW within the antiferromagnetic (AFM) ordered phase of kagome lattice FeGe. The CDW in FeGe occurs at wavevectors identical to that of AV 3 Sb 5 , enhances the AFM ordered moment, and induces an emergent anomalous Hall effect. Furthermore, our findings suggest that CDW in FeGe arises from the combination of electron correlations-driven AFM order and van Hove singularities-driven instability possibly associated with a chiral flux phase, in stark contrast to strongly correlated copper oxides and nickelates, where the CDW precedes or accompanies the magnetic order.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Experimental Investigation of Interactions Between Two Closely Spaced Azimuthal Modes in a Multinozzle Can Combustor

Thermoacoustic instabilities in annular or circular combustors are often coupled with azimuthal modes. These modes can be characterized by a spin ratio (SR), which quantifies the dominant mode between two counter-rotating waves, and a phase difference between them, which is directly related to the orientation of the antinodal line. This study investigates the instability amplitudes, SR, and phase difference of two closely spaced (3% of their mean frequency), yet distinct azimuthal modes; one is the first azimuthal (1A) mode, and the other is a combination of first azimuthal and first longitudinal (1A1L) mode. Each mode itself consists of two peaks that are spaced even more closely in frequency (0.8%). Furthermore, distinct harmonics at 2× and 3× of these frequencies, presumably associated with nonlinearities, are also evident in the spectra. Each mode is bandpass filtered in spectrum to analyze them separately. For the 1A mode, the SR and phase difference exhibit a variety of behaviors—including quasi-periodic standing waves, spinning waves, and intermittency—depending on operating conditions such as thermal power and azimuthal fuel staging. Similar trends are observed for the 1A1 L mode. Moreover, there is clear coupling between the 1A and 1A1 L modes, as their SRs are almost synchronized during the quasi-periodic standing wave. This synchronization is observed in phase differences as well, but not in the instability amplitude. For spinning dominant wave conditions, the SRs of each mode have similar average values, but they fluctuate in a seemingly random fashion. For the phase difference, both average and fluctuation are not correlated. In contrast, the instability amplitudes are strongly correlated, with modulation of the 1A mode leading to that of the 1A1 L mode. Furthermore, these results clearly indicate that complex coupling occurs across closely spaced frequencies under instability conditions, coupling that must be understood in order to capture limit cycle dynamics.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2020

Multi-orbital-phase and Multiband Characterization of Exoplanetary Atmospheres with Reflected Light Spectra

Direct imaging of widely separated exoplanets from space will obtain their reflected light spectra and measure atmospheric properties. Previous calculations have shown that a change in the orbital phase would cause a spectral signal, but whether this signal may be used to characterize the atmosphere has not been shown. We simulate starshade-enabled observations of the planet 47 UMa b, using the present most realistic simulator Starshade Imaging Simulation Toolkit for Exoplanet Reconnaissance to estimate the uncertainties due to residual starlight, solar glint, and exozodiacal light. We then use the Bayesian retrieval algorithm ExoReL{sup R} to determine the constraints on the atmospheric properties from observations using a Roman- or Habitable Exoplanet Observatory (HabEx)-like telescope, comparing the strategies to observe at multiple orbital phases or in multiple wavelength bands. With a ∼20% bandwidth in 600–800 nm on a Roman-like telescope, the retrieval finds a degenerate scenario with a lower gas abundance and a deeper or absent cloud than the truth. Repeating the observation at a different orbital phase or at a second 20% wavelength band in 800–1000 nm, with the same integration time and thus degraded signal-to-noise ratio (S/N), would effectively eliminate this degenerate solution. Single observation with a HabEx-like telescope would yield high-precision constraints on the gas abundances and cloud properties, without the degenerate scenario. These results are also generally applicable to high-contrast spectroscopy with a coronagraph with a similar wavelength coverage and S/N, and can help design the wavelength bandwidth and the observation plan of exoplanet direct-imaging experiments in the future.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

High-pressure CO 2 permeation properties and stability of ceramic-carbonate dual-phase membranes

CO 2 permeation properties and stability of ceramic-carbonate dual-phase membranes at high pressures/temperatures are critical to their CO 2 separation and membrane reactor applications, but such data are not available in the literature. Here, this work aims to study the effect of high transmembrane pressure on CO 2 permeation flux and the stability of molten carbonate in the dual-phase samarium-doped ceria (SDC) and molten-carbonate (MC) membranes. Dead-end porous SDC tubular supports were made by a cold isostatic press (CIP)/sintering method with a low porosity (below 7%), and gas-tight SDC-MC membranes were prepared by direct infiltration of molten lithium and sodium carbonate mixture into SDC pores, with a MC volume fraction less than 7%. CO 2 permeation/separation tests were performed on the SDC-MC membranes using feed gas of equal molar CO 2 /N 2 mixture at feed pressures up to 15 atm and sweep gas of helium at 1 atm. CO 2 permeation flux for the SDC-MC membranes depends logarithmically on feed/permeate CO 2 pressure ratio in 660–810°C. The temperature dependence of CO 2 permeation shows activation energy of 30 kJ/mol. Due to the small MC volume fraction and hence low effective carbonate conductivity, CO 2 permeation of the SDC-MC membranes is dominated by the carbonate ionic conduction in the MC phase. The SDC-MC membranes remain in the same structure, morphology, and gas-tightness after CO 2 separation tests at high feed pressures and temperatures, showing high stability of SDC-MC membranes for high-temperature, high-pressure separation and chemical reaction applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Antiphase boundary migration as a diffusion mechanism in a P3 sodium layered oxide

The electrode materials of Na-ion batteries must exhibit fast ion transport, a property that is often negatively impacted when mobile cations order. Many layered Na (and K) intercalation compounds adopt the P3 crystal structure, which tends to stabilize cation-vacancy orderings over a wide range of Na concentrations. The ordered phases have been predicted to consist of domains that are periodically separated by antiphase boundaries (APBs) to accommodate variations in Na concentration. The mechanisms and rates with which Na diffuses within such ordered phases of P3 are not understood. We have conducted a first-principles study of Na diffusion in the P3 structure, using Na x CoO 2 as a model system. We find that most simple nearest-neighbor hops in Na-vacancy ordered phases in P3 result in unstable configurations and are therefore forbidden. We identify an alternative mechanism of Na transport that is mediated by APB migration via the formation and expansion of kinks along domain boundaries. The limiting kinetic barriers for this mechanism are quite low (0.03 to 0.30 eV). Vacancy defects are not required, and furthermore have formation energies that are higher than those of the APB kink defects. Furthermore, our results suggest that APB migration is a fundamental diffusion mechanism in the P3 structure.

36 MATERIALS SCIENCE↗
NASA NTRS1996

Early Energetic Particle Irradiation of the HED Parent Body Regolith

Previous studies have shown that many individual grains within the dark phase of the Kapoeta howardite were irradiated with energetic particles while residing on the surface of the early HED regolith. Particle tracks in these grains vary in density by more than an order of magnitude and undoubtedly were formed by energetic heavy (Fe) ions associated with early solar flares. Early Irradiation of HED Regolith: Concentrations of excess Ne alone are not sufficient to decide between competing galactic and solar irradiation models. However, from recent studies of depth samples of oriented lunar rocks, we have shown that the cosmogenic 21-Ne/22-Ne ratio produced in feldspar differs substantially between Galactic Cosmic Radiation (GCR) and solar protons, and that this difference is exactly that predicted from cross-section data. Using Ne literature data and new isotopic data we obtained on acid-etched, separated feldspar from both the light and dark phases of Kapoeta, we derive 21-Ne/22-Ne = 0.80 for the recent GCR irradiation and 21-Ne/22-Ne = 0.68 for the early regolith irradiation. This derived ratio indicates that the early Ne production in the regolith occurred by both galactic and solar protons. If we adopt a likely one-component regolith model in which all grains were exposed to galactic protons but individual grains had variable exposure to solar protons, we estimate that this early GCR irradiation lasted for about 3-6 m.y. More complex two-component regolith models involving separate solar and galactic irradiation would permit this GCR age to be longer. Higher-energy solar protons would permit the GCR to be longer. Higher-energy solar protons would permit the GCR age to be shorter. Further, cosmogenic 126(Xe) in Kapoeta dark is no more than a factor of about 2 higher than that observed in Kapoeta light. Because 126(Xe) can only be formed by galactic protons and not solar protons, these data support a short GCR irradiation for the HED regolith. This would also be the maximum time peRiod for the solar irradiation. Various asteroidal regolith models, based on Monte Carlo modeling of impact rates as a function of size and on irradiation features of meteorites, predict surface exposure times of about 0.1 to 10 m.y., and depend on such factors as gravity, rock mechanical properties, and micrometeoroid flux. Because the depth at which solar Fe tracks are produced (is much less than 1 micrometer) is much less than the depth at which Solar Cosmic Rays (SCR) Ne is produced (about 1 cm), for a reasonably well-stirred HED regolith the "surface exposure time" for SCR 21-Ne production should be significantly longer than that for solar tracks and some other surface irradiation features. Enhanced Solar Proton Irradiation: For bulk samples of Kapoeta dark feldspar and a one-component regolith model, the derived ratio of 21-Ne/22-Ne = 0.68 implies that the early production ratio of SCR 21-Ne to GCR 21-Ne was about 0.5-1.5. This ratio is independent of any assumptions about the fraction of dark grains that are irradiated or of the variability in the degree of solar irradiation among grains. The 21-Ne SCR/GCR ratio indirectly derived from bulk Kapoeta pyroxene is somewhat larger, as is the ratio derived for simple two-component regolith models. Individual feldspar grains that were extensively solar irradiated would require even larger 21-Ne SCR/GCR production ratios. In contrast, the theoretical SCR/GCR production ratio for lunar feldspar with 0 g/CM2 shield ing is is less than or equal to 2, and the lowest ratio observed in near-surface samples of lunar anorthosites is less than or equal to 1. Considering the greater solar distance of Vesta (compared to the Moon), the likelihood that SCR 21-Ne was acquired under some shielding where production rates are lower, and the likelihood that the exposure time to galactic protons exceeded the exposure time to solar protons because of their very different penetration depths, the 21-Ne SCR/GCR production ratio on the HED parent body was probably < 0.1. The relatively large difference between the derived 21-Ne SCR/GCR ratio in Kapoeta dark feldspar and the estimated production ratio strongly indicates that the early solar irradiation involved a flux -20-50x the recent solar flux. This enhanced proton flux was probably associated with an overall greater solar activity in the first approximately 10(exp 7) to 10(exp 8) years of solar history.

Bogard, D. D.↗
DOE OSTI2023

Thermal Characterization of Acid Treated Anion Exchange Resins

Anion exchange is a chemical separation and purification technique in which a solid phase ion exchanging material (i.e., anion exchange resin beads) interchanges its anions with the desired anions from a solution phase. Typical anion exchange resins (e.g., Bio-Rad AG 1-X8 strongly basic anion exchange resin) consist of a polymer resin bead of cross-linked polystyrene with quaternary ammonium functional groups (Figure 1). Anion exchange occurs at the resin functional groups by exchange of the counter ion of the quaternary ammonium (typically chloride or nitrate) for the anionic species of interest. Other resin polymers have been developed—such as cross-linked vinylpyridine/divinylbenzene utilized in Reillex HPQ anion exchange resin—to improve the resins’ resistance against degradation by oxidizing agents, strong acids, and radiation. Anion exchange is performed for the separation of transuranic (TRU) elements throughout the Department of Energy complex. At the Los Alamos National Laboratory (LANL), production scale quantities of these resins are handled at the Chemistry and Metallurgy Research Facility, the Plutonium Facility, and the Transuranic Waste Facility. Spent anion exchange resin will eventually be disposed of as TRU waste. This has prompted concerns regarding its safe disposal under potential hazard scenarios, in particular a thermal excursion of a TRU waste drum. There is a concern that a potential thermal excursion of a TRU waste drum containing anion exchange resin previously contacted with nitric acid may result in energetic side reactions and pressure buildup due to resin degradation by nitric acid and heat. Therefore, the objective of the experiments described in this report was to gather qualitative and quantitative data to support decisions regarding the thermal stability and safe disposal strategy of nitric acid treated anion exchange resins utilized in TRU processing operations.

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

Predicting Multicomponent Aqueous Phase Adsorption Equilibria of Organic Acids Using the Generalized Brunauer–Emmett–Teller Isotherm Model

Here, to support process development of adsorptive separation of organic acids, this work presents a thermodynamic modeling methodology to predict multicomponent aqueous phase organic acid adsorption equilibria from single-component adsorption isotherms using the generalized Brunauer–Emmett–Teller isotherm model (gBET). With the organic acid fugacities rigorously accounting for the aqueous phase organic acid solution chemistry and solution nonideality, gBET precisely represents the single-component adsorption isotherms and accurately predicts the binary and ternary mixed-acid adsorption equilibria for the ranges of initial pH (∼3–7), acid concentration (100–400 mmol/L), and temperature (298.15–328.15 K) with less than 10% average absolute relative deviation. In addition, gBET with pH-independent parameters provides insights into the underlying adsorption phenomena, including the adsorbate loadings and compositions in the monolayer and subsequent layers under varying initial pH, temperature, concentration, and composition. The gBET model predictions outperform the predictions from the overloading model and the Ideal Dilute Solution Theory.

09 BIOMASS FUELS↗
NASA NTRS2002

Food-anticipatory activity and liver per1-luc activity in diabetic transgenic rats

The mammalian Per1 gene is an important component of the core cellular clock mechanism responsible for circadian rhythms. The rodent liver and other tissues rhythmically express Per1 in vitro but typically damp out within a few cycles. In the liver, the peak of this rhythm occurs in the late subjective night in an ad lib-fed rat, but will show a large phase advance in response to restricted availability of food during the day. The relationship between this shift in the liver clock and food-anticipatory activity (FAA), the circadian behavior entrained by daily feeding, is currently unknown. Insulin is released during feeding in mammals and could serve as an entraining signal to the liver. To test the role of insulin in the shift in liver Per1 expression and the generation of FAA, per-luciferase transgenic rats were made diabetic with a single injection of streptozotocine. Following 1 week of restricted feeding and locomotor activity monitoring, liver was collected for per-luc recording. In two separate experiments, FAA emerged and liver Per1 phase-shifted in response to daytime 8-h food restriction. The results rule out insulin as a necessary component of this system.

NASA Discipline Space Human Factors↗
DOE OSTI2026

Pinning ångström-size solid ionic channels for rare-earth element separation

High-purity rare-earth elements are essential for modern technologies, yet current solvent extraction processes are energy-intensive and environmentally harmful because of inadequate selectivity and ligand toxicity. Although combining size exclusion and binding affinity can improve lanthanide separation, the role of long-range confinement remains underexplored. Here we report lanthanide separation in aqueous systems using extremely confined manganese oxide solid ionic channels with optimized layer spacing. Different lanthanides induce distinct solid-state phase transformations in manganese oxide, creating a strong driving force for separation. Two lanthanide groups, differing by ~1.4 Å in spacing, were identified and confirmed to be stable by density functional theory. The narrower confinement of heavier Group II lanthanides improves cross-group separation by increasing the dehydration barrier for lighter Group I lanthanides without inducing strong binding. Here, we further developed a strategy to pin the confinement dimensions and enhance same-group separation, increasing enrichment factors for La–Nd and La–Pr pairs from 1.6 ± 0.1 and 1.5 ± 0.1 to 5.4 ± 0.1 and 4.2 ± 0.1, respectively.

Chemical engineering↗
DOE OSTI2026

Separation and Recovery of High-Purity Dysprosium from Electric Vehicle Scrap Permanent Magnets Using Cyanex 572, a Cationic Extractant in a Membrane Solvent Extraction Process

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.

electrical vehicle magnets↗
DOE OSTI2024

Formation of Disordered Cocontinuous Phases by Randomly Linked Star Copolymers

Cocontinuous polymeric nanostructures have garnered significant interest due to their ability to combine different properties of two separate polymer domains. Randomly linked copolymer networks have proven to be especially robust for formation of disordered cocontinuous phases across wide composition ranges (≈30 wt % or more). While theoretical treatments of microphase-separated networks have focused primarily on the role of random elastic forces imposed on the self-assembled nanostructures by virtue of the network architecture, experimental studies seeking to disentangle these contributions from other potential effects, such as dispersity in preferred interfacial curvatures, have been scarce. To provide insight into this matter, we here study the self-assembly of randomly linked star copolymers (RSCs), constructed by linking premade polymer arms of polystyrene (PS) and poly(d,l-lactide) (PLA) using 3, 4, and 6-functional connectors. This architecture yields similar distributions of preferred curvature as networks made using corresponding difunctional strands, but lacks the elastic forces imposed by a network architecture. Gravimetry and small-angle X-ray scattering, coupled with scanning electron microscopy, were performed to identify the percolation of PS/PLA RSCs. Remarkably, the 4-arm RSC system exhibited a disordered cocontinuous window of ≈25 wt %, indicating that dispersity in preferred curvature can in some cases be sufficient to robustly drive formation of this morphology. However, the other RSC architectures showed smaller cocontinuous ranges, which we interpret in terms of the influence of homopolymer stars in the 3-arm case and the narrower distribution of preferred interfacial curvatures in the 6-arm case. Finally, thin layers of interconnected porous PS were achieved by solution-processing, suggesting that RSCs have the potential to serve as a robust and easily processable cocontinuous polymeric nanomaterials in both bulk and membrane geometries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2019

The Non-Destructive Separation of Diverse Astrobiologically Relevant Organic Molecules By Customizable Capillary Zone Electrophoresis and Monolithic Capillary Electrochromatography

The in situ detection of organic molecules in space is key to understanding the variety and the distribution of the building blocks of life, and possibly the detection of extraterrestrial life itself. Gas chromatography mass spectrometry (GC-MS) has been the most sensitive analytical instrument for organic analyses in flight, and was used on missions from NASA’s Viking, Phoenix, Curiosity missions to ESA’s Rosetta space probe. While pyrolysis GC-MS revealed the first organics on Mars, this step alters or degrades certain fragile molecules that are excellent biosignatures including polypeptides, oligonucleotides and polysaccharides, rendering the intact precursors undetectable. We have identified a solution tailored to the detection of biopolymers and other biomarkers by the use of liquid-based capillary electrophoresis and electrochromatography. In this study, we show that a capillary electrochromatography (CEC) approach using monolithic stationary phases with tailor-made surface chemistry can separate and identify various polycyclic aromatic hydrocarbons (PAHs), nucleobases and aromatic acids that could be formed under astrophysically relevant conditions. In order to simulate flyby organic sample capture, we conducted hypervelocity impact experiments which consisted of accelerating peptide-soaked montmorillonite particles to a speed of 5.6 km/sec, and capturing them in an amorphous silica aerogel of 10 and 30 mg/cc bulk density. Bulk peptide extraction from aerogel followed by capillary zone electrophoresis led to the detection of only two stereoisomeric peptide peaks. The recovery rates of each step of the extraction procedure after the hypervelocity impact suggest that major peptide loss occurred during the impact. Our study provides initial exploration of feasibility of this approach for capturing intact peptides, and subsequently detecting candidate biomolecules during flight missions that would be missed by GC-MS alone. As the monolith-based electrochromatography technology could be customized to detect specific classes of compounds as well as miniaturized, these results demonstrate the potential of the instrumentation for future astrobiology-related spaceflight missions.

Flyby sample return↗
DOE OSTI2020

Experimental Study of the Effect of Start of Injection and Blend Ratio on Single Fuel Reformate RCCI

Abstract A new concept of single fuel reactivity-controlled compression ignition (RCCI) has been proposed through the catalytic partial oxidation (CPOX) reformation of diesel fuel. The reformed fuel mixture is then used as the low reactivity fuel and diesel itself is used as the high reactivity fuel. In this paper, two reformate mixtures from the reformation of diesel were selected for further analysis. Each reformate fuel mixture contained a significant fraction of inert gases (89% and 81%). The effects of the difference in the molar concentrations of the reformate mixtures were studied by experimenting with diesel as the direct injected fuel in RCCI over a varying start of injection timings and different blend ratios (i.e., the fraction of low and high reactivity fuels). The reformate mixture with the lower inert gas concentration had earlier combustion phasing and shorter combustion duration at any given diesel start of injection timing. The higher reactivity separation between reformate mixture and diesel, compared with gasoline and diesel, causes the combustion phasing of reformate-diesel RCCI to be more sensitive to the start of injection timing. The maximum combustion efficiency was found at a CA50 before top dead center (TDC), whereas the maximum thermal efficiency occurs at a CA50 after TDC. The range of energy-based blend ratios in which reformate-diesel RCCI is possible is between 25% and 45%, limited by ringing intensity (RI) at the low limit of blend ratios, and coefficient of variance (COV) of net indicated mean effective pressure (IMEPn) and combustion efficiency at the high limit. Intake boosting becomes necessary due to the oxygen deficiency caused by the low energy density of the reformate mixtures as it displaces intake air.

Engineering↗

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