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At least 181 records · Page 10

Hydrocyclization/Defluorination of CF 3 ‐Substituted Acrylamides: Insights from Kinetics of Hydrogen Atom Transfer

Abstract The introduction of F‐containing groups into organic molecules can significantly alter their physical and chemical properties. Particularly, gem ‐difluoroalkenes serve as versatile precursors for a broad variety of organofluorine compounds, commonly used in agrochemicals, pharmaceuticals, and materials science. Based on the kinetics of H• transfer to acrylamide ( k H = 2.28 × 10 −4 M −1 s −1 at 300 K in toluene), the study describes a nickel‐hydride‐(or Li[BEt 3 H]) initiated hydrocyclization/defluorination of CF 3 ‐substituted acrylamides, offering alternative access to 4‐fluorovinyl‐substituted 2‐pyrrolidones (Seletracetam derivatives that are antiepileptic drug candidates). This process proceeds with high yields and remarkable chemo‐ and regioselectivity. The hydrocyclization/defluorination can be initiated by either H• or H – transfer, followed by a 5‐exo‐trig cyclization and subsequent fluorine elimination. The strategy has been applied in the late‐stage functionalization of drug molecules, providing a valuable tool in the synthesis of pharmaceutical compounds.

Wan, Yanjun [College of Pharmaceutical Sciences Zh↗

Polymer coatings on zirconia microspheres via rotating flow fluid dynamics

Conventional tristructural isotropic (TRISO) coatings for nuclear fuels require multi-step and expensive formation processes; any breakage of the coatings may lead to fission species release. Polymer derived ceramic (PDC) coatings can be a suitable alternative to address these issues. In this study, allylhydridopolycarbosilane (SMP-10) coatings were created on yttria stabilized zirconia (YSZ) microspheres using a Rotating Flow Fluid Dynamics (RFFD) coating method. The effects of curing temperature, rotation speed, and coating cycle/time on the coating were analyzed. Surface functionalization of YSZ microspheres with NaOH resulted in good adhesion between the polymer precursor and the YSZ kernel particles. Spectroscopy analysis revealed complete curing of SMP-10 coated YSZ at 160 °C. Rotation speed and coating time significantly affect the coating characteristics. After 3 cycles at lower rotation speed (50 rpm) for 10 min each, the coating obtained was uniform and homogeneous. In comparison, the coating showed almost 10 times less eccentricity at a high rotation speed of 300 rpm. Compared with the coatings prepared at 300 rpm condition, the coatings have higher sphericity and lower eccentricity at 50 rpm. Overall, this study provides a novel and effective route for fabricating and curing SMP-10 precursor coatings on YSZ microspheres.

Ravi, Nivetha [University of Alabama, Birmingham]↗

Thermodynamics of MgO Atomic Layer Deposition Surface Reactions

The realities of atomic layer deposition (ALD) surface reactions often deviate from the simple ligand exchange frequently used to illustrate the technique. A detailed understanding of these reactions is necessary to develop greater surface synthetic control including chemical selectivity for patterning or to target defects. Here, the thermodynamics of surface reactions relevant to MgO ALD were investigated using pyroelectric calorimetry to measure the time-resolved heat generation. These reactions show exothermic heat generation of 0.12 mJ/cm 2 and 0.15 mJ/cm 2 for alternating Mg(CpEt) 2 and H 2 O reactions, respectively. The total reaction heat closely matches the standard reaction enthalpy for bulk MgO, supplemented with first-principles molecular calculations. First-principles models further reveal that while simple ligand exchange is favorable during surface reactions, the required increase in Mg-coordination number from two in the precursor to six in bulk MgO requires additional coverage-dependent surface reactions, which depend on the availability and stability of proximal surface hydroxyls.

36 MATERIALS SCIENCE↗

Global Warming in the Twenty-First Century: An Alternative Scenario

A common view is that the current global warming rate will continue or accelerate. But we argue that rapid warming in recent decades has been driven mainly by non-CO2 greenhouse gases (GHGs), such as chlorofluorocarbons, CH4, and N2O, not by the products of fossil fuel burning, CO2 and aerosols, the positive and negative climate forcings of which are partially offsetting. The growth rate of non-CO2 GHGs has declined in the past decade. If sources of CH4 and O3 precursors were reduced in the future, the change in climate forcing by non-CO2 GHGs in the next 50 years could be near zero. Combined with a reduction of black carbon emissions and plausible success in slowing CO2 emissions, this reduction of non-CO2 GHGs could lead to a decline in the rate of global warming, reducing the danger of dramatic climate change. Such a focus on air pollution has practical benefits that unite the interests of developed and developing countries. However, assessment of ongoing and future climate change requires composition specific long-term global monitoring of aerosol properties.

Hansen, James↗

Global Warming in the Twenty-First Century: An Alternative Scenario

A common view is that the current global warming rate will continue or accelerate. But we argue that rapid warming in recent decades has been driven mainly by non-CO2 greenhouse gases (GHGs), such as chlorofluorocarbons, CH4, and N2O, not by the products of fossil fuel burning, CO2 and aerosols, the positive and negative climate forcings of which are partially offsetting. The growth rate of non-CO2 GHGs has declined in the past decade. If sources of CH4 and O3 precursors were reduced in the future, the change in climate forcing by non-CO2 GHGs in the next 50 years could be near zero. Combined with a reduction of black carbon emissions and plausible success in slowing CO2 emissions, this reduction of non-CO2 GHGs could lead to a decline in the rate of global warming, reducing the danger of dramatic climate change. Such a focus on air pollution has practical benefits that unite the interests of developed and developing countries. However, assessment of ongoing and future climate change requires composition specific long-term global monitoring of aerosol properties.

Hansen, James↗

Robust and tunable oxide nanoscrolls for solar-driven H 2 generation and storage

Hydrogen gas is a promising alternative to fossil fuels due to its high energy output and environmentally safe byproducts. Various morphologies of photocatalytic materials have been explored for high-efficiency H 2 production, for instance, quasi-1D nanoscroll structures that provide a larger surface-to-volume ratio. Recently, we predicted layer-by-layer formation of stable oxide nanoscrolls directly from dichalcogenide precursors, eliminating the need for costly formation of two-dimensional oxides for a roll-up synthesis of nanoscrolls. Here, in this study, we evaluate the suitability of those oxide nanoscroll materials—MoO 3 , WO 3 , PdO 2 , HfO 2 , and GeO 2 —for solar-driven photocatalytic H 2 production and storage. Using excited state theory coupled with Bethe–Salpeter equation simulations, we discern their electronic and optical properties as a function of interlayer scroll spacing and find them to be highly conducive for solar-driven photocatalysis. Additionally, using ab initio molecular dynamics simulations, we show that they are also suitable for H 2 storage as the nanoscrolls exhibit an effective trapping of hydrogen, even in the presence of defects and vacancies in the oxides. This work thus demonstrates the discovery of robust and tunable oxide nanoscrolls as materials for advancing solar-driven hydrogen technologies.

Chemical compounds↗

A requirement for an active proton delivery network supports a compound I-mediated C–C bond cleavage in CYP51 catalysis

CYP51 enzymes (sterol 14α-demethylases) are cytochromes P450 that catalyze multistep reactions. The CYP51 reaction occurs in all biological kingdoms and is essential in sterol biosynthesis. It removes the 14α-methyl group from cyclized sterol precursors by first forming an alcohol, then an aldehyde, and finally eliminating formic acid with the introduction of a Δ14–15 double bond in the sterol core. The first two steps are typical hydroxylations, mediated by an electrophilic compound I mechanism. The third step, C–C bond cleavage, has been proposed to involve either compound I (i.e. FeO 3+ ) or, alternatively, a proton transfer-independent nucleophilic ferric peroxo anion (compound 0, i.e. Fe 3+ O 2 – ). In this work, using comparative crystallographic and biochemical analyses of WT human CYP51 (CYP51A1) and its D231A/H314A mutant, whose proton delivery network is destroyed (as evidenced in a 1.98-Å X-ray structure in complex with lanosterol), we demonstrate that deformylation of the 14α-carboxaldehyde intermediate requires an active proton relay network to drive the catalysis. These results indicate a unified, compound I-based mechanism for all three steps of the CYP51 reaction, as previously established for CYP11A1 and CYP19A1. We anticipate that our approach can be applied to mechanistic studies of other P450s that catalyze multistep reactions, such as C–C bond cleavage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Annealing of aromatic polyimide precursors

A study has been made of the thermal behavior of polyimide precursors: an isomeric pair of crystals of the complex formed by p-phenylenediamine with the separated isomers of the di-isopropyl ester of pyromellitic acid. Specimens of this material were isothermally annealed in the temperature range 120 C to 170 C for periods of time up to 1 week. Although this temperature range is well below that customarily used for imidizations, the working hypothesis was that it would be more likely that a polymer embodying at least part of the precursor structure could be formed if the molecular motion was minimized to that actually required for the formation of the imide linkage. The progress of the annealing was followed by: infrared spectroscopy, differential thermal analysis, powder X-ray diffraction, and thermal gravimetric analysis. Single crystal X-ray analysis of the meta monomer yields a structure of chains of alternating acid and base and suggests that this monomer is amenable to polymerization with a minimum of geometrical disruption.

Wakelyn, N. T.↗

Regulation of body fluid volume and electrolyte concentrations in spaceflight

Despite a number of difficulties in performing experiments during weightlessness, a great deal of information has been obtained concerning the effects of spaceflight on the regulation of body fluid and electrolytes. Many paradoxes and questions remain, however. Although body mass, extracellular fluid volume, and plasma volume are reduced during spaceflight and remain so at landing, the changes in total body water are comparatively small. Serum or plasma sodium and osmolality have generally been unchanged or reduced during the spaceflight, and fluid intake is substantially reduced, especially during the first of flight. The diuresis that was predicted to be caused by weightlessness, has only rarely been observed as an increased urine volume. What has been well established by now, is the occurrence of a relative diuresis, where fluid intake decreases more than urine volume does. Urinary excretion of electrolytes has been variable during spaceflight, but retention of fluid and electrolytes at landing has been consistently observed. The glomerular filtration rate was significantly elevated during the SLS missions, and water and electrolyte loading tests have indicated that renal function is altered during readaptation to Earth's gravity. Endocrine control of fluid volumes and electrolyte concentrations may be altered during weightlessness, but levels of hormones in body fluids do not conform to predictions based on early hypotheses. Antidiuretic hormone is not suppressed, though its level is highly variable and its secretion may be affected by space motion sickness and environmental factors. Plasma renin activity and aldosterone are generally elevated at landing, consistent with sodium retention, but inflight levels have been variable. Salt intake may be an important factor influencing the levels of these hormones. The circadian rhythm of cortisol has undoubtedly contributed to its variability, and little is known yet about the influence of spaceflight on circadian rhythms. Atrial natriuretic peptide does not seem to play an important role in the control of natriuresis during spaceflight. Inflight activity of the sympathetic nervous system, assessed by measuring catecholamines and their metabolites and precursors in body fluids, generally seems to be no greater than on Earth, but this system is usually activated at landing. Collaborative experiments on the Mir and the International Space Station should provide more of the data needed from long-term flights, and perhaps help to resolve some of the discrepancies between U.S. and Russian data. The use of alternative methods that are easier to execute during spaceflight, such as collection of saliva instead of blood and urine, should permit more thorough study of circadian rhythms and rapid hormone changes in weightlessness. More investigations of dietary intake of fluid and electrolytes must be performed to understand regulatory processes. Additional hormones that may participate in these processes, such as other natriuretic hormones, should be determined during and after spaceflight. Alterations in body fluid volume and blood electrolyte concentrations during spaceflight have important consequences for readaptation to the 1-G environment. The current assessment of fluid and electrolyte status during weightlessness and at landing and our still incomplete understanding of the processes of adaptation to weightlessness and readaptation to Earth's gravity have resulted in the development of countermeasures that are only partly successful in reducing the postflight orthostatic intolerance experienced by astronauts and cosmonauts. More complete knowledge of these processes can be expected to produce countermeasures that are even more successful, as well as expand our comprehension of the range of adaptability of human physiologic processes.

NASA Discipline Number 18-10↗

Supported Organoiridium-Pincer Catalysts for the Nonoxidative Dehydrogenation of High-Density Polyethylene

The iridium-pincer complex {p-OP( t Bu) 2 -C 6 H 2 -2,6-OP( t Bu) 2 ] 2 }Ir(C 2 H 4 ) ( P [Ir]) has been reported as a stable and active catalyst toward alkane dehydrogenation in homogeneous and supported heterogeneous systems. Dehydrogenation has been shown as a practical method toward functional polyolefins, with dehydrogenated high-density polyethylene (deHDPE) demonstrated as a valuable synthon for upcycling, as orthogonal C-H strategies are key to end-of-life upcycling. The heterogenization of P [Ir] on oxides (SiO 2 , Al 2 O 3 , and TiO 2 ; P [Ir]/E y O x ) yields a mixture of organometallic Ir-fragments whose catalytic nonoxidative dehydrogenation activity is modulated by the binding modes of the active metal on the surface. The binding mode was elucidated by a combination of solid-state NMR and XAFS analyses and supported by DFT calculations. Surface binding through the ligand enables active organoiridium that catalyzes internal olefination of deHDPE up to 1.23 mol % at 200 °C under dynamic vacuum. Alternatively, when the organoiridium is bonded though the metal center (Ir-O SiO ), catalyst activity is negligible. Furthermore, the catalytic activity of P [Ir]/SiO 2 showed comparable reactivity with the homogeneous analogue under the same catalytic conditions, and the heterogenized catalyst can be reused up to three cycles. In conclusion, this work highlights the importance of understanding how organometallic precursors react with hydroxylated metal oxide surfaces to establish structure-property relationships.

Hunt, Samuel B. [Argonne National Laboratory (ANL)↗

Development of a Techno-Economic Analysis Framework for a Solar Thermochemical Fuel Production Process

Synthetic liquid fuels can provide a drop-in substitute for fossil-based fuels in sectors such as aviation and maritime, where electrification is not a viable option due to the need for high specific energy density. However, for these alternative fuels to be adopted at a commercial scale, their price must be competitive compared to their fossil-based counterparts. The reverse water-gas shift (RWGS) reaction offers a promising pathway, using hydrogen (sourced from electrolysis) and carbon dioxide as the feed and reacting to produce syngas - a mixture of H2 and CO at a specific ratio. Syngas is a useful precursor that can be converted into fuels and chemicals via known downstream processes, such as liquid transportation fuels via Fischer-Tropsch (FT) synthesis. The RWGS reaction is currently not applied in commercial scale, unlike the rest of the components in the process chain (electrolyzers and syngas-to-fuel synthesis units). The RWGS reaction poses several challenges due to its restrictive thermodynamics. Being an equimolar reaction, high temperatures and a large excess of H2 are needed to achieve reasonable CO2 conversion at equilibrium. This has detrimental effects on practical process implementation and the quality of syngas that can be produced, with direct effect on the energy and capital requirements, as well as the need for expensive downstream separation. In this work, we are proposing to develop a new concentrating solar thermal (CST) compatible RWGS reactor, performing the reaction in a 2-step chemical looping process using metal oxide at a temperature range of 600-800 degrees Celsius. By decoupling the reactor from the solar receiver, the Generation 3 (Gen3) CST technology could be utilized, together with its proposed thermal energy storage (TES) technology, benefitting from a good match to the required temperatures. CST technology is a viable option for supplying the heat that could be rapidly deployed in scale, thus being a good match to the gas-to-liquid (GTL) process which requires a large minimal scale to be commercially viable. The integration of TES with CST also allows operating the plant at large annual capacity factors and avoids multiple shutdown/startup cycles, thus fitting into the steady-state operation mode that most GTL processes require. The main innovation in the proposed design hinges on a countercurrent reaction design using a packed bed reactor. In 2019 Metcalfe et al. showed the benefits of countercurrent species exchange could be realized in a redox chemical-looping processes, by storing the favorable countercurrent chemical potential profiles in a packed bed of non-stoichiometric oxide. Metcalfe et al. applied this breakthrough concept to the WGS reaction, which is conventionally a co-feed catalytic process, showing a dramatic improvement. Bulfin et al. (2023) performed a similar proof-of-concept demonstration for the RWGS reaction using CeO2, achieving cumulative and peak CO2 conversions of 88% and 95%, respectively, compared to a thermodynamic limit of 58% for the co-feed catalytic process at the same conditions. In our new REGENLOOP project, we are developing a reactor prototype from the heat-exchange packed bed reactor-type, a commonly used reactor in the chemical industry. The endothermic heat of reduction will be supplied to the reactor using CST, while the same heat transfer fluid (HTF) mechanism will be used to extract the exothermic heat of oxidation. An array of multiple reactors is used to supply constant high-purity CO stream, that is then mixed with H2 from electrolysis to produce a high-purity syngas at the required composition. By removing the CO-CO2 separation after the RWGS process, significant energy and cost reduction can be achieved. A physics-based TEA framework is currently being developed, covering all the major plant processes, from the solar collection through storage, chemical looping RWGS, GTL, and auxiliary unit operations, up to the liquid hydrocarbon product. This modeling framework will utilize reduced-order models for the chemical looping RWGS and TES, CST modeling using SolarPILOT, and Aspen Plus for the GTL. By using this combined physics-based approach, the effects of design/operating parameters on the performance and cost can be elucidated. In our presentation, the modeling framework will be presented in detail, including preliminary cost predictions of using this plant configuration under a few selected relevant case studies. This study will be used to identify the major cost drivers, informing further system design and optimization needed to chart the way for a commercially viable pathway.

14 SOLAR ENERGY↗

Comparison of chemical lateral boundary conditions for air quality predictions over the contiguous United States during pollutant intrusion events

The National Air Quality Forecast Capability (NAQFC) operated in U.S.’s National Oceanic and Atmospheric Administration (NOAA) provides the operational forecast guidance for ozone and fine particulate matters with aerodynamic diameters less than 2.5μm (PM2.5) over the contiguous 48 U.S. states (CONUS) using the Community Multi-scale Air Quality (CMAQ) model. The existing NAQFC uses climatological chemical lateral boundary conditions ( CLBCs), which cannot capture pollutant intrusion events originating outside of the model domain. In this study, we developed a model framework to use dynamic CLBCs from the Goddard Earth Observing System Model, version 5 (GEOS) to drive NAQFC. A mapping of the GEOS chemical species to the CMAQ’s Carbon Bond 5 (CB05)-Aero6 species was developed. The utilization of the GEOS dynamic CLBCs in NAQFC showed the best overall performance in simulating the surface observations during the Saharan dust intrusion and Canadian wildfire events in summer 2015.The simulated PM2.5 was improved from 0.18 to 0.37 and the mean bias was reduced from -6.74 μg/m3 to -2.96 μg/m3 over CONUS. Although the effect of CLBCs on the PM2.5 correlation was mainly near the inflow boundary, its impact on the background concentrations reached further inside the domain. The CLBCs could affect background ozone concentrations through the inflows of ozone itself and its precursors, such as CO. It was further found that the aerosol optical thickness (AOT) from satellite retrievals correlated well with the column CO and elemental carbon from GEOS. The satellite-derived AOT CLBCs generally improved the model performance for the wildfire intrusion events during a summer 2018 case study, and demonstrated how satellite observations of atmospheric composition could be used as an alternative method to capture the air quality effects of intrusions when the global model CLBCs, such as GEOS CLBCs, are not available.

Community Multi-scale Air Quality (CMAQ) model↗

Order-disorder charge density wave instability in the kagome metal (Cs,Rb)V 3 Sb 5

The origin of the charge density wave phases in the kagome metal compound AV 3 Sb 5 is still under great scrutiny. Here, we combine diffuse and inelastic x-ray scattering to identify a 3-dimensional precursor of the charge order at the L point that condenses into a CDW through a first order phase transition. The quasi-elastic critical scattering indicates that the dominant contribution to the diffuse precursor is the elastic central peak without phonon softening. However, the inelastic spectra show a small broadening of the Einstein-type phonon mode on approaching T CDW . Our results point to the situation where the Fermi surface instability at the L point is of order-disorder type with critical growth of quasi-static domains. The experimental data indicate that the CDW consists on an alternating Star of David and trihexagonal distortions and its dynamics goes beyond the classical weak-coupling scenario and is discussed within strong-electron phonon coupling and non-adiabatic models.

36 MATERIALS SCIENCE↗

Ultraviolet-Activated Solid-State Nitrene Cross-Linking: A Scalable Pathway to Prolonged Lifespan in Anion Exchange Membranes

Anion exchange membranes (AEMs) offer a cost-effective alternative to proton exchange membranes as alkaline fuel cells and electrolyzers permit the use of non-platinum group electrodes and components. Despite continued progress, the operational lifetime and stability of these membranes limit the widespread adoption of AEM-based electrochemical technologies. This study presents a flexible and easily implemented ultraviolet (UV)-initiated nitrene-based cross-linking method which uses a small, facile organic azide precursor. As a proof of concept, we demonstrate this approach on the well-studied poly(2,6-dimethyl-1,4-phenylene oxide) quaternary ammonium AEM (QPPO) polyelectrolyte. Further, a survey of cross-linker density (2.5–10 mol %) found that the addition of 10 mol % results in a 59% reduction in water uptake, a 58.8% decrease in the swell ratio, and a 31% increase in tensile strength vs the un-cross-linked material. Nitrene cross-linking also enhanced the membrane’s durability, enabling 1000 h of stable performance under electrochemical load. This UV-initiated cross-linking method may be easily integrated into production processes, allowing chemical cross-linking at any stage, including posthydration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Certify for success: A methodology for human-centered certification of advanced aviation systems

This position paper uses the methodology in Design for Success as a basis for a human factors certification program. The Design for Success (DFS) methodology espouses a multi-step process to designing and developing systems in a human-centered fashion. These steps are as follows: (1) naturalizing - understand stakeholders and their concerns; (2) marketing - understand market-oriented alternatives to meeting stakeholder concerns; (3) engineering - detailed design and development of the system considering tradeoffs between technology, cost, schedule, certification requirements, etc.; (4) system evaluation - determining if the system meets its goal(s); and (5) sales and service - delivering and maintaining the system. Because the main topic of this paper is certification, we will focus our attention on step 4, System Evaluation, since it is the natural precursor to certification. Evaluation involves testing the system and its parts for their correct behaviors. Certification focuses not only on ensuring that the system exhibits the correct behaviors, but ONLY the correct behaviors.

Small, Ronald L.↗

The Fourier-Kelvin Stellar Interferometer (FKSI): A Discovery Class TPF/DARWIN Pathfinder Mission Concept

The Fourier-Kelvin Stellar Interferometer (FKSI) is a mission concept for an imaging and nulling interferometer for the mid-infrared spectral region (5-30 microns). FKSI is conceived as a scientific and technological pathfinder to TPF/DARWIN as well as SPIRIT, SPECS, and SAFIR. It will also be a high angular resolution system complementary to NGST. The scientific emphasis of the mission is on the evolution of protostellar systems, from just after the collapse of the precursor molecular cloud core, through the formation of the disk surrounding the protostar, the formation of planets in the disk, and eventual dispersal of the disk material. FKSI will also search for brown dwarfs and Jupiter mass and smaller planets, and could also play a very powerful role in the investigation of the structure of active galactic nuclei and extra-galactic star formation. We have been studying alternative interferometer architectures and beam combination techniques, and evaluating the relevant science and technology tradeoffs. Some of the technical challenges include the development of the cryocooler systems necessary for the telescopes and focal plane array, light and stiff but well-damped truss systems to support the telescopes, and lightweight and coolable optical telescopes. We present results of detailed design studies of the FKSI starting with a design consisting of five one meter diameter telescopes arranged along a truss structure in a linear non-redundant array, cooled to 35 K. A maximum baseline of 20 meters gives a nominal resolution of 26 mas at 5 microns. Using a Fizeau beam combination technique, a simple focal plane camera could be used to obtain both Fourier and spectral data simultaneously for a given orientation of the array. The spacecraft will be rotated to give sufficient Fourier data to reconstruct complex images of a broad range of astrophysical sources. Alternative and simpler three and two telescope designs emphasizing nulling and spectroscopy also have been investigated and will be discussed.

Danchi, W. C.↗

Potential Lunar In-Situ Resource Utilization Experiments and Mission Scenarios

The extraction and use of resources on the Moon, known as In-Situ Resource Utilization (ISRU), can potentially reduce the cost and risk of human lunar exploration while also increasing science achieved. By not having to bring all of the shielding and mission consumables from Earth and being able to make products on the Moon, missions may require less mass to accomplish the same objectives, carry more science equipment, go to more sites of exploration, and/or provide options to recover from failures not possible with delivery of spares and consumables from Earth alone. The concept of lunar ISRU has been considered and studied for decades, and scientists and engineers were theorizing and even testing concepts for how to extract oxygen from lunar soil even before the Apollo 11 mission to the Moon. There are four main areas where ISRU can significantly impact how human missions to the Moon will be performed: mission consumable production, civil engineering and construction, energy production, storage, and transfer, and manufacturing and repair. The area that has the greatest impact on mission mass, hardware design and selection, and mission architecture is mission consumable production, in particular, the ability to make propellants, life support consumables, and fuel cell reagents. Mission consumable production allows for refueling and reuse of spacecraft, increasing power production and storage, and increased capabilities and failure tolerance for crew life support. The other three areas allow for decreased mission risk due to radiation and plume damage, alternative power systems, and failure recover capabilities while also enabling infrastructure growth over Earth delivered assets. However, while lunar ISRU has significant potential for mass, cost, and risk reduction for human lunar missions, it has never been demonstrated before in space. To demonstrate that ISRU can meet mission needs and to increase confidence in incorporating ISRU capabilities into mission architectures, terrestrial laboratory and analog field testing along with robotic precursor missions are required. A stepwise approach with international collaboration is recommended. The first step is to understand the resources available through orbital and surface exploration missions. Resources of particular interest are hydrogen, hydroxyl, water, and other polar volatile resources recently measured by Chandrayaan, Lunar Reconnaissance Orbiter (LRO), and the Lunar Crater Observation and Sensing Satellite (LCROSS). The second step is to demonstrate critical aspects of ISRU systems to prove ISRU is feasible under lunar environmental and resource conditions (ex. subscale oxygen extraction from regolith). The third step is to perform integrated missions with ISRU and other connected systems, such as power, consumable storage, surface mobility, and life support at a relevant mission scale to demonstrate ISRU capabilities as well as the critical interfaces with other exploration systems. If possible, the mission should demonstrate the use of ISRU products (ex. in a rocket engine or fuel cell). This dress rehearsal mission would be the final step before full implementation of ISRU into human missions, and may be performed during human lunar exploration activities. This stepwise approach is the most conservative approach, and may only be possible with international cooperation due to the limited number of robotic missions each nation/space agency can perform within their budget.

Sanders, Gerald B.↗