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563 records · Page 32

Chemical constraints governing the origin of metabolism: the thermodynamic landscape of carbon group transformations under mild aqueous conditions

The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies (deltaG) were estimated for four types of reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed (1) that generally when carbon-carbon bond cleavage involves groups from different functional group classes (i.e., carboxylic acids, carbonyl groups, alcohols, and hydrocarbons), the transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) that the energy of carbon-carbon bond transformation is primarily determined by the functional group class of the group that changes oxidation state in the reaction (i.e., the functional group class of the group that donates the shared electron-pair during cleavage, or that accepts the incipient shared electron-pair during synthesis). In contrast, the energy of hydrogen transfer between carbon groups is determined by the functional group class of both the hydrogen-donor group and the hydrogen-acceptor group. From these and other observations we concluded that the chemistry involved in the origin of metabolism (and to a lesser degree modern metabolism) was strongly constrained by (1) the limited redox-based transformation energy of organic substrates that is readily dissipated in a few energetically favorable irreversible reactions; (2) the energy dominance of a few transformation half-reactions that determines whether carbon-carbon bond transformation (cleavage or synthesis) is energetically favorable (deltaG < -3.5 kcal/mol), reversible (deltaG between +/-3.5 kcal/mol), or unfavorable (deltaG > +3.5 kcal/mol); and (3) the dependence of carbon group transformation energy on the functional group class (i.e., oxidation state) of participating groups that in turn is contingent on prior reactions and precursors in the synthetic pathway.

Carbon/chemistry/metabolism↗

ISO Spectroscopy of Proto-Planetary Nebulae

The goal of this program was to determine the chemical properties of the dust shells around protoplanetary nebulae (PPNs) through a study of their short-wavelength (6-45 micron) infrared spectra. PPNs are evolved stars in transition from the asymptotic giant branch to the planetary nebula stages. Spectral features in the 10 to 20 gm region indicate the chemical nature (oxygen- or carbon-rich), and the strengths of the features relate to the physical properties of the shells. A few bright carbon-rich PPNs have been observed to show PAH features and an unidentified 21 micron emission feature. We used the Infrared Space Observatory (ISO) to observe a sample of IRAS sources that have the expected properties of PPNs and for which we have accurate positions. Some of these have optical counterparts (proposal SWSPPN01) and some do not (SWSPPN02). We had previously observed these from the ground with near-infrared photometry and, for those with visible counterparts, visible photometry and spectroscopy, which we have combined with these new ISO data in the interpretation of the spectra. We have completed a study of the unidentified emission feature at 21 micron in eight sources. We find the shape of the feature to be the same in all of the sources, with no evidence of any substructure. The ratio of the emission peak to continuum ranges from 0.13 to 1.30. We have completed a study of seven PPNs and two other carbon-rich objects for which we had obtained ISO 2-45 micron observations. The unidentified emission features at 21 and 30 micron were detected in six sources, including four new detections of the 30 micron feature. This previously unresolved 30 micron feature was resolved and found to consist of a broad feature peaking at 27.2 micron (the "30 micron" feature) and a narrower feature peaking at 25.5 micron (the "26 micron" feature). This new 26 micron feature is detected in eight sources and is particularly strong in IRAS Z02229+6208 and 16594-4656. The unidentified features at 3.3, 6,2, 7.7, and 11.3 micron, which are commonly observed in planetary nebulae and HII regions, are also seen in these PPNs. However, their strengths relative to the continuum plateaus at 8 and 12 micron are weaker than in planetary nebulae. The 6.9 micron feature, seen almost exclusively in PPNs, is strong. The spectral energy distributions of these PPNs were fitted with a radiative-transfer model, taking into account the emission features at 21, 26, and 30 micron. A significant fraction of the total energy output is emitted in these features: as high as 20% in the 30 micron feature and 8% in the 21 micron feature. The fact that so much energy is carried in these features suggests that the material responsible for this feature must be made of abundant elements, and most likely involves carbon. The change in the in feature strengths from stronger aliphatic bonds in PPNs to stronger aromatic bonds in PNs suggests a chemical and physical evolution in the carbonaceous circumstellar dust during this transition time scale of a few thousand years.

Hrivnak, Bruce J.↗

NASA's Space Launch System Begins Integration, Stacking in Preparation for Artemis I Launch

The Artemis era of human lunar exploration is nearing take-off as NASA’s new super heavy-lift launch vehicle, the Space Launch System (SLS), begins stack-ing and integration operations in mid-2020 at Kennedy Space Center (KSC) in Florida. With a planned upgrade path to progressively more powerful vehicles and availability in crew and cargo configurations, SLS provides a unique and flexible launch solution to send crew, large-scale infrastructure and robotic probes to deep space. The SLS Block 1 vehicle, the initial variant to fly, is optimized for lunar missions with a proven propulsion system consisting of four liquid hydrogen (LH2)/liquid oxygen (LOX)-fed RS-25 engines and twin five-segment solid rocket boosters (SRBs). The Block 1 vehicle can also be outfitted with an industry-standard 5 m-class payload fairing (the “cargo” configuration) and will launch at least 27 metric tons (t) of mass to trans-lunar injection (TLI). SLS is the backbone of NASA’s Artemis program, which will return the agency’s human spaceflight program to the Moon for the first time since 1972. For the Artemis I mission, SLS will send an uncrewed Orion spacecraft to TLI, where it will enter a distant retrograde lunar orbit and fly 38,000 nmi past the Moon – farther than any spacecraft built for humans has ever traveled. The SLS Block 1 vehicle for Artemis I completed manufacturing in 2019. Several elements, including the upper stage, have been delivered to the Exploration Ground Systems (EGS) program at KSC and are being prepped for integration and stack-ing. The five-segment solid rocket boosters – the largest and most powerful ever built for flight – are also complete. The booster motor segments for the Artemis I flight are scheduled to ship from prime contractor Northrop Grumman’s Utah facilities and begin stacking and integration at KSC in June 2020. The SLS core stage is the largest rocket stage NASA has ever built in terms of volume and height, and includes the avionics and the tanks that feed cryogenic propellant to the four RS-25s (formerly Space Shuttle Main Engines [SSMEs]). They have been modified with an updated controller and nozzle insulation to protect them from the hotter launch environment. The SLS core stage is currently being test-ed at NASA’s Stennis Space Center (SSC) in a series of “green run” tests to verify it meets design and performance requirements. Following the green run test series, which is scheduled to culminate with a full-duration hot-fire of the four RS-25 engines, the core stage will ship to KSC and be stacked between the sol-id rocket boosters in the Vehicle Assembly Building (VAB). Integration of the vehicle will continue with the upper stage, known as the Interim Cryogenic Propulsion Stage (ICPS) and the Launch Vehicle Stage Adapter (LVSA) on the core stage. Another adapter, the Orion Stage Adapter (OSA), connects SLS to Orion and provides housing for 13 6U CubeSat payloads manifested on Artemis I. The CubeSats will be released in deep space after Orion separates from the vehicle, and the flight marks the first ride share opportunity for independent small-sats to deep space. The second major SLS variant to come online, Block 1B, replaces the single-engine ICPS with a four-engine LH2/LOX Exploration Upper Stage (EUS). This more powerful upper stage, along with other vehicle up-grades, will enable the Block 1B vehicle to launch 38-42 t to TLI, depending on crew or cargo configuration. The final evolution of the vehicle, Block 2, will onramp evolved solid rocket boosters to increase mass to TLI to 43-46 t, de-pending on crew or cargo configuration. The Block 1B/Block 2 vehicles can be outfitted with an 8.4 m-diameter payload fairing in 19.1 m or 27.4 m lengths, to provide unprecedented volume for payloads. With the initial Block 1 vehicle completely manufactured and the core stage in final testing before shipping to KSC, the SLS Program and its industry partners have made significant progress manufacturing subsequent vehicles. For the second Block 1 vehicle, the solid rocket motor segments are complete, as are the RS-25 engines with controllers. All five major components of the Artemis II core stage – the forward skirt, LOX and LH2 tanks, intertank and engine section – are manufactured and technicians are installing subsystems at NASA’s rocket factory, Michoud Assembly Facility. The RL-10 engine for the Artemis II ICPS is complete and panels have been machined for its LH2 tank. In addition, panels are machined for the vehicle’s two adapters, with welding scheduled to begin in summer 2020. Flight hard-ware is also in production for the third SLS vehicle, with several booster motor segments cast. The pace of development on the EUS has increased, with the goal to complete Critical Design Review (CDR) in December 2020. Several EUS test rings have been machined at Michoud. The EUS is designed to exe-cute a variety of missions – human spaceflight, deployment of deep-space infra-structure, or high-C3 missions to the outer solar system – with crew and cargo configurations available beginning in the mid-2020s. The near-term goal for the nation’s powerful new space exploration asset, however, is to launch the Arte-mis program, and send the first woman and the next man to the lunar surface. At the Astrodynamics Specialist Conference, the SLS program will update the community on the progress of the initial Block 1 vehicle in final green run test-ing, integration and stacking. In addition, this paper will provide an update to the community on the manufacturing status of subsequent Block 1 and Block 1B vehicles.

Steve Creech↗

Open-source Numerical Modeling of Solidification Cracking Susceptibility: Application to Refractory Alloy Systems

Introduction. Alloys such as aluminum, nickel-base, and austenitic stainless steels are susceptible to solidification cracking during welding and 3D printing. Compositional optimization is one method used to effectively mitigate solidification cracking of those alloy systems. With the surge in hypersonic and in-space propulsion activities, refractory metals (Nb, Mo, Ta, W, and Re) and their alloy derivatives are increasing in importance due to their extreme high melting point and retention of high-temperature strength; however, their chemistry was most typically optimized to promote ductility during mechanical operations such as drawing and forming. Welding of such alloys has been a challenge due to a number of issues including solidification cracking, atmospheric contamination (O, C, and N), as well as a shift in ductile-to-brittle transition to higher temperature following grain growth induced by welding. Compositional optimization of refractory alloys for solidification cracking resistance in particular is desirable as their usage increases with the advent of advanced manufacturing methods such as 3D printing. This work evaluates the effect of compositional variation in refractory metal systems on the solidification cracking susceptibility with the goals of optimizing existing alloys and joining process techniques, and formulating new alloys with increased solidification cracking resistance. Experimental Procedures. A python code was developed in a Jupyter notebook environment (Michael and Sowards, 2023) to facilitate the calculation of crack susceptibility index proposed by Kou (2015). Composition is entered as a single point, or as a 1-D or 2-D array. The notebook calls pycalphad (Otis and Liu, 2017 and Bocklund et al, 2020) to calculate the evolution of fraction solid as a function of temperature (under either Scheil or equilibrium assumptions) and then evaluates steepness of the fraction solid curve near the terminal stage of solidification to predict solidification cracking resistance. Open source thermodynamic databases available at online repositories are used (van de Walle). The process is setup in an automated fashion to generate plots that show variation in solidification cracking susceptibility according to composition on 1-D line plots or 2-D contour plots. The Jupyter notebook and crack susceptibility algorithm was also integrated with a widely used commercial CALPHAD code for validation and alloy exploration. Results and Discussion. The crack susceptibility model was first validated against a series of refractory alloy compositions evaluated in past work which utilized a specialized Varestraint test built inside a vacuum chamber environment (Lessman and Gold, 1971). The alloys tested in the Varestraint apparatus included T-111 (Ta-8W-2Hf), ASTAR-811C (Ta-8W-1Re-0.7Hf-0.025C), FS-85 (Nb-27Ta-10W-1Zr), T-222 (Ta-9.6W-2.4Hf-0.01C), Ta-10W, B-66 (Nb-5Mo-5V-1Zr), and SCb-291 (Nb-10W-10Ta). The initial test of the model showed a strong correlation with empirical Varestraint data, i.e., a Spearman rank correlation between model predictions and hot cracking measurements was observed to be greater than 0.8. Following the validation, a set of refractory metal binary mixtures was investigated to evaluate sensitivity of Nb, Mo, W, and Ta to C, N, and O content. A series of plots were produced that suggest ppmw ranges of C, N, and O where solidification cracking increases significantly and reaches a maximum. Also comparative ranking of each primary refractory metal to each interstitial was produced. For example C produces greater cracking response in Mo whereas O produces greater cracking response in Ta and Nb. Such compositional values have utility in setting limits on pickup of these interstitial elements during welding and printing rather than using a one-size-fits-all approach. Furthermore, the results have use in determining additive powder recycling requirements, which is especially pertinent for refractory metal powders due to their high cost compared to conventional alloys. Another application created thousands of hypothetical alloys within the nominal specified composition range of two widely used refractory alloys C103 (Nb-10Hf-1Ti) and TZM (Mo-0.5Ti-0.1Zr). The cracking index was calculated for the alloys and results were fed into machine learning regression techniques including Multiple Linear Regression, Ridge Regression, and Lasso Regression to determine relative potency each alloying element had on computed solidification cracking index. A series of linear equations were produced that relate composition of C103 and TZM to solidification cracking index. The crack susceptibility of C103 for example is described by an equation of the form: cracking index ~ O + 0.667*C + 0.635*N + 0.00037*Ta – 0.0008*Hf (in wt.%) From that equation, it is clear that O has strong propensity to induce solidification cracking. Interestingly, Hf is shown to reduce calculated cracking response. Finally, realizing the potential of this method to discover new refractory alloy formulations across the period table that have low solidification cracking sensitivity, the code was applied to new untested alloy systems including W-Zr-C, W-Ta-C, and others. Conclusions. In summary, an open source numerical method has been developed using Python code to calculate Kou’s crack susceptibility index. The method was applied to refractory metals which are inherently difficult to study from a weldability testing standpoint since inert shielding gas is not sufficient and welding is typically done in vacuum, especially in light of findings presented here where oxygen has profound influence on solidification cracking. This work revealed the effect of compositional variations on a series of refractory metals and showed the framework defined here will be useful in 1) the development of new alloys that have improved weldability and 3D printability, 2) placing compositional limits on existing alloys, and 3) ensuring adequate controls of manufacturing processes such as 3D printing where powder reuse is critical. Keywords. pycalphad; Python; refractory metals; solidification cracking. References. B. Bocklund et. al. (2020) http://doi.org/10.5281/zenodo.3630657. S. Kou. (2015) https://doi.org/10.1016/j.actamat.2015.01.034. G.G. Lessmann and R.E. Gold. Welding Journal, issue 1, pp. 1-s – 8-s (1971). F.N. Michael and J.W. Sowards. NASA/TM-20230002218 (2023). R. Otis and Z.-K. Liu. (2017) http://doi.org/10.5334/jors.140. A. Van de Wallle et. al. (2018) https://doi.org/10.1016/j.calphad.2018.04.003.

pycalphad↗

Uncrewed Lunar Surface Operations and Support Activities

Sustained human presence on the surface of the Moon and future missions to Mars require increased independence from surface crews and Earth-based mission control to operate efficiently, safely, and reliably. The time for surface crews to perform tasks will be limited. Extravehicular activities by surface personnel are burdensome and time-consuming, even when a continuous human presence on the surface occurs. Identifying and balancing human/automation roles and tasks and infusing automation and autonomy practices early in a system’s lifecycle will be essential to achieve mission objectives. Among these objectives are attaining a sustained human presence, improving performance and mission effectiveness, reducing operations and maintenance (O&M) costs, and ensuring operations that are robust to communication delays. To achieve these objectives, an operational shift toward increased automation and autonomy with less reliance on humans is needed. Uncrewed lunar surface operations and support activities occur when surface crews are not present or are independent of surface crew timeline activities requiring no surface crew oversight or intervention. These uncrewed surface opportunities can also be planned to minimize crew workload that avoids routine maintenance and support tasks, thus maximizing crew exploration time. Uncrewed preparations such as staging and prepositioning equipment and materials before the crew arrives could improve crew task efficiency. Additional opportunities exist to conduct uncrewed science, exploration, and utilization. Uncrewed surface architecture functions can include science and exploration; habitation; launch and landing support; surface communication and navigation; surface power generation and distribution; human surface mobility; lifting, handling, manipulating; excavation, construction, and site preparation; logistics management; maintenance and repair; surface resource utilization; integrated site operations and shared support services (e.g., site scheduling/prioritization, dust mitigation/contamination control, and surface safety). Early robotic lunar surface campaigns will provide information on the availability of resources, such as oxygen and water, and demonstrate surface-based technologies. After the Artemis III human lunar return mission, a series of landers will deliver surface systems, cargo, supplies, science packages, spare parts, and commodities. A balance of crewed and uncrewed surface operations will enable a sustained lunar surface presence at the South Pole of the Moon at a site that will be known as the Artemis Base Camp (ABC). It is envisioned that base camp operations on and around the Moon will then help prepare for the mission durations and activities needed to support the first human mission to Mars. Before long-duration crew missions to the base camp can occur, the necessary surface infrastructure will be pre-deployed and verified operational. Surface assets will be teleoperated and remotely managed from Earth. Additionally, robotic and short-duration crewed missions to the ABC will ensure the site’s merit to achieve long-term science objectives, availability of usable resources, and that terrain, seasonal variations, and illumination conditions are acceptable. ABC will consist of different areas where specific functions and services are rendered, including: • Launch and Landing Area • Habitation Area • Power Production Area • Resource Areas Launch and Landing Area—The launch and landing area will support associated functions for the arrival and departure of vehicles, such as crewed landing and ascent and uncrewed cargo deliveries and offloading. It will evolve from an unimproved site at the beginning of the exploration campaign to a more sustainable landing and launch area that can support repeated arrivals and departures. Initial uncrewed Lunar Terrain Vehicle (LTV) surface operations may include emplacement of navigation beacons and communication equipment, real-time video and photography of landing/liftoff events, and element repositioning, such as portable utility power (PUP) (applicable for other landed assets at other areas). Site preparations, such as surface leveling, soil compaction, and berm/path construction, may be needed for a more sustainable launch and landing area capable of accommodating vehicles that are increasingly more reusable and reduce the effects of plume surface interactions and ejecta impacts on nearby surface assets. During the ABC missions, cargo and logistics will be delivered to the lunar surface via robotic cargo landers before the crew arrives. These shipments, which can arrive in pressurized logistics carriers, will deliver the logistics necessary to support a crewed mission and include items such as food, water, equipment spares, etc. Providing the capability to retrieve, offload, and transport the logistics closer to the ABC site before the arrival of the crew will increase the overall efficiency of crew operations once they arrive. In the sustained phase of exploration, other supporting services may be needed, such as lander propellant servicing, surface power services, commodity refreshes, and additional inspection, maintenance, and repair capabilities, to sustain a cadence of extended personnel stays and cargo arrivals and departures. Habitation Area—Uncrewed support to surface habitation could involve supporting activation and pre-entry operations of the habitat while the crew is in orbit at the Gateway outpost preparing for a surface landing. Surface Habitat (SH) uncrewed operations may include bringing the cabin environment to a habitable temperature and air mix and activating other critical crew support systems. Potential crop production uncrewed tasks in the SH could also include autonomous watering and tending. Additionally, when the crew departs, the SH enters dormancy for the long period of uncrewed operation. A logistical staging area could also be collocated near the SH. If so, staging operations for crew supplies, waste re-location, and recycling operations may be opportunities for uncrewed operations. Power Production Area—The Fission Surface Power (FSP) element and its supporting distribution equipment provide power to surface elements as needed across the ABC to supplement day-to-day operations and survive lunar nights. Uncrewed support of this power system includes any initial LTV-assisted deployments of cables and other distributed equipment, associated electrical connections, and system testing and activation operations. Robotically performing some inspections, maintenance, or repair tasks on the power distribution equipment could reduce the surface crew workload. Resource Area— Uncrewed resource prospecting, mapping, and characterizing possible resource sites is likely to be time-consuming and represents an opportunity for uncrewed operations between crewed missions. Uncrewed mobile equipment operations will be needed in the extreme environments of permanently shadowed locations where resource extractions occur. As In-Situ Resource Utilization (ISRU) pilot plant operations begin, uncrewed surface support activities with available mobile and portable assets (LTV, PUP, etc.) will better support these operations. Any produced commodities can be stored at a centralized storage location for future use. Also associated with these operations is the use of mobile robotic excavators for resource acquisition and robotic/autonomous regolith processing. The waste tailings generated during excavation and regolith processing would also need to be transported and deposited at a dedicated location. Surface assets will continue operating between crew visits to maintain surface capabilities, conduct lunar surface science, technology demonstrations, and public outreach opportunities. Additionally, certain sustaining tasks that would consume valuable crew time could be performed before crew arrival, or after their departure. This capability may offer more affordable options to construct, activate, test, and maintain a broad set of surface assets. Telerobotically operated human surface mobility systems, such as the LTV and Pressurized Rover (PR), can be utilized for various tasks. Surface environmental conditions pose a distinct challenge for all these activities. Surface illumination and localized shadows are one such factor. Night-survival operations could consist of thermal management, battery pre-charging, and load shedding. Some surface systems may hibernate through the night and then awake and continue nominal operations. Uncrewed mobile assets may use a more adaptive approach to optimize their power and operations; one method is to follow the sunlight. Night-survival operations may be initiated remotely by teleoperation, automated, or accomplished by supervised autonomous operation. The ability to pre-deploy and control remote assets in orbit or on Mars before the arrival of the mission crew is a key capability that can be simulated on the moon. The base camp provides a venue where these advanced operational concepts, technologies, and autonomous methods and techniques, including the incorporation of time delays to simulate Earth-Mars latency can be replicated to help buy down future Mars mission risks. This paper will examine the evolution of uncrewed lunar surface operations and support activities. It will also discuss the lunar surface environmental conditions (thermal, lighting, terrain, topography, communications) along with the challenges they pose on uncrewed surface operations, and the performance of these activities with limited to minimal human interaction and/or teleoperation. Since lunar missions include Mars mission analogs, such investigation provides the framework for future uncrewed Mars mission support.

Mark E Lewis↗