Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “inert atmosphere”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

410 records · Page 23
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Precipitation Processes developed during ARM (1997), TOGA COARE(1992), GATE(1 974), SCSMEX(1998) and KWAJEX(1999): Consistent 2D and 3D Cloud Resolving Model Simulations

Real clouds and clouds systems are inherently three dimensional (3D). Because of the limitations in computer resources, however, most cloud-resolving models (CRMs) today are still two-dimensional (2D). A few 3D CRMs have been used to study the response of clouds to large-scale forcing. In these 3D simulations, the model domain was small, and the integration time was 6 hours. Only recently have 3D experiments been performed for multi-day periods for tropical cloud system with large horizontal domains at the National Center for Atmospheric Research. The results indicate that surface precipitation and latent heating profiles are very similar between the 2D and 3D simulations of these same cases. The reason for the strong similarity between the 2D and 3D CRM simulations is that the observed large-scale advective tendencies of potential temperature, water vapor mixing ratio, and horizontal momentum were used as the main forcing in both the 2D and 3D models. Interestingly, the 2D and 3D versions of the CRM used in CSU and U.K. Met Office showed significant differences in the rainfall and cloud statistics for three ARM cases. The major objectives of this project are to calculate and axamine: (1)the surface energy and water budgets, (2) the precipitation processes in the convective and stratiform regions, (3) the cloud upward and downward mass fluxes in the convective and stratiform regions; (4) cloud characteristics such as size, updraft intensity and lifetime, and (5) the entrainment and detrainment rates associated with clouds and cloud systems that developed in TOGA COARE, GATE, SCSMEX, ARM and KWAJEX. Of special note is that the analyzed (model generated) data sets are all produced by the same current version of the GCE model, i.e. consistent model physics and configurations. Trajectory analyse and inert tracer calculation will be conducted to identify the differences and similarities in the organization of convection between simulated 2D and 3D cloud systems.

Tao, W.-K.↗
NASA NTRS1961

Development of Ceramic Fibers for Reinforcement in Composite Materials

Refinements of the vertical arc fiberizing apparatus resulted in its ability to fiberize very different refractory glasses having wide ranges of properties. Although the apparatus, was originally designed as a laboratory research tool for the evaluation of many compositions daily, up to one quarter pound of fibers of a single composition could be produced in an 8-hour day. Fibers up to six and a half feet long were produced with the apparatus. Studies were conducted of two methods of fiberizing refractory glasses requiring rapid freezing from the melt. The first method consisted of fiberizing droplets of molten glass passing through an annular nozzle. The second method consisted of reconstructing the annular nozzle in. the shape of a horseshoe to achieve a shorter delay in blasting a molten droplet from the tip of a rod. Both methods were judged feasible for producing fibers of glasses requiring rapid freezing. The first method would be more amenable to volume fiber production. Studies of induction heating for fiber formation did not lead to its designation as a very efficient heating method. Problems. remain to be solved, in the design of a suitable susceptor for a higher heating rate, in protecting the susceptor from oxidation with an inert gas, in contamination of the melt from a refractory crucible, and in the protective radiation shielding of the induction concentrator coil. It is not considered practical to continue studies of this heating method. In the course of this program 151 refractory glass compositions were evaluated for fiber, forming characteristics. Of the various types of materials studied, the following showed promise in producing acceptable refractory fibers: sIlica- spinel (magnesium aluminate), silica- spinel-zirconia, silica-zirconia, silica-zinc spinel, aluminum phosphate glasses, and fluoride glasses. Compositions which did not produce acceptable fibers were high zirconia materials, barium spinels, and calcium aluminates. Improvements in the. testing apparatus for single fiber tensile strength increased the precision. of tests conducted on nine fibers. The highest mean tensile strength, a value of 295,000 pounds per square inch, was obtained with R-141 fibers. Treatment of R-74 fibers with anhydrous Linde A-1100 silane finish improved its mean fiber tensile strength by 25 percent. The lapse of time after fiber formation had no measurable effect on tensile strength. A static heating test conducted with various high melting fibers indicated that Fiberfrax and R-108 underwent no significant changes in bulk volume or resiliency on exposure to 2750 degrees Fahrenheit (1510 degrees Centigrade) in an oxidizing atmosphere. For fiber-resin composition fabrication, ten fiber materials were selected on the bases of high fiber yield, fusion temperature, and type of composition. Fiberfrax, a commercial ceramic fiber, was included for comparison. A new, more effective method of removing pellets from blown fibers was developed. The de-pelletized fibers were treated with a silane finish and felted into ten-inch diameter felts prior to resin impregnation. Composites containing 30 percent by weight of CTL 91-LD phenolic resin were molded under high pressure from the impregnated felts and post-cured to achieve optimum properties. Flexural strength, flexural modules of elasticity, and punch shear strength tests were conducted on the composite specimens. The highest average flexural strength obtained was 19,958 pounds per square inch with the R-74-fiber-resin composite. This compares very favorably with the military specification of 13,000 pounds per square inch flexural strength for randomly oriented fiber reinforced composites. The highest punch shear strength (11,509 pounds per square inch) was obtained with the R-89 fiber-resin composite. The effects of anhydrous fiber finishes on composite strength were not clearly indicated. Plasma arc tests at a heat flux of 550 British Thermal Units per square foot per second on eight composite materials indicated ablation rates generally equivalent to Fiberglas-Micarta No. 259-2. The composite reinforced with R-99 fibers had an average ablation rate of 0.008 inch per second and appears quite promising on the basis of these tests. Preliminary studies for processing fibers into yarn and fabric were conducted with R-99 fibers. The use of certain organic gums aided in 2 fabricating by hand several relatively strong yarns and a crude fabric swatch. This indicated the practicality of developing techniques for processing these fibers into yarn and fabric without significant damage to the fibers.

Gates, L. E.↗
DOE OSTI2025

Sensitivities of Large Eddy Simulations of Aerosol Plume Transport and Cloud Response

Abstract Cloud responses to surface‐based sources of aerosol perturbation partially depend on how turbulent transport of the aerosol to cloud base affects the spatial and temporal distribution of aerosol. Here, scenarios of plume injection below a marine stratocumulus cloud are modeled using large eddy simulations coupled to a prognostic bulk aerosol and cloud microphysics scheme. Both passive plumes, consisting of an inert tracer, and active plumes are investigated, where the latter are representative of saltwater droplet plumes such as have been proposed for marine cloud brightening. Passive plume scenarios show higher in‐plume cloud brightness (relative to out‐of‐plume) due to the predominant transport of the passive plume tracer from the near‐surface to the cloud layer within updrafts. These updrafts rise into brighter areas within the cloud deck, even in the absence of an aerosol perturbation associated with an active plume. Comparing albedo at in‐plume to out‐of‐plume locations associates the inert plume with the brightest cloud locations, without any causal effect of the plume on the cloud. Numerical sensitivities are first assessed to establish a suitable model configuration. Then sensitivity to particle injection rate is investigated. Trade‐offs are identified between the number of injected particles and the suppressive effect of droplet evaporation on plume loft and spread. Furthermore, as the near‐field in‐plume brightening effect does not depend significantly on injection rate given a suitable definition of perturbed versus unperturbed regions of the flow, plume area is a key controlling factor on the overall cloud brightening effect of an aerosol perturbation.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2012

Calibration and Sequence Development Status for the Sample Analysis at Mars Investigation on the Mars Science Laboratory

The measurement goals of the Sample Analysis at Mars (SAM) instrument suite on the "Curiosity" Rover of the Mars Science Laboratory (MSL) include chemical and isotopic analysis of organic and inorganic volatiles for both atmospheric and solid samples [1,2]. SAM directly supports the ambitious goals of the MSL mission to provide a quantitative assessment of habitability and preservation in Gale crater by means of a range of chemical and geological measurements [3]. The SAM FM combined calibration and environmental testing took place primarily in 2010 with a limited set of tests implemented after integration into the rover in January 2011. The scope of SAM FM testing was limited both to preserve SAM consumables such as life time of its electromechanical elements and to minimize the level of terrestrial contamination in the SAM instrument. A more comprehensive calibration of a SAM-like suite of instruments will be implemented in 2012 with calibration runs planned for the SAM testbed. The SAM Testbed is nearly identical to the SAM FM and operates in a ambient pressure chamber. The SAM Instrument Suite: SAM's instruments are a Quadrupole Mass Spectrometer (QMS), a 6-column Gas Chromatograph (GC), and a 2-channel Tunable Laser Spectrometer (TLS). Gas Chromatography Mass Spectrometry is designed for identification of even trace organic compounds. The TLS [5] secures the C, H, and O isotopic composition in carbon dioxide, water, and methane. Sieved materials are delivered from the MSL sample acquisition and processing system to one of68 cups of the Sample Manipulation System (SMS). 59 of these cups are fabricated from inert quartz. After sample delivery, a cup is inserted into one of 2 ovens for evolved gas analysis (EGA ambient to >9500C) by the QMS and TLS. A portion of the gas released can be trapped and subsequently analyzed by GCMS. Nine sealed cups contain liquid solvents and chemical derivatization or thermochemolysis agents to extract and transform polar molecules such as amino acids, nucleobases, and carboxylic acids into compounds that are sufficiently volatile to transmit through the GC columns. The remaining 6 cups contain calibrants. SAM FM Calibration Overview: The SAM FM calibration in the Mars chamber employed a variety of pure gases, gas mixtures, and solid materials. Isotope calibration runs for the TLS utilized 13C enriched C02 standards and 0 enriched CH4. A variety of fluorocarbon compounds that spanned the entire mass range of the QMS as well as C3-C6 hydrocarbons were utilized for calibration of the GCMS. Solid samples consisting of a mixture of calcite, melanterite, and inert silica glass either doped or not with fluorocarbons were introduced into the SAM FM cups through the SAM inlet funnel/tube system.

Mahaffy, Paul R.↗
NASA NTRS1960

Oxidation Behavior of Binary Niobium Alloys

This investigation concludes a study to determine the effects of up to 25 atomic percent of 55 alloying additions on the oxidation characteristics of niobium. The alloys were evaluated by oxidizing in an air atmosphere for 4 hours at 1000 C and 2 hours at 1200 C. Titanium and chromium improved oxidation resistance at both evaluation conditions. Vanadium and aluminum improved oxidation resistance at 1000 C, even though the V scale tended to liquefy and the Al specimens became brittle and the scale powdery. Copper, cobalt, iron, and iridium improved oxidation resistance at 1200 C. Other investigations report tungsten and molybdenum are protective up to about 1000 C, and tantalum at 1100 C. The most important factor influencing the rate of oxidation was the ion size of the alloy additions. Ions slightly smaller than the Nb(5+) ion are soluble in the oxide lattice and tend to lower the compressive stresses in the bulk scale that lead to cracking. The solubility of the alloying addition also depends on the valence to some extent. All of the elements mentioned that improve the oxidation resistance of Nb fit this size criterion with the possible exception of Al, whose extremely small size in large concentrations would probably lead to the formation of a powdery scale. Maintenance of a crack-free bulk scale for as long as possible may contribute to the formation of a dark subscale that ultimately is rate- controlling in the oxidation process. The platinum-group metals, especially Ir, appear to protect by entrapment of the finely dispersed alloying element by the incoming Nb2O5 metal-oxide interface. This inert metallic Ir when alloyed in a sufficient amount with Yb appears to give a ductile phase dispersed in the brittle oxide. This scale would then flow more easily to relieve the large compressive stresses to delay cracking. Complex oxide formation (which both Ti and Zr tend to initiate) and valence effects, which probably change the vacancy concentration in the scale, are masked by the overriding tendency for a porous scale.

Barrett, Charles A.↗
NASA NTRS2011

Cloud Condensation in Titan's Lower Stratosphere

A 1-D condensation model is developed for the purpose of reproducing ice clouds in Titan's lower stratosphere observed by the Composite Infrared Spectrometer (CIRS) onboard Cassini. Hydrogen cyanide (HCN), cyanoacetylene (HC3N), and ethane (C2H6) vapors are treated as chemically inert gas species that flow from an upper boundary at 500 km to a condensation sink near Titan's tropopause (-45 km). Gas vertical profiles are determined from eddy mixing and a downward flux at the upper boundary. The condensation sink is based upon diffusive growth of the cloud particles and is proportional to the degree of supersaturation in the cloud formation regIOn. Observations of the vapor phase abundances above the condensation levels and the locations and properties of the ice clouds provide constraints on the free parameters in the model. Vapor phase abundances are determined from CIRS mid-IR observations, whereas cloud particle sizes, altitudes, and latitudinal distributions are derived from analyses of CIRS far-IR observations of Titan. Specific cloud constraints include: I) mean particle radii of2-3 J.lm inferred from the V6 506 cm- band of HC3N, 2) latitudinal abundance distributions of condensed nitriles, inferred from a composite emission feature that peaks at 160/cm , and 3) a possible hydrocarbon cloud layer at high latitudes, located near an altitude of 60 km, which peaks between 60 and 80 cm l . Nitrile abundances appear to diminish substantially at high northern latitudes over the time period 2005 to 2010 (northern mid winter to early spring). Use of multiple gas species provides a consistency check on the eddy mixing coefficient profile. The flux at the upper boundary is the net column chemical production from the upper atmosphere and provides a constraint on chemical pathways leading to the production of these compounds. Comparison of the differing lifetimes, vapor phase transport, vapor phase loss rate, and particle sedimentation, sheds light on temporal stability of the clouds.

Romani, Paul N.↗
DOE OSTI2021

Examining the Ice Nucleating Particles from Southern Great Plains Part II (ExINP-SGP). Field Campaign Report

Knowledge of airborne particulate matter (PM), especially the particles that have supermicron diameters, is key for understanding ice-nucleating particles (INPs). Supported by the Atmospheric Radiation Measurement (ARM) user facility, recent INP measurements at the Southern Great Plains observatory (SGP; 36'' 36' 18→ N, 97° 29' 6'' W) during multiple campaigns, such as SINCE-2014 (DeMott et al. 2015), Examining the Ice-Nucleating Particles from SGP (ExINP-2019; Hiranuma and Vepuri 2020), and Aerosol-Ice Formation Closure Pilot Study (AEROICESTUDY; Knopf et al. 2021a), strongly suggested the contribution of supermicron aerosol particles to observed INP abundance at SGP. However, verification of this hypothesis was hampered since additional offline laboratory analyses require sufficient amounts of collected airborne PM, which was lacking. Therefore, the principal investigators (PIs) conducted a field campaign, named ExINP-SGP II, to collect airborne PM at SGP for complementary laboratory characterization of the particles’ physicochemical properties (including ice nucleation properties). We used a passive particle sampler, which is a 4’ x 4’ x 2” (L x W x D) aluminum pan inside the 12”-high wooden windshield wall at the rooftop deck of the ARM Aerosol Observing System (AOS) trailer to collect dry PM deposits from January to April 2021. Figure 1 shows images of our experimental setup at the site. Additionally, we also collected surface soil near the ARM AOS trailer on 20 November 2020 (Figure 1b) to examine the ground soil dust particles (< 63 µm sieved) for their propensities to initiate immersion freezing compared to collected ambient PM. Surface soil and airborne samples were stored in the chemically inert container separately and kept in a dry, cool place until analyzed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Challenging conventional assumptions in PV: a high-throughput open-air approach to low-cost perovskite module production

Perovskite solar modules (PSMs) offer a promising pathway to low-cost photovoltaics, yet their commercialization is challenged by manufacturing scalability, device uniformity, additive costs, interlayer complexity, and module stability. This study introduces a comprehensive technoeconomic analysis of single junction PSM's and projections for tandem perovskite-Si modules that integrate all materials and manufacturing steps, module performances, projected lifetimes, and manufacturing costs across scales. Here, we highlight an open-air manufacturing approach to fabricate all active layers of serially interconnected PSMs, including electrodes and charge transport layers, enabling high-throughput production without inert or vacuum environments. The analysis reveals two orders of magnitude throughput enhancement and cost reductions of 24% in all-open-air production, escalating to over 60% at 1 GW factory capacity compared to conventional methods. Levelized cost of energy (LCOE) projections for utility-scale installations over 30 years, accounting for module replacement and recycling, demonstrate the potential to achieve the 2030 US target of $0.03 per kWh with realistic 7–11-year PSM lifetimes, outperforming incumbent silicon-based modules. Neither four terminal (4T) nor two terminal (2T) tandem-Si PSMs improve over single junction perovskite or silicon LCOE regardless of higher efficiencies at any modeled lifetime. Addressing PSM technical challenges with a cost-modeling framework guides commercialization efforts and provides a convincing pathway for challenging incumbent Si-based PV.

14 SOLAR ENERGY↗
NASA NTRS1988

Cultural systems for growing potatoes in space

Higher plants are being evaluated for life support to provide needed food, oxygen and water as well as removal of carbon dioxide from the atmosphere. The successful utilization of plants in space will require the development of not only highly productive growing systems but also highly efficient bioregenerative systems. It will be necessary to recycle all inedible plant parts and all human wastes so that the entire complement of elemental compounds can be reused. Potatoes have been proposed as one of the desirable crops because they are 1) extremely productive, yielding more than 100 metric tons per hectare from field plantings, 2) the edible tubers are high in digestible starch (70%) and protein (10%) on a dry weight basis, 3) up to 80% of the total plant production is in tubers and thus edible, 4) the plants are easily propagated either from tubers or from tissue culture plantlets, 5) the tubers can be utilized with a minimum of processing, and 6) potatoes can be prepared in a variety of different forms for the human diet (Tibbitts et al., 1982). However potatoes have a growth pattern that complicates the development of growing the plants in controlled systems. Tubers are borne on underground stems that are botanically termed 'rhizomes', but in common usage termed 'stolons'. The stolons must be maintained in a dark, moist area with sufficient provision for enlargement of tubers. Stems rapidly terminate in flowers forcing extensive branching and spreading of plants so that individual plants will cover 0.2 m2 or more area. Thus the growing system must be developed to provide an area that is darkened for tuber and root growth and of sufficient size for plant spread. A system developed for growing potatoes, or any plants, in space will have certain requirements that must be met to make them a useful part of a life support system. The system must 1) be constructed of materials, and involve media, that can be reused for many successive cycles of plant growth, 2) involve a minimum quantity of media, 3) contain media that is essentially inert and not oxidize or degrade with use, 4) utilize a recirculating nutrient solution to permit regulation of pH and nutrient concentrations, and 5) be capable of complete automation of all planting, maintenance and harvesting procedures.

NASA Discipline Number 61-10↗
NASA NTRS2015

Orion Launch Abort System Performance on Exploration Flight Test 1

This paper will present an overview of the flight test objectives and performance of the Orion Launch Abort System during Exploration Flight Test-1. Exploration Flight Test-1, the first flight test of the Orion spacecraft, was managed and led by the Orion prime contractor, Lockheed Martin, and launched atop a United Launch Alliance Delta IV Heavy rocket. This flight test was a two-orbit, high-apogee, high-energy entry, low-inclination test mission used to validate and test systems critical to crew safety. This test included the first flight test of the Launch Abort System preforming Orion nominal flight mission critical objectives. NASA is currently designing and testing the Orion Multi-Purpose Crew Vehicle (MPCV). Orion will serve as NASA's new exploration vehicle to carry astronauts to deep space destinations and safely return them to earth. The Orion spacecraft is composed of four main elements: the Launch Abort System, the Crew Module, the Service Module, and the Spacecraft Adapter (Fig. 1). The Launch Abort System (LAS) provides two functions; during nominal launches, the LAS provides protection for the Crew Module from atmospheric loads and heating during first stage flight and during emergencies provides a reliable abort capability for aborts that occur within the atmosphere. The Orion Launch Abort System (LAS) consists of an Abort Motor to provide the abort separation from the Launch Vehicle, an Attitude Control Motor to provide attitude and rate control, and a Jettison Motor for crew module to LAS separation (Fig. 2). The jettison motor is used during a nominal launch to separate the LAS from the Launch Vehicle (LV) early in the flight of the second stage when it is no longer needed for aborts and at the end of an LAS abort sequence to enable deployment of the crew module's Landing Recovery System. The LAS also provides a Boost Protective Cover fairing that shields the crew module from debris and the aero-thermal environment during ascent. Although the Orion Program has tested a number of the critical systems of the Orion spacecraft on the ground, the launch environment cannot be replicated completely on Earth. A number of flight tests have been conducted and are planned to demonstrate the performance and enable certification of the Orion Spacecraft. Exploration Flight Test 1, the first flight test of the Orion spacecraft, was successfully flown on December 5, 2014 from Cape Canaveral Air Force Station's Space Launch Complex 37. Orion's first flight was a two-orbit, high-apogee, high-energy entry, low-inclination test mission used to validate and test systems critical to crew safety, such as heat shield performance, separation events, avionics and software performance, attitude control and guidance, parachute deployment and recovery operations. One of the key separation events tested during this flight was the nominal jettison of the LAS. Data from this flight will be used to verify the function of the jettison motor to separate the Launch Abort System from the crew module so it can continue on with the mission. The LAS nominal jettison event on Exploration Flight Test 1 occurred at six minutes and twenty seconds after liftoff (See Fig. 3). The abort motor and attitude control motors were inert for Exploration Flight Test 1, since the mission did not require abort capabilities. A suite of developmental flight instrumentation was included on the flight test to provide data on spacecraft subsystems and separation events. This paper will focus on the flight test objectives and performance of the LAS during ascent and nominal jettison. Selected LAS subsystem flight test data will be presented and discussed in the paper. Exploration Flight Test -1 will provide critical data that will enable engineering to improve Orion's design and reduce risk for the astronauts it will protect as NASA continues to move forward on its human journey to Mars. The lessons learned from Exploration Flight Test 1 and the other Flight Test Vehicles will certainly contribute to the vehicle architecture of a human-rated space launch vehicle.

McCauley, R.↗
DOE OSTI2024

Impacts of future nuclear power generation on the international monitoring system

Many countries are considering nuclear power as a means of reducing greenhouse gas emissions, and the IAEA (IAEA, 2022) has forecasted nuclear power growth rates up to 224% of the 2021 level by 2050. Nuclear power plants release trace quantities of radioxenon, an inert gas that is also monitored under international agreements as a signature of nuclear weapons tests. To better understand how nuclear energy growth (and resulting Xe emissions) could affect this global nonproliferation architecture, we modeled daily releases of radioxenon isotopes used for nuclear explosion detection in the International Monitoring System (IMS) that is part of the Comprehensive Nuclear Test-Ban Treaty: 131m Xe, 133 Xe, 133m Xe, and 135 Xe to examine the change in the number of radioxenon detections as compared to the 2021 detection levels. If a 40-station IMS network is used, the detections of 133 Xe in 2050 would range from 82% for the low-power scenario to 195% for the high-power scenario, compared to the detections in 2021. If an 80-station IMS network is used, the detections of 133 Xe in 2050 would range from 83% of the 2021 detection rate for the low-power scenario to 209% for the high-power scenario. Essentially no detections of 131m Xe and 133m Xe are expected. The high growth scenario could lead to a six-fold increase in 135 Xe detections, but the total number of detections is still small (on the order of 1 detection per day in the entire network).

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Insights into Sustainable Nitrogen Fixation by Gas-phase Spectroscopic Measurements and Global Modeling of Reaction Intermediates in Humid Nitrogen Plasma

In this article, there is growing interest in reacting molecular nitrogen and water to sustainably synthesize fixed forms of nitrogen such as ammonia. In particular, low-temperature plasmas can activate these relatively inert feedstocks at or near room temperature without a catalyst. However, because of the enhanced reactivity and nonequilibrium chemistry, a diverse range of products is formed, and the underlying reaction mechanisms are exceedingly complex. In this work, we studied a simplified reactor consisting of a gaseous plasma containing controlled mixtures of nitrogen gas and water vapor. Densities of key chemical species such as N, H, OH, NH, and NO were measured by emission and laser-based spectroscopy as a function of the relative humidity. A global model was constructed and the reaction network was validated by comparing calculated species densities with experiments. We discover that N, a key initial intermediate for ammonia, strongly decreases in the presence of water vapor, and as a result, ammonia formation becomes limited at high relative humidity. This decrease is surprisingly not because N itself reacts, but because one of its main sources, an excited molecular nitrogen state, is reacted away. In addition, oxidation pathways for nitrogen, which lead to NO and related products, are found to be favored over reduction pathways because the corresponding reverse reactions are less significant. Together, this understanding helps explain previously reported observations of selectivity toward nitrogen oxides over ammonia, particularly at higher relative humidities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Controlling Structural, Electronic, and Energy Flow Dynamics of Catalytic Processes through Tailored Nanostructures

MoS 2 (molybdenum disulfide) is a highly-versatile catalyst material for support of numerous reactions from hydrodesulfurization and denitrogenation to the focus of this renewal proposal: hydrogenation of CO/CO 2 towards (higher) alcohols. At the same time, MoS 2 is a non-toxic, environmentally-benign and rather inert material- which under ambient conditions for some time has served as a lubricant and, more recently, as next-generation electronic material. The apparent contrast between inertness and stability in ambient, and catalytic activity under reactive conditions is puzzling and calls for a synergistic theoretical and experimental investigation with the long-term objective of enabling the rational design of MoS 2 -based catalysts for alcohol-formation reactions by providing a microscopic understanding of the environmental factors that determines site activity and selectivity. Our research project seeks answers to the questions (a) what conformation does MoS 2 adopt under reaction conditions (as opposed to that under ultrahigh vacuum and low temperatures)?; (b) what reaction pathways exist on such a material?; (c) how can the local environment of the active sites be manipulated so as to make MoS 2 an efficient catalyst for production of higher alcohol from syngas? In particular, research strategies will explore how the basal plane composed of sulfur atoms can be activated so as to exhibit a reactivity of its own, by addressing three research targets and building on extensive preliminary and enabling work: (1) vacancies and vacancy aggregates on the basal plane; (2) non-local catalyst transformation through alkali doping, hydrogenation and phase transition; (3) fabrication of a metal-nanoparticle-activated MoS 2 system, in which particle anchoring, reactive sites and pathways as well as selectivity are controlled by design, as an example of predictive development of a catalyst material,. All strategies are directed to improve the efficacy of the key reactive sites and selectivity of chemical pathways by design, to replace the inefficient methodology of trial and error in catalyst development. This research project represents a synergistic combination of computational guidance, foundational surface-science-based experiments and validation under reactive conditions that aims at transformative new insights into the working of MoS 2 -based hydrogenation-catalysts, a topic squarely at the center of the interest of DOE BES. Guided and led by Talat Rahman, a computational physicist, this project will apply density functional theory to understand structure, reaction pathways and chemical potentials associated with MoS 2 -based CO/CO 2 hydrogenation, augmented by kinetic Monte Carlo methods for reaction rates and prefactors as well as ab-initio molecular dynamics for evaluation of thermal stability. Complementary experimental input and validation will originate from co-PI Ludwig Bartels, a physical chemist and materials scientist, whose group focuses on local imaging and preparation of MoS 2 materials, from co-PI Peter Dowben, an experimental physicist, whose group is expert in the spectroscopy of occupied and unoccupied electronic states, and from senior collaborator Michael White of Brookhaven National Laboratory, whose group generates high-resolution electronic and activity information on size-selected well-defined metal chalcogenide clusters. This collaborative effort will enable a comprehensive understanding of the correlation of structural integrity and catalytic activity of MoS 2 in forms ranging from extended films to individual particles with known geometries and binding sites. Alcohol formation from syngas is a rapidly emerging application that has great potential through facile, economic, and decentralized biomass gasification. CO 2 activation is one of the most pressing concerns of our time: increasing CO 2 levels in the atmosphere change the climate and expose the globe to environmental transformations with the potential for enormous economic and societal impact. We will investigate CO/CO 2 hydrogenation via an interdisciplinary research collaboration with established synergy – one that, in accordance with the mission of the DOE, involves accredited Hispanic-Serving Institutions and that, through student exchange with international collaborators and National Labs, will directly benefit a broad spectrum of communities and generate human resources in sciences essential to their future.

2D materials↗
NASA NTRSDate not supplied

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↗