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NASA NTRS2000

Treatability Study of Pentaborane(9)

Procedures for the safe destruction of liquid pentaborane(9), B5H9, by solvolysis were investigated. The objective of the study was to establish the optimum conditions for a pilot plant operation that would use water, or alcohol, or water-alcohol mixtures as the solvolysis reagent. Small amounts of B5H9 sprayed from a syringe will not necessarily enflame, nor will a small pool on a spot plate. Therefore, a procedure was developed to reproducibly demonstrate the flammability of B5H9. In these tests every sample of neat B5H9 ignited and burned with a very sooty flame till the sample was consumed. The spontaneous self-ignition of B5H9 was quenched by the addition of small concentrations of ethers THF (tetrahydrofuran) or DME (1,2-dimethoxy ethane). It was found that ten percent (volume) of either provided total quenching with a large margin of safety. When these stabilized solutions were exposed to air, they decomposed and evaporated leaving a residue that was identified by nuclear magnetic resonance (NMR) analysis as boric acid. Most of the laboratory solvolysis experiments used the 90 percent B5H9, 10 percent THF solution. This mixture was safer to handle and its solvolysis reactivity was virtually identical to that of 100 percent B5H9. Reaction rates were analyzed by measurement of hydrogen evolved during the solvolysis reactions. In terms of the minimum overall complete reaction time, the data indicate that 50/50 alcohol/water is the optimum solvolysis reagent. This reaction produced a mixture of boric acid, B(OH)3, and triethoxyborane, B(OEt)3[Et = C2H5], and mixed exchange derivatives thereof.

McDonald, Joseph K.↗

NASA NTRS2003

Trace Gas Measurements in Nascent, Aged and Cloud-processed Smoke from Africa Savanna Fires by Airborne Fourier Transform Infrared Spectroscopy (AFTIR)

We measured stable and reactive trace gases with an airborne Fourier transform infrared spectrometer (AFTIR) on the University of Washington Convair-580 research aircraft in August/September 2000 during the SAFARI 2000 dry season campaign in Southern Africa. The measurements included vertical profiles of C02, CO, H20, and CH4 up to 5.5 km on six occasions above instrumented ground sites and below the TERRA satellite and ER-2 high-flying research aircraft. We also measured the trace gas emissions from 10 African savanna fires. Five of these fires featured extensive ground-based fuel characterization, and two were in the humid savanna ecosystem that accounts for most African biomass burning. The major constituents we detected in nascent CH3OOH, HCHO, CH30H, HCN, NH3, HCOOH, and C2H2. These are the first quantitative measurements of the initial emissions of oxygenated volatile organic compounds (OVOC), NH3, and HCN from African savanna fires. On average, we measured 5.3 g/kg of OVOC and 3.6 g/kg of hydrocarbons (including CH4) in the initial emissions from the fires. Thus, the OVOC will have profound, largely unexplored effects on tropical tropospheric chemistry. The HCN emission factor was only weakly dependent on fire type; the average value (0.53 g/kg) is about 20 times that of a previous recommendation. HCN may be useful as a tracer for savanna fires. Delta O3/Delta CO and Delta CH3COO/Delta CO increased to as much as 9% in <1 h of photochemical processing downwind of fires. Direct measurements showed that cloud processing of smoke greatly reduced CH30H, NH3, CH3COOH, SO2, and NO2 levels, but significantly increased HCHO and NO.

Yokelson, Robert J.↗

DOE OSTI2021

Efficient connection of reactive shock wave profiles to reaction models

The future of energetic materials development, especially high-performance high explosives, demands new efficient and cost-effective experimental methods to understand the performance of new materials when only limited, development-scale quantities are available. Indeed, perhaps thousands of new molecules that have promising thermodynamic properties have been synthesized, only to be documented in the literature and never evaluated for their potential due to the cost of scaling up to produce quantities needed for traditional performance measurements.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Zinc aluminate (ZnAl 2 O 4 ) refractory aggregates: Dilatometric sintering studies and thermal expansion coefficient

ZnAl 2 O 4 has recently been reported to enhance thermomechanical properties and slag corrosion resistance of refractory castables. The pore generation and deleterious expansion during in situ ZnAl 2 O 4 formation can limit their amount in a refractory composition. A comprehensive dilatometric study is presented, identifying the optimum raw materials and processing conditions. Preformed ZnAl 2 O 4 refractory aggregates were synthesized from industrial ZnO and reactive Al 2 O 3 by two-stage firing at 1050 °C and 1700 °C resulting in 0% open porosity. The ZnAl 2 O 4 powder calcined at 1050 °C is also a good refractory matrix material as it has better sinterability than preformed refractory-grade MgAl 2 O 4 and calcined alumina. The thermal expansion coefficient of ZnAl 2 O 4 aggregate in the range of 70–1600 °C was found to be 10.7 × 10 –6 K –1 , which is similar to tabular Al 2 O 3 (10.3 × 10 –6 K –1 ) and MgAl 2 O 4 (10.3 × 10 –6 K –1 ), but lower than dead burned MgO (16.4 × 10 –6 K –1 ), creating the possibility of developing thermal shock resistant refractories by utilizing this mismatch.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Transformational challenge reactor design characteristics

The Transformational Challenge Reactor (TCR) program was conceived with the goal to reduce costs and time frames associated with advanced reactor deployment by leveraging developments in advanced manufacturing, advanced materials, data science, and rapid prototyping and testing. The final deliverable of the TCR program was to be an operational test of a novel reactor design. The TCR core design incorporates a dense tri-structural-isotropic/SiC fuel form and volumetrically efficient yttrium hydride moderator, both of which were manufactured and characterized under the TCR program. The TCR is a 3 MW{sub th} He-cooled experimental nuclear reactor designed to reach a total integrated burnup of less than 24 effective full-power hours to keep the radioactive source term to a very low level. TCR design process revealed a positive moderator coefficient; however, the negative doppler coefficients for the fuel and thermal expansion of fuel, moderator, and core support plate yield an overall negative reactivity coefficient. Calculated fuel element temperatures and stresses are well within safety margins. The maximum hypothetical accident (i.e., de-pressurized loss of forced cooling) yields only a modest increase in reactor temperatures that are all within safety margins. This paper summarizes the high-level TCR design characteristics, which were derived from neutronics, thermohydraulics, thermomechanics, and safety analyses.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2020

Designing Catalysts for Dehydrogenation of Methane for Reducing Greenhouse Gas during Natural Gas Extraction

Catalytic conversion of methane (CH 4 ) into useful products is critical for maximizing the utility of natural gas output and for reducing green house gas release associated with flaring (burning off CH 4 at natural gas extraction sites). One particular useful technique is methane dry reforming (DRM), which involves the chemical reaction of CH 4 with carbon dioxide (CO 2 ) to generate carbon monoxide (CO), hydrogen gas (H 2 ), and subsequently other useful products. New and improved catalysts are required to facilitate efficient dry methane reforming. In this report, we apply the Density Functional Theory (DFT) computational technique to investigate a catalyst consisting of small nickel clusters (Ni n , n < 10) on ceria (Ce0 2 (111) surfaces) support. One main thrust of this project is to study the initial CH 4 and CO 2 reactions with the catalyst. We find that CH 4 exhibits barrierless reactive adsorption on to the catalyst. In order words, this step is likely not the rate-determining step. A second thrust is to perform detailed studies of the catalyst itself and examine the role of oxygen vacancies. Using a specific DFT method and a hypothesis about the absence of the Ce(III) redox state, we obtain predictions about oxygen vacancies in good agreement with experimental observations.

03 NATURAL GAS↗

DOE OSTI2024

An exploration of anomalous electrical noise in shocked cyclotrimethylenetrinitramine (RDX)-based explosives

Gas gun shock experiments on cyclotrimethylenetrinitramine (RDX)-based explosive compositions that employ embedded gauge particle velocity tracers have noted a significant amount of electrical noise when compared to other explosive formulations. This paper reexamines previously published embedded gauge data on Cyclotols (60–80 wt. % RDX) to quantify the electromagnetic behavior of these materials. The primary observation is a fourfold increase in the electrical noise when Cyclotols are shocked above 4.22 ± 0.08 GPa. Electromagnetic gauge noise is also observed within particle velocity traces in reactive growth and off-Hugoniot shocks, although at higher pressures than the direct shock case, suggesting a temperature- or kinetically dependent transition. In all cases, the electrical noise disappears upon detonation. By comparing with the static high-pressure phase diagram of RDX, we interpret this change in electromagnetic behavior to be a change in the RDX crystal structure to a piezoelectric phase, although it is uncertain whether the γ or ε phase is responsible for the observed behavior.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

NASA NTRS2018

Air Quality Modeling Using the NASA GEOS-5 Multispecies Data Assimilation System

The NASA Goddard Earth Observing System (GEOS) data assimilation system (DAS) has been expanded to include chemically reactive tropospheric trace gases including ozone (O3), nitrogen dioxide (NO2), and carbon monoxide (CO). This system combines model analyses from the GEOS-5 model with detailed atmospheric chemistry and observations from MLS (O3), OMI (O3 and NO2), and MOPITT (CO). We show results from a variety of assimilation test experiments, highlighting the improvements in the representation of model species concentrations by up to 50% compared to an assimilation-free control experiment. Taking into account the rapid chemical cycling of NO2 when applying the assimilation increments greatly improves assimilation skills for NO2 and provides large benefits for model concentrations near the surface. Analysis of the geospatial distribution of the assimilation increments suggest that the free-running model overestimates biomass burning emissions but underestimates lightning NOx emissions by 5-20%. We discuss the capability of the chemical data assimilation system to improve atmospheric composition forecasts through improved initial value and boundary condition inputs, particularly during air pollution events. We find that the current assimilation system meaningfully improves short-term forecasts (1-3 day). For longer-term forecasts more emphasis on updating the emissions instead of initial concentration fields is needed.

Keller, Christoph A.↗

NASA NTRS2016

Development of Hydroxyl Tagging Velocimetry for Low Velocity Flows

Hydroxyl tagging velocimetry (HTV) is a molecular tagging technique that relies on the photo-dissociation of water vapor into OH radicals and their subsequent tracking using laser induced fluorescence. Velocities are then obtained from time-of-flight calculations. At ambient temperature in air, the OH species lifetime is relatively short (<50 μs), making it suited for high speed flows. Lifetime and radicals formation increases with temperature, which allows HTV to also probe low-velocity, high-temperature flows or reacting flows such as flames. The present work aims at extending the domain of applicability of HTV, particularly towards low-speed (<10 m/s) and moderate (<500 K) temperature flows. Results are compared to particle image velocimetry (PIV) measurements recorded in identical conditions. Single shot and averaged velocity profiles are obtained in an air jet at room temperature. By modestly raising the temperature (100-200 degC) the OH production increases, resulting in an improvement of the signal-to-noise ratio (SNR). Use of nitrogen - a non-reactive gas with minimal collisional quenching - extends the OH species lifetime (to over 500 μs), which allows probing of slower flows or, alternately, increases the measurement precision at the expense of spatial resolution. Instantaneous velocity profiles are resolved in a 100degC nitrogen jet (maximum jet-center velocity of 6.5 m/s) with an uncertainty down to 0.10 m/s (1.5%) at 68% confidence level. MTV measurements are compared with particle image velocimetry and show agreement within 2%.

Andre, Matthieu A.↗

DOE OSTI2021

Incidence of chronic respiratory conditions among oil spill responders: Five years of follow-up in the Deepwater Horizon Oil Spill Coast Guard Cohort study

Background: Over ten years after the Deepwater Horizon (DWH) oil spill, our understanding of long term respiratory health risks associated with oil spill response exposures is limited. Here we conducted a prospective analysis in a cohort of U.S. Coast Guard personnel with universal military healthcare. Methods: For all active duty cohort members (N = 45,193) in the DWH Oil Spill Coast Guard Cohort Study we obtained medical encounter data from October 01, 2007 to September 30, 2015 (i.e., ~2.5 years pre-spill; ~5.5 years post-spill). We used Cox Proportional Hazards regressions to calculate adjusted hazard ratios (aHR), comparing risks for incident respiratory conditions/symptoms (2010–2015) for: responders vs. non-responders; responders reporting crude oil exposure, any inhalation of crude oil vapors, and being in the vicinity of burning crude oil versus responders without those exposures. We also evaluated self-reported crude oil and oil dispersant exposures, combined. Within-responder comparisons were adjusted for age, sex, and smoking. Results: While elevated aHRs for responder/non-responder comparisons were generally weak, within-responder comparisons showed stronger risks with exposure to crude oil. Notably, for responders reporting exposure to crude oil via inhalation, there were elevated risks for all sinusitis (aHR = 1.48; 95%CI, 1.06–2.06), unspecified chronic sinusitis (aHR = 1.55; 95%CI, 1.08–2.22), chronic obstructive pulmonary disease (COPD) and other allied conditions (aHR = 1.43; 95%CI, 1.00–2.06), and dyspnea and respiratory abnormalities (aHR = 1.29; 95%CI, 1.00–1.67); there was a suggestion of elevated risk for diseases classified as asthma and reactive airway diseases (aHR = 1.18; 95%CI, 0.98–1.41), including the specific condition, asthma (aHR = 1.35; 95%CI, 0.80–2.27), the symptom, shortness of breath (aHR = 1.50; 95%CI, 0.89–2.54), and the overall classification of chronic respiratory conditions (aHR = 1.18; 95%CI, 0.98–1.43). Exposure to both crude oil and dispersant was positively associated with elevated risk for shortness of breath (HR = 2.24; 95%CI, 1.09–4.64). Conclusions: Among active duty Coast Guard personnel, oil spill clean-up exposures were associated with moderately increased risk for longer term respiratory conditions.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2003

Correction to "Asian chemical Outflow to the Pacific in Spring: Origins, Pathways, and Budgets" by Isabelle Bey et al.

We analyze the Asian outflow of CO, ozone, and nitrogen oxides (NOx) to the Pacific in spring by using the GEOS-CHEM global three-dimensional model of tropospheric chemistry and simulating the Pacific Exploratory Mission-West (PEM-West B) aircraft mission in February-March 1994. The GEOS-CHEM model uses assimilated meteorological fields from the NASA Goddard Earth Observing System (GEOS). It reproduces relatively well the main features of tropospheric ozone, CO, and reactive nitrogen species observed in PEM-West B, including latitudinal and vertical gradients of the Asian pollution outflow over the western Pacific although simulated concentrations of CO tend to be too low (possibly because biogenic sources are underestimated). We use CO as a long-lived tracer to diagnose the processes contributing to the outflow. The highest concentrations in the outflow are in the boundary layer (0-2 km), but the strongest outflow fluxes are in the lower free troposphere (2-5 km) and reflect episodic lifting of pollution over central and eastern China ahead of eastward moving cold fronts. This frontal lifting, followed by westerly transport in the lower free troposphere, is the principal process responsible for export of both anthropogenic and biomass burning pollution from Asia. Anthropogenic emissions from Europe and biomass burning emissions from Africa make also major contributions to the Asian outflow over the western Pacific; European sources dominate in the lower troposphere north of 40 degrees N, while African sources are important in the upper troposphere at low latitudes. For the period of PEM-West B (February-March) we estimate that fossil fuel combustion and biomass burning make comparable contributions to the budgets of CO, ozone, and NO, in the Asian outflow. We find that 13% of NO, emitted in Asia is exported as NO, or PAN, a smaller fraction than for the United States because of higher aerosol concentrations that promote heterogeneous conversion of NOx to HNO3. Production and export of ozone from Asia in spring is much greater than from the United States because of the higher photochemical activity.

Bey, Isabelle↗

NASA NTRS2022

Photochemical Evolution of the 2013 California Rim Fire: Synergistic Impacts of Reactive Hydrocarbons and Enhanced Oxidants

Large wildfires markedly alter regional atmospheric composition, but chemical complexity challenges model predictions of downwind impacts. Here, we elucidate key facets of gas-phase photochemistry and assess novel chemical processes via a case study of the 2013 California Rim Fire plume. Airborne in situ observations, acquired during the NASA Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) mission, illustrate the evolution of volatile organic compounds (VOC), oxidants, and reactive nitrogen over 12 hours of atmospheric aging. Measurements show rapid formation of ozone and peroxyacyl nitrates (PNs), sustained peroxide production, and prolonged enhancements in oxygenated VOC and nitrogen oxides (NOX). Measurements and Lagrangian trajectories constrain a 0-D puff model that approximates plume photochemical history and provides a framework for evaluating key processes. Simulations examine the effects of 1) previously-unmeasured reactive VOC identified in recent laboratory studies, and 2) emissions and secondary production of nitrous acid (HONO). Inclusion of estimated unmeasured VOC leads to a 250% increase in OH reactivity and a 70% increase in radical production via oxygenated VOC photolysis. HONO amplifies radical cycling and serves as a downwind NOX source, although two different HONO production mechanisms (particulate nitrate photolysis and heterogeneous NO2 conversion) exhibit markedly different effects on ozone, NOX, and PNs. Analysis of radical initiation rates suggests that oxygenated VOC photolysis is a major radical source, exceeding HONO photolysis when averaged over the first 2 hours of aging. Ozone production chemistry transitions from VOC-sensitive to NOX-sensitive within the first hour of plume aging, with both peroxide and organic nitrate formation contributing significantly to radical termination. To simulate smoke plume chemistry accurately, models should simultaneously account for the full reactive VOC pool and all relevant oxidant sources.

SEAC4RS↗

NASA NTRS2006

Opposed Jet Burner Approach for Characterizing Flameholding Potentials of Hydrocarbon Scramjet Fuels

Opposed Jet Burner (OJB) tools have been used extensively by the authors to measure Flame Strength (FS) extinction limits of laminar H2/N2 air and (recently) hydrocarbon (HC) air Counterflow Diffusion Flames (CFDFs) at one atm. This paper details normalization of FSs of N2- diluted H2 and HC systems to account for effects of fuel composition, temperature, pressure, jet diameter, inflow Reynolds number, and inflow velocity profile (plug, contoured nozzle; and parabolic, straight tube). Normalized results exemplify a sensitive accurate means of validating, globally, reduced chemical kinetic models at approx. 1 atm and the relatively low temperatures approximating the loss of non-premixed idealized flameholding, e.g., in scramjet combustors. Laminar FS is defined locally as maximum air input velocity, U(sub air), that sustains combustion of a counter-jet of g-fuel at extinction. It uniquely characterizes a fuel. And global axial strain rate at extinction (U(sub air) normalized by nozzle or tube diameter, D(sub n or (sub t)) can be compared directly with computed extinction limits, determined using either a 1-D Navier Stokes stream-function solution, using detailed transport and finite rate chemistry, or (better yet) a detailed 2-D Navier Stokes numerical simulation. The experimental results define an idealized flameholding reactivity scale that shows wide ranging (50 x) normalized FS s for various vaporized-liquid and gaseous HCs, including, in ascending order: JP-10, methane, JP-7, n-heptane, n-butane, propane, ethane, and ethylene. Results from H2 air produce a unique and exceptionally strong flame that agree within approx. 1% of a recent 2-D numerically simulated FS for a 3 mm tube-OJB. Thus we suggest that experimental FS s and/or FS ratios, for various neat and blended HCs w/ and w/o additives, offer accurate global tests of chemical kinetic models at the Ts and Ps of extinction. In conclusion, we argue the FS approach is more direct and fundamental, for assessing, e.g., idealized scramjet flameholding potentials, than measurements of laminar burning velocity or blowout in a Perfectly Stirred Reactor, because the latter characterize premixed combustion in the absence of aerodynamic strain. And FS directly measures a chemical kinetic characteristic of non-premixed combustion at typical flameholding temperatures. It mimics conditions where gfuels are typically injected into a subsonic flameholding recirculation zone that captures air, where the effects of aerodynamic strain and associated multi-component diffusion become important.

Pellett, Gerald L.↗

DOE OSTI2023

Modeling the Impact of the Organic Aerosol Phase State on Multiphase OH Reactive Uptake Kinetics and the Resultant Heterogeneous Oxidation Timescale of Organic Aerosol in the Amazon Rainforest

Accurate predictions of chemical lifetime, i.e., oxidation timescale and change in the mass of organic aerosols (OAs) in atmospheric models, are critical to quantify the impacts of OA on aerosol–cloud interactions, radiative forcing, and air quality. The heterogeneous oxidation of OA by hydroxyl (OH) radicals is a key process governing OA mass changes during their oxidation. Recently, laboratory observations of the OH uptake coefficient (γ OH ) and heterogeneous reaction rate (k het,OH ) for different OA systems with varying phase states have been combined to develop a new parameterization of γ OH and k het,OH as a function of the OA phase state, i.e., viscosity (η OA ). Here, in this work, we use a recently published viscosity prediction framework to analyze the new γ OH and k het,OH parameterization with a box model. Subsequently, we implement this box model to predict γ OH and k het,OH over the Amazon rainforest in the dry-to-wet transition season with both significant biomass burning and biogenic influences. Relevant parameters within our box model are specified based on detailed regional model simulations over the Amazon using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). η OA is predicted as a function of species volatility, OA composition (including water uptake) along with ambient relative humidity (RH), and temperature. Based on ambient conditions simulated by WRF-Chem over the entire atmospheric column, we use the box model to predict the upper bounds of the heterogeneous oxidation timescale of OA. Based on previous laboratory measurements, we assume that this heterogeneous OH oxidation causes fragmentation (carbon loss) of OA, followed by the evaporation of the fragmented molecules that results in the exponential decay of OA. We predict that the oxidation timescale of OA is ~1 month near the Earth’s surface in the pristine Amazonian background because of low OH concentrations. But OA is oxidized more rapidly within urban and wildfire plumes near the Earth’s surface with an order of magnitude higher OH concentrations compared to the pristine background, causing the simulated oxidation timescale of OA to be much shorter, ~3–4 days. At 3–5 km altitudes where biomass burning OA is predicted to be semisolid, the heterogeneous oxidation timescale is estimated as ~6 days to 3 weeks and decreases with increasing OH concentrations within plumes. We show that the simulated mass loss of OA is strongly size-dependent, where smaller particles oxidize more rapidly compared to larger particles due to their greater per-particle surface area-to-volume ratio. Increasing urbanization and deforestation in the Amazon in the future might increase OH concentrations in the background Amazon, causing faster oxidation of OA. At higher altitudes above liquid clouds, especially in the upper troposphere where temperatures approach ~250 K, future measurements are needed to reduce the uncertainties related to the mass loss of OA at colder temperatures and low relative humidity conditions due to its heterogeneous OH oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2018

Chapter 12: Materials for Liquid Propulsion Systems

Earth to orbit launch vehicles are propelled by rocket engines and motors, both liquid and solid. This chapter will discuss liquid engines. The heart of a launch vehicle is its engine. The remainder of the vehicle (with the notable exceptions of the payload and guidance system) is an aero structure to support the propellant tanks which provide the fuel and oxidizer to feed the engine or engines. The basic principle behind a rocket engine is straightforward. The engine is a means to convert potential thermochemical energy of one or more propellants into exhaust jet kinetic energy. Fuel and oxidizer are burned in a combustion chamber where they create hot gases under high pressure. These hot gases are allowed to expand through a nozzle. The molecules of hot gas are first constricted by the throat of the nozzle (de-Laval nozzle) which forces them to accelerate; then as the nozzle flares outwards, they expand and further accelerate. It is the mass of the combustion gases times their velocity, reacting against the walls of the combustion chamber and nozzle, which produce thrust according to Newton's third law: for every action there is an equal and opposite reaction. Solid rocket motors are cheaper to manufacture and offer good values for their cost. Liquid propellant engines offer higher performance, that is, they deliver greater thrust per unit weight of propellant burned. They also have a considerably higher thrust to weigh ratio. Since liquid rocket engines can be tested several times before flight, they have the capability to be more reliable, and their ability to shut down once started provides an extra margin of safety. Liquid propellant engines also can be designed with restart capability to provide orbital maneuvering capability. In some instances, liquid engines also can be designed to be reusable. On the solid side, hybrid solid motors also have been developed with the capability to stop and restart. Solid motors are covered in detail in chapter 11. Liquid rocket engine operational factors can be described in terms of extremes: temperatures ranging from that of liquid hydrogen (-423 F) to 6000 F hot gases; enormous thermal shock (7000 F/sec); large temperature differentials between contiguous components; reactive propellants; extreme acoustic environments; high rotational speeds for turbo machinery and extreme power densities. These factors place great demands on materials selection and each must be dealt with while maintaining an engine of the lightest possible weight. This chapter will describe the design considerations for the materials used in the various components of liquid rocket engines and provide examples of usage and experiences in each.

Halchak, John A.↗

NASA NTRSDate not supplied

Atmospheric Formaldehyde Trend and Its Source Attributions in the Recent Decades

Formaldehyde (CH 2 O) is one of the most important reactive trace gases in the atmosphere with an important role in tropospheric chemistry and in the control of surface air quality. Sources of CH 2 O includes direct emissions and in situ production from the oxidation of volatile organic compounds (VOCs). In this study, we investigate spatial-temporal variations in atmospheric CH 2 O and how changes in CH 2 O couple with tropospheric ozone variability during the past two decades using recently available retrievals from the Ozone Monitoring Instrument (OMI) aboard NASA’s Aura satellite and the RefD1 simulation from the NASA Goddard Earth Observing System Chemistry Climate Model (GEOSCCM). Our initial analysis provides evidence of significant increases in atmospheric CH 2 O concentrations over several of the world’s major anthropogenic regions, including China, India, and the Middle East, and several biomass burning regions, including South America, southern Africa, boreal regions and Indonesia. We furthermore will identify regional source contributions to CH 2 O trends, including anthropogenic VOCs emissions, biogenic isoprene emissions and open fires. In particular, we will focus on anthropogenic emission regions to examine the role of changing anthropogenic VOC emissions on CH 2 O abundance.

Atmospheric Formaldehyde↗

DOE OSTI2024

Computational analysis of flame initiation, quenching, and re-ignition in a prechamber natural gas engine under varying EGR-dilution levels

The on-road natural-gas (NG) fueled transportation relies on stoichiometric spark-ignition engines for the advantages of simple after-treatment system despite the efficiency penalty relative to lean-burn combustion strategies. Exhaust gas recirculation (EGR) has the potential to reduce this efficiency gap at low to moderate loads without the need for complex lean-exhaust aftertreatment systems. However, EGR dilution leads to reduced combustion stability and increased cycle-to-cycle variability. A promising technology that has the potential to achieve reliable operation under diluted conditions is the prechamber ignition (or turbulent jet ignition) which uses chemically active turbulent jets generated from combustion inside a prechamber to initiate, stabilize and accelerate combustion of the mixture inside the main chamber. The present work focusses on developing a RANS-based CFD approach to accurately reproduce in-cylinder phenomena in a stoichiometric NG prechamber-assisted heavy-duty engine without relying on complex combustion models that account for turbulence-chemistry interactions. This is necessary because reactive prechamber jets at high EGR dilution tend to extinguish while emerging into the main chamber, which is followed by a phase of re-ignition — a phenomenon that conventional G-equation or well-stirred reactor combustion models cannot reproduce. With addition of a damping multiplier to the well-stirred reactor model, the predictions are seen to show good agreement with experimental pressure evolution and combustion images acquired from a single cylinder Cummins N-14 optical diesel engine retrofitted with a prechamber ignition system. Model predictions of local heat release in the flame and temperature evolution inside the flame are used to investigate combustion dynamics in the prechamber and the main chamber. It is seen that the well-stirred reactor model with the inclusion of damping is able to reproduce the temporary reduction in heat release within the flame, which can be considered equivalent to quenching of jets, and the subsequent re-ignition of the flame inside the main chamber. The delay between quenching and re-ignition depends on the amount of dilution, as explained by an illustration of flame evolution in a Borghi diagram.

Prechamber ignition↗

DOE OSTI2021

Aircraft measurements of aerosol and trace gas chemistry in the eastern North Atlantic

The Aerosol and Cloud Experiment in the Eastern North Atlantic (ACE-ENA) investigated properties of aerosols and subtropical marine boundary layer (MBL) clouds. Low subtropical marine clouds can have a large effect on Earth's radiative budget, but they are poorly represented in global climate models. In order to understand their radiative effects, it is imperative to understand the composition and sources of the MBL cloud condensation nuclei (CCN). The campaign consisted of two intensive operation periods (IOPs) (June–July 2017 and January–February 2018) during which an instrumented G-1 aircraft was deployed from Lajes Field on Terceira Island in the Azores, Portugal. The G-1 conducted research flights in the vicinity of the Atmospheric Radiation Measurement (ARM) Eastern North Atlantic (ENA) atmospheric observatory on Graciosa Island. An Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and Ionicon proton-transfer-reaction mass spectrometer (PTR-MS) were deployed aboard the aircraft, characterizing chemistry of non-refractory aerosol and trace gases, respectively. The eastern North Atlantic region was found to be very clean, with an average non-refractory submicrometer aerosol mass loading of 0.6 µg m −3 in the summer and 0.1 µg m −3 in the winter, measured by the AMS. Average concentrations of the trace reactive gases methanol and acetone were 1–2 ppb; benzene, toluene and isoprene were even lower, <1 ppb. Mass fractions of sulfate, organics, ammonium and nitrate in the boundary layer were 69 %, 23 %, 7 % and 1 % and remained largely similar between seasons. The aerosol chemical composition was dominated by sulfate and highly processed organics. Particulate methanesulfonic acid (MSA), a well-known secondary biogenic marine species, was detected, with an average boundary layer concentration of 0.021 µg m −3 , along with its gas-phase precursor, dimethyl sulfide (DMS). MSA accounted for no more than 3 % of the submicron, non-refractory aerosol in the boundary layer. Examination of vertical profiles of aerosol and gas chemistry during ACE-ENA reveals an interplay of local marine emissions and long-range-transported aged aerosol. A case of transport of biomass burning emissions from North American fires has been identified using back-trajectory analysis. In the summer, the non-refractory portion of the background CCN budget was heavily influenced by aerosol associated with ocean productivity, in particular sulfate formed from DMS oxidation. Episodic transport from the continents, particularly of biomass burning aerosol, periodically increased CCN concentrations in the free troposphere. In the winter, with ocean productivity lower, CCN concentrations were overall much lower and dominated by remote transport. These results show that anthropogenic emissions perturb CCN concentrations in remote regions that are sensitive to changes in CCN number and illustrate that accurate predictions of both transport and regional aerosol formation from the oceans are critical to accurately modeling clouds in these regions.

54 ENVIRONMENTAL SCIENCES↗