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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.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

4D Printing via an Unconventional Fused Deposition Modeling Route to High-Performance Thermosets

An unprecedented four-dimensional (4D) printing process allowing high-performance and shape memory thermoset to be printed, for the first time, by fused deposition modeling (FDM) with isotropic properties has been achieved. Here, bisphenol A-based epoxy and benzoxazine were formulated to a low-temperature thermoplastic and high-temperature thermoset resin, which is melt-extrudable and can be postcured into covalently cross-linked material. Carbon nanotube (CNT) was added in the resin to work as both mechanical enhancement filler and rheology modifier to prevent shape deformation during postcuring process. The cross-layer reaction fuses individual layers into an integrity, thus eliminating layer delamination induced by FDM, offering isotropic mechanical properties regardless of the printing orientations. The highly cross-linked network provides outstanding mechanical strength and superb thermal stability. The excellent shape memory performance with fast recovery rate and large recovery degree is also obtained in the three-dimensional (3D) printed composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Handling Qualities Results of an Initial Geared Flap Tilt Wing Piloted Simulation

An exploratory simulation study of a novel approach to pitch control for a tilt wing aircraft was conducted in 1990 on the NASA-Ames Vertical Motion Simulator. The purpose of the study was to evaluate and compare the handling qualities of both a conventional and a geared flap tilt wing control configuration. The geared flap is an innovative control concept which has the potential for reducing or eliminating the horizontal pitch control tail rotor or reaction jets required by prior tilt wing designs. The handling qualities results of the geared flap control configuration are presented in this paper and compared to the conventional (programmed flap) tilt wing control configuration. This paper also describes the geared flap concept, the tilt wing aircraft, the simulation model, the simulation facility and experiment setup, and the pilot evaluation tasks and procedures.

Guerrero, Lourdes M.↗
NASA NTRS2010

Orion Touchdown Heading Control

At touchdown Orion must be aligned so that the crew person's feet are forward in the direction of the horizontal velocity. To ensure that this requirement is met active heading control is being implemented on the Orion crew module. This technique reduces probability of roll-over during splashdown, assures axial loads on the crew at touchdown, and alleviates structural requirements on impact allowing for a light-weight structural design. On-board sensors are used to measure current vehicle orientation and horizontal velocity used in generation of the heading error signal. Linear velocity measured by the IMU drifts while under parachutes due to wind gusts and has to be corrected by GPS; this makes GPS critical for successful landing. Jet fire logic is achieved by use of a phase-plane and commands are realized by using roll jets from the reaction control system (RCS); using pre existing hardware eliminates additional hardware and structural requirements. Touchdown performance is measured by an orientation envelope that was co-developed with structures so that the performance requirements overlap adding system redundancy. Heading control also introduces new difficulties to be addressed such as parachute line twist torque as well as increasing vehicle sensitivity to wind shifts and sea states. Solving these difficulties requires added complexity to flight software as well as increasing the propellant required to achieve successful touchdown. while offering promising results, the criticality of GPS along with a significant propellant cost raises questions on the effectiveness of using touchdown heading control.

Kane, Mark A.↗
DOE OSTI2020

Formation of phenanthrene via H–assisted isomerization of 2–ethynylbiphenyl produced in the reaction of phenyl with phenylacetylene

Model chemistry G3(MP2,CC)//B3LYP/6–311G(d,p) calculations of the potential energy surface for the reaction of phenyl radical (C 6 H 5 ) with phenylacetylene (C 8 H 6 ) have been carried out and combined with Rice–Ramsperger–Kassel–Marcus/Master Equation calculations of temperature– and pressure–dependent rate constants. The results showed that the reaction can serve as a viable source for the formation of phenanthrene via an indirect route involving a primary reaction of phenyl addition to the ortho carbon in the ring of phenylacetylene and H elimination producing 2–ethynylbiphenyl followed by secondary H–assisted isomerization of 2–ethynylbiphenyl to phenanthrene. In the secondary reaction, the H atom adds to the α carbon of the ethynyl side chain, then a six–member ring closure takes place followed by aromatization via an H loss. The channel of H addition to the side chain of 2–ethynylbiphenyl appears to be much faster than H addition to the ortho carbon in the ethynyl–substituted ring leading back to the initial C 6 H 5 + C 8 H 6 reactants. Rate constants for the primary C 6 H 5 + C 8 H 6 ⇌2–ethynylbiphenyl (p1) + H and secondary p1 + H⇌phenanthrene (p2) + H reactions have been computed in the temperature range of 500–2500 K at pressures of 30 Torr, 1, 10, and 100 atm and fitted to modified Arrhenius expressions. Here, the suggested kinetic scheme and rate constants are proposed as a prototype for the modeling of the growth of polycyclic aromatic hydrocarbons via the phenyl addition–dehydrocyclization (PAC) mechanism involving an addition of a PAH radical to an ethynyl–substituted PAH molecule.

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

Kinetic Model for Moisture-Controlled CO 2 Sorption

The understanding of the sorption/desorption kinetics is essential for practical applications of moisture-controlled CO 2 sorption. We introduce an analytic model of the kinetics of moisture-controlled CO 2 sorption and its interpretation in two limiting cases. In one case, chemical reaction kinetics on pore surfaces dominates, in the other case, diffusive transport through the sorbent defines the kinetics. Here, we show that reaction kinetics, which is dominant in the first case, can be expressed as a linear combination of 1st and 2nd order kinetics in agreement with the static isotherm equation derived and validated in a previous paper. The interior transport kinetics can be described by non-linear diffusion equations. By combining all carbon species into a single equation, we can eliminate — in certain limits — the source terms associated with chemical reactions. In this case, the governing equation is ∂θ/∂t = –∇ · (–D eff ∇ θ ). For a sorbent in a form of a flat sheet or a membrane, one can maintain the same functional form of a diffusion equation by introducing a generalized effective diffusivity D M that combines contributions from both surface chemical reaction kinetics and interior diffusive transport kinetics. Experimental data of transient CO 2 flux in a preconditioned commercial anion exchange membrane fit well to the 1st order model as long as very dry states are avoided, validating the theory. The observed DM for a preconditioned commercial anion exchange membrane ranges from 6.6× 10 -14 to 7.1× 10 -14 m 2 s -1 at 35°C. These small values compared to typical ionic diffusivities imply a very slow kinetics, which will be the largest issue that needs to be addressed for practical application. The collected transient CO 2 flux data are used to predict the magnitude of a continuous CO 2 pumping flux in an active membrane that transports CO 2 against a CO 2 concentration gradient. The pumped CO 2 flux is supported by water flux due to a water concentration gradient.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

Combustion of Metals in Reduced-Gravity and Extraterrestrial Environments

As a result of the ongoing exploration of Mars and the several unmanned and possibly manned missions planned for the near future, increased attention has been given to the use of the natural resources of the planet for rocket propellant production and energy generation. Since the atmosphere of Mars consists of approximately 95% carbon dioxide (CO2), this gas is the resource of choice to be employed for these purposes. Since many metals burn vigorously with CO2, these may be used as an energy source or as propellants for a research vehicle on the surface of Mars. Shafirovich and Goldshleger conducted experiments with spherical particles up to 2.5 mm in diameter and found that the burning process was controlled by diffusion and that the particles exhibited pulsating combustion due to superheating of the Mg vapor trapped inside a protective oxide shell. They also proposed a reaction mechanism based on the gas-phase reaction, Mg + CO2 yields MgO + CO and the heterogeneous reaction Mg + CO yields MgO + C occurring on the sample surface. In all the above studies with large Mg particles, the burning process is invariably influenced by strong convective currents that accelerate the combustion reaction and shorten the burning times. Although these currents are nearly absent in the burning of small particles, the high emissivity of the flames, rapid reaction, and small length scales make the gathering of any useful information on burning rates and flame structure very difficult. The goal of this investigation is to provide a detailed study of flame structure by taking advantage of large, free-floating spherical metal samples and their corresponding long burning times available in a weightless environment. The use of reduced gravity is essential to eliminate the intrusive buoyant flows that plague high temperature metal reactions, to remove the destructive effect of gravity on the shape of molten metal samples, and to study the combustion behavior of metals in the presence of solid oxides undisturbed by natural convection. This work presents the most complete modeling of metal particle burning to date for Mg with CO2 and O2.

Branch, M. C.↗
NASA NTRS2001

Combustion of Metals in Carbon Dioxide and Reduced-Gravity Environments

Ongoing exploration and future mission2001110444 s to Mars have given impetus to research on the use of natural resources of the planet. Since carbon dioxide (CO2) constitutes approximately 95% of the Mars atmosphere and since it reacts directly and vigorously with several metals, this investigation focuses on metal-CO2 reactions as a possible combination for rocket-propellant production and energy generation. Magnesium (Mg) has been initially selected as the metal fuel owing to its low ignition temperature and high specific impulse and burning rate in CO2. Our studies in this field started with low gravity (g) combustion tests of Mg in O2, CO2, and CO. Reduced gravity provided a clear picture of the burning phenomena by eliminating the intrusive buoyant flows in high-temperature metal reactions and by removing the destructive effect of gravity on the shape of molten metal samples. Suspended cylindrical metal samples of 2, 3, and 4-mm in diameter and length were radiatively ignited in low-g to generate free-floating samples exhibiting a spherically symmetric flame with increasing metal-oxide accumulation in an outer shell. For the Mg-CO2 combination, burning times twice as long as in normal-g and five times longer than in Mg-O2 flames were observed, revealing a diffusion-controlled reaction. The burning time is proportional to the square of the sample diameter. In tests conducted with pure CO, combustion was not possible without constant heating of the sample due to the formation of a thick carbon-containing coating around the Mg sample generated by surface reactions. The following work presents two new studies that attempt to explain some of the low-g experimental observations. First, a simplified one-dimensional, quasi-steady numerical model is developed to obtain temperature, species concentrations, and burning rates of the spherically symmetric diffusion flame around the Mg sample burning in O2 and CO2. Second, a Planar Laser Induced Fluorescence (PLIF) technique is implemented to provide spatially resolved measurements of magnesium oxide (MgO) in the reaction zone of Mg samples burning in O2 and CO2. These experiments reveal fundamental differences between the two combustion systems.

Branch, M. C.↗
DOE OSTI2022

Nitrogen-doped carbon for selective pseudo-metal-free hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran: Importance of trace iron impurity

Heteroatoms-doped carbon materials have recently emerged as effective catalysts for various chemical and electrochemical reactions. The free of metals especially noble metals reduces cost and eliminates issues like sintering or leaching of metals at elevated temperatures in solvents. In this work, selective hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is for the first time achieved over simple nitrogen-doped carbon (N-C) catalysts. Further, at optimal reaction conditions, a 91% yield of DMF is obtained with excellent catalyst stability. Extensive characterization, including extended X-ray absorption fine-structure (EXAFS) and soft X-ray absorption spectroscopy (sXAS), model reactions, basic data science analysis, and DFT calculations suggest that ppm of Fe in particular FeN 3 sites formed in pyrolysis, rather than non-metallic elements, drive key steps such as H 2 activation and deoxygenation of –OH during HMF HDO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Leveraging chiral induced spin selectivity to improve the efficiency and selectivity of electrocatalytic reduction

Energy production is a fundamental pillar of modern society, but it remains heavily reliant on fossil fuel combustion, which leads to environmental degradation and resource depletion. Electrocatalytic reduction reactions (ERRs) offer a cleaner alternative by functioning under mild conditions, eliminating the need for high temperatures or pressures. However, their widespread adoption is hindered by challenges such as low efficiency, inadequate selectivity, and sluggish kinetics. Here, the introduction of chiral-induced spin selectivity (CISS) offers a promising strategy to address these limitations by reducing energy barriers in reactions involving spin-sensitive intermediates or transition states. By leveraging CISS, ERR pathways can be manipulated to favor desired reactions, enhance product yield, and suppress unwanted byproducts, improving selectivity. Beyond reducing the impact of competing side reactions, CISS also enhances the kinetics of ERRs by accelerating reaction rates and lowering the energy barriers associated with multi-electron transfer steps. Thanks to its straightforward and versatile application, CISS shows significant potential in optimizing well-studied ERRs, such as the hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO2RR), facilitating the future transition of these technologies from research laboratories to commercial energy plants worldwide.

14 SOLAR ENERGY↗
DOE OSTI2023

Simplified Models of the Bicarbonate Buffer for Scaled Simulations of CO 2 Electrolyzers

Bicarbonate electrolytes are used in a range of chemical processes; however, resolved simulation of these electrolytes is difficult, as disparate reaction time scales lead to numerical stiffness and the formation of fine boundary layers. Based on several physically motivated approximations, we reduce the full set of chemical reactions within a bicarbonate electrolyte to a simpler subset, eliminating the numerical stiffness. We supported this simplification via a two-variable singular perturbation expansion and demonstrated that under neutral conditions (6 < pH < 10) typically found within a fluid-fed CO 2 electrolyzer, the simplifications lead to negligible error. Here, we also discuss two alternative simplifications, one valid at high pH and another valid at arbitrary pH. These simplifications reduce the condition number of the matrices resulting from spatiotemporal discretization by up to 10 orders of magnitude and enable three-dimensional (3D) simulation of CO 2 electrolyzers containing carbonate solutions.

10 SYNTHETIC FUELS↗
DOE OSTI2023

High-Temperature Dissociation of Neopentanol: Shock Tube/Photoionization Mass Spectrometry Studies

Herein, the pyrolysis mechanism of 2,2-dimethylpropan-1-ol (neopentanol) has been investigated at high temperatures (1128–1401K) and high pressures (5 and 15 bar). The experiments were performed in a miniature shock tube coupled to a time-of-flight mass spectrometer. Cations were generated by tunable vacuum ultraviolet photoionization resulting in multidimensional data sets containing mass and photoionization spectra and the time histories of species. At the elevated temperatures and pressures of this work, neopentanol was determined to dissociate primarily by the scission of a C–C bond yielding tert-butyl and hydroxymethyl radicals. These promptly form isobutene and formaldehyde by H-atom elimination. In the structurally similar molecule neopentane, roaming radical reactions have previously been found to be important under conditions close to the present work (1260–1459 K, 1.1 bar). There are two possible roaming radical reactions for neopentanol. However, no experimental evidence for these reactions was found at the elevated pressures in this study, and the dissociation of neopentanol is dominated by bond scission yielding radical products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrochemical Cycling of Liquid Organic Hydrogen Carriers as a Sustainable Approach for Hydrogen Storage and Transportation

Hydrogen (H 2 ), as a high-energy-density molecule, offers a clean solution to carry energy. However, the high diffusivity and low volumetric density of H 2 pose a challenge for long-term storage and transportation. Liquid organic hydrogen carriers (LOHCs) have been suggested as a strategic way to store and transport hydrogen in stable molecules. More so, electrochemical LOHC cycling renders an opportunity to utilize renewable energy for hydrogen storage and transportation toward the goal of eliminating carbon emissions. In this Perspective, examples of electrochemical reactions of organic molecules and their suitability for LOHC couples are examined. A comparative carbon footprint assessment of electrochemical LOHC cycling processes against thermochemical and hybrid LOHC cycling processes was performed. The electrochemical LOHC cycling process had the lowest relative carbon footprint only when highly concentrated LOHCs were used as the feed or when purification of the LOHC product was not required. The carbon footprint in electrochemical cycling of diluted LOHC was primarily contributed to by the LOHC distillation separation process. A sensitivity analysis showed the carbon footprint LOHC concentration dependence during the electrochemical cycling process. Moreover, the electrolyte composition significantly affects the carbon footprint during electrochemical LOHC cycling. Energy utilization, water usage, and toxicity for electrochemical LOHC cycling are discussed to provide an overview for better economic and environmental practices. There are significant opportunities in the electrochemical cycling of LOHCs if appropriate conditions such as high concentrations of reactant, reversible redox cycling ability, high Faradaic efficiencies, and catalyst stabilities are achieved.

25 ENERGY STORAGE↗
DOE OSTI2022

Understanding Novel Lewis Acid Doping Mechanisms in Organic Semiconductors

Recent studies supported by this DOE grant have provided a more detailed understanding of the doping mechanism of organic semiconductors by the Lewis acid, tris(pentafluorophenyl)borane (BCF). Our studies have examined the intermolecular semiconductor-dopant interactions as well as the thermodynamic feasibility of different doping mechanisms. Most notably, we found a different proposed doping scheme is much more thermodynamically favoured (exergonic) than our proposed two-step BCF doping mechanism. The state-of-the-art experimental and theoretical techniques of High-Field Multi-Dimensional Solid State NMR spectroscopy and Time-Dependent Density Functional theory (TD-DFT) and DFT were employed in this work. The data obtained helped identify the structural details and intermolecular interactions which impact the organic semiconductor doping efficiency for BCF and how these compare to the case of doping by the standard integer charge transfer dopant molecule F 4 TCNQ. We have, for the first time, assigned specific chemical shift values for the F 4 TCNQ molecules clustered outside of polymer chains as well as those intercalated between the polymer backbones. Further, we provide theoretical support for a novel doping mechanism which combines those proposed in previous literature involving the evolution of hydrogen gas along with a doping species more complex than the simple BCF·H 2 O. While our previously proposed doping mechanism was found to be highly thermodynamically unfavorable, the formation of large anion [BCF(OH)(OH 2 )BCF]- is the key change making the proposed mechanism exergonic while the elimination of gaseous H 2 helps drive the doping reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1970

Control of Nitrogen Dioxide in Stack Emission by Reaction with Ammonia

The development of an acid base gas-phase reaction system which utilizes anhydrous ammonia as the reactant to remove nitrogen dioxide from hydrazine-nitrogen tetroxide rocket combustion exhaust is reported. This reaction reduced NO2 levels in exhaust emissions so that the resulting stack emission is completely white instead of the earlier observed typical reddish-brown coloration. Preliminary analyses indicate the importance of reaction time and ammonia concentration on removal efficiency and elimination of the health hazard to individuals with respiratory problems.

Metzler, A. J.↗
NASA NTRS1977

Fast measurement of bacterial susceptibility to antibiotics

Method, based on photoanalysis of adenosine triphosphate using light-emitting reaction with luciferase-luciferin technique, saves time by eliminating isolation period required by conventional methods. Technique is also used to determine presence of infection as well as susceptibilities to several antibiotics.

Chappelle, E. W.↗
NASA NTRS1985

Improved cross section calculations for astrophysical applications

Modifications are proposed for the semiempirical equations and parameters of Silberberg and Tsao (1973) for partial cross section calculations of proton-nucleus reactions in cosmic rays. These modifications include: adjustment of general parameters; modification of energy dependence; effects of nuclear alpha-particle structure, deuteron emission, and even-charged products; peripheral reactions; fission reactions; averaging cross sections near boundaries of different parameters; elimination of certain special cases; and treatment of the Pt to Pb group that cannot yet be generalized to Z(t) less than 76.

Silberberg, R.↗
NASA NTRS1997

Mineral induced phosphorylation of glycolate ion--a metaphor in chemical evolution

Bilateral surface-active minerals with excess positive charge concentrate glycolate and trimetaphosphate ion from l0(-3) m aqueous solution to half-saturation of the internal surface sites, and induce phosphorylation of glycolate ion in the mineral with trimetaphosphate, sorbed from l0(-2) m solution. By utilizing reactants from dilute solution at near-neutral pH, and eliminating the need for participating organic nitrogen compounds, the reaction comprises several elements considered necessary for geochemical realism in models for molecular evolution.

NASA Discipline Exobiology↗
NASA NTRSDate not supplied

Sensor-based Prognostics for Safe Batteries for Electric Aircraft

With a new start awarded under CAS for Fiscal Year 2020, the Sensor-based Prognostics to Avoid Runaway Reactions and Catastrophic Ignition project, or SPARRCI, aims to eliminate safety risks of lithium-ion and next-generation lithium-based batteries. SPARRCI is taking a deeper dive into the inner workings of battery cells by introducing miniature multifunctional sensors within the cells to detect early signs of failure. Combined with nondestructive evaluation techniques to gather complementary battery health data, battery data will be monitored in real-time via prognostics which will ultimately be able to identify when the cell is exhibiting abnormal behavior bordering on failure, with the ability to provide early warning such that the battery may be taken offline prior to catastrophic failure events.

Brianne Demattia↗