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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS2010

Refinements in an Mg/MgH2/H2O-Based Hydrogen Generator

Some refinements have been conceived for a proposed apparatus that would generate hydrogen (for use in a fuel cell) by means of chemical reactions among magnesium, magnesium hydride, and steam. The refinements lie in tailoring spatial and temporal distributions of steam and liquid water so as to obtain greater overall energy-storage or energy-generation efficiency than would otherwise be possible. A description of the prior art is prerequisite to a meaningful description of the present refinements. The hydrogen-generating apparatus in question is one of two versions of what was called the "advanced hydrogen generator" in "Fuel-Cell Power Systems Incorporating Mg-Based H2 Generators" (NPO-43554), NASA Tech Briefs, Vol. 33, No. 1 (January 2009), page 52. To recapitulate: The apparatus would include a reactor vessel that would be initially charged with magnesium hydride. The apparatus would exploit two reactions: The endothermic decomposition reaction MgH2-->Mg + H2, which occurs at a temperature greater than or equal to 300 C, and The exothermic oxidation reaction MgH2 + H2O MgO + 2H2, which occurs at a temperature greater than or equal to 330 C.

Kindler, Andrew↗
DOE OSTI2025

Thermodynamics of MgO Atomic Layer Deposition Surface Reactions

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

36 MATERIALS SCIENCE↗
DOE OSTI2024

The chlorination and separation of aluminum using low-temperature sulfur chloride reagents

There is currently no strategy for the permanent waste disposal or recycling for used nuclear fuelsfrom research reactors. For this reason, low-temperature reactions have been developed for thechlorination of the Al alloys and subsequent separation from used nuclear fuels to reducethe volume of high-level waste in storage. Three sulfur chloride reagents – S 2 Cl 2 , SOCl 2 , and SO 2 Cl 2 —were tested, and two were found to quantitatively chlorinate Al metal and Al alloys undermild conditions. Further, these low-temperature reactions proceed between 298 and 411 K, and up to 5 gof metal is chlorinated in 1–3 h. Preliminary results indicate that the reactivity and exothermicity ofthe reaction between the Al and sulfur chloride reagents is highly dependent on the surface area-to-volume ratio of the metal and the volume of solvent. Elemental S is produced as a by-productduring the chlorination with S 2 Cl 2 but can be quantitatively rechlorinated under mild conditions toregenerate the initial chlorination reagent. Therefore, in this case, chlorine is the only elementconsumed in the reaction, thus minimizing the waste generated during the chlorination process.The AlCl 3 may then be separated from other materials present in Al 6061 or Al 8001 because of itshigh solubility in the sulfur chloride reagents. This process may also be extended to chlorinate Alfrom research reactor fuels.

aluminum↗
NASA NTRS2000

Gravity Effects on Combustion Synthesis of Glasses

The Combustion Synthesis technique has been used to produce glasses based on B2O3-Al2O3-MgO and CaO-Al2O3. The combustion characteristics of these combustion synthesis reactions using both small cylindrical pellets (SCP) and large spherical pellets (LSP) are presented. Low density pellets (approx. 35% of their theoretical density) were used, which made synthesis of low exothermic combustion reactions possible. Microstructural analysis of reacted samples was carried out to identify the glass-forming compositions. The effects of gravity on the glass formation were studied aboard the KC-135 using SCP samples. Gravity seemed to have such obvious effects on the combustion characteristics that the wave velocity was lower and the Width of the combustion wave was larger under reduced gravity conditions. Samples produced under low gravity also had more enhanced vitrification than those on ground, while some systems also exhibited lower combustion temperatures. It was also found that the container significantly affects both the combustion characteristics and microstructure. Substantially more divitrification occurred at the area which was in contact with the support (container).

Yi, H. C.↗
DOE OSTI2025

Reaction-induced departures from continuum Navier–Stokes turbulence

Reactive hydrodynamic turbulence is an inherently multiscale phenomenon, characterized by the separation between energy-containing, viscous, and molecular length and time scales. The separation between the viscous scale (the Kolmogorov scale) and the molecular mean free path ostensibly justifies a macroscopic description of reactive turbulence via the Navier–Stokes (NS) equations. However, here we use molecular-level simulations to demonstrate that exothermic bimolecular reactions can cause the NS description of turbulence to break down in the near-continuum regime. Sufficiently energetic heat-releasing reactive collisions strongly distort the Maxwell–Boltzmann velocity distribution function, modifying not only the macroscopic chemical rate law but the kinetic-energy-transfer processes as well. This translational nonequilibrium ultimately introduces significant departures from the NS description in the kinetic energy spectra at scales orders of magnitude larger than both the molecular mean free path and the Kolmogorov length scale. These departures prove substantial enough to meaningfully alter integrated quantities, including the overall turbulence kinetic energy itself.

molecular gas dynamics↗
NASA NTRS1999

Observations from the Microgravity Smoldering Combustion (MSC) Ultrasound Imaging System (UIS)

The Microgravity Smoldering Combustion (MSC) experiment is a study of the smolder characteristics of porous combustible materials in a microgravity environment. The objective of the study is to provide a better understanding of the controlling mechanisms of smolder, both in microgravity and normal earth gravity. Experiments have been conducted aboard the NASA Space Shuttle in the GAS-CAN, an apparatus requiring completely remote operation. Future GAS-CAN experiments will utilize an ultrasound imaging system (UIS). Thermocouples are currently used to measure temperature and reaction front velocities, but a less intrusive method is desirable, as smolder is affected by heat transfer along the thermocouple. It is expected that the UIS will eventually replace the existing array of thermocouples as a non-intrusive technique without compromising data acquisition. Smoldering is defined as a non-flaming, self-sustaining, propagating, exothermic, surface reaction, deriving its principal heat from heterogeneous oxidation of the fuel. Smolder of cable insulation is of particular concern in the space program; to date there have been a few minor incidents of overheated and charred cables and electrical components reported on Space Shuttle flights. Recently, the establishment of the International Space Station and other space facilities has increased interest in the study of smoldering in microgravity because of the need to preempt the possibility, and/or to minimize the effect of a smolder initiated fire during the operation of these facilities. The ignition and propagation of smolder are examined using both thermocouples and the UIS. The UIS has been implemented into the MSC flight hardware. The system provides information about local permeability variations within a smoldering sample, which can, in turn, be interpreted to track the propagation of the smolder reaction. The method utilizes the observation that transmission of an ultrasonic signal through a porous material increases with increasing permeability. Since a propagating smolder reaction leaves behind a char that is higher in permeability than the original (unburnt) material, ultrasonic transmission can be employed to monitor the progress of the primary reaction front, char evolution (i.e. material left by the smolder reaction), pyrolysis, and condensation fronts.

Walther, D.C.↗
NASA NTRS1980

Shock tube propellant reactions: Ignition of M-9 and catalysis of RDX

The preliminary results of shock tube experiments to study RDX catalysis are presented. It is shown that using N2 as the test gas (P approximately equal to 90 KPa, T bar approximately equal to 650K), the replacement of RDX powder with NaBH4 (20% by weight) leads to a large increase in the amount of RDX reacting and a small decrease in ignition delays T sub i. It is further shown that higher temperatures due to exothermic pyrolysis reactions of NaBH4 are not responsible for these effects. Replacement of N2 by NO2 (10% by volume) in the environment of RDX powders (T bar approximately equal to 650K, P = 90-400 KPa) leads to an increase in T sub i and T sub i is directly proportional to NO2 pressure. Inhibition appears to be initiated by reactions between NO2 and either RDX or the RDX decomposition products.

Cohen, A.↗
DOE OSTI2025

Open‐Air Combustion Synthesis with Rapid Plasma Processing of Large‐Area Transparent Conducting Oxides

A vacuum-free, high-throughput synthesis of indium tin oxide (ITO) via Combustion Oxidation with Rapid Plasma Processing (CORP) utilizes a solution-based exothermic combustion reaction to generate the oxide with tunable control of either amorphous or crystalline phases. A subsequent open-air, forming gas plasma treatment is used to introduce oxygen vacancies and promote crystallization. Here, the evolution of the oxide structure is elucidated by extended X-ray absorption spectroscopy fine structure analysis. Using CORP, fabrication of 300 cm 2 of ITO possessing a champion sheet resistance of 38 Ω sq. −1 , visible transmission of 89%, conductivity stability for over 250 days, roughness < 2nm, and Haacke figure of merit (%T 550nm 10 /R s ) of 0.012 Ω −1 is achieved. Cost modeling of CORP demonstrates up to a 67% reduction in price for TCOs using fully continuous, in-line unit operations compared with vacuum sputtering. The work shows a path toward a low-cost, vacuum-free manufacturing method for TCOs at commercial scales.

42 ENGINEERING↗
NASA NTRS1973

Chemistry in interstellar space

The particular characteristics of chemistry in interstellar space are determined by the unique environmental conditions involved. Interstellar matter is present at extremely low densities. Large deviations from thermodynamic equilibrium are, therefore, to be expected. A relatively intense ultraviolet radiation is present in many regions. The temperatures are in the range from 5 to 200 K. Data concerning the inhibiting effect of small activation energies in interstellar clouds are presented in a table. A summary of measured activation energies or barrier heights for exothermic exchange reactions is also provided. Problems of molecule formation are discussed, taking into account gas phase reactions and surface catalyzed processes.

Donn, B.↗
NASA NTRS1974

Thermal stresses in chemically hardening elastic media with application to the molding process

A method has been formulated for the determination of thermal stresses in materials which harden in the presence of an exothermic chemical reaction. Hardening is described by the transformation of the material from an inviscid liquid-like state into an elastic solid, where intermediate states consist of a mixture of the two, in a ratio which is determined by the degree of chemical reaction. The method is illustrated in terms of an infinite slab cast between two rigid mold surfaces. It is found that the stress component normal to the slab surfaces vanishes in the residual state, so that removal of the slab from the mold leaves the remaining residual stress unchanged. On the other hand, the residual stress component parallel to the slab surfaces does not vanish. Its distribution is described as a function of the parameters of the hardening process.

Levitsky, M.↗
NASA NTRS1974

Theory of flame spread above solids

A theory for flame spread above a solid fuel is presented. The special case is considered whereby the oxidation is an exothermic surface reaction. The spreading rate is predicted as a function of the thermochemical properties, fuel-bed thickness, and convective velocity. Also, the theory predicts temperature, mass fraction, and heat flux as a function of position.

Sirignano, W. A.↗
NASA NTRS1976

A kinetic study of the interaction between atomic oxygen and aerosols

This study was concerned with the effects of NH4Cl and (NH4)2SO4 aerosols on the kinetics of disappearance of atomic oxygen. Atomic oxygen was generated by a 2.45-GHz microwave discharge and the kinetics of disappearance measured in a fast flow system using NO2 titration. Values of the recombination coefficient for heterogeneous wall recombination were determined for clean, H2SO4-coated, and (NH4)2SO4-coated Pyrex to be 0.000050, 0.000020, and 0.000019, respectively. A rapid exothermic chemical reaction was found to occur between atomic oxygen and an NH4Cl wall coating; the products were NH3, NO, H2O, and HCl. The NH4Cl aerosol was generated by gas phase reaction of NH3 with HCl. The aerosol particles were approximately spherical and nearly monodisperse with a mean diameter of 1.6 plus or minus 0.2 micron. The rate constant for the disappearance of atomic oxygen in the presence of NH4Cl aerosol was measured. No significant decrease was observed in the rate of disappearance of atomic oxygen in the presence of an (NH4)2SO4 aerosol at a concentration of 285 mg per cu m.

Akers, F. I.↗
NASA NTRS1977

Some speculations about the origin of the high speed HCN jets in Comet Kohoutek /1973f/

The origin of the high-speed HCN jets observed in Comet Kohoutek (1973f) is considered. It is argued that the occurrence of these jets with Doppler shifts corresponding to velocities of approximately 3-5 km/s with respect to the nucleus cannot be explained in terms of either explosive outbursts of trapped sub-surface volatiles, highly exothermic chemical reactions involving free radicals, or the outward expansion of the cometary atmosphere with additional heating. Instead, acceleration of the precursor ions of HCN by energetic electrons in the ionospheric current sheets or current arcs is suggested to play an important role.

Ip, W.-H.↗
NASA NTRS1980

Chemical energy in cold-cloud aggregates - The origin of meteoritic chondrules

If interstellar particles and molecules accumulate into larger particles during the collapse of a cold cloud, the resulting aggregates contain a large store of internal chemical energy. It is here proposed that subsequent warming of these accumulates leads to a thermal runaway when exothermic chemical reactions begin within the aggregate. These, after cooling, are the crystalline chondrules found so abundantly within chondritic meteorites. Chemical energy can also heat meteoritic parent bodies of any size, and both thermal metamorphism and certain molten meteorites are proposed to have occurred in this way. If this new theory is correct, (1) the model of chemical condensation in a hot gaseous solar system is eliminated, and (2) a new way of studying the chemical evolution of the interstellar medium has been found. A simple dust experiment on a comet flyby is proposed to test some features of this controversy.

Clayton, D. D.↗
NASA NTRS1980

Interplanetary gas. XXV - A solar wind and interplanetary magnetic field interpretation of cometary light outbursts

Possible relationships of cometary brightness outbursts with the solar wind and interplanetary magnetic field are examined. Two types of outburst are distinguished: those which involve a significant brightening of both the head and the tail in a comet with a conspicuous plasma tail (Class I), and those involving the brightening of the central condensation of a previously faint comet with no detectable plasma tail (Class II). Class I bursts, as exemplified by Comet Morehouse 1908c, are attributed to the generation in the head of enhanced amounts of ions and their injection into the tail shortly before it disconnects, with ionization provided by sector boundary crossings. Class II events, as exhibited by Comet P/Tuttle-Giacobini-Kresak 1973b, are interpreted as the result of the bombardment of the nucleus by disturbed solar wind near corotated high-speed streams and sector boundaries, leading to highly exothermic chemical reactions.

Niedner, M. B., Jr.↗
NASA NTRS1981

Origin of Ca-Al-rich inclusions. II - Sputtering and collisions in the three-ph8se interstellar medium

The theory put forward by Clayton (1977) for the formation of the Ca-Al-rich inclusions within C3 meteorites is extended to an evolutionary history in a three-phase interstellar medium. Widespread supersonic turbulence in the hot interstellar medium is maintained by supernova shock waves, giving rise to heavy sputtering of the refractory dust. Subsequent reaccumulation with varying dust/gas ratios or varying particle sizes produces isotopically fractionated Ca-Al-rich accumulates. It is thought that the Ca-Al-rich inclusions themselves are formed by the following sequence in the solar system: (1) cold accumulation of larger-than-average Ca-Al-rich particles containing supernova condensate cores into macroscopic (approximately 1 cm) Ca-Al-rich agglomerates, probably by sedimentation; and (2) fusion of the supernova condensates into macroscopic minerals by exothermic chemical reactions that begin when the accumulate has been warmed, thereby releasing energy from the unequilibrated forms accumulated from the interstellar medium.

Clayton, D. D.↗