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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
NASA NTRS1983

Kinetics and mechanism of the oxidation of S(IV) by ozone in aqueous solution with particular reference to SO2 conversion in nonurban tropospheric clouds

Results are presented from a laboratory study of the kinetics of the S(IV)-O3 reaction in aqueous solution, including measurements of the effects of UV radiation, dissolved transition metals, and an antioxidant (hydroquinone) on the rate. On the basis of the results, relative rates of S(IV) conversion by O3 in tropospheric cloud water are compared with those predicted for H2O2 and for O2. The reaction mechanism is discussed, with an outline given of the elements of a possible reaction scheme. Application of the rate constants obtained to SO2 conversion in cloud water predicts conversion rates by ozone to be competitive with those by H2O2 at pH above about 4.5 and to dominate at pH above about 5.5. It is pointed out that since these pH's are typical for nonurban tropospheric cloud water, ozone is a potentially important contributor to the overall oxidative conversion of SO2 to sulfate in the nonurban troposphere.

Maahs, H. G.↗
NASA NTRSDate not supplied

Computational Assessment of the Impact of Wave Count on Rotating Detonation Engine Performance

The impact of the number of azimuthally propagating waves on the performance of a Rotating Detonation Engine (RDE) is investigated using a simplified two-dimensional computational fluid dynamic simulation. The basic RDE configuration examined has no exit throat. The inlet is assumed lossless and does not allow backflow. The adiabatic, inviscid, and premixed simulation utilizes a particularly simple finite rate reaction mechanism that allows user control over the relative amounts of deflagration and detonation that occur, the presence and extent of a reaction delay associated with fuel and oxidizer mixing, and the number of waves present in the domain. The simplifications and idealizations decouple the effect of wave count from other potential loss mechanisms. Performance is measured using exhaust flow total pressure gain relative to the inlet total pressure. One, two, and three wave solutions are computed under identical boundary conditions and grid resolution. For simulations with no mixing delay and minimal deflagration, the number of waves present has negligible impact on performance. With a mixing delay, performance decreases with increasing wave number. With increased deflagration, performance increases with increasing wave number. With both effects simulated it is found that the two wave solution performs better than either the one or three wave solutions. The causes of these trends are explored. They imply that for practical, RDE’s, the number of waves that are present can impact performance.

Detonation↗
NASA NTRSDate not supplied

Computational Assessment of the Impact of Wave Count on Rotating Detonation Engine Performance

The impact of the number of azimuthally propagating waves on the performance of a Rotating Detonation Engine (RDE) is investigated using a simplified two-dimensional computational fluid dynamic simulation. The basic RDE configuration examined has no exit throat. The inlet is assumed lossless and does not allow backflow. The adiabatic, inviscid, and premixed simulation utilizes a particularly simple finite rate reaction mechanism that allows user control over the relative amounts of deflagration and detonation that occur, the presence and extent of a reaction delay associated with fuel and oxidizer mixing, and the number of waves present in the domain. The simplifications and idealizations decouple the effect of wave count from other potential loss mechanisms. Performance is measured using exhaust flow total pressure gain relative to the inlet total pressure. One, two, and three wave solutions are computed under identical boundary conditions and grid resolution. For simulations with no mixing delay and minimal deflagration, the number of waves present has negligible impact on performance. With a mixing delay, performance decreases with increasing wave number. With increased deflagration, performance increases with increasing wave number. With both effects simulated it is found that the two wave solution performs better than either the one or three wave solutions. The causes of these trends are explored. They imply that for practical, RDE’s, the number of waves that are present can impact performance.

Detonation↗
NASA NTRS1972

Electrochemical behavior of the boron anode in aqueous solutions

The electrochemical oxidation of p-type boron in 0.2 N NaNO3 solutions of pH 0.4 to 13.1 was studied by galvanostatic techniques. The capacitance of the electrode, Tafel slopes, and a limited analysis of reaction mechanisms are reported. The anodic dissolution in acid solution is a charge-transfer-limited one-electron reaction to form a monovalent species in the over-potential region of 0.25 to 0.70 V. The dissolution in basic solution is most probably a one-electron charge-transfer reaction from a monovalent to divalent species involving three hydroxyl ions. Open circuit potentials were mixed potentials, probably due to hydrogen formation at open circuit but not contributing to the electrochemical reaction at the applied overpotential. Exchange current, estimated by extrapolation of the Tafel line to the standard oxidation potential for the boron reaction, were of the order of 10 to the minus 6th power A/cm2 in acid solution and 10 to the minus 12th power A/cm2 in basic solution. The reaction order of the rate determining acidic and basic reactions was determined with regard to (H+) and (OH-). The level of illumination had no effect on the electrochemical behavior of the electrode.

Delduca, B. S.↗
NASA NTRS1988

Molten-salt corrosion of silicon nitride. I - Sodium carbonate. II - Sodium sulfate

An experimental study of the corrosion of Si3N4 under thin films of Na2CO3 at 1000 C has been conducted using both pure Si3N4 and Si3N4 with various additives. The reaction mechanism is shown to consist of: (1) the decomposition of Na2CO3 and the formation of Na2SiO3; (2) rapid oxidation; and (3) the formation of a protective silica layer below the silicate. In the second part, the corrosion mechanism of Si3N4 + Na2SO4/O2 at 1000 C was studied for both pure and additive-containing Si3N4. The reaction of Si3N4 + Na2SO4 was found to involve an initial period of slow weight loss (due to Na2SO4 vaporization and oxidation-dissolution) followed by further oxidation or the near termination of the reaction, depending on the Si3N4 additive.

Fox, Dennis S.↗
NASA NTRS1991

Examination of the discharge mechanism of Li/CF(x) cells: Comparison of the electrochemical reduction mechanisms of PTFE and (CF(x))n by lithium

Swelling of (CF(x))(sub n) electrodes in commercial Li/(CF(x))(sub n) cells presents a limiting factor in cell design optimization. Examination of cathodes from such cells, after discharge, reveals a relation between cell operating temperatures and cathode swelling. Attempts to explain the swelling using the prevailing model for the cathode reaction have failed. A more suitable reaction mechanism is proposed based on the observed behavior of (CF(x))(sub n) electrodes on discharge and a comparison of the reaction products of (CF(x))(sub n) and polytetra fluoroethylene (PTFE) with lithium amalgams. The proposed mechanism is in agreement with the experimental data found in the literature.

Baxam, Carl C.↗
NASA NTRS1995

Ozone, Tropospheric

In the early part of the 20th century, ground-based and balloon-borne measurements discovered that most of atmosphere's ozone is located in the stratosphere with highest concentrations located between 15 and 30 km (9,3 and 18.6 miles). For a long time, it was believed that tropospheric ozone originated from the stratosphere and that most of it was destroyed by contact with the earth's surface. Ozone, O3, was known to be produced by the photo-dissociation of molecular oxygen, O2, a process that can only occur at wavelengths shorter than 242 nm. Because such short-wave-length radiation is present only in the stratosphere, no tropospheric ozone production is possible by this mechanism. In the 1940s, however, it became obvious that production of ozone was also taking place in the troposphere. The overall reaction mechanism was eventually identified by Arie Haagen-Smit of the California Institute of Technology, in highly polluted southern California. The copious emissions from the numerous cars driven there as a result of the mass migration to Los Angeles after World War 2 created the new unpleasant phenomenon of photochemical smog, the primary component of which is ozone. These high levels of ozone were injuring vegetable crops, causing women's nylons to run, and generating increasing respiratory and eye-irritation problems for the populace. Our knowledge of tropospheric ozone increased dramatically in the early 1950s as monitoring stations and search centers were established throughout southern California to see what could be done to combat this threat to human health and the environment.

Fishman, Jack↗
NASA NTRS1992

The swelling mechanism of cathodes in Li/(CFx)(sub n) cells

Active material particles spatial arrangement in combination with the nature of the electrochemical reduction mechanism were found to be the major cause of excessive swelling in cathodes in Li/(CF(x))n cells. A better understanding of the chemical reaction mechanism, a possible new role for the carbon, and a model for cathode growth are discussed.

Margalit, Nehemiah↗
NASA NTRS1999

Development of a Computational Chemical Vapor Deposition Model: Applications to Indium Nitride and Dicyanovinylaniline

A computational chemical vapor deposition (CVD) model is presented, that couples chemical reaction mechanisms with fluid dynamic simulations for vapor deposition experiments. The chemical properties of the systems under investigation are evaluated using quantum, molecular and statistical mechanics models. The fluid dynamic computations are performed using the CFD-ACE program, which can simulate multispecies transport, heat and mass transfer, gas phase chemistry, chemistry of adsorbed species, pulsed reactant flow and variable gravity conditions. Two experimental setups are being studied, in order to fabricate films of: (a) indium nitride (InN) from the gas or surface phase reaction of trimethylindium and ammonia; and (b) 4-(1,1)dicyanovinyl-dimethylaminoaniline (DCVA) by vapor deposition. Modeling of these setups requires knowledge of three groups of properties: thermodynamic properties (heat capacity), transport properties (diffusion, viscosity, and thermal conductivity), and kinetic properties (rate constants for all possible elementary chemical reactions). These properties are evaluated using computational methods whenever experimental data is not available for the species or for the elementary reactions. The chemical vapor deposition model is applied to InN and DCVA. Several possible InN mechanisms are proposed and analyzed. The CVD model simulations of InN show that the deposition rate of InN is more efficient when pulsing chemistry is used under conditions of high pressure and microgravity. An analysis of the chemical properties of DCVA show that DCVA dimers may form under certain conditions of physical vapor transport. CVD simulations of the DCVA system suggest that deposition of the DCVA dimer may play a small role in the film and crystal growth processes.

Cardelino, Carlos↗
NASA NTRS1988

Hydrazine vapor detonations

The detonation velocity and cell widths for hydrazine decomposition were measured over a wide range of temperatures and pressures. The detonation velocity in pure hydrazine was within 5 percent of the calculated C-J velocity. The detonation cell width measurements were interpreted using the Zeldovich-Doering-von Neumann model with a detailed reaction mechanism for hydrazine decomposition. Excellent agreement with experimental data for pure hydrazine was obtained using the empirical relation that detonation cell width was equal to 29 times the kinetically calculated reaction zone length.

Pedley, M. D.↗
NASA NTRS1994

Simulations of isoprene: Ozone reactions for a general circulation/chemical transport model

A parameterized reaction mechanism has been created to examine the interactions between isoprene and other tropospheric gas-phase chemicals. Tests of the parameterization have shown that its results match those of a more complex reaction set to a high degree of accuracy. Comparisons between test runs have shown that the presence of isoprene at the start of a six day interval can enhance later ozone concentrations by as much as twenty-nine percent. The test cases used no input fluxes beyond the initial time, implying that a single input of a biogenic hydrocarbon to an airmass can alter its ozone chemistry over a time scale on the order of a week.

Makar, P. A.↗
NASA NTRS1990

A unifying picture of gas-phase formation and growth of PAH (Polycyclic Aromatic Hydrocarbons), soot, diamond and graphite

A variety of seemingly different carbon formation processes -- polycyclic aromatic hydrocarbons and diamond in the interstellar medium, soot in hydrocarbon flames, graphite and diamond in plasma-assisted-chemical vapor deposition reactors -- may all have closely related underlying chemical reaction mechanisms. Two distinct mechanisms for gas-phase carbon growth are discussed. At high temperatures it proceeds via the formation of carbon clusters. At lower temperatures it follows a polymerization-type kinetic sequence of chemical reactions of acetylene addition to a radical, and reactivation of the resultant species through H-abstraction by a hydrogen atom.

Frenklach, Michael↗
NASA NTRS1989

PAH formation in carbon-rich circumstellar envelopes

While there is growing observational evidence that some fraction of interstellar carbon is in polycyclic aromatic hydrocarbons (PAH's), the mechanisms by which these molecules might be formed have not been extensively studied. A detailed investigation of PAH production in the outflowing molecular envelopes of carbon-rich red giant star is presented. The gasphase kinetics of a chemical reaction mechanism developed to study soot production in hydrocarbon flames is modified to apply in circumstellar environments. It was found that astrophysically significant quantities of PAH's can be formed in carbon star envelopes provided the gas is sufficiently dense and resides for a long time in the temperature range of 900 to 1100 k. The precise yield of PAH's is very sensitive to astronomical parameters of the envelope (e.g., mass loss rate, outflow velocity, and acetylene abundance) and certain poorly determined chemical reaction rates.

Feigelson, Eric D.↗
NASA NTRS2000

Changing genetic information through RNA editing

RNA editing, the post-transcriptional alteration of a gene-encoded sequence, is a widespread phenomenon in eukaryotes. As a consequence of RNA editing, functionally distinct proteins can be produced from a single gene. The molecular mechanisms involved include single or multiple base insertions or deletions as well as base substitutions. In mammals, one type of substitutional RNA editing, characterized by site-specific base-modification, was shown to modulate important physiological processes. The underlying reaction mechanism of substitutional RNA editing involves hydrolytic deamination of cytosine or adenosine bases to uracil or inosine, respectively. Protein factors have been characterized that are able to induce RNA editing in vitro. A supergene family of RNA-dependent deaminases has emerged with the recent addition of adenosine deaminases specific for tRNA. Here we review the developments that have substantially increased our understanding of base-modification RNA editing over the past few years, with an emphasis on mechanistic differences, evolutionary aspects and the first insights into the regulation of editing activity.

Review↗
NASA NTRS1990

An assessment of potential degradation products in the gas-phase reactions of alternative fluorocarbons in the troposphere

Tropospheric chemical transformations of alternative hydrofluorocarbons (HCF's) and hydrochlorofluorocarbons (HCFC's) are governed by hydroxyl radical initiated oxidation processes, which are likely to be analogous to those known for alkanes and chloroalkanes. A schematic diagram is used to illustrate plausible reaction mechanisms for their atmospheric degradation, where R, R', and R'' denote the F- and/or Cl-substituted alkyl groups derived from HCF's and HCFC's subsequent th the initial H atom abstraction by HO radicals. At present, virtually no kinetic data exist for the majority of these reactions, particularly for those involving RO. Potential degradation intermediates and final products include a large variety of fluorine- and/or chlorine-containing carbonyls, acids, peroxy acids, alcohols, hydrogen peroxides, nitrates and peroxy nitrates, as summarized in the attached table. Probably atmospheric lifetimes of these compounds were also estimated. For some carbonyl and nitrate products shown in this table, there seem to be no significant gas-phase removal mechanisms. Further chemical kinetics and photochemical data are needed to quantitatively assess the atmospheric fate of HCF's and HCFC's, and of the degradation products postulated in this report.

Niki, Hiromi↗
NASA NTRS1995

The effect of gravity on the combustion synthesis of Ni-Al and Ni3Al-TiB2 composites from elements

Previous studies on the combustion synthesis of advanced materials indicate that combustion and structure formation mechanisms involve several stages including melting of reactants and products, spreading of the melt, droplet coalescence, diffusion and convection, buoyancy of solid particles, and densification of the liquid product. Most of these processes are affected by gravity. Conducting the combustion synthesis under microgravity conditions is expected to help elucidate the reaction mechanisms. Two systems were examined. The first involves Ni/AI cladded particles, which is an ideal system to examine the individual particle and liquid flow before combustion occurs. For comparison, elemental Ni and Al powders with the same stoichiometry as that of the cladded particles were also used in some experiments. The second system was the Ni3AITiB2 composite in which the Ni3AI (-delta H(sub f) = 153.1 kJ/mol) phase melts during reaction enabling us to examine settling of the liquid phase. The amount of liquid phase was controlled by varying the TiB2 (-delta H(sub f) = 323.8 kJ/mol) content which generates the additional heat. The overall reactions for the two systems can be expressed as follows. System 1: 4Ni + 2AI yields Ni3AI + NiA and System 2: 3Ni + Al + x (Ti + 2B) yields Ni3Al + x(TiB2). For the first system, pellets were pressed directly from the cladded particles, at green densities about 77 +/- 3% of theoretical value. For the second, the pellets were prepared by mixing the elemental reactant powders in the required stoichiometry by ball-milling and then pressing uniaxially at green densities about 70 +/- 3 percent of theoretical. The pellets were cylindrical in shape, 10 mm in diameter and length typically 20-30 mm. The pellet samples were reacted in UHP Argon (1 atm) using the experimental setup and procedure described previously. After reaction, the samples were sectioned axially in order to conduct the microstructural analysis in the longitudinal direction. The phase composition of the reacted product was determined by X-ray diffraction (XRD) and the microstructure was analyzed using scanning electron microscopy (SEM) along with energy dispersive X-ray spectrometry (EDX).

Varma, Arvind↗
NASA NTRS1992

Reduction of iron-bearing lunar minerals for the production of oxygen

The kinetics and mechanism of the reduction of simulants of the iron-bearing lunar minerals olivine ((Fe,Mg)2SiO4), pyroxene ((Fe,Mg,Ca)SiO3), and ilmenite (FeTiO3) are investigated, extending previous work with ilmenite. Fayalite is reduced by H2 at 1070 K to 1480 K. A layer of mixed silica glass and iron forms around an unreacted core. Reaction kinetics are influenced by permeation of hydrogen through this layer and a reaction step involving dissociated hydrogen. Reaction mechanisms are independent of Mg content. Augite, hypersthene, and hedenbergite are reduced in H2 at the same temperatures. The products are iron metal and lower iron silicates mixed throughout the mineral. Activation energy rises with calcium content. Ilmenite and fayalite are reduced with carbon deposited on partially reduced minerals via the CO disproportionation reaction. Reduction with carbon is rapid, showing the carbothermal reduction of lunar minerals is possible.

Massieon, Charles↗
NASA NTRS1975

Diffusion in mixed solvents - On the viscosity question

Linear plots of reaction rate vs reciprocal of solvent viscosity are generally used as the classifying criteria for diffusion controlled reactions in fluid solutions and to determine reaction mechanisms in mixed hydroxylic solvents like glycerol and water. This paper presents data which shows that the above-mentioned criteria are insufficient in many cases where nonideal mixed solvent systems are used to increase solvent viscosity. Data correlations suggest that the excess functions determine the variation in reaction rate constants. Kinetic parameters are presented for sucrose-water and methanol-water solvent systems for a reaction involving Fe(CN)6 and zinc uroporphyrin.

Carapellucci, P. A.↗