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At least 145 records · Page 8

DSMC Simulation of Etch Pit Formation Through Active Sites in Carbon Fiber Micro-Structures

Erosion of carbon due to oxidation does not occur uniformly but through localized etch pit formation because of active surface sites. In this work we demonstrate a newly developed capability to capture pitting of carbon fiber microstructures such as FiberForm, which is commonly used as the base material for NASA’s spacecraft ablative thermal protection systems (TPS). The simulations are performed at the meso-scale in order to capture the pit formation and growth using direct simulation Monte Carlo (DSMC), specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code. Legacy and latest models both assume uniform reactivity of carbon surface sites with oxygen even at the meso-scale level. However, in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale. The defective nature of these sites enhances their reactivity with atmospheric gases compared to the non-defective sites (2-3 orders of magnitude) and are termed as “active sites”. Thus, these sites tend to be the first to react and eventually get removed through the formation of gases such as CO, CO2, and CN. Their removal results in all the neighboring atoms becoming defective, thus leading to chain reaction of localized carbon removal and formation of etch pits. Capturing the formation of pits during the ablation simulation of carbon micro-structures is critical to predicting their structural failure. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various detailed surface reaction mechanisms. We have implemented the capability of a single surface having multiple site sets with different reactivities within this framework. We have used this feature to model the presence of active sites on carbon surfaces, whose reactivity is orders of magnitude higher than that of the passive sites due to the presence of defects. The active site fraction is a property of surface elements within SPARTA and is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we can capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗

Applications of Atomic Layer Deposition in the Modification of Carbon Nanotubes

Atomic Layer Deposition (ALD) is a cost-effective nanoadditive-manufacturing technique that allows for conformal coating of substrates with atomic control in a benign temperature and pressure environment. Using paired precursor gases, thin films can be deposited on flat or textured surfaces ranging from glass, polymers, aerogels, and metals. Through atomic layer control, where single layers of atoms are deposited, fabrication of metal transparent films, nano-laminates, and coatings of nano-channels and pores is achievable. Reaction mechanisms in ALD are normally self-limiting, allowing for atomically accurate control of nanometer (nm) thicknesses. Therefore, high uniformity and precise thickness control make ALD an attractive process for the creation of novel nano-scale devices. Decreases in resistivity and density of electrical wire are needed to improve the function of electronics, electric motors and cables. Such improvements may be accomplished by adding ballistically conducting, metallic carbon nanotubes (CNT) to Cu. ALD was used to coat multiple substrates including CNT with Cu in an effort to make CNT-Cu composites which is more conductive and less dense than Cu. In addition, ALD can be used to as a method to deposit the catalyst layer seed layer for CNT growth using Ni. The ALD of copper metallic films can follow multiple reaction pathways depending on the ALD precursors used. For this work the reaction pathway was deposition of copper oxide and then post process annealing in a hydrogen environment. Copper(II) diacetylacetonate (Cu(acac)2) and ozone are used as precursors for copper oxide. As-deposited copper oxide films prepared at 180°C resulted in a growth per cycle of 1.0 A/cycle with low film resistivity.

Dwivedi, Vivek H.↗

Photoionization in Ultraviolet Processing of Astrophysical Ice Analogs at Cryogenic Temperatures

Two recent experimental studies have demonstrated that amino acids or amino acid precursors are generated when astrophysical ice analogs are subjected to ultraviolet (UV) irradiation at cryogenic temperatures. Understanding the complete phenomenology of photoprocessing is critical to elucidating chemical reaction mechanisms that can function within an ice matrix under very cold conditions. Pushing beyond the much better characterized study of photolytic dissociation of chemical bonds through electronic excitation, this work explored the ability of UV radiation present in the interstellar medium to ionize small molecules embedded in ices. Quantum chemical calculations, including bulk solvation effects, were used to study the ionization of hydrogen (H2), water, and methanol (CH3OH) bound in small clusters of water. Ionization potentials were found to be much smaller in the condensed phase than in the gas phase; even a small cluster can account for large changes in the ionization potentials in ice, as well as the known formation of an OH--H3O+ pair in the case of H2O photoionization. To gauge the impact of photoionization on subsequent grain chemistry, the reaction between OH and CO in the presence of H3O+ was studied and compared with the potential energy surface without hydronium present, which is relevant to chemistry following photolysis. The differences indicate that the reaction is somewhat more likely to proceed to products (H + CO2) in the case of photoionization.

Woon, David E.↗

A Simple Mechanism for Fractionating Oxygen Isotopes in the Solar Nebula

Lightning in the Solar Nebula is caused by the tribo-electric charging of dust grains carried by massive turbulent flows and driven by the accretion energy in the disk: it has long been one agent assumed responsible for the formation of chondrules. The degree to which charge separation can occur is dependent upon a number of factors, including the concentration of radioactive sources and the total level of ionization in the nebula, and these factors determine the maximum energy likely to be released by a single bolt. While chondrule formation requires a massive discharge, even a small lightning bolt can vaporize grains in the ionized discharge channel. Experimental studies have shown that silica, iron silicate and iron oxide grains formed from a high voltage discharge in hydrogen rich gas containing some oxygen produces solids that are enriched in O-17 and O-18 relative to the composition of the starting gas. Vaporization of silicates produces SiO, metal and free oxygen atoms in each discharge and these species will immediately begin to recondense from the hot plasma. Freshly condensed grains are incrementally enriched in heavy oxygen while the gas is enriched in O-16. Repeated evaporation and condensation of silicates in continuously occurring lightning discharges will monotonically increase the fractionation of oxygen isotopes between the O-17 and O-18 rich dust and the O-16 rich gas. The first mass independently fractionated refractory oxide particles were produced in the lab following the condensation of a flowing gas mixture containing variable amounts of hydrogen, silane, pentacarbonyl iron and oxygen that passed through a high voltage discharge powered by a Tesla coil. While the exact chemical pathway is still uncertain, the most probable reaction mechanisms involve oxidation of the growing refractory clusters by O3, OH or O atoms. This model has some interesting consequences for chemical processes in the early solar nebula. Chemical fractionation of recondensed dust evaporated via lightning discharges should be strongly time dependent. At earlier times, the accretion rate is maximal, thus driving strong turbulence, energetic grain-grain collisions, tribo-electric charging and charge separation, leading to frequent, powerful lightning discharges. As the accretion rate diminishes, turbulence decreases and lightning discharges will become both less powerful and less frequent, thus decreasing the rate of dust-gas fractionation. The most rapid increase in the formation of O-16 poor dust will occur early in nebular history. Generation of fractionated dust should be distributed throughout the inner disk. Once condensed, grain dispersal would average out any significant isotopic anomalies within the inner disk.

Nuth, Joseph A., III↗

Plant response to solar ultraviolet radiation

Plant reactions and mechanisms of reaction to solar UV radiation are reviewed, along with characteristics of plants which enhance UV tolerance. Wavelength regions to which proteins are particularly sensitive are examined and the possibility of synergistic effects from photoreactions to multiple wavelengths is considered, along with available evidence of nonadditive plant spectral responses to UV radiation. Decreases in atmospheric ozone content are explored in terms of UV wavelengths which would increase with the ozone decreases, particularly for UV-B, which depresses photosynthesis and would increase 1% with a 16% reduction of stratospheric ozone. Higher elevations are projected to display effects of increased UV incident flux first, and global distributions of UV increases due to atmospheric inhomogeneity and water surface clarity are examined. Finally, the response of plant nucleic acids, DNA, chlorophyll to enhanced UV are described, along with repair, avoidance, and optical mechanisms which aid plant survival

Caldwell, M. M.↗

Combustion chemistry

Reaction mechanisms and rate data for predicting combustion chemistry

Belles, F. E.↗

Use of radiation in preparative chemistry

A summary and updating of previous work on the use of radiation chemistry for the preparation of pure materials are presented. Work was chiefly concerned with the reduction of metal salts in solution to the free metal using 2 MeV electrons. Metals deposited from aqueous solution are copper, silver, zinc, cadmium, thallium, tin, lead, antimony, iron, nickel, cobalt, and palladium. Dry organic solvents were evaluated for the deposition of metals based on a study involving deposition of antimony from soltions of antimony (III) chloride. The use of organic liquids for the preparation of anhydrous metal halides is also presented. Reaction mechanisms for both organic liquids and aqueous system are discussed.

Philipp, W. H.↗

A heat flow calorimeter

Reaction mechanism for nickel-cadmium cell is not known well enough to allow calculation of heat effects. Calorimeter can measure heat absorbed or evolved in cell, by determining amount of external heat that must be supplied to calorimeter to maintain constant flow isothermal heat sink.

Johnston, W. V.↗

Further analytical study of hybrid rocket combustion

Analytical studies of the transient and steady-state combustion processes in a hybrid rocket system are discussed. The particular system chosen consists of a gaseous oxidizer flowing within a tube of solid fuel, resulting in a heterogeneous combustion. Finite rate chemical kinetics with appropriate reaction mechanisms were incorporated in the model. A temperature dependent Arrhenius type fuel surface regression rate equation was chosen for the current study. The governing mathematical equations employed for the reacting gas phase and for the solid phase are the general, two-dimensional, time-dependent conservation equations in a cylindrical coordinate system. Keeping the simplifying assumptions to a minimum, these basic equations were programmed for numerical computation, using two implicit finite-difference schemes, the Lax-Wendroff scheme for the gas phase, and, the Crank-Nicolson scheme for the solid phase.

Hung, W. S. Y.↗

Radiolytic preparation of anhydrous tin (2) chloride

Anhydrous tin (2) chloride (SnCl2) is prepared by radiolysis with high energy electrons of a tin (4) chloride (SnCl4) solution in heptane. The SnCl4 is reduced to insoluble SNCl2. The energy yield, G(SnCl2), molecules of SnCl2, produced per 100 eV, increases with SnCl4 concentration from 1.6 at 0.15 M SnCl4 to 3.1 at 3.0 M SnCl4. Other parameters such as temperature total dose and beam current have little influence on G(SnCl2). The method may be used to prepare other metal halides if the higher valence, more covalent metal halide is soluble in aliphatic hydrocarbons and the lower more ionic metal halide is insoluble. The reaction mechanism is discussed; the radiolysis of both heptane and SnCl4 is involved. At high SnCl4 concentration G(SnCl2) appears to be limited by the yield of SnC13 radicals.

Philipp, W. H.↗

Silicon-germanium technology program of the Jet Propulsion Laboratory.

The outer planetary exploration missions studied by the Jet Propulsion Laboratory require silicon-germanium radioisotope thermoelectric generators (RTGs) in which the factors of safety are as low as is compatible with the reliable satisfaction of the power needs. Work on silicon germanium sublimation performed at the Jet Propulsion Laboratory is presented. Analytical modeling work on the solid-diffusion process involved in the steady-state (free) sublimation of silicon germanium is described. Analytical predictions are made of the sublimation suppression which can be achieved by using a cover gas. A series of accelerated (high-temperature) tests which were performed on simulated hardware (using four SiGe couples) to study long-term sublimation and reaction mechanisms are also discussed.

De Winter, F.↗

A mass spectrometric system for analyzing thermal desorption spectra of ion-implanted argon and cesium in tungsten

A mass spectrometric system for determining the characteristics of materials used in instrumental development and aerospace applications was developed. The desorption spectra of cesium that was ion-implanted into polycrystalline tungsten and the effects on the spectra of bombardment of the tungsten by low energy (70 eV) electrons were investigated. Work function changes were measured by the retarding potential diode method. Flash desorption characteristics were observed and gas-reaction mechanisms of the surface of heated metal filaments were studied. Desorption spectra were measured by linearly increasing the sample temperature at a selected rate, the temperature cycling being generated from a ramp-driven dc power supply, with the mass spectrometer tuned to a mass number of interest. Results of the study indicate an anomolous desorption mechanism following an electron bombardment of the sample surface. The enhanced spectra are a function of the post-bombardment time and energy and are suggestive of an increased concentration of cesium atoms, up to 10 or more angstroms below the surface.

Wood, G. M., Jr.↗

Predicted exhaust emissions from a methanol and jet fueled gas turbine combustor

A computer model of a gas turbine combustor has been used to predict the kinetic combustion and pollutant formation processes for methanol and simulated jet fuel. Use of the kinetic reaction mechanisms has also allowed a study of ignition delay and flammability limit of these two fuels. The NOX emissions for methanol were predicted to be from 69 to 92% lower than those for jet fuel at the same equivalence ratio which is in agreement with experimentally observed results. The high heat of vaporization of methanol lowers both the combustor inlet mixture temperatures and the final combustion temperatures. The lower combustion temperatures lead to low NOX emissions while the lower inlet mixture temperatures increase methanol's ignition delay. This increase in ignition delay dictates the lean flammability limit of methanol to be 0.8, while jet fuel is shown to combust at 0.4.

Adelman, H. G.↗

Inelastic scattering of 61 MeV protons by pb-207

Differential cross sections for the excitation of the first four neutron-hole states and the doublet at 2.61 MeV by 61.2 MeV protons were measured. The data are analyzed in terms of both a purely collective model description and a microscopic model supplemented by macroscopic core polarization. A realistic two-body interaction is used and knock-on amplitudes are included. Core polarization is found to be important but represents a relatively smaller contribution than in most nuclei previously studied. A parallel analysis of similar data at lower proton bombarding energies reveals a surprisingly strong energy dependence of the reaction mechanisms.

Owais, M.↗

Space biosynthesis systems

Model reactions based on chemical, enzymatic or cellular conversion of D glucose into d gluconic acid are designed to unequivocally define the advantages of microgravity on reaction mechanisms, mass-transfers and separation of organic chemicals and to serve as procedures to test the performance characteristics of space bioprocessing equipment.

Nyiri, L. K.↗

Influence of temperature and the role of chromium on the kinetics of sulfidation of 310 stainless steel

The sulfidation of 310 stainless steel was studied over the temperature range from 910 K to 1285 K. By adjusting the ratio of hydrogen sulfide, variations in sulfur potential were obtained. The effect of temperature on sulfidation was determined at three different sulfur potentials: 39/sqNm, 0.014/sqNm, and 0.00015/sqNm. All sulfide scales contained one or two surface layers in addition to a subscale. The second outer layer (OL-II), furthest from the alloy, contained primarily Fe-Ni-S. The first outer layer (OL-I), nearest the subscale, contained FE-Cr-S. The subscale consisted of sulfide inclusions in the metal matrix. At a given temperature and sulfur potential, the weight gain data obeyed the parabolic rate law after an initial transient period. The parabolic rate constants obtained at the sulfur potential of 39/sqNm did not show a break when the logarithm of the rate constant was plotted as a function of the inverse of absolute temperature. Sulfidation carried out at sulfur potentials below 0.02/sqNm, however, did show a break at 1145 K, which is termed as the transition temperature. This break was found to be associated with the changes which had occurred in the Fe:Cr ratio of OL-I. Below the transition temperature the activation energy was found to be approximately 125 kj/mole. Above the transition temperature the rate of sulfidation decreased with temperature but dependent on the Fe:Cr ratio in the iron-chromium-sulfide layers of the OL-I. A reaction mechanism consistent with the experimental results has been proposed.

Rao, D. B.↗