Search NASA⌕ Search

SEARCH · Search NASA

Results for “Degradation kinetics”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7

Escarpment evolution on high-elevation rifted margins: Insights derived from a surface processes model that combines diffusion, advection and reaction

Experiments with a surface processes model of large-scale (1-1000 km) long-term (1-100 m.y.) erosional denudation are used to establish the controls on the evolution of a model escarpment that is related to the rifting of a continent. The mdoel describes changes in topographic form as a result of sumultaneous short- and long-range mass transport representing hillslope (diffusive) processes and fluvial transport (advection), repsectively. Fluvial entrainment is modeled as a first-order kinetic reaction which reflects the erodibility of the substrate, and therefore the fluvial system is not necessarily carrying at capacity. One dimensional and planform models demonstrate that the principal controls on the evolution of an initially steep model escarpment are (1) antecedent topography/drainage; (2) the timesale (or equivalently a length scale) in the fluvial entrainment reaction; (3) the flexural response of the lithosphere to denudation; and (4) the relative efficiencies of the short- and long-range transport processes. When rainfall and substrate lithology are uniform, a significant amount of discharge draining over the escarpment top causes it to degrade. Only when the top of the model escarpment coincides with a drainage divide can escarpment retreat occur for these conditions. An additional requirement for retreat of a model escarpment without decline is a long reaction time scale for fluvial entrainment. This corresponds to a substrate that is hard to detach by flucial erosion, and therefore to fluvial erosion that is not transport limited. Coninuous backtilting of an escarpment due ot flexural isostatic uplift in response to denudational unloading helps maintain the scarp top as a divide. It is essntial if the escarpment gradient is to be preserved during retreat in a uniform lithology. Low flexural rigidieties propote steep and slowly retreating escarpments. For given rainfall and substrate conditions, the morphology of a retraeating model escarpment is determined by the ratio of hte short-range diffusive and long range advective transport efficiencies. A low ration (which is interpreted to correspond to a more humid, temperate climate) produces a convex upper slope, and concave lower slope morphology and only major escarpments are predicted to preserve a high scarp gradient. Lithological contrasts in hte model produce more complex morphologies and predict the formation of scarps crowned by an erosionaly resistant caprock. However, resistant caprocks are not an essential requirement for model scarps to retreat. We conclude that the inferred controls and model behavior are both consistent with the present-day morphology of rifted continental margins and with modern conceptual models of landscape evolution.

Kooi, Henk↗

Bare Conductive Tether for Decelerating a Spacecraft

A document describes a prototype of electrically conductive tethers to be used primarily to decelerate spacecraft and/or generate electric power for the spacecraft. Like prior such tethers, this tether is designed so that when it is deployed from a spacecraft in orbit, its motion across the terrestrial magnetic field induces an electric current. The Lorentz force on the current decelerates the spacecraft. Optionally, the current can be exploited to convert some orbital kinetic energy to electric energy for spacecraft systems. Whereas the conductive portions of prior such tethers are covered with electrical insulation except for end electrodes that make contact with the ionosphere, this tether includes a conductive portion that is insulated along part of its length but deliberately left bare along a substantial remaining portion of its length to make contact with the ionosphere. The conductive portions of the tether are made of coated thin aluminum wires wrapped around strong, lightweight aromatic polyamide braids. The main advantages of the present partly-bare-tether design over the prior all-insulated-tether design include greater resistance to degradation by the impact of monatomic oxygen at orbital altitude and speed and greater efficiency in collecting electrons from the ionosphere.

Johnson, Les↗

Phosphate Reactions as Mechanisms of High-Temperature Lubrication

One of the major problems preventing the operation of advanced gas turbine engines at higher temperatures is the inability of currently used liquid lubricants to survive at these higher temperatures under friction and wear conditions. Current state-of-the-art organic liquid lubricants rapidly degrade at temperatures above 300 C; hence some other form of lubrication is necessary. Vapor-phase lubrication is a promising new technology for high-temperature lubrication. This lubrication method employs a liquid phosphate ester that is vaporized and delivered to bearings or gears; the vapor reacts with the metal surfaces, generating a solid lubricious film that has proven very stable at high temperatures. In this study, solid lubricious films were grown on cast-iron foils in order to obtain reaction and diffusion rate data to help characterize the growth mechanism. A phenomenological mathematical model of the film deposition process was derived incorporating transport and kinetic parameters that were coupled to the experimental data. This phenomenological model can now be reliably used as a predictive and scale-up tool for future vapor-phase lubrication studies.

Nagarajan, Anitha↗

An outgassing model of non-metallic materials for the ascent of a Titan 4 launch vehicle

Outgassing of nonmetallic materials and components inside Titan IV's 2A compartment during ascent may present a problem to the payload community in relation to molecular deposition and degradation of sensitive payload surfaces. The procedure currently being developed to model the amounts, transport, and deposition of outgassed molecular contaminants onto a payload's sensitive surface consists of three phases. The first phase involves the development of a thermogravimetric method that recreates the increasing temperature and decreasing pressure profiles expected in the 2A compartment of the TIV launch vehicle during ascent. The second phase involves the determination of deposition rates of outgassed materials onto a payload surface, and the subsequent evaporation rate as a function of temperature of deposited material. The third phase takes the temperature and pressure profiles from phase one, the deposition and evaporation rates and kinetic coefficients determined in phase two, and incorporates them into the SPACE II computer program to determine which payload surfaces are most susceptible to molecular deposition from TIV's outgassing sources, and the level of permanent deposition expected on those surfaces.

Barrows, R. D.↗

Thermochemical Degradation Mechanisms for the Reinforced Carbon/Carbon Panels on the Space Shuttle

The wing leading edge and nose cone of the Space Shuttle are fabricated from a reinforced carbon/carbon material (RCC). The material attains its oxidation resistance from a diffusion coating of SiC and a glass sealant. During re-entry, the RCC material is subjected to an oxidizing high temperature environment, which leads to degradation via several mechanisms. These mechanisms include oxidation to form a silica scale, reaction of the SiO2 with the SiC to evolve gaseous products, viscous flow of the glass, and vaporization of the glass. Each of these is discussed in detail. Following extended service and many missions, the leading-edge wing surfaces have exhibited small pinholes. A chloridation/oxidation mechanism is proposed to arise from the NaCl deposited on the wings from the sea-salt laden air in Florida. This involves a local chloridation reaction of the SiC and subsequent re-oxidation at the external surface. Thermodynamic calculations indicate the feasibility of these reactions at active pits. Kinetic calculations predict pore depths close to those observed.

Jacobson, Nathan S.↗

Development of Methods of Characterizing Coal in Its Plastic State

Coal in its plastic state (typically 400-460 C) was examined by the isothermal Gieseler plastometry of seven selected coals of widely varying plastic properties. Kinetic models were proposed for the isothermal plastometric curves. Plastic behavior was compared with a variety of laboratory analyses and characterizations of these coals, including classical coal analysis; mineral analysis; microstructural analysis (extractable fractions, surface area measurement, and petrographic analysis); and thermal analysis (thermogravimetric analysis, thermomechanical analysis, and differential scanning calorimetry). The phenomenon of a sharp, large, poorly reproducible exotherm in the differential scanning calorimetric analysis of coking coals was examined. Several coal extrudates show mineral distribution, organic maceral composition and overall calorific value to be little affected by 800 F extrusion. Volatile matter and plastic properties are moderately reduced, and the network structure (as gauged by extractables) appears to be slightly degraded in the extrusion process.

Lloyd, W. G.↗

Theoretical approach to oxygen atom degradation of silver

Based on available Rutherford backscattering spectrometry (RBS), proton induced X-ray emission (PIXE) and ellipsometry data obtained on silver specimens subjected to atomic oxygen attack in low Earth orbit STS flight 41-G, a theory was developed to model the oxygen atom degradation of silver. The diffusion of atomic oxygen in a microscopically nonuniform medium is an essential constituent of the theory. The driving force for diffusion is the macroscopic electrochemical potential gradient developed between the specimen surface exposed to the ambient and the bulk of the silver specimen. The longitudinal electric effect developed parallel to the gradient is modified by space charge of the diffusing charged species. Lateral electric fields and concentration differences also exist due to the nonuniform nature of the medium. The lateral concentration differences are found to be more important than the lateral electric fields in modifying the diffusion rate. The model was evaluated numerically. Qualitative agreement exists between the kinetics predicted by the theory and kinetic data taken in ground-based experiments utilizing a plasma asher.

Fromhold, Albert T., Jr.↗

Oxidation characteristics of Ti-25Al-10Nb-3V-1Mo intermetallic alloy

Static oxidation kinetics of the super-alpha 2 titanium-aluminide alloy Ti-25Al-10Nb-3V-1Mo (at. percent) were investigated in air over the temperature range of 650 to 1000 C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to three distinct oxidation rates. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using x ray diffraction techniques, electron microprobe analysis, and energy dispersive x ray analysis. Oxide scale morphology was examined by scanning electron microscopy of the surfaces and cross sections of oxidized specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3, and a thin bottom layer of TiN. The transition between the second and third parabolic stage was found to be linked to the formation of a TiAl layer at the oxide-metal interface. Porosity was formed during the third stage, causing degradation of the oxide and the beginning of breakaway oxidation.

Wallace, Terryl A.↗

Oxidation characteristics of Ti-25Al-10Nb-3V-1Mo

Static oxidation kinetics of the super-alpha 2 titanium-aluminide alloy Ti-25Al-10Nb-3V-1Mo (at. percent) were investigated in air over the temperature range of 650 to 1000 C using thermogravimetric analysis. The oxidation kinetics were complex at all exposure temperatures and displayed up to three distinct oxidation rates. Breakaway oxidation occurred after long exposure times at high temperatures. Oxidation products were determined using X-ray diffraction techniques, electron microprobe analysis, and energy dispersive X-ray analysis. Oxide scale morphology was examined by scanning electron microscopy of the surfaces and cross sections of oxidized specimens. The oxides during the parabolic stages were compact and multilayered, consisting primarily of TiO2 doped with Nb, a top layer of Al2O3, and a thin bottom layer of TiN. The transition between the second and third parabolic stage was found to be linked to the formation of a TiAl layer at the oxide-metal interface. Porosity was formed during the third stage, causing degradation of the oxide and the beginning of breakaway oxidation.

Wallace, T. A.↗

Trace Contaminant Control: An In-Depth Study of a Silica-Titania Composite for Photocatalytic Remediation of Closed-Environment Habitat Air

This collection of studies focuses on a PCO system for the oxidation of a model compound, ethanol, using an adsorption-enhanced silica-TiO2 composite (STC) as the photocatalyst; studies are aimed at addressing the optimization of various parameters including light source, humidity, temperature, and possible poisoning events for use as part of a system for gaseous trace-contaminant control system in closed-environment habitats. The first goal focused on distinguishing the effect of photon flux (i.e., photons per unit time reaching a surface) from that of photon energy (i.e., wavelength) of a photon source on the PCO of ethanol. Experiments were conducted in a bench-scale annular reactor packed with STC pellets and irradiated with either a UV-A fluorescent black light blue lamp O max=365 nm) at its maximum light intensity or a UV-C germicidal lamp O. max=254 nm) at three levels of light intensity. The STC-catalyzed oxidation of ethanol was found to follow zero-order kinetics with respect to CO2 production, regardless of the photon source. Increased photon flux led to increased EtOH removal, mineralization, and oxidation rate accompanied by lower intermediate concentration in the effluent. The oxidation rate was higher in the reactor irradiated by UV-C than by UV-A (38.4 vs. 31.9 nM s-1 ) at the same photon flux, with similar trends for mineralization (53.9 vs. 43.4%) and reaction quantum efficiency (i.e., photonic efficiency, 63.3 vs. 50.1 nmol C02 ~mol photons-1 ). UV-C irradiation also led to decreased intermediate concentration in the effluent compared to UV -A irradiation. These results demonstrated that STC-catalyzed oxidation is enhanced by both increased photon flux and photon energy. The effect of temperature and relative humidity on the STC-catalyzed degradation of ethanol was also determined using the UV-A light source at its maximum intensity.

Coutts, Janelle L.↗

Zoledronate Prevents Simulated Weightlessness-Induced Bone Loss in the Cancellous Compartment While Blunting the Efficacy of a Mechanical Loading Countermeasure

Astronauts using high-force resistance training while weightless show a high-turnover remodeling state within the skeletal system, with resorption and formation biomarkers being elevated. One countermeasure for the skeletal health of astronauts includes an antiresorptive of the bisphosphonate (BP) drug class. We asked, does the combination of an anti-resorptive and high-force exercise during weightlessness have negative effects on bone remodeling and strength? In this study, we developed an integrated model to mimic the mechanical strain of exercise via cyclical loading (CL) in mice treated with the BP Zoledronate (ZOL) combined with hind limb unloading (HU) to simulate weightlessness. We hypothesized that ZOL prevents structural degradation from simulated weightlessness and that CL and ZOL interact to render CL less effective. Thirty-two C57BL/6 mice (male, 16 weeks old, n=8/group) were exposed to 3 weeks of either HU or normal ambulation (NA). Cohorts of mice received one subcutaneous injection of ZOL (45μg/kg), or saline vehicle (VEH), prior to the start of HU. The right tibia was axially compressed in vivo 60x/day to 9N (+1200μstrain on the periosteal surface) and repeated 3x/week during HU. Left tibiae served as a within subject, non-compressed control. Ex vivo μCT was performed on all subjects to determine cancellous and cortical architectural parameters. Static and dynamic histomorphometry were carried out for the left and right tibiae to determine osteoclast- and osteoblast relevant surfaces. Further, micro damage was assessed in select groups by basic-fuchsin staining to test whether CL had an effect. For all assays, a multivariate (2x2x2) ANCOVA model was used to account for body weight changes. Additionally, for the tibiae, we incorporated a random effect for the subject (hence, a mixed model) to account for observations of both left and right tibiae within each subject. P < 0.05 was considered significant. In the cancellous compartment of the proximal tibial metaphysis, we observed a main effect from each independent variable, as determined by structural and histomorphometric assays. Specifically, as expected, ZOL showed an increase in the cancellous bone volume to total volume fraction (BV/TV, +32%) and trabecular number (+18%) compared to the VEH. As expected, ZOL decreased osteoclast surface (OC/BS) by -45% compared to VEH. Surprisingly, ZOL reduced mineralizing surface (MS/BS) and bone formation rate (BFR), indicators of osteoblast activity, by -40% and -54%, respectively, compared to VEH. Altogether, ZOL-treated mice displayed a low turnover state of remodeling in the metaphysis. In the context of skeletal aging, we speculate that ZOL prevented age-related cancellous strut loss during the experiment. As a main effect, as expected, HU decreased BV/TV by - 31% via reductions in both trabecular thickness (-11%) and number (-22%) compared to NA controls. Additionally, HU decreased MS/BS by -38% and bone formation rate (BFR) by -50% compared to NA controls. Altogether, these data are consistent with structural degradation resulting from imbalanced remodeling that favors resorption. As a main effect, CL increased BV/TV by +15% via increased trabecular thickness (+12%) compared to the noncompressed limb. As expected, CL increased MS/BS (+20%) and BFR (+24%), indicating osteoblast mineralization contributed to bone gains. These data show that CL provided an anabolic stimulus to the cancellous tissue. We observed unique interactions in ZOL*CL and HU*CL. First, ZOL prevented CL-induced increases in BV/TV and trabecular number, as compared to VEH. In the context of skeletal aging, these data suggest no added benefit from CL in the ZOL-treated mice. Interestingly, no microdamage was observed in mice that were unloaded and treated with ZOL (independent of CL). Secondly, HU prevented CL-induced increases in BFR, as compared to NA controls. These data suggest that either exercise is less effective or the kinetics of formation are slower during simulated weightlessness. Osteoclast surface was unchanged by either treatment. Thus, in contrast to exercising astronauts, these data do not suggest a high-turnover state in the metaphysis. To assess mechanical properties as a function of HU or ZOL, we tested the left femur in three-point bending ex vivo. As expected, HU decreased stiffness (-30%) compared to NA, and ZOL increased stiffness compared to VEH (+28%). Interestingly, HU increased the post-yield displacement, related to collagenous tensile loading, compared to NA (+20%). ZOL increased yield force (+11%) and ultimate force (+17%), which seems to explain the significant effect of ZOL increasing total energy (work-to-fracture, +15%), while not affecting the post yield displacement. Taken together, ZOL did not have detrimental affect on mechanical properties. Our integrated model simulates the combination of weightlessness, exercise-induced mechanical strain, and anti-resorptive treatment that astronauts experience during space missions. We conclude that Zoledronate was an effective countermeasure against weightlessness-induced bone loss, though zoledronate, as well as weightlessness, rendered exercise-related mechanical loading less effective.

bone↗

The role of oxygen in porous molybdenum electrodes for the alkali metal thermoelectric converter

A model for chemical reactions in porous molybdenum electrodes is presented which is based on thermochemical and kinetic data, known sodium-molybdenum-oxygen chemistry, X-ray diffraction analysis of molybdenum and molybdenum oxide electrodes, and the electrochemical behavior of the cell. Enhanced sodium transport through the electrode in its optimum performance state is found to be due to the high sodium ion conductivity of molten Na2MoO4 in the pores, and the electrical conduction to the molybdenum matrix by Na2Mo3O6. The decline of electrode performance is shown to be due to a combination of loss mechanisms for the Na-Mo-O compounds including reduction at short circuit, disproportionation of Na2Mo3O6 at open circuit, and the evaporation of Na2MoO4 at elevated temperature. It is suggested that operation of the cell at moderate voltage of about 0.5 V corresponding to maximum power may be a more stable condition for the porous electrode than open-circuit stand or short-circuit, where degradation reactions are heightened.

Williams, R. M.↗

Oxidation of SiC/BN/SiC Composites in Reduced Oxygen Partial Pressures

SiC fiber-reinforced SiC composites with a BN interphase are proposed for use as leading edge structures of hypersonic vehicles. The durability of these materials under hypersonic flight conditions is therefore of interest. Thermogravimetric analysis was used to characterize the oxidation kinetics of both the constituent fibers and composite coupons at four temperatures: 816, 1149, 1343, and 1538 C (1500, 2100, 2450, and 2800 F) and in oxygen partial pressures between 5% and 0.1% (balance argon) at 1 atm total pressure. One edge of the coupons was ground off so the effects of oxygen ingress into the composite could be monitored by post-test SEM and EDS. Additional characterization of the oxidation products was conducted by XPS and TOF-SIMS. Under most conditions, the BN oxidized rapidly, leading to the formation of borosilicate glass. Rapid initial oxidation followed by volatilization of boria lead to protective oxide formation and further oxidation was slow. At 1538C in 5% oxygen, both the fibers and coupons exhibited borosilicate glass formation and bubbling. At 1538C in 0.1% oxygen, active oxidation of both the fibers and the composites was observed leading to rapid SiC degradation. BN oxidation at 1538C in 0.1% oxygen was not significant.

Opila, Elizabeth J.↗

Mechanism of Na2SO4-induced corrosion of molybdenum containing nickel-base superalloys at high temperatures. I - Corrosion in atmospheres containing O2 only. II - Corrosion in O2 + SO2 atmospheres

Kinetics of the Na2SO4-induced corrosion of the molybdenum-containing nickel-base superalloys, B-1900 and Udimet 700, coated with Na2MoO4, has been studied in oxygen atmosphere at temperatures ranging from 750 to 950 C. Because the gas turbine atmosphere always contains some SO2 and SO3, the effect of atmospheric SO2 content on corrosion of Udimet-700 has also been studied. It was found that in the O2 atmosphere the melt in the catastrophic corrosion phase consists of Na2MoO4 plus MoO3, with the onset of the catastrophic corrosion coinciding with the appearance of MoO3. In the presence of low levels of atmospheric SO2 (below 0.24 percent), the melt during catastrophic corrosion contains, in addition to Na2MoO4 and MoO3, some quantities of Na2SO4. At the levels of SO2 above 1 percent, no catastrophic corrosion was observed. At these SO2 levels, internal sulfidation appears to be the primary mode of degradation.

Misra, A. K.↗

Incompressible Turbulent Wing-Body Junction Flow

The overall objective of this study is to contribute to the optimized design of fan bypass systems in advanced turbofan engines. Increasing the engine bypass ratios have provided a major boost in engine performance improvement over the last fifty years. An engine with high bypass ratio (11-16:1) such as the Advanced Ducted Propulsion (ADP) is being developed and is expected to provide an additional 25% improvement in overall efficiency over the early turbofans. Such significant improvements in overall efficiency would reduce the cost per seat mile, which is a major government and Industry challenge for the 21th century. The research is part of the Advanced Subsonic Technology (AST) program that involves a NASA, U.S. Industry and FAA partnership with the goal of a safe and highly productive global air transportation system. The immediate objective of the study is to perform numerical simulation of duct-strut interactions to elucidate the loss mechanisms associated with this configuration that is typical of advanced turbofan engines such as ADP. However, at present experimental data for a duct-strut configuration are not available. Thus, as a first step a wing-body junction flow would be studied and is the specific objective of the present study. At the outset it is to be recognized that while duct-strut interaction flow is similar to that of wing-body junction flows, there are some differences owing to the presence of a wall at both ends of the strut. Likewise, some differences are due to the sheared inflow (as opposed to a uniform inflow) velocity profile. It is however expected that some features of a wing-body junction flow would persist. Next, some of the salient aspects of the complex flow near a wing-body junction, as revealed by various studies reported in the literature will be reviewed. One of the principle characteristics of the juncture flow, is the presence of the mean flow components in a plane perpendicular to the direction of the oncoming free-stream flow. The lateral curvature of the wing/strat causes the oncoming turbulent layer to skew about am axis (x-axis) parallel to the plane (xz-plane) of the mean shear. This is the principle mechanism for the generation of secondary flow. Such skew-induced secondary flows are slow to be attenuated by Reynolds stresses. Additional contribution to the generation of secondary flow comes from anisotropies in Reynolds stresses. Upstream of the strut, the mean-vorticity is directed span wise (along the y-direction). The presence of secondary flow in the vicinity of the strut causes the vorticity to stretch around the obstacle in a horse-shoe shape, with each leg having a vorticity of the opposite sense. The blockage effect of the strut imposes a severe adverse pressure gradient on the oncoming turbulent shear layer, causing boundary layer separation ahead of the leading edge, resulting in a vortex that rolls up and flows downstream into the juncture region. The separation vortices trailing in the wake of the wing can alter the lift or drag characteristics of the surfaces downstream of the wing-body juncture. Likewise, on submarines, the wake flow behind the appendage can degrade the performance of the propeller located downstream. The complex nature of this flow is caused by the presence of all six components of Reynolds stresses. Devenport and Simpson report that in the vicinity of the horse-shoe vortex there is intense recirculation with turbulent stresses being much larger than those normally observed in turbulent flows. These features contribute to making this flow a challenge to predict numerically. Some of the past studies provide useful insights into this flow that would guide our numerical efforts. In measurements reported by Shabaka and Bradshaw, the eddy viscosity tensor is seen to be non-isotropic and has negative components in certain regions. In an effort to evaluate the closure assumptions of various turbulence models, Devenport and Simpson used their own extensive measurements in juncture flows around the nose of a wing-body junction. Measured values of mean-velocity and/or turbulence kinetic energy was used to predict the magnitude of the shear stress vector. Algebraic stress models performed the best followed by Cebeci-Smith eddy viscosity model. The flow is reported to be dominated by a pressure field produced by the wing and the velocity field generated by the horseshoe vortex that is wrapped around the junction between the wing and wall. Kubendran et al. conclude from an experimental study that the shape of leading edge of the wing as characterized by its slenderness ratio is a major factor in determining the flow fields in the juncture region. The more thinner the leading edge of the juncture, the weaker the horseshoe vortex is. Also, with a slender leading edge, the secondary flow in the juncture would be due mainly to the cross-stream gradients of Reynolds stresses rather than due to a lateral skewing of the shear layer.

Krishnamurthy, R.↗

Gas Sensor Evaluations in Polymer Combustion Product Atmospheres

Toxic gases produced by the combustion or thermo-oxidative degradation of materials such as wire insulation, foam, plastics, or electronic circuit boards in space shuttle or space station crew cabins may pose a significant hazard to the flight crew. Toxic gas sensors are routinely evaluated in pure gas standard mixtures, but the possible interferences from polymer combustion products are not routinely evaluated. The NASA White Sands Test Facility (WSTF) has developed a test system that provides atmospheres containing predetermined quantities of target gases combined with the coincidental combustion products of common spacecraft materials. The target gases are quantitated in real time by infrared (IR) spectroscopy and verified by grab samples. The sensor responses are recorded in real time and are compared to the IR and validation analyses. Target gases such as carbon monoxide, hydrogen cyanide, hydrogen chloride, and hydrogen fluoride can be generated by the combustion of poly(vinyl chloride), polyimide-fluoropolymer wire insulation, polyurethane foam, or electronic circuit board materials. The kinetics and product identifications for the combustion of the various materials were determined by thermogravimetric-IR spectroscopic studies. These data were then scaled to provide the required levels of target gases in the sensor evaluation system. Multisensor toxic gas monitors from two manufacturers were evaluated using this system. In general, the sensor responses satisfactorily tracked the real-time concentrations of toxic gases in a dynamic mixture. Interferences from a number of organic combustion products including acetaldehyde and bisphenol-A were minimal. Hydrogen bromide in the products of circuit board combustion registered as hydrogen chloride. The use of actual polymer combustion atmospheres for the evaluation of sensors can provide additional confidence in the reliability of the sensor response.

Delgado, Rafael H.↗

Attenuation of Glass Dissolution in the Presence of Natural Additives

The study described here explored the dissolution kinetics of glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase. The results demonstrated the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. The study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses as well as to better understanding of the environmental degradation of natural and ancient glasses.

Sang, Jing C.↗

The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

Koontz, Steve L.↗