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Atomic Oxygen Task

This report details work performed by the Center for Applied Optics (CAO) at the University of Alabama in Huntsville (UAH) on the contract entitled 'Atomic Oxygen Task' for NASA's Marshall Space Flight Center (contract NAS8-38609, Delivery Order 109, modification number 1). Atomic oxygen effects on exposed materials remain a critical concern in designing spacecraft to withstand exposure in the Low Earth Orbit (LEO) environment. The basic objective of atomic oxygen research in NASA's Materials & Processes (M&P) Laboratory is to provide the solutions to material problems facing present and future space missions. The objective of this work was to provide the necessary research for the design of specialized experimental test configurations and development of techniques for evaluating in-situ space environmental effects, including the effects of atomic oxygen and electromagnetic radiation on candidate materials. Specific tasks were performed to address materials issues concerning accelerated environmental testing as well as specifically addressing materials issues of particular concern for LDEF analysis and Space Station materials selection.

Hadaway, James B.↗

Recent Development on O(+)-O Collision Frequency and Ionosphere-Middle Atmosphere Coupling

The collision frequency between an oxygen atom and its singly charged ion controls the transfer of energy between the solar radiation and the thermosphere. There were a long standing discrepancy, extending over a decade, between the theoretical and empirical determination of this frequency, and the empirical value of this frequency exceeded the theoretical value by a factor of 1.7. Recent improvements in theory were obtained by using accurate oxygen ion-oxygen atom potential energy curves, and partial wave quantum mechanical calculations. Similarly, recently three independent statistical methods were applied to the empirical determination of this frequency. These methods give results consistent with each other, and together with the recent theoretical improvements, bring the ratio close to unity, as it should be. It will be shown that the old statistical method for this determination contained accumulative errors, leading to a larger value for this ratio. The recent improvements lead to an average value of the empirical to the theoretical ratio equal to 0.98, with an uncertainty of +/- 8%, resolving the old discrepancy between theory and observations. The main source of uncertainties are errors in the profile of the oxygen atom density, which is of the order of 11 %. An alternative method to find the oxygen atom density is being suggested.

Omidvar, K.↗

Recent Development on O(+) - O Collision Frequency and Ionosphere-Thermosphere Coupling

The collision frequency between an oxygen atom and its singly charged ion controls the momentum transfer between the ionosphere and the thermosphere. There has been a long standing discrepancy, extending over a decade, between the theoretical and empirical determination of this frequency: the empirical value of this frequency exceeded the theoretical value by a factor of 1.7. Recent improvements in theory were obtained by using accurate oxygen ion-oxygen atom potential energy curves, and partial wave quantum mechanical calculations. We now have applied three independent statistical methods to the observational data, obtained at the MIT/Millstone Hill Observatory, consisting of two sets A and B. These methods give results consistent with each other, and together with the recent theoretical improvements, bring the ratio close to unity, as it should be. The three statistical methods lead to an average for the ratio of the empirical to the theoretical values equal to 0.98, with an uncertainty of +/-8%, resolving the old discrepancy between theory and observation. The Hines statistics, and the lognormal distribution statistics, both give lower and upper bounds for the Set A equal to 0.89 and 1.02, respectively. The related bounds for the Set B are 1.06 and 1.17. The average values of these bounds thus bracket the ideal value of the ratio which should be equal to unity. The main source of uncertainties are errors in the profile of the oxygen atom density, which is of the order of 11%. An alternative method to find the oxygen atom density is being suggested.

Omidvar, K.↗

Runtime Verification: From Propositional to First-Order Temporal Logic

Runtime Verification is a branch of formal methods concerned with analysis of execution traces for the purpose of determining the state or general quality of the executing system. The field covers numerous approaches, one of which is specification-based runtime verification, where execution traces are checked against formal specifications. The paper presents syntax, semantics, and monitoring algorithms for respectively propositional and first-order temporal logics. In propositional logics the observed events in the execution trace are represented using atomic propositions, while first-order logic allows universal and existential quantification over data occurring as arguments in events. Monitoring of the first-order case is drastically more challenging than the propositional case, and we present a solution for this problem based on BDDs. We furthermore discuss monitorability of temporal properties by dividing them into different classes representing different degrees of monitorability.

Peled, Doron↗

Cavities in molecular liquids and the theory of hydrophobic solubilities

Thermal configurational data on neat liquids are used to obtain the work of formation of hard spherical cavities of atomic size in six molecular solvents: n-hexane, n-dodecane, n-undecyl alcohol, chloroform, carbon tetrachloride, and water. These results are used to test a recent suggestion that the differences between nonaqueous solvents and liquid water in solvation of inert gases are not principally due to the hydrogen-bonded structure of liquid water but rather to the comparatively small size of the water molecule. The frequencies of occurrence of cavities in liquid water can be meaningfully distinguished from those in the organic solvents. Liquid water has a larger fractional free volume, but that free volume is distributed in smaller packets. With respect to cavity work, water is compared to a solvent of the same molecular density and composed of hard spheres of the same size as the water molecule. That comparison indicates that the hard-sphere liquid finds more ways to configure its free volume in order to accommodate an atomic solute of substantial size and thus, would be more favorable solvent for inert gases. The scaled particle model of inert gas solubility in liquid water predicts cavity works 20% below the numerical data for TIP4P water at 300 K and 1.0 g/cm3 for cavity radii near 2.0 angstroms. It is argued that the sign of this difference is just the sign that ought to be expected and that the magnitude of this difference measures structural differences between water and the directly comparable hard-sphere liquid. In conjunction with previous data, these results indicate that atomic sized cavities should be considered submacroscopic.

NASA Discipline Exobiology↗

Atomic Oxygen Exposure of Power System and other Spacecraft Materials: Results of the EOIM-3 Experiment

In order to test their reactivity with Atomic Oxygen, twenty five materials were flown on the EOIM-3 (Evaluation of Oxygen Interactions with Materials) portion of the STS-46 Mission. These materials include refractory metals, candidate insulation materials, candidate radiator coatings, and a selection of miscellaneous materials. This report documents the results of the pre- and post-flight analysis of these materials.

Morton, Thomas L.↗

Solid/liquid interfacial free energies in binary systems

Description of a semiquantitative technique for predicting the segregation characteristics of smooth interfaces between binary solid and liquid solutions in terms of readily available thermodynamic parameters of the bulk solutions. A lattice-liquid interfacial model and a pair-bonded regular solution model are employed in the treatment with an accommodation for liquid interfacial entropy. The method is used to calculate the interfacial segregation and the free energy of segregation for solid-liquid interfaces between binary solutions for the (111) boundary of fcc crystals. The zone of compositional transition across the interface is shown to be on the order of a few atomic layers in width, being moderately narrower for ideal solutions. The free energy of the segregated interface depends primarily upon the solid composition and the heats of fusion of the component atoms, the composition difference of the solutions, and the difference of the heats of mixing of the solutions.

Nason, D.↗

Variational principle for scattering of light by dielectric particles

Consideration is given to the work of Purcell and Pennypacker (1973) where a dielectric particle is taken to be an aggregate of N polarizable elements mounted on a cubic lattice. The simultaneous equations which result from the scattering problem are presented. This theory has been discussed in the case of nonspherical and inhomogeneous objects whose dimensions are smaller than or comparable to the wavelength of incident light. A more precise numerical treatment is derived for further progress. The variational principle is invoked and the practical limit for the current version of the scheme is a dipole array on the order of 10,000 atoms. Limits to the scattering parameter due to the phase difference between neighboring atoms are discussed.

Yung, Y. L.↗

The ionization structure of the circumstellar envelope of Alpha Orionis

The physical processes which affect the ionization of the outer circumstellar envelope of Alpha Ori are analyzed and evaluated. The ultraviolet radiation fields of the chromosphere and the interstellar medium dominate the envelope, and the most common forms of all species are neutral atoms and first ions. Hydrogen recombines just outside the chromosphere, where atoms with smaller ionization potential are essentially fully ionized. The heavier ions gradually recombine with increasing distance from the star, until the interstellar radiation field reverses this trend. The electron fraction in the outer envelope is approximately equal to the abundance of all such heavy atoms, i.e., of the order of 0.0001. The analysis is applied to the case of neutral K, whose density in the envelope has been determined by scattering experiments. The theory predicts that the slope of the K I density distribution should decrease from -1.5 to -3.5 in the outer envelope. The mass loss rate of Alpha Ori implied by the K I scattering experiments is 4 x 10 to the -6th solar mass/yr.

Glassgold, A. E.↗

The effect of leveling coatings on the atomic oxygen durability of solar concentrator surfaces

Space power systems for Space Station Freedom will be exposed to the harsh environment of low earth orbit (LEO). Neutral atomic oxygen is the major constituent in LEO and has the potential of severely reducing the efficiency of solar dynamic power systems through degradation of the concentrator surfaces. Several transparent dielectric thin films have been found to provide atomic oxygen protection, but atomic oxygen undercutting at inherent defect sites is still a threat to solar dynamic power system survivability. Leveling coatings smooth microscopically rough surfaces, thus eliminating potential defect sites prone to oxidation attack on concentrator surfaces. The ability of leveling coatings to improve the atomic oxygen durability of concentrator surfaces was investigated. The application of a EPO-TEK 377 epoxy leveling coating on a graphite epoxy substrate resulted in an increase in solar specular reflectance, a decrease in the atomic oxygen defect density by an order of magnitude and a corresponding order of magnitude decrease in the percent loss of specular reflectance during atomic oxygen plasma ashing.

Degroh, Kim K.↗

Theoretical calculations of pressure broadening coefficients for H2O perturbed by hydrogen or helium gas

Halfwidths were calculated for H2O with H2 as a broadening gas and were estimated for He as the broadening species. The calculations used the model of Robert and Bonamy with parabolic trajectories and all relevant terms in the interaction potential. The calculations investigated the dependence of the halfwidth on the order of the atom-atom expansion, the rotational states, and the temperature in the range 200 to 400K. Finally, calculations were performed for many transitions of interest in the 5 micrometer window region of the spectrum. The resulting data will be supplied to Dr. R. Freedman for extracting accurate water mixing ratios from the analysis of the thermal channels for the Net Flux experiment on the Galileo probe.

Gamache, Robert R.↗

Whisker/Cone growth on the thermal control surfaces experiment no. S0069

An unusual surface 'growth' was found during scanning electron microscope (SEM) investigations of the Thermal Control Surface Experiment (TCSE) S0069 front thermal cover. This 'growth' is similar to the cone type whisker growth phenomena as studied by G. K. Wehner beginning in the 1960's. Extensive analysis has identified the most probable composition of the whiskers to be a silicate type glass. Sources of the growth material are outgassing products from the experiment and orbital atomic oxygen, which occurs naturally at the orbital altitudes of the LDEF mission in the form of neutral atomic oxygen. The highly ordered symmetry and directionality of the whiskers are attributed to the long term (5.8 year) stable flight orientation of the LDEF.

Zwiener, James M.↗

Effects of Rhenium Addition on the Temporal Evolution of the Nanostructure and Chemistry of a Model Ni-Cr-Al Superalloy: Analysis of the Coarsening Behavior - 2

The temporal evolution of the nanostructure and chemistry of a model Ni-8.5 at.% Cr-10 at.% Al alloy with the addition of 2 at.% Re was studied using transmission electron microscopy and atom-probe tomography in order to measure the number density and mean radius of the y' (LIZ) precipitates and the chemistry of the y'-precipitates and the y (fcc)-matrix. In this article, the coarsening behavior of the y'-precipitates is discussed in detail and compared with the Umantsev-Olson model for multi-component alloys. In addition, the experimental results are evaluated with PrecipiCalc(TradeMark) simulations. The results show that the diffusivities of the solute elements play a major role in the coarsening behavior of the y'-precipitates and that the addition of Re retards the coarsening kinetics and stabilizes the spheroidal morphology of the precipitates by reducing the interfacial energy.

Yoon, Kevin E.↗

The Erosion of Diamond and Highly Oriented Pyrolytic Graphite After 1.5 Years of Space Exposure

Polymers and other oxidizable materials on the exterior of spacecraft in the low Earth orbit (LEO) space environment can be eroded due to reaction with atomic oxygen (AO). Therefore, in order to design durable spacecraft, it is important to know the LEO AO erosion yield (Ey, volume loss per incident oxygen atom) of materials susceptible to AO reaction. The Polymers Experiment was developed to determine the AO Ey of various polymers and other materials flown in ram and wake orientations in LEO. The experiment was flown as part of the Materials International Space Station Experiment 7 (MISSE 7) mission for 1.5 years on the exterior of the International Space Station (ISS). As part of the experiment, a sample containing Class 2A diamond (100 plane) and highly oriented pyrolytic graphite (HOPG, basal and edge planes) was exposed to ram AO and characterized for erosion. The materials were salt-sprayed prior to flight to provide isolated sites of AO protection. The Ey of the samples was determined through post-flight electron microscopy recession depth measurements. The experiment also included a Kapton H witness sample for AO fluence determination. This paper provides an overview of the MISSE 7 mission, a description of the flight experiment, the characterization techniques used, the mission AO fluence, and the LEO Ey results for diamond and HOPG (basal and edge planes). The data is compared to the Ey of pyrolytic graphite exposed to four years of space exposure as part of the MISSE 2 mission. The results indicate that diamond erodes, but with a very low Ey of 1.58 +/- 0.04 x 10(exp -26) cm(exp 3)/atom. The different HOPG planes displayed significantly different amounts of erosion from each other. The HOPG basal plane had an Ey of 1.05 +/- 0.08 x 10(exp -24) cm(exp 3)/atom while the edge plane had a lower Ey of only 5.38 +/- 0.90 x 10(exp -25) -cm(exp 3)/atom. The Ey data from this ISS spaceflight experiment provides valuable information for understanding of chemistry and chemical structure dependent modeling of AO erosion.

erosion↗

Erosion Results of the MISSE 7 Polymers Experiment and Zenith Polymers Experiment After 1.5 Years of Space Exposure

Polymers and other oxidizable materials on the exterior of spacecraft in the low Earth orbit (LEO) space environment can be eroded due to reaction with atomic oxygen (AO). Therefore, in order to design durable spacecraft it is important to know the LEO AO erosion yield (E(sub y), volume loss per incident oxygen atom) of materials susceptible to AO reaction. Two spaceflight experiments, the Polymers Experiment and the Zenith Polymers Experiment, were developed to determine the AO E(sub y) of various polymers flown in ram, wake or zenith orientations in LEO. These experiments were flown as part of the Materials International Space Station Experiment 7 (MISSE 7) mission for 1.5 years on the exterior of the International Space Station (ISS). The experiments included Kapton H(TradeMark) witness samples for AO fluence determination in ram and zenith orientations. The Polymers Experiment also included samples to determine whether AO erosion of high and low ash containing polymers is dependent on fluence. This paper provides an overview of the MISSE 7 mission, a description of the flight experiments with details on the polymers flown, the characterization techniques used, the AO fluence for each exposure orientation, and the LEO E(sub y) results. The E(sub y) values ranged from 7.99x10(exp -28)cu cm/atom for TiO2/Al2O3 coated Teflon(TradeMark) fluorinated ethylene propylene (FEP) flown in the ram orientation to 1.22x10(exp -23cu cm/atom for polyvinyl alcohol (PVOH) flown in the zenith orientation. The E(sub y) of similar samples flown in different orientations has been compared to help determine solar exposure and associated heating effects on AO erosion. The E(sub y) data from these ISS spaceflight experiments provides valuable information for LEO spacecraft design purposes.

Teflon↗

Erosion Results of the MISSE 8 Polymers Experiment After 2 Years of Space Exposure on the International Space Station

Polymers and other oxidizable materials on the exterior of spacecraft in the low Earth orbit (LEO) space environment can be eroded due to reaction with atomic oxygen (AO). Therefore, in order to design durable spacecraft, it is important to know the LEO AO erosion yield (E(sub y), volume loss per incident oxygen atom) of materials susceptible to AO reaction. A spaceflight experiment, called the Polymers Experiment, which contained 42 samples, was developed to determine the effect of solar exposure on the AO E(sub y) of fluoropolymers flown in ram, wake, or zenith orientations. The Polymers Experiment was exposed to the LEO space environment on the exterior of the International Space Station (ISS) as part of the Materials International Space Station Experiment 8 (MISSE 8) mission. The MISSE 8 mission included samples flown in a zenith/nadir orientation for 2.14 years in the MISSE 8 Passive Experiment Container (PEC), and samples flown in a ram/wake orientation for 2.0 years in the Optical Reflector Materials Experiment-III (ORMatEIII) tray. The experiment included Kapton H (Registered Trademark) witness samples for AO fluence determination in each orientation. This paper provides an overview of the MISSE 8 mission, a description of the flight experiment with details on the polymers flown, the characterization techniques used, the AO fluence for each exposure orientation, and the LEO E(sub y) results. The E(sub y) of Teflon fluorinated ethylene propylene (FEP) samples flown in ram, wake, and zenith orientations have been compared, and the E(sub y) was found to be highly dependent on orientation and therefore environmental exposure. The FEP E(sub y) was found to directly correlate with the solar exposure/AO fluence ratio showing the effect of solar radiation and/or heating due to solar exposure on FEP erosion. In addition, back-surface carbon painted FEP (C-FEP) flown in the zenith orientation had a significantly higher E(sub y) than clear FEP or Al-FEP further indicating that heating has a significant impact on the erosion of FEP. This experiment provides valuable LEO flight data on the erosion of Teflon FEP, a commonly used spacecraft thermal insulation.

Teflon↗

Rapid solidification of metallic particulates

In order to maximize the heat transfer coefficient the most important variable in rapid solidification is the powder particle size. The finer the particle size, the higher the solidification rate. Efforts to decrease the particle size diameter offer the greatest payoff in attained quench rate. The velocity of the liquid droplet in the atmosphere is the second most important variable. Unfortunately the choices of gas atmospheres are sharply limited both because of conductivity and cost. Nitrogen and argon stand out as the preferred gases, nitrogen where reactions are unimportant and argon where reaction with nitrogen may be important. In gas atomization, helium offers up to an order of magnitude increase in solidification rate over argon and nitrogen. By contrast, atomization in vacuum drops the quench rate several orders of magnitude.

Grant, N. J.↗

Rapid solidification of metallic particulates

In order to maximize the heat transfer coefficient the most important variable in rapid solidification is the powder particle size. The finer the particle size, the higher the solidification rate. Efforts to decrease the particle size diameter offer the greatest payoff in attained quench rate. The velocity of the liquid droplet in the atmosphere is the second most important variable. Unfortunately the choices of gas atmospheres are sharply limited both because of conductivity and cost. Nitrogen and argon stand out as the preferred gases, nitrogen where reactions are unimportant and argon where reaction with nitrogen may be important. In gas atomization, helium offers up to an order of magnitude increase in solidification rate over argon and nitrogen. By contrast, atomization in vacuum drops the quench rate several orders of magnitude. Previously announced in STAR as N82-26433

Grant, N. J.↗