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NASA NTRS2017

Revised Models of Interstellar Nitrogen Isotopic Fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom–molecular ion and ion–molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirström et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral–neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

astrochemistry – molecular processes – comets: gen↗
NASA NTRS2017

Revised Models of Interstellar Nitrogen Isotopic Fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of (15)N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense loud chemistry show that the revised (15)N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirstrom et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included (15)N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing (15)N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching (14)N/(15)N ratios of > 2000. Taking the updated nitrogen chemistry into account, no sigificant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the (14)N/(15)N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk (15)N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

Astrochemistry↗
NASA NTRS1987

Effects of charged particles on the surfaces of the satellites of Uranus

Measurements of the ion and electron fluxes in the Uranian magnetosphere made by the low-energy charged-particle (LECP) instrument on the Voyager 2 spacecraft are used to discuss possible particle-induced modifications of the moons and rings of Uranus. The energy spectra of the orbit-integrated particle dosages expected on the major moons are derived from the LECP measurements of particle intensities and pitch-angle distributions. Laboratory-derived results on charged-particle-induced chemical and physical modifications of H2O, CH4, CO, and CO2 ions are used. The erosion rates of water ice and the darkening of organic ices on the surfaces of the moons are estimated from the orbit-integrated fluxes. Significant darkening of fresh organic ices to depths of the order of 1 micron is expected to occur for times as short as a few thousand years. Darkening at deeper depths will occur at increasingly longer times. The implications of these results for the interpretation of remote-sensing data are discussed.

Lanzerotti, L. J.↗
NASA NTRS1997

Effect of Artificial Gravity: Central Nervous System Neurochemical Studies

The major objective of this project was to assess chemical and morphological modifications occurring in muscle receptors and the central nervous system of animals subjected to altered gravity (2 x Earth gravity produced by centrifugation and simulated micro gravity produced by hindlimb suspension). The underlying hypothesis for the studies was that afferent (sensory) information sent to the central nervous system by muscle receptors would be changed in conditions of altered gravity and that these changes, in turn, would instigate a process of adaptation involving altered chemical activity of neurons and glial cells of the projection areas of the cerebral cortex that are related to inputs from those muscle receptors (e.g., cells in the limb projection areas). The central objective of this research was to expand understanding of how chronic exposure to altered gravity, through effects on the vestibular system, influences neuromuscular systems that control posture and gait. The project used an approach in which molecular changes in the neuromuscular system were related to the development of effective motor control by characterizing neurochemical changes in sensory and motor systems and relating those changes to motor behavior as animals adapted to altered gravity. Thus, the objective was to identify changes in central and peripheral neuromuscular mechanisms that are associated with the re-establishment of motor control which is disrupted by chronic exposure to altered gravity.

Fox, Robert A.↗
NASA NTRS1991

Stratospheric soot - Cloud forming properties and transport processes

Soot enters the stratosphere either from the troposphere in deep thunderstorm convection, predominantly in the tropics, from midlatitude forest fires, and directly from aircraft flying above the tropopause. Particles emitted from jet aircraft are relatively ineffective as cloud droplet condensation nuclei (less than 1 percent) compared with those from forest fires (above 50 percent). Chemical and other modification during aging of the particles may influence these results in some circumstances; cloud nucleating properties can be used as a soot tracer. Such aerosols, as they grow to haze drops and ilute in increasing humidity, may form ice particles in the cold polar stratosphere or in tropical cumuli anvils at 18 to 20 km altitude at temperatures as low as -90 C. Ice may also form as particles are removed by descent through troposphere folds and enter midlatitude cirrus at levels below -40 C. In the stratosphere, ice particles may provide surfaces that catalyze heterogeneous chemical reactions; in the upper troposphere, the optical depths of cirrus clouds may be significantly increased.

Hallett, John↗
NASA NTRS1989

Navier-Stokes analysis of cold scramjet-afterbody flows

The progress of two efforts in coding solutions of Navier-Stokes equations is summarized. The first effort concerns a 3-D space marching parabolized Navier-Stokes (PNS) code being modified to compute the supersonic mixing flow through an internal/external expansion nozzle with multicomponent gases. The 3-D PNS equations, coupled with a set of species continuity equations, are solved using an implicit finite difference scheme. The completed work is summarized and includes code modifications for four chemical species, computing the flow upstream of the upper cowl for a theoretical air mixture, developing an initial plane solution for the inner nozzle region, and computing the flow inside the nozzle for both a N2/O2 mixture and a Freon-12/Ar mixture, and plotting density-pressure contours for the inner nozzle region. The second effort concerns a full Navier-Stokes code. The species continuity equations account for the diffusion of multiple gases. This 3-D explicit afterbody code has the ability to use high order numerical integration schemes such as the 4th order MacCormack, and the Gottlieb-MacCormack schemes. Changes to the work are listed and include, but are not limited to: (1) internal/external flow capability; (2) new treatments of the cowl wall boundary conditions and relaxed computations around the cowl region and cowl tip; (3) the entering of the thermodynamic and transport properties of Freon-12, Ar, O, and N; (4) modification to the Baldwin-Lomax turbulence model to account for turbulent eddies generated by cowl walls inside and external to the nozzle; and (5) adopting a relaxation formula to account for the turbulence in the mixing shear layer.

Baysal, Oktay↗
NASA NTRS1975

A nonlinear model for gas chromatograph systems

Fundamental engineering design techniques and concepts were studied for the optimization of a gas chromatograph-mass spectrometer chemical analysis system suitable for use on an unmanned, Martian roving vehicle. Previously developed mathematical models of the gas chromatograph are found to be inadequate for predicting peak heights and spreading for some experimental conditions and chemical systems. A modification to the existing equilibrium adsorption model is required; the Langmuir isotherm replaces the linear isotherm. The numerical technique of Crank-Nicolson was studied for use with the linear isotherm to determine the utility of the method. Modifications are made to the method eliminate unnecessary calculations which result in an overall reduction of the computation time of about 42 percent. The Langmuir isotherm is considered which takes into account the composition-dependent effects on the thermodynamic parameter, mRo.

Feinberg, M. P.↗
NASA NTRS1984

Formation of ion damage tracks

A new model is proposed to explain both localized damage regions and preferential etching of damage tracks caused by the passage of energetic ions in insulators. The formation of each region of extended defects is initiated by the Auger decay of a vacancy produced in an inner electronic shell of an atom of the insulator by an incident ion. This decay produces an intense source of ionization within a small volume around the decaying atom, which causes decomposition of the material in a manner similar to that observed in pulsed laser irradiation. The resulting chemical or crystalline modification of the material is the latent track, which can be preferentially etched due to its changed structure.

Tombrello, T. A.↗
NASA NTRS1985

Silicon carbide-silicon nitride fibers: Preparation and characterization of polycarbosilazane precursors

This study examines the effect of modifications of the chemical structure of the monomers on the properties of the polymeric precursor and and ceramic fibers. A group of silaneamines, R'-Si (NH-R) sub 3, taken from the series where R' is methyl or phenyl and R is n-propyl, n-butyl, phenyl or allyl, are converted to polycarbosilazanes by heating in excess of 500 C. Resins obtained from this polymerization are characterized by NMR and IR spectroscopy and GPC. Each resin is tested for fiber-forming properties. Resin samples and fibers are hydrolytically cured. Thermogravimetric analyses are conducted on the cured resins to compare the relative thermal stability and examine the pyrolysis process. Cured fibers are tested for tensil strength.

Crouse, D. J.↗
NASA NTRS1995

Active Experiments in Space Plasmas; Symposium D4.1 of Commission D, COSPAR Scientific Assembly, 30th, Hamburg, Germany, July 11-21, 1994

Papers from the conference are presented and cover the following topics: ion and electron beams; ionospheric modification; spacecraft interactions; chemical releases; and plasma waves. Auroras and plasma emissions are reported from electron beam injection experiments on the EXCEDE 3 rocket and APEX satellite respectively. The important parameters affecting the charging of spacecraft during the operation of electron guns is covered. The Active Magnetospheric Particle Acceleration Satellite (AMPAS) mission utilizing dual-payload tethered satellites and both up and downward directed electron beams is proposed to study the magnetosphere. Recent results and associated theories from the Sura, Arecibo and Troms ionospheric heating facitlites are presented. The effects of neutral gases on spacecraft charging are examined in a series of rocket flights. Many results from the Combined Release and Radiation Effects Satellite chemical release experiments are presented.

Rietveld, M. T.↗
NASA NTRS1998

X-ray Diffraction Studies of the Structure and Thermochemistry of Alkaline-Earth Oxide-Coated Thermionic Cathodes

NASA LeRC has a broad, active cathode technology development program in which both experimental and theoretical studies are being employed to further development of thermionic cathodes for use as electron sources in vacuum devices for communications and other space applications. One important type of thermionic cathode under development is the alkaline-earth oxide-coated (BaO, SrO, CaO) cathode. Significant improvements in the emission characteristics of this cathode have been obtained through modification of the chemical composition and morphology of the oxide coating, with the best result thus far coming from the addition of In2O3 and Sc2O3. Whereas the In2O3 produces a finer, more uniform particle structure, the exact chemical state and role of the Sc2O3 in the emission enhancement is unknown. The purpose of this cooperative agreement is to combine the studies of the surface chemistry and electron emission at NASA LeRC of chemically modified oxide coatings with a study of the thermochemistry and crystal structure using X-ray diffraction equipment and expertise at Clark Atlanta University (CAU). The study at CAU is intended to provide the description and understanding of the structure and thermochemistry needed for further improvement and optimization of the modified coatings. A description of the experimental procedure, preliminary X-ray diffraction test results, together with the design of an ultrahigh vacuum chamber necessary for high temperature thermochemistry studies will be presented.

Karikari, E. K.↗
NASA NTRS1997

Measurements of Ice Nucleating Aerosols in the Upper Troposphere and Lower Stratosphere

Our major accomplishments during Year 1 were: Development of aerosol and crystal collection techniques. Development of single-particle chemical characterization techniques. Modification of system design for DC-8 and initial testing. Our major accomplishments during Year 2 were: Completion of system design and proof-of-concept experiments. Participation in SUCCESS mission. Reporting of theoretical and laboratory findings in the scientific literature. Reporting of initial SUCCESS results at scientific meetings. Our major accomplishments during Year 3 were: Data reduction and submission of all SUCCESS data to the archive. Participation in SUCCESS data comparison workshops. Reporting of SUCCESS results at the AEAP Meeting. Organization of CN counter intercomparison workshop. Preparation of three manuscripts submitted to the GRL SUCCESS Special Issue.

Kreidenweis, S. M.↗
NASA NTRS2006

Stability of Atmospheric-Pressure Plasma Induced Changes on Polycarbonate Surfaces

Polycarbonate films are subjected to plasma treatment in a number of applications such as improving adhesion between polycarbonate and silicon alloy in protective and optical coatings. The changes in surface chemistry due to plasma treatment have tendency to revert back. Thus stability of the plasma induced changes on polymer surfaces over desired time period is very important. The objective of this study was to examine the effect of ageing on atmospheric pressure helium-plasma treated polycarbonate (PC) sample as a function of treatment time. The ageing effects were studied over a period of 10 days. The samples were plasma treated for 0.5, 2, 5 and 10 minutes. Contact angle measurements were made to study surface energy changes. Modification of surface chemical structure was examined using, X-ray Photoelectron Spectroscopy (XPS). Contact angle measurements on untreated and plasma treated surfaces were made immediately, 24, 48, 72 and 96 hrs after treatment. Contact angle decreased from 93 deg for untreated sample to 30 deg for sample plasma treated for 10 minutes. After 10 days the contact angles for the 10 minute plasma treated sample increased to 67 deg, but it never reverted back to that of untreated surface. Similarly the O/C ratio increased from 0.136 for untreated sample to 0.321 for 10 minute plasma treated sample indication increase in surface energy.

Sharma, Rajesh↗
NASA NTRSDate not supplied

Unraveling Solar Wind Space Weathering of Carbon-Rich Asterods: Low-Flux VS. High-Flux Ion Irradiation of Murchison

Introduction: Space weathering processesalter the microstructural, compositional, and optical properties of airless planetary surfaces.Solar wind space weatheringforms ion-damaged rims within the outermost ~100 nm of regolith grains through atomic-displacements and implantation of energetic H+and He+ions[1]. Transmission electron microscope(TEM)studies of space weathered Itokawa and lunar olivine particles reveal predominantly nanocrystalline solar wind-damaged rims with only minor regions of amorphization[2-5]. This finding differs from laboratoryion irradiation experiments in which samples become amorphous at fluences 2-3 orders of magnitude lower than the independentlyconstrained fluences for still-crystalline natural samples [6-7].Ion flux is generally considered to have a secondaryeffectcompared to fluence in these irradiation experiments. However, solar wind irradiation of natural samples occurs at a flux that is ~4-5 orders of magnitude lower than whatisused inlaboratory simulations (e.g., [6,8-9]). Constraining how the very low ion flux of solar wind influences the microstructural, chemical, and spectral alteration of silicate minerals will improve our understanding of solar wind space weathering and aid in the analysis of returned samples from the Hayabusa2 and OSIRIS-REx missions. Here we report results from low-and high-flux ion irradiation experiments on the Murchison (CM2)meteoritewithcomparable total fluences. Methods: We performed low-flux and high-flux He+(4 keV) and H+(1 keV) irradiation experiments on separate, dry-cut Murchison slabs. Low-flux He+irradiation reached a total fluence of 2.1 x 1016ions/cm2(~400 years of exposure at Bennu) using a flux of 3.6 x 1011ions/cm2/s; low-flux H+irradiation reached a total fluence of 3.9 x 1016ions/cm2(~30 years) using a flux of 6.6 x 1011ions/cm2/s. High-flux He+irradiation reached a total fluence of 2.0 x 1016ions/cm2(~400 years)using a flux of 9.1 x 1012ions/cm2/s; high-flux H+irradiation reached a total fluence of 5.8 x 1016ions/cm2(~50 years)using flux of 8.4 x 1012ions/cm2/s. By irradiating to similar total fluences in both the low-flux and high-flux experiments, we can better isolate and evaluatethe effects of ion flux. Differences between unirradiatedand irradiated surfaces are determined using threeanalytical techniques:(1) in situX-ray photoelectron spectroscopy(XPS) reveals changes in surface chemistry,(2) visible to near-infrared spectroscopy (VNIR; 0.35-2.5 μm) highlights changes in spectraltrends, such as albedo and slope, and (3) TEM and energy-dispersive X-ray spectroscopy (EDS) identifieschanges in nanoscale structure and elemental composition within olivine and matrix electron-transparent thin sections prepared using focused ion beam scanning electron microscopy (FIB-SEM). Results and Discussion: XPS analyses of the low-fluxand high-fluxHe+-and H+-irradiated samples showa minorreduction in surface carbon contentand chemicalreduction ofFe3+to Fe2+. The latter result is consistent with the higher Fe2+/Fe3+ratios observed in phyllosilicate-rich space weathered rims of Ryugu grains [10].VNIR analyses suggest that the low-flux H+-irradiated spectrum has a slightly bluer slope (over 0.65-2.5 μm) compared to the unirradiated VNIR spectrum from [9] while the low-flux He+-irradiated spectral slope is comparable to the unirradiated surface. Both the high-flux He+-and H+-irradiated VNIR spectra exhibitslightlyhigheralbedos at shorter wavelengths relativeto their unirradiated counterparts, with He+irradiation yielding a greater change. Thus far, the low-flux He+-irradiated matrix and olivine FIBsections as well as the low-flux H+-irradiated olivine FIBsection have been examined with TEM. The surfaces of all three samplesshowless vesiculation than high-flux/high-fluenceirradiated matrix and olivine samples from [9]. The depth of phyllosilicate amorphization in thelow-fluxHe+-irradiated matrix FIBsection varieslaterally, with crystalline domains occurring as shallow as ~25 nm in some regions. Thelow-flux He+-irradiated olivine FIBsection has acontinuous,~40-90 nm thick ion-affected layer with polycrystalline and amorphous microstructures. The low-flux H+-irradiated olivine sampleexhibits a distinct, ~10-40 nm ion-affected layer whose uppermost ~20 nmin thicker regions is predominantly amorphous.Continuing to compare results from this work to those from [9] will provide a comprehensive understanding of how ion flux impacts the microstructural, chemical, and optical modification of various mineral phases and, in turn,help identify space weathering features from parent body alteration in Hayabusa2 and OSIRIS-REx returned samples.

D L Laczniak↗
NASA NTRS1979

Carbon fiber modification

The effect of several chemical treatments on the electrical and mechanical properties of carbon fibers was investigated with an optimum goal of increasing the electrical resistivity by a factor of 1000 without appreciably changing the mechanical properties. It was possible to effect resistivity increases from 10 to 50 percent without adversely affecting the tensile strength or Young's modulus for T-300 and C-6000 PAN fibers by treatments with either AlCl3 or nitric acid mixtures. Larger increases in the resistivity were produced with pitch fibers treated with nitric acid mixtures. This treatment also produced a partial decomposition of the pitch fiber and deterioration of the mechanical properties. The rationale behind the approch was to immobilize the conductivity producing pi electrons in the microscopic aromatic structure of the carbon fibers without destroying the strength producing sigma bonds. The investigations indicate that certain chemical treatments can produce such results, but the total reduction in the electrical conductivity which was achieved was not large enough to impact on problems which might arise from the high conductivities of the fibers.

Thompson, T. E.↗
NASA NTRS1983

Statistical mechanics of neocortical interactions - Dynamics of synaptic modification

A recent study has demonstrated that several scales of neocortical interactions can be consistently analyzed with the use of methods of modern nonlinear nonequilibrium statistical mechanics. The formation, stability, and interaction of spatial-temporal patterns of columnar firings are explicitly calculated, to test hypothesized mechanisms relating to information processing. In this context, most probable patterns of columnar firings are associated with chemical and electrical synaptic modifications. It is stressed that synaptic modifications and shifts in most-probable firing patterns are highly nonlinear and interactive sets of phenomena. A detailed scenario of information processing is calculated of columnar coding of external stimuli, short-term storage via hysteresis, and long-term storage via synaptic modification.

Ingber, L.↗
NASA NTRS1995

CRRES combined radiation and release effects satellite program

The various regions of the magnetosphere-ionosphere system are coupled by flows of charged particle beams and electromagnetic waves. This coupling gives rise to processes that affect both technical and non-technical aspects of life on Earth. The CRRES Program sponsored experiments which were designed to produce controlled and known input to the space environment and the effects were measured with arrays of diagnostic instruments. Large amounts of material were used to modify and perturb the environment in a controlled manner, and response to this was studied. The CRRES and PEGSAT satellites were dual-mission spacecraft with a NASA mission to perform active chemical-release experiments, grouped into categories of tracer, modification, and simulation experiments. Two sounding rocket chemical release campaigns completed the study.

Giles, B. L.↗
NASA NTRS1993

Vaporization by shock loading of albite, jadeite, and pyrex glass: Experimental study

Produced by shock experiments impact melts of albite, jadeite, and Pyrex glass demonstrate a loss of both Na and Al relative to Si, which can be due to selective vaporization. It is suggested that the high volatility of Al is related to volatility of a Na-Al compound of proposed NaAlO2 composition. The similar loss of Al and Na seems to be possible during tektite-forming processes. A degree of selective vaporization and modification of a melt chemical composition during impact processes is still poorly understood. The selective vaporization of some elements has been shown by shock experiments. The vaporization and condensation processes can take place in the lunar regolith. On this basis, there are hypotheses explaining differentiation of planetary bodies through the impact vaporization. On the other hand, studies of tektites, impact glasses, and lunar soils show that bulk compositions of impact melts are not modified significantly. In order to estimate degree of the vaporization during shock fusion, chemical compositions of experimentally produced impact melts were studied. We chose Al-containing compositions, because a high volatilization of Al during unequlibrated evaporization had been demonstrated.

Badjukov, D. D.↗