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Wavelengths, f-Values, and Cross Sections in the UV Spectra of Astrophysical, Atoms, Ions, and Molecules

Data analysis for Fe III was completed in 2004. The new spectra give wavelengths and some energy levels for Fe III that are at least an order of magnitude more accurate than values in the literature. However, the data set is missing - because they are outside the wavelength range that we can study at Imperial College or with ancillary FT spectroscopy measurements at NIST - important transitions that would allow all energy levels to be determined with improved accuracy. We are assessing collaborations at other labs. We have made test runs with a number of cathodes (pure metals and alloys) in the Penning discharge source and selected four iron group (3d) elements, Cr, Mn, Co, and Ni, for further measurements. Cathodes of pure Cr and Co and an alloy of Ni were found to be best. Mn has not nm stably yet, and other cathode geometries or alloys may need to be assessed. Optimum Penning discharge (PD) lamp conditions (buffer gas, gas pressure, and current/voltage) were established for Co, and investigations are underway for Cr and Ni. Definitive measurements for Co await purchase of new mirrors and photomultiplier tubes that will improve signal to noise ratio. Our plan for the next year is to continue evaluating cathodes and operating conditions through March 05, and then to begin definitive measurements. The UV wavelength measurements made at Imperial College with the unique UV FT spectrometer will be complemented by visible and near IR range measurements at NIST in June and/or July. Approximately one year from now, we intend to visit Lund University to collaborate on lifetime measurements that will allow our branching ration data to be used to determine f-values.

Raymond, John C.↗

Iron Catalyst Chemistry in High Pressure Carbon Monoxide Nanotube Reactor

The high-pressure carbon monoxide (HiPco) technique for producing single wall carbon nanotubes (SWNT) is analyzed using a chemical reaction model coupled with properties calculated along streamlines. Streamline properties for mixing jets are calculated by the FLUENT code using the k-e turbulent model for pure carbon monixide. The HiPco process introduces cold iron pentacarbonyl diluted in CO, or alternatively nitrogen, at high pressure, ca. 30 atmospheres into a conical mixing zone. Hot CO is also introduced via three jets at angles with respect to the axis of the reactor. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Cluster reaction rates are from Krestinin, et aI., based on shock tube measurements. Another model is from classical cluster theory given by Girshick's team. The calculations are performed on streamlines that assume that a cold mixture of Fe(CO)5 in CO is introduced along the reactor axis. Then iron forms clusters that catalyze the formation of SWNTs from the Boudouard reaction on Fe-containing clusters by reaction with CO. To simulate the chemical process along streamlines that were calculated by the fluid dynamics code FLUENT, a time history of temperature and dilution are determined along streamlines. Alternative catalyst injection schemes are also evaluated.

Scott, Carl D.↗

Texturing and residual stress in metals as a result of sliding

Pole figures of the texturing produced by friction in the alloys Cu - 10 at. % Sn, Cu - 10 at. % Si, 440 C stainless steel, and AISI 52100 bearing steel were obtained with an energy-dispersive X-ray diffractometer. While the texturing behavior of these alloys is generally similar to that of pure metals, the 52100 steel and the Cu5Si phase of Cu - 10 at. % Si show no texturing at the loads and speeds used in this experiment. Photographic methods were used in an attempt to measure the uniform residual stress in the wear tracks produced on some pure metals. The stress in copper and iron was, however, below the limit of detectability - about 4.3 x 10 to the 7th power N/sq m (6000 psi). Line broadening under all test conditions in the case of copper and at high load and speed conditions in iron is attributed, at least in part, to the reduction of crystallite size and, perhaps, to nonuniform residual stress, as well.

Wheeler, D. R.↗

High temperature deformation of hot-pressed polycrystalline orthoenstatite

Artificial hot pressed polycrystalline samples were prepared from purified powder of Bamble, Norway, orthoenstatite, (Mg0.86Fe0.14)SiO3. The uniaxial creep behavior of the polycrystalline orthoenstatite was studied over stress ranges of 10-180 MPa and temperatures of 1500-1700 K (0.82-0.93 T sub m) under two different oxygen fugacities, namely equilibrium (Mo-MoO2 buffer) and a reducing (graphite heating element) atmosphere, respectively. An intergranular glassy phase of different compositions with a cavitational creep deformation were observed. In the Mo-MoO2 buffer atmosphere with PO2 approx. 10 to the minus 11 power - 10 to the minus 13 power atmospheres, the results of an analytical electron microscopy analysis indicate that the glassy phases are richer in Ca and Al due to the residual impurities after hot pressing. In the reducing atmosphere with an oxygen fugacity of PO2 approx. 10 to the minus 3 power - 10 to the minus 25 power atmospheres, the results of analytical electron microscopy analysis indicate that the glassy phase is almost pure silica with the presence of free iron precipitate on grain facets and at triple junctions due to the reduction of bulk materials.

Dehghan-Banadaki, A.↗

Chromosomal Aberrations in DNA Repair Defective Cell Lines: Comparisons of Dose Rate and Radiation Quality

Chromosome aberration yields were assessed in DNA double-strand break repair (DSB) deficient cells after acute doses of gamma-rays or high-LET iron nuclei, or low dose-rate (0.018 Gy/hr) gamma-rays. We studied several cell lines including fibroblasts deficient in ATM (product of the gene that is mutated in ataxia telangiectasia patients) or NBS (product of the gene mutated in the Nijmegen breakage syndrome), and gliomablastoma cells that are proficient or lacking in DNA-dependent protein kinase, DNA-PK activity. Chromosomes were analyzed using the fluorescence in-situ hybridization (FISH) chromosome painting method in cells at the first division post-irradiation and chromosome aberrations were identified as either simple exchanges (translocations and dicentrics) or complex exchanges (involving >2 breaks in 2 or more chromosomes). Gamma radiation induced higher yields of both simple and complex exchanges in the DSB repair defective cells than in the normal cells. The quadratic dose-response terms for both chromosome exchange types were significantly higher for the ATM and NBS defective lines than for normal fibroblasts. However, the linear dose-response term was significantly higher only for simple exchanges in the NBS cells. Large increases in the quadratic dose response terms indicate the important roles of ATM and NBS in chromatin modifications that facilitate correct DSB repair and minimize aberration formation. Differences in the response of AT and NBS deficient cells at lower doses suggests important questions about the applicability of observations of radiation sensitivity at high dose to low dose exposures. For all iron nuclei irradiated cells, regression models preferred purely linear and quadratic dose responses for simple and complex exchanges, respectively. All the DNA repair defective cell lines had lower Relative biological effectiveness (RBE) values than normal cells, the lowest being for the DNA-PK-deficient cells, which was near unity. To further investigate the sensitivity differences for low and low high doses, we performed chronic low dose-rate irradiation, and have begun studies with ATM and Nibrin inhibitors and siRNA knockout of these proteins. Results support the conclusion that for the endpoint of simple chromosomal aberrations (translocation or dicentrics), the increased radiation sensitivity of AT cells found at high doses (>1 Gy) does not carry over to low doses or doserates, while NBS cells show increased sensitivity for both high and low dose exposures.

George, K. A.↗

Comparison of Nickel XANES Spectra and Elemental Maps from a Ureilite, a LL3.8 Ordinary Chondrite, Two Carbonaceous Chondrites and Two Large Cluster IDPs

Nickel in the extraterrestrial world is commonly found in both Fe-Ni sulfide and Fe-Ni met-al forms [1] and in the pure metal state in the interior of iron meteorites where it is not easily oxidized. Ni is also found in olivine, pyroxene and glasses and in some melts the partitioning of Ni between the olivines and glass is controlled by the amount of S in the melt [2]. Its most common valence state is Ni(2+) but Ni also occurs as Ni(0), Ni(+), and Ni(3+) and rarely as Ni(2-), Ni(1-) and Ni(4+) [3]. It's valence state in olivines is Ni(2+) in octa-hedral coordination on the M1 site and rarely on the M2 site.[4]. The chemical sensitivity of X-ray absorp-tion near-edge structure (XANES) spectroscopy is well established and can be used to determine not only va-lence states but also coordination sites [5]. We report here Ni XANES spectroscopy and elemental maps collected from 2 carbonaceous chondrites, 2 large clus-ter IDPs, 1 ureilite and 1 LL3 orginary chondrite.Using XANES it may be possible to find a common trait in the large cluster IDPs that will also be found in mete-orite samples.

Wirick, S.↗

Adhesion, friction, wear, and lubrication research by modern surface science techniques.

The field of surface science has undergone intense revitalization with the introduction of low-energy electron diffraction, Auger electron spectroscopy, ellipsometry, and other surface analytical techniques which have been sophisticated within the last decade. These developments have permitted submono- and monolayer structure analysis as well as chemical identification and quantitative analysis. The application of a number of these techniques to the solution of problems in the fields of friction, lubrication, and wear are examined in detail for the particular case of iron; and in general to illustrate how the accumulation of pure data will contribute toward the establishment of physiochemical concepts which are required to understand the mechanisms that are operational in friction systems. In the case of iron, LEED, Auger and microcontact studies have established that hydrogen and light-saturated organic vapors do not establish interfaces which prevent iron from welding, whereas oxygen and some oxygen and sulfur compounds do reduce welding as well as the coefficient of friction. Interpretation of these data suggests a mechanism of sulfur interaction in lubricating systems.

Keller, D. V., Jr.↗

Reaction of iron with hydrogen chloride-oxygen mixtures at 550 C

The reaction of iron with 1 percent HCl/0-50 percent O2/Ar has been studied at 550 C with thermogravimetry to monitor kinetics and scanning electron microscopy to characterize product morphologies. In addition, the volatile species were identified with an atmospheric pressure sampling mass spectrometer. The reaction of 1 percent HCl/Ar produces FeCl2. The reactions of 1 percent HCl/1, 10, 50 percent O2/Ar produce Fe2O3, Fe3O4, FeCl2, and FeCl3. In each case condensed phase chlorides form at the oxide/metal interface where the oxygen potential is low. The 10 and 50 percent oxygen mixtures have kinetics in the first 3 hr similar to pure oxidation with some deviations due to iron-chloride formation. The 1 percent oxygen mixture shows enhanced reaction rates over oxidation, very likely due to the formation of a porous scale.

Jacobson, N. S.↗

The Investigation of Magnesium Perchlorate/Iron Phase-mineral Mixtures as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detect-ed O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumber-land (CB) drill hole materials in Gale Crater (Fig. 1) [1,2]. Chlorinated hydrocarbons have also been detect-ed by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS) [1,2,3,4]. These detections along with the detection of perchlorate (ClO4(-)) by the Mars Phoenix Lander's Wet Chemistry Laboratory (WCL) [5] suggesting perchlo-rate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of individual per-chlorates has yet to provide an unequivocal tempera-ture match to the SAM O2 and HCl release data [1,2]. Catalytic reactions of Fe phases in the Gale Crater ma-terial with perchlorates can potentially reduce the de-composition temperatures of these otherwise pure per-chlorate/chlorate phases [e.g., 6,7]. Iron mineralogy found in the Rocknest materials when mixed with Ca-perchlorate was found to cause O2 release temperatures to be closer match to the SAM O2 release data and enhance HCl gas releases. Exact matches to the SAM data has unfortnunately not been achieved with Ca-perchlorate-Fe-phase mixtures [8]. The effects of Fe-phases on magnesium perchlorate thermal decomposi-tion release of O2 and HCl have not been evaluated and may provide improved matches to the SAM O2 and HCl release data. This work will evaluate the thermal decomposition of magnesium perchlorate mixed with fayalite/magnetite phase and a Mauna Kea palagonite (HWMK 919). The objectives are to 1) summarize O2 and HCl releases from the Gale Crater materials, and 2) evaluate the O2 and HCl releases from the Mg-perchlorate + Fe phase mixtures to determine if Mg-perchlorate mixed with Fe-phases can explain the Gale Crater O2 and HCl releases.

Sutter, B.↗

Apollo 14 very low titanium glasses - Melting experiments in iron-platinum alloy capsules

This paper describes two techniques that have been developed to produce Fe-Pt alloy capsules for hgh-pressure experiments, and reports liquidus-phase relations of the Apollo 14 very low titanium glasses determined using Fe-rich capsules (a/Fe/ approximately 0.6). The liquid is multiply saturated with olivine and clinopyroxene at equal to or greater than 22 kbar. The multiple saturation is at least 3 kbar higher than that determined using pure Fe capsules and corresponds to a source region at least 60 km deeper if olivine and clinopyroxene were the residual phases. However, independent data on iron activity or oxygen fugacity of the glasses are still needed in order to choose a container of optimum composition. Preliminary experiments in Fe-poor alloy capsules suggest that the valence state of iron and the crystallization sequence in the melt have changed, possibly as a result of oxidizing materials entrapped during the iron-plating processes. The FeO content of the charge decreases linearly with increasing run duration in experiments using pure Fe capsules. The observation that iron-rich globules grow with time suggests that the equilibrium Fe (bleb) + Fe2O3 (liq) = 3 FeO (liq) might be established in the liquid at high pressure. If this explanation is correct, an appreciable amount of 'FeO' in the liquid could actually be Fe2O3, and some natural lunar volcanic glasses may contain ferric iron as well.

Chen, H.-K.↗

s-process studies in the light of new experimental cross sections - Distribution of neutron fluences and r-process residuals

A best set of neutron-capture cross sections has been evaluated for the most important s-process isotopes. With this data base, s-process studies have been carried out using the traditional model which assumes a steady neutron flux and an exponential distribution of neutron irradiations. The calculated sigma-N curve is in excellent agreement with the empirical sigma-N-values of pure s-process nuclei. Simultaneously, good agreement is found between the difference of solar and s-process abundances and the abundances of pure r-process nuclei. The abundance pattern of the iron group elements where s-process results complement the abundances obtained from explosive nuclear burning is discussed. The results obtained from the traditional s-process model such as seed abundances, mean neutron irradiations, or neutron densities are compared to recent stellar model calculations which assume the He-burning shells of red giant stars as the site for the s-process.

Kaeppeler, F.↗

Tribological characteristics of nitrogen (N+) implanted iron

The effect of implantation of nitrogen ions (1.5 MeV) on the friction and wear characteristics of pure ion sliding against M-50 steel (unimplanted) was studied in a pin-on-disk sliding friction apparatus. Test conditions included room temperature (25 C), a dry air atmosphere, a load of 1/2 kg (4.9 N), sliding velocities of 0.043 to 0.078 m/sec (15 to 25 rpm), a pure hydrocarbon lubricant (n-hexadecane), or a U.S.P. mineral oil and nitrogen ion implantation doses of 5x10 to the 15th power and 5x10 to the 17th power ions/sq cm. No differences in wear rates were observed in the low dose experiments. In the high dose experiments, small reductions in initial (40 percent) and steady state (20 percent) wear rates were observed for nitrogen implanted iron riders as compared with unimplanted controls. No differences in average friction coefficients were noted for either dose. Auger electron spectroscopy combined with argon ion bombardment revealed a subsurface Gaussian nitrogen distribution with a maximum concentration of 6 atomic percent at a depth of 0.8 microns. Similar analysis within the wear scar of an implanted rider after 20 microns of wear yielded only background nitrogen concentration. No inward migration of nitrogen ions was observed.

Jones, W. R.↗

Tribological characteristics of nitrogen (N+) implanted iron

The effect of implantation of nitrogen ions (1.5 MeV) on the friction and wear characteristics of pure ion sliding against M-50 steel (unimplanted) was studied in a pin-on-disk sliding friction apparatus. Test conditions included room temperature (25 C), a dry air atmosphere, a load of 1/2 kg (4.9 N), sliding velocities of 0.043 to 0.078 m/sec (15 to 25 rpm), a pure hydrocarbon lubricant (n-hexadecane), or a U.S.P. mineral oil and nitrogen ion implantation doses of 5x10 to the 15th power and 5x10 to the 17th power ions/sq cm. No differences in wear rates were observed in the low dose experiments. In the high dose experiments, small reductions in initial (40 percent) and steady state (20 percent) wear rates were observed for nitrogen implanted iron riders as compared with unimplanted controls. No differences in average friction coefficients were noted for either dose. Auger electron spectroscopy combined with argon ion bombardment revealed a subsurface Gaussian nitrogen distribution with a maximum concentration of 6 atomic percent at a depth of 0.8 microns. Similar analysis within the wear scar of an implanted rider after 20 microns of wear yielded only background nitrogen concentration. No inward migration of nitrogen ions was observed. Previously announced in STAR as N82-24322

Jones, W. R., Jr.↗

Effects of compositional variation on absorption spectra of lunar pyroxenes

Polarized absorption spectra of lunar pyroxenes with a range of iron, calcium, magnesium, titanium and chromium contents were measured on polished, oriented single crystals; spectral data on pure synthetic FeSiO3 were also recorded. The bands at 1 and 2 microns were found to vary significantly in position with composition within the pyroxene quadrilateral; wavelengths increased with increasing calcium and iron. In the visible region, a weak band at 640 nm correlates in intensity with Cr2O3, but not with titanium as had been previously suggested. The 505-nm ferrous iron peak is a sharp doublet in most low-calcium pyroxenes but a singlet in augites. A peak at 475 nm and an intense absorption edge below 700 nm correlated with titanium content.

Hazen, R. M.↗

Magnetic beneficiation of lunar soils

We will present a review of recent laboratory results obtained in dry magnetic separation of one gram samples of the minus 1 mm size fraction of five lunar soils of widely differing maturities. Two highland soils were investigated as potential sources of low iron content feed stocks for space manufacture of metals, including aluminum, silicon, and calcium. Pure anorthite was separated from the diamagnetic fraction of immature highland regolith. Three high titanium mare soils were investigated as potential sources of ilmenite for production of hydrogen and for recovery of He-3. Ilmenite and pyroxene were separated from the paramagnetic fractions of the mare basalts. Agglutinates and other fused soil components containing metallic iron were separated from the strongly magnetic fractions of all soils. We will present conceptual magnetic separation flow sheets developed from the laboratory data and designed for production of anorthite from highland soils and for production of ilmenite from mare soils. Using these flow sheets, we will discuss problems and opportunities associated with the magnetic separation of lunar soils. Separation of high-grade anorthite or other diamagnetic components at moderately high recovery can be achieved in processing immature highland soils. Further, while magnet weight is always an issue in magnetic separation technology, recent developments in both low temperature and high temperature superconductivity present unusual opportunities for magnet design specific to the lunar environment.

Mckay, D. S↗

Non-LTE line-blanketed model atmospheres of hot stars. 2: Hot, metal-rich white dwarfs

We present several model atmospheres for a typical hot metal-rich DA white dwarf, T(sub eff) = 60,000 K, log g = 7.5. We consider pure hydrogen models, as well as models with various abundances of two typical 'trace' elements-carbon and iron. We calculte a number of Local Thermodynamic Equilibrium (LTE) and non-LTE models, taking into account the effect of numerous lines of these elements on the atmospheric structure. We demostrate that while the non-LTE effects are notvery significant for pure hydrogen models, except for describing correctly the central emission in H-alpha they are essential for predicting correctly the ionization balance of metals, such as carbon and iron. Previously reported discrepancies in LTE abundances determinations using C III and C IV lines are easily explained by non-LTE effects. We show that if the iron abundance is larger than 10(exp -5), the iron line opacity has to be considered not only for the spectrum synthesis, but also in the model construction itself. For such metal abundances, non-LTE metal line-blanketed models are needed for detailed abundance studies of hot, metal-rich white dwarfs. We also discuss the predicted Extreme Ultraviolet (EUV) spectrum and show that it is very sensitive to metal abundances, as well as to non-LTE effects.

Lanz, T.↗

Additive Manufacturing and Characterization of Polylactic Acid (PLA) Composites Containing Metal Reinforcements

Additive manufacturing of polymeric systems using 3D printing has become quite popular recently due to rapid growth and availability of low cost and open source 3D printers. Two widely used 3D printing filaments are based on polylactic acid (PLA) and acrylonitrile butadiene styrene (ABS) systems. PLA is much more environmentally friendly in comparison to ABS since it is made from renewable resources such as corn, sugarcane, and other starches as precursors. Recently, polylactic acid-based metal powder containing composite filaments have emerged which could be utilized for multifunctional applications. The composite filaments have higher density than pure PLA, and the majority of the materials volume is made up of polylactic acid. In order to utilize functionalities of composite filaments, printing behavior and properties of 3-D printed composites need to be characterized and compared with the pure PLA materials. In this study, pure PLA and composite specimens with different metallic reinforcements (Copper, Bronze, Tungsten, Iron, etc) were 3D printed at various layer heights and resulting microstructures and properties were characterized. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) behavior of filaments with different reinforcements were studied. The microscopy results show an increase in porosity between 3-D printed regular PLA and the metal composite PLA samples, which could produce weaker mechanical properties in the metal composite materials. Tensile strength and fracture toughness behavior of specimens as a function of print layer height will be presented.

brass↗

The role of biomineralization in microbiologically influenced corrosion

Synthetic iron oxides (goethite, alpha-FeO.OH; hematite, Fe2O3; and ferrihydrite, Fe(OH)3) were used as model compounds to simulate the mineralogy of surface films on carbon steel. Dissolution of these oxides exposed to pure cultures of the metal-reducing bacterium, Shewanella putrefaciens, was followed by direct atomic absorption spectroscopy measurement of ferrous iron coupled with microscopic analyses using confocal laser scanning and environmental scanning electron microscopies. During an 8-day exposure the organism colonized mineral surfaces and reduced solid ferric oxides to soluble ferrous ions. Elemental composition, as monitored by energy dispersive x-ray spectroscopy, indicated mineral replacement reactions with both ferrihydrite and goethite as iron reduction occurred. When carbon steel electrodes were exposed to S. putrefaciens, microbiologically influenced corrosion was demonstrated electrochemically and microscopically.

Non-programmatic↗