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High molecular weight products were detected on the wear track of an iron disk at the end of a sliding friction and wear test using benzene as a lubricant. Size exclusion chromagography in conjunction with UV analysis gave evidence that the high molecular weight products are polyphenyl ether type substances. Organic electrochemistry was used to elucidate the possible surface reaction mechanisms.
The growth rate of laser-photoenhanced thermally grown native oxides of InP in a N2O ambient and its dependence on growth condition are presented. Increased laser power, substrate temperature, and N2O pressure are observed to increase the growth rate. The topography and the composition of these oxides have been studied using secondary electron microscopy and X-ray photoemission spectroscopy, respectively. The oxide layers contain In2O3 and a phosphate, probably InPO4. The enhanced growth appears to be caused by both excited oxidizing species and a photon-enhanced surface reaction.
In this letter, far-infrared spectrophotometry (30-55 microns) and photometry (53-200 microns) are presented which define, for the first time, the long wavelength limit of the previously unidentified 30 micron emission feature found in certain extreme carbon star spectra. The spectral similarities are sufficiently similar to those of solid MgS that MgS is proposed to be the band carrier. This is interpreted as the first direct evidence that chemical surface reactions occur on dust grains in circumstellar environments. The presence of MgS indicates that either the oxygen abundance is relatively low and/or the sulfur abundance is high in extreme carbon stars.
The cold plasma techniques for deposition of various types of protective coatings are reviewed. The main advantage of these techniques for deposition of ceramic films is the lower process temperature, which enables heat treating of the metal prior to deposition. In the field of surface hardening of steel, significant reduction of treatment time and energy consumption were obtained. A simple model for the plasma - surface reactions in a cold plasma system is presented, and the plasma deposition techniques are discussed in view of this model.
Interstellar molecular grain mantles are an important component of the interstellar dust inside dense molecular clouds as evidenced by the detection of absorption bands at 2.97, 3.08, 4.61, 6.0 and 6.8 microns. Mantles may also be the precursors of more complex grain mantles in the diffuse interstellar medium. The molecular composition of these icy grain mantles were calculated employing gas phase as well as grain surface reactions. The calculated mixtures consist mainly of the molecules H2O, H2CO, N2, CO, O2, H2O2, NH2, and their deuterated counterparts in varying ratios. The exact compositions depend strongly on the physical conditions in the gas phase. The absorption spectra of H2O with other molecules was studied in the laboratory. Optical constants were determined for a few selected mixtures. Extinction and polarization cross sections across the 3 micron ice band were calculated. A comparison with the observations towards BN shows that the low frequency wing observed on this feature is due to absorption by a mixture of H2O and other molecules rather than scattering by large, pure H2O ice grains.
The present theoretical and experimental consideration of processes that are expected to occur when the porous regoliths on outer solar system bodies lacking atmospheres are subjected to energetic ion bombardment indicates that porosity reduces the effective sputtering yield of a soil by more than an order of magnitude. Between 90 and 97 percent of the sputtered atoms are trapped within the regolith and subjected to differential desorption fractionation, which emerges as the most important path for the alteration of chemical and optical properties in sputtered regoliths. Sputtered porous mixtures of water, ammonia and methane frosts suffer a loss of H, and surface reactions of C, N, and O that should yield complex hydrocarbons and carbohydrates; such reactions may have played a role in the formation of carbonaceous chondrites' matrix material prior to agglomeration.
Several processes that are expected to occur when the porous regoliths of outer solar system bodies (without atmospheres) are subjected to energetic ion bombardment are discussed. The conclusions reached in much of the literature addressing sputtering are quantitatively or qualitatively incorrect because effects of soil porosity have been neglected. It is shown theoretically and experimentally that porosity reduces the effective sputtering yield of a soil by more than an order of magnitude. Between 90 and 97% of the sputtered atoms are trapped within the regolith, where they are factionated by differential desorption. Experiments indicate that more volatile species have higher desorption probabilities. This process is the most important way in which alteration of chemical and optical properties occurs when a regolith is sputtered. When a basic silicate soil is irradiated these effects lead to sputter-deposited films enriched in metallic iron, while O, Na and K are preferentially lost. The Na and K are present in the atmosphere above the sputtered silicate in quantities much greater than their abundances in the regolith. Icy regoliths of SO2 should be enriched in elemental S and/or S2O. This prediction is supported by the probable identification of S2O and polysulfur oxide bands in the IR spectra of H-sputtered SO2 reported by Moore. When porous mixtures of water, ammonia and methane frosts are sputtered, the loss of H and surface reactions of C, N and O in the deposits should produce complex hydrocarbons and carbohydrates, some of which may be quite dark. Such reactions may have played a role in the formation of the matrix material of carbonaceous chondrites prior to agglomeration.
The likely role of atmospheric atomic oxygen in the recession of spacecraft surfaces and in the shuttle glow has revived interest in the accurate measurement of atomic oxygen densities in the upper atmosphere. The Air Force Geophysics Laboratory is supplying a quadrupole mass spectrometer for a materials interactions flight experiment being planned by the Johnson Space Center. The mass spectrometer will measure the flux of oxygen on test materials and will also identify the products of surface reactions. The instrument will be calibrated at a new facility for producing high energy beams of atomic oxygen at the Los Alamos National Laboratory. The plans for these calibration experiments are summarized.
The AFGL Quadrupole Ion/Neutral Mass Spectrometer (QINMS), its flight capabilities, and a few examples of QINMS data from the STS-4 flight are discussed in addition to the beam facility and calibration procedures used at the Los Alamos National Laboratory facility. A 5-eV atomic oxygen beam is produced using a continuous optical discharge technique, and the resulting pumped beam has sufficient high flux and velocity to simulate orbital conditions. The calibrated instrument will be used in the NASA Johnson Space Center Evaluation of Oxygen Interactions with Materials experiment to measure the density of ambient oxygen and to identify the products of oxygen-surface reactions.
The kinetics of low pressure CVD growth of SiO2 from SiH4 and O2 has been investigated for the case of an indirect (remote) plasma process. Homogeneous (gas phase) and heterogeneous operating ranges have been experimentally identified. The process was shown to be consistent within the heterogeneous surface-reaction dominated range of operation. A kinetic rate equation is given for growth at 14 W RF power input and 400 mtorr total pressure on both InP and Si substrates. The process exhibits an activation energy of 8.4 + or - 0.6 kcal/mol.
In the flight materials exposure data base extensive quantitative data is available from limited exposures in a narrow range of orbital environments. More data is needed in a wider range of environments as well as longer exposure times. Synergistic effects with other environmental factors; polar orbit and higher altitude environments; and real time materials degradation data is needed to understand degradation kinetics and mechanism. Almost no laboratory data exists from high fidelity simulations of the LEO environment. Simulation and test system are under development, and the data base is scanty. Theoretical understanding of hyperthermal atom surface reactions in the LEO environment is not good enough to support development of reliable accelerated test methods. The laser sustained discharge, atom beam sources are the most promising high fidelity simulation-test systems at this time.
The detection of prominant infrared absorption bands at 3250, 2170, 2138, 1670 and 1470 cm(-1) (3.08, 4.61, 4.677, 5.99 and 6.80 micron m) associated with molecular clouds show that mixed molecular (icy) grain mantles are an important component of the interstellar dust in the dense interstellar medium. These ices, which contain many organic molecules, may also be the production site of the more complex organic grain mantles detected in the diffuse interstellar medium. Theoretical calculations employing gas phase as well as grain surface reactions predict that the ices should be dominated only by the simple molecules H2O, H2CO, N2, CO, O2, NH3, CH4, possibly CH3OH, and their deuterated counterparts. However, spectroscopic observations in the 2500 to 1250 cm(-1)(4 to 8 micron m) range show substantial variation from source reactions alone. By comparing these astronomical spectra with the spectra of laboratory-produced analogs of interstellar ices, one can determine the composition and abundance of the materials frozen on the grains in dense clouds. Experiments are described in which the chemical evolution of an interstellar ice analog is determined during irradiation and subsequent warm-up. Particular attention is paid to the types of moderately complex organic materials produced during these experiments which are likely to be present in interstellar grains and cometary ices.
Interstellar H2S has been detected toward the cold, dark clouds L134N and TMC 1. Total column densities at the SO peak of L134N and the NH3 peak of TMC 1 are found to be about 2.6 X 10 to the 13th/sq cm and 7.0 X 10 to the 12th/sq cm, respectively. The results suggest that grain surface reactions may play a major role in the synthesis of H2S in cold, dark clouds.
Synchrotron-radiation sources and their characteristics are overviewed along with recent synchrotron-based research on earth materials and future earth-science applications utilizing the next generation of synchrotron-radiation sources presently under construction. Focus is placed on X-ray scattering studies of earth materials (crystalline and noncrystalline) under ambient conditions, diffraction studies of earth materials at high pressures and/or temperatures, spectroscopic studies, primarily X-ray absorption spectroscopy, and spatially resolved X-ray fluorescence studies of compositional variations in earth materials. It is noted that other synchrotron-based methods, such as X-ray tomography and topography may become important in characterizing earth materials, while soft X-ray/vacuum ultraviolet radiation from synchrotron sources can be applied to problems involving the structural environments of low-atomic-number elements and the characterization of surface reactions of minerals with liquids and gases.
A recently detected absorption feature at 3.53 microns in the spectrum of W33A has been assigned to methanol (CH3OH). Its optical depth implies that methanol is the second most abundant molecule (7 percent relative to H2O) in the grain mantles in the line of sight toward W33A observed to date. Laboratory experiments have shown that the implied abundance is difficult to explain by UV irradiation of the dust grains alone. Grain surface reactions or condensation directly out of the gas phase must also play roles, but the relative contributions of the various processes are difficult to estimate. The optical depth of the 3.53-micron feature constrains the contribution of methanol to the 6.8-micron feature in W33A to be 10 percent or less, requiring the contribution of at least one other compound to this feature, while the estimated contribution to the 4.9-micron absorption band is even smaller. Only a small contribution of formaldehyde (H2CO) is consistent with the observed 3.53-micron band profile. In contrast to methanol, formaldehyde can be produced readily by photochemical reactions within the ice mantle.
A feasibility study assessing the utility of the adaptation of near infrared correlation spectroscopy to quantifying iron and adsorbed water in some clay-based Mars soil analog materials (MarSAM's). The work was intended to constitute Phase 1 of an approach to identifying optical analytical wavelength regions, not only for important mineral classes, but for chemically active centers within them. Many of these centers are common to unrelated mineral classes and of disproportionate influence relative to the mineral structure as a whole in determining the surface reactivity of mineral surfaces. We previously reported linearity between reflectance and total iron and total moisture over a large range of both key variables. We also discovered interesting relationships between the intensity of iron bands and the relative humidity of the systems. These relationships were confirmed. We also show that, in the low humidity range, reflectance is linearly dependent on a different kind of water from that best representing the full humidity range (the kind of water associated, in clays, with surface acidity). These relationships and the sensitivity and capability of quantitation of near infrared data indicate high promise with the production of reactive surface intermediates of products of surface reactions.
A knowledge of the original volatile endowment of Mars is essential for any discussion of atmospheric loss on this planet. Cosmochemical models which postulate that planetary bulk compositions and volatile contents were controlled by the radial temperature profile in the solar nebula, and estimated bulk compositions based on the assumption that Mars is the parent body for the SNC meteorites predicts that Mars is volatile-rich. However, contrary views can also be found. For illustrative purposes, it is assumed that Mars was volatile-rich initially like the Earth. Taking terrestrial volatiles as the sum of the atmospheric, crustal, and oceanic volatiles and assuming that Mars accreted with the same volatile content on a g/g basis, the volatile endowments for an Earth-like Mars correspond to approximately 14 bars CO2, 800 mbars N2, and 1.2 km H2O. Subsequent topics discussed are: composition of outgassing volatiles; rates of present day atmospheric-surface reactions; constraints on CO2 loss via carbonate formation; constraints on H2O loss; and loss of other volatiles.
This paper describes an analytical model of an incompressible, isothermal reacting jet in crossflow. The model represents the flow in the jet cross-section by a counter rotating vortex pair, a flow structure that has been observed to dominate the jet behavior. The reaction surface surrounding the fuel jet is represented as a composite of strained diffusion flames that are stretched and deformed by the vortex pair flow. The results shed new light on the interaction between the vortex pair circulation and flame structure evolution and their relation to the concept of entrainment.