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Porous metal structure with very small pore diameters is produced by heating the structure in oxygen for an oxidized surface layer, cooling it, and heating it in hydrogen to deoxidize the oxidized portion. Such structures are superior catalyst beds and filters.
This research effort is aimed at providing further insight into this multi-variable dependent phenomena by looking at the effects of gravity on the ignition and combustion behavior of metals. Since spacecraft are subjected to higher-than-1g gravity loads during launch and reentry and to zero-gravity environments while in orbit, the study of ignition and combustion of bulk metals at different gravitational potentials is of great practical concern. From the scientific standpoint, studies conducted under microgravity conditions provide simplified boundary conditions since buoyancy is removed, and make possible the identification of fundamental ignition mechanisms. The effect of microgravity on the combustion of bulk metals has been investigated by Steinberg, et al. on a drop tower simulator. However, no detailed quantitative work has been done on ignition phenomena of bulk metals at lower or higher-than-normal gravitational fields or on the combustion characteristics of metals at elevated gravity. The primary objective of this investigation is the development of an experimental system capable of providing fundamental physical and chemical information on the ignition of bulk metals under different gravity levels. The metals used in the study, iron (Fe), titanium (Ti), zirconium (Zr), magnesium (Mg), zinc (Zn), and copper (Cu) were selected because of their importance as elements of structural metals and their simple chemical composition (pure metals instead of multi-component alloys to avoid complication in morphology and spectroscopic studies). These samples were also chosen to study the two different combustion modes experienced by metals: heterogeneous or surface oxidation, and homogeneous or gas-phase reaction. The experimental approach provides surface temperature profiles, spectroscopic measurements, surface morphology, x-ray spectrometry of metals specimens and their combustion products, and high-speed cinematography of the heating, ignition and combustion stages of the metal specimen. This paper summarizes the results obtained to date from experiments conducted under normal and high-gravity conditions.
The development of advanced high performance constant-volume-combustion-cycle engines (CVCCE) requires robust design of the engine components that are capable of enduring harsh combustion environments under high frequency thermal and mechanical fatigue conditions. In this study, a simulated engine test rig has been established to evaluate thermal fatigue behavior of a candidate engine combustor material, Haynes 188, under superimposed CO2 laser surface impulsive thermal loads (30 to 100 Hz) in conjunction with the mechanical fatigue loads (10 Hz). The mechanical high cycle fatigue (HCF) testing of some laser pre-exposed specimens has also been conducted under a frequency of 100 Hz to determine the laser surface damage effect. The test results have indicated that material surface oxidation and creep-enhanced fatigue is an important mechanism for the surface crack initiation and propagation under the simulated CVCCE engine conditions.
Two commercially available additive-containing silicon nitride materials were exposed in four environments which range in severity from dry oxygen at 1 atm pressure, and low gas velocity to an actual turbine engine. Oxidation and volatilization kinetics were monitored at temperatures ranging from 1066 to 1400 C. The main purpose of this paper is to examine the surface oxide morphology resulting from the exposures. It was found that the material surface was enriched in rare earth silicate phases in combustion environments when compared to the oxides formed on materials exposed in dry oxygen. However, the in situ formation of rare earth disilicate phases offered little additional protection from the volatilization of silica observed in combustion environments. It was concluded that externally applied environmental barrier coatings are needed to protect additive-containing silicon nitride materials from volatilization reactions in combustion environments. Introduction Si3N4 is proposed for use as components, such as vanes, in turbine applications. Tens of thousands of hours of life are needed for both land-based turbines and aeropropulsion applications. Additive-containing SisN4 materials are
Effect of surface roughness, damage, and films on thermal emission
Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m(PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. The cobalt levels ranged from 0 wt % to the nominal commercial content in each alloy. The alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200 and 100 hr respectively. An oxidation attack parameter, Ka derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the CR/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr alloys while a 5.0 wt % Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides perhaps due to the formation of the omni-present trirutile Ni(Ta,Cb,Mo,W)2O6. Both scales break down as increasing amounts of NiO is formed.
Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m (PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. the cobalt levels ranged from 0 wt pct to the nominal commercial content in each alloy. the alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200, and 100 hr, respectively. An oxidation attack parameter, Ka, derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the Cr/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr allys while a 5.0 wt pct Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides, perhaps due to the formation of the omnipresent trirutile Ni(Ta, Cb, Mo, W)2O6. Both scales break down as increasing amounts of NiO are formed.
This paper examines results with cyclic oxidation tests of Ni(9-20) Cr(15-30) Al-(x)Zr alloys carried out at 1100 C and 1200 C in static air. The concentration of zirconium varies from 0 to 0.63 atomic percent. Significant aluminum penetration is found in metallographic and electron microscopic examination of oxidized surfaces. Small amounts of zirconium lead to minimal penetration, and with increased zirconium content pronounced oxide penetration is observed.
Initial steps in oxidation of nickel surface studied using low energy back-reflection electron diffraction
Oxidation tests of TD-NiCr alloy with different surface pretreatments were conducted in a Mach-5 arc-jet at 1200 C and 0.002 lb/sec flowing air environment. The mechanisms responsible for the observed oxidation behavior are examined. The presence of atomic oxygen in the air stream plays a significant role in determining the oxidation characteristic of the alloy. The rate of Cr2O3 vaporization by formation of volatile CrO3 is greatly enhanced by the flowing conditions. The typical microstructure of oxides formed in the dynamic tests consists of an external layer of NiO with a porous mushroom-type morphology, an intermediate layer of NiO and Cr2O3 oxide mixture, and a continuous inner layer of Cr2O3 in contact with the Cr-depleted alloy substrate. Three basic processes underlying the formation of mushroom-type NiO are identified and discussed. The oxidation rate is determined by the rate of vaporization of NiO. Surface pretreatment has a significant effect on the oxidation behavior of the alloy in the early stage of oxidation, but becomes less important as exposure time increases. Mechanical polishing induces surface recrystallization, but promotes the concurrence of external growth of NiO and internal oxidation of the alloy in the dynamic atmosphere.
Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.
Many structural materials rely on the formation of chromia, silica or alumina as a protective layer when exposed in high temperature oxidizing environments. The presence of these oxide layers provides a protective diffusion barrier which slows down further oxidation. In atmospheres containing water vapor, however, reactions to form volatile hydroxide species occur which remove the surface oxide, thus, lowering the protective capability of the oxide scale. This paper summarizes the current understanding of volatility of chromia, silica and alumina in water vapor containing combustion environments. In addition unanswered questions in each system are discussed. Th current paper represents an update on the considerable information learned in the past five years for these systems.
The climate of Mars has been more similar to that of Earth than has the climate of any other planet in our Solar System. But Mars still provides a valuable alternative example of how planetary processes and environments can affect the potential presence of life elsewhere. For example, although Mars also differentiated very early into a core, mantle and crust, it then evolved mostly if not completely without plate tectonics and has lost most of its early atmosphere. The Martian crust has been more stable than that of Earth, thus it has probably preserved a more complete record of its earliest history. Orbital observations determined that near-surface water was once pervasive. Orbiters have identified the following diverse aqueous sedimentary deposits: layered phyllosilicates, phyllosilicates in intracrater fans, plains sediments potentially harboring evaporitic minerals, deep phyllosilicates, carbonate-bearing deposits, intracrater clay-sulfate deposits, Meridiani-type layered deposits, valles-type layered deposits, hydrated silica-bearing deposits, and gypsum plains. These features, together with evidence of more vigorous past geologic activity, indicate that early climates were wetter and perhaps also somewhat warmer. The denser atmosphere that was required for liquid water to be stable on the surface also provided more substantial protection from radiation. Whereas ancient climates might have favored habitable environments at least in some localities, clearly much of the Martian surface for most of its history has been markedly less favorable for life. The combination of dry conditions, oxidizing surface environments and typically low rates of sedimentation are not conducive to the preservation of evidence of ancient environments and any biota. Thus a strategy is required whereby candidate sites are first identified and then characterized for their potential to preserve evidence of past habitable environments. Rovers are then sent to explore the most promising candidates. The Mars Exploration Rover (MER) Opportunity revealed that water once flowed to the surface across the vast Meridiani plains, creating saline lakes whose waters were roiled by ancient winds that also sculptured their salt deposits into sand dunes. Opportunity then drove more than 30 km to explore even older deposits on a crater rim. MER Spirit found evidence that thermal waters (heated by volcanism or by impacts?) altered rocks to create sulfate salts, and siliceous sinters. These discoveries indicate that an early hydrological cycle apparently sustained precipitation, streams and lakes. Liquid water participated in rock weathering reactions, such as iron and sulfur oxidation, that created distinctive weathering regimes. Volcanism, impacts, groundwater and ice interacted at least locally. Redox chemical energy from volcanism, hydrothermal activity and weathering of crustal materials would have been available for any life. Thus conditions might have supported life in the past, at least locally. The main objective of the Mars Science Laboratory (MSL) Curiosity rover is to determine the extent to which Gale crater hosted environments capable of supporting microbial life. The rover has already found stream gravels as well as sediments that might have been deposited in an ancient lake. The rover is now traversing to Mt. Sharp, a 5 km-high mound that is located on the crater floor and that exhibits layered sedimentary rocks having diverse minerals (sulfates and clays) that apparently formed in the presence of liquid water. This rock sequence was deposited over an extended time period in diverse potentially habitable watery environments. Curiosity is poised to characterize a a well-preserved rock record of hundreds of millions of years of diverse environments and profound climate change.
Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produced degradation products in the Martian regolith. By analogy with terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato- and hydroxo-complex ions and sols formed gossans above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite) and silica (opal). Underlying groundwater, now permafrost, contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, etc., which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates and phyllosilicates during dust storms on Mars.
Lubricating materials for use in a vacuum environment have been the subject of a series of experimental investigations. Evaporation properties were evaluated for solid polymeric compositions. Friction and wear studies explored the behavior during sliding contact for series of polymeric compositions, binary alloys containing soft film-forming phases, complex alloys with film-forming materials, and a burnished MoS2 film. Friction and wear experiments were conducted at 10(exp-9)mm Hg with a 3/16-inch-radius-hemisphere rider specimen sliding on the flat surface of a rotating 2-1/2-inch-diameter disk specimen with materials that had low rates of evaporation. The influence of fillers in polytetrafluoroethylene (PTFE) on decomposition during vacuum friction studies was determined with a mass spectrometer. A real advantage in reducing decomposition and improving friction wear properties is gained by adding fillers (e.g., copper) that improve thermal conductivity through the composite materials. A polyimide and an epoxy-MoS2 composition material were found to have better friction and wear properties than PTFE compositions. A series of alloys (cast binary as well as more complex alloys) that contained microinclusions of potential film-forming material was studied. These materials replaced the normal surface oxides as they were worn away on sliding contact. Iron sulfide, nickel oxide, and tin are typical film-forming materials employed and were demonstrated to be effective in inhibiting surface welding and reducing friction. A burnished MoS2 film applied to type 440-C stainless steel in argon with a rotating soft wire brush had good endurance properties but somewhat higher friction than commercially available bonded films. An oil film applied to the burnished MoS2 markedly reduced its endurance life.
Si3N4-base ceramics were made from milled Si3N4 containing 11.1 wt% SiO2 and oxide additives by pressureless sintering at 1760 C. The four-point-average moduli of rupture were 460, 515, and 515 MPa at room temperature and 270, 256, and 227 MPa at 1400 C for compositions with 3.67, 7.22, and 14.0 wt% Y2O3, respectively. The oxidation resistance of these compositions decreased with increasing Y2O3 in the 600 to 1400 C range, and no surface oxide cracking or spalling was noted. Partial substitution of Al2O3 for Y2O3 reduced both strength and oxidation resistance.
Results are presented for the use of surface analytical tools including field ion microscopy, Auger emission spectroscopy analysis (AES), cylindrical mirror Auger analysis and X-ray photoelectron spectroscopy (XPS). Data from the field ion microscope reveal adhesive transfer (wear) at the atomic level with the formation of surface compounds not found in the bulk, and AES reveals that this transfer will occur even in the presence of surface oxides. Both AES and XPS reveal that in abrasive wear with silicon carbide and diamond contacting the transition metals, the surface and the abrasive undergo a chemical or structural change which effects wear. With silicon carbide, silicon volatilizes leaving behind a pseudo-graphitic surface and the surface of diamond is observed to graphitize.
NASA requirements for computing and memory for microspacecraft emphasize high density, low power, small size, and radiation hardness. The distributed nature of storage elements in nanocrystal floating-gate memories leads to intrinsic fault tolerance and radiation hardness. Conventional floating-gate non-volatile memories are more susceptible to radiation damage. Nanocrystal-based memories also offer the possibility of faster, lower power operation. In the pursuit of filling these requirements, the following tasks have been accomplished: (1) Si nanocrystal charging has been accomplished with conducting-tip AFM; (2) Both individual nanocrystals on an oxide surface and nanocrystals formed by implantation have been charged; (3) Discharging is consistent with tunneling through a field-lowered oxide barrier; (4) Modeling of the response of the AFM to trapped charge has allowed estimation of the quantity of trapped charge; and (5) Initial attempts to fabricate competitive nanocrystal non-volatile memories have been extremely successful.