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NASA NTRS1998

Monitoring Direct Effects of Delta, Atlas, and Titan Launches from Cape Canaveral Air Station

Launches of Delta, Atlas, and Titan rockets from Cape Canaveral Air Station (CCAS) have potential environmental effects that could arise from direct impacts of the launch exhaust (e.g., blast, heat), deposition of exhaust products of the solid rocket motors (hydrogen chloride, aluminum oxide), or other effects such as noise. Here we: 1) review previous reports, environmental assessments, and environmental impact statements for Delta, Atlas, and Titan vehicles and pad areas to clarity the magnitude of potential impacts; 2) summarize observed effects of 15 Delta, 22 Atlas, and 8 Titan launches; and 3) develop a spatial database of the distribution of effects from individual launches and cumulative effects of launches. The review of previous studies indicated that impacts from these launches can occur from the launch exhaust heat, deposition of exhaust products from the solid rocket motors, and noise. The principal effluents from solid rocket motors are hydrogen chloride (HCl), aluminum oxide (Al2O3), water (H2O), hydrogen (H2), carbon monoxide (CO), and carbon dioxide (CO2). The exhaust plume interacts with the launch complex structure and water deluge system to generate a launch cloud. Fall out or rain out of material from this cloud can produce localized effects from acid or particulate deposition. Delta, Atlas, and Titan launch vehicles differ in the number and size of solid rocket boosters and in the amount of deluge water used. All are smaller and use less water than the Space Shuttle. Acid deposition can cause damage to plants and animals exposed to it, acidify surface water and soil, and cause long-term changes to community composition and structure from repeated exposure. The magnitude of these effects depends on the intensity and frequency of acid deposition.

Schmalzer, Paul A.↗

NASA NTRS1998

Performance Improvements to the Lidar Atmospheric Sensing Experiment (LASE)

Lidar Atmospheric Sensing Experiment (LASE) is the first fully-engineered, modular, tunable, autonomous Differential Absorption Lidar (DIAL) system for the remote measurement of water vapor, aerosols and clouds across the troposphere. It was designed, built and environmentally tested at LARC. LASE was designed to fly aboard a NASA/Ames ER-2 aircraft (NASA's high altitude aircraft) and operate at altitudes from 58,000 to 70,000 feet. Since its first flight on May 11, 1994, it has flown 28 total missions on board the ER-2. LASE has been validated with results showing an accuracy better than the initial requirement for vertical profiles of water vapor in the troposphere. LASE can also deploy on several other aircraft including the NASA P-3 and will fly aboard the NASA DC-8 during the Convection And Moisture EXperiment (CAMEX) in July-September 1998. The tunable laser system of LASE was designed to operate in a double-pulse mode at 5Hz, with energy outputs of up to 15OmJ per pulse in the 813 to 819nm wavelength region and with 99% of the output energy within a spectral interval of 1.06 pm. Sixteen wavelengths were selected to cover the various water vapor absorption cross sections needed for the DIAL measurement. The Ti:Sapphire laser was constructed using a frequency-doubled Nd:YAG laser as the pump source and a single mode diode laser as a injection seeder for the Ti:Al2O3 laser. We have improved the LASE instrument in several important ways. Improvements to the seed source have demonstrated that DFB laser diodes can be used as reliable seed sources on airborne DIAL instruments. The DFB diode has enabled LASE to gather more data and significantly reduced the maintenance required to insure that the system performance requirements are met. The multiwavelength sequential seeding technique is the current method of data collection for LASE. It has the advantages of providing an entire atmospheric coverage of H2O(v) from the ground to the aircraft altitude along a single ground track. The development of a flight deployable system to measure spectral purity will insure that the LASE instrument or any future flight based DIAL system can meet the performance specifications to insure data accuracy.

Edwards, W. C.↗

NASA NTRS1998

Laser Heated Oxide Fiber Growth Using Melt Modulation Technique

As a reinforcement for structural composites, single crystal alumina fibers offer low density, high modulus, and high creep resistance. In this study, the laser heated float zone approach was employed to grow c-axis Al2O3 continuous fibers of high purity and high strength. A new melt modulation technique, laser scanning, avoids the formation of surface induced ripples and allows the growth of 50 micro-m diameter sapphire fibers with strengths (approx. 7 GPa) significantly greater than either commercially available fibers grown by the edge-defined film growth process (approx. 2-3 GPa) or laboratory fibers grown by stationary laser heating (approx. 5 GPa). The present work suggests that surface striations are the predominant defects controlling the tensile strength of laser-scanned fibers at room temperature. Several possible mechanisms for inducing surface striations are systematically discussed for several oxide fiber compositions.

Sayir, Ali↗

NASA NTRS1998

Magnetic Fluid Friction and Wear Behavior

The friction and wear properties of two groups of magnetic fluids, one developed at NASA Lewis Research Center and a commercial fluid, were evaluated for boundary lubrication. Friction and wear measurements were made using a pin-on-disk apparatus. Three different ball materials were evaluated, (1) 440C, (2) Al2O3, and (3) Si3N4 against 440C disks. The first class of magnetic fluids have a low vapor pressure hydrocarbon base oil and are suitable for space application. Four variations of this fluid were evaluated: (1) the base oil, (2) base oil with anti-wear additives, (3) a 100 Gauss strength magnetic fluid, and (4) a 400 gauss magnetic fluid. The commercial fluid base oil and four different magnetic particle concentration levels have been evaluated. A space qualified fluorinated lubricant was tested for base line comparison. Hardness, optical microscopy, surface profilometry, and surface analysis were used to characterize the test specimens. Friction was unaffected by the concentration of magnetic particles. Wear rates for magnetic fluids were slightly higher than the base oil. The low vapor pressure magnetic fluid has better wear characteristics than the space qualified fluorinated lubricant.

Keith, Theo G., Jr.↗

NASA NTRS1999

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) are candidate refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermo-mechanical reliability of these components in severe thermal environments during the space mission sun/shade transition is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions, and thus provide vital information for the component design. In this paper, a controlled heat flux thermal shock test approach is established for the single crystal oxide materials using a 3.0 kW continuous wave CO2 laser, with a wavelength 10.6 micron. Thermal fracture behavior and failure mechanisms of these oxide materials are investigated and critical temperature gradients are determined under various temperature and heating conditions. The test results show that single crystal sapphire is able to sustain the highest temperature gradient and heating-cooling rate, and thus exhibit the best thermal shock resistance, as compared to the yttria-stabilized zirconia, yttrium aluminum garnet, and magnesium oxide.

Zhu, Dongming↗

NASA NTRS1999

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

Zhu, Dongming↗

NASA NTRS1999

Controlled Thermal Expansion Coat for Thermal Barrier Coatings

A improved thermal barrier coating and method for producing and applying such is disclosed herein. The thermal barrier coating includes a high temperature substrate, a first bond coat layer applied to the substrate of MCrAlX, and a second bond coat layer of MCrAlX with particles of a particulate dispersed throughout the MCrAlX and the preferred particulate is Al2O3. The particles of the particulate dispersed throughout the second bond coat layer preferably have a diameter of less then the height of the peaks of the second bond coat layer, or a diameter of less than 5 microns. The method of producing the second bond coat layer may either include the steps of mechanical alloying of particles throughout the second bond coat layer, attrition milling the particles of the particulate throughout the second bond coat layer, or using electrophoresis to disperse the particles throughout the second bond coat layer. In the preferred embodiment of the invention, the first bond coat layer is applied to the substrate, and then the second bond coat layer is thermally sprayed onto the first bond coat layer. Further, in a preferred embodiment of die invention, a ceramic insulating layer covers the second bond coat layer.

Brindley, William J.↗

NASA NTRS1998

Analyses at High Spatial Resolution of Organic Molecules in Extraterrestrial Samples: Two-Step Laser Mass Spectrometry: Search for Polycyclic Aromatic Hydrocarbons in Antarctic Meteorite and Micrometeorite Samples

Perhaps the best way to summarize the past three-year grant period is to cite the publications and present a brief synopsis of each: 1. "Indigenous Polycyclic Aromatic Hydrocarbon Molecules in Circumstellar Graphite Grains." Bulk C-12/C-13 isotope ratios observed in some graphite grains extracted from primitive meteorites point strongly to a circumstellar origin. By applying our technique of microprobe two-step laser desorption laser ionization mass spectrometry ((mu)L(sup 2)MS) to individual circumstellar graphite grains we have measured the C-12/C-13 isotope ratio of various polycyclic aromatic hydrocarbons (PAHS) found in these grains. 2. "Deuterium Enrichments in Cluster IDPS," Large enrichments in the D/H isotope ratios in IDPs likely arise from the preservation of presolar molecules. 3. "Evidence for thermalization of surface-disorder molecules at heating rates of 10(exp 8) K/s". A careful study of the ((mu)L(sup 2)MS) of aniline-d(sub 7) from a single-crystal surface (0001) of sapphire (al2O3) shows that all measured properties are consistent with a thermal mechanism for desorption. 4. "Search for past life on Mars; possible relic biogenic activity in Martian meteorite ALH 84001. The authors examined the Martian meteorite ALH 84001 and found several lines of evidence compatible with existence of past primitive (single-cell) life on early Mars. 5. "Microprobe two-step laser mass spectrometry as an analytical tool for meteorite samples". THis paper presents a comprehensive review of (mu)L(sup 2)MS and how this technique can be applied to meteoritic samples. 6. "Indigenous polycyclic aromatic hydrocarbons in circumstellar graphite grains from primitive meteorites". The C-12/C-13 isotope ratios were measured for PAHs in a total of 89 spherical graphite grains. 7. "Observation of indigenous polycyclic aromatic hydrocarbons in "Giant" carbonaceous antarctic micrometeorites." The (mu)L(sup 2)MS method was used to establish the nature and distribution of PAHs in fragments of fifteen (approx. 200 microns) carbonaceous antarctic micrometeorites (AMMs). 8. "Evidence for the extraterrestrial origin of polycyclic aromatic hydrocarbons in the Martian meteorite ALH 84001" We have undertaken additional contamination studies of ALH 84001.

Zare, Richard N.↗

NASA NTRS1999

Compositions of Mars Rocks: SNC Meteorites, Differentiates, and Soils

The 13 samples from Mars identified in the terrestrial meteorite collections vary from dunite to pyroxenite to microgabbro or basalt. All of these rocks appear to have formed from primitive melts with similar major element compositional characteristics; i.e., FeO-rich and Al2O3-Poor melts relative to terrestrial basalt compositions. Although all of the SNC rocks can be derived by melting of the same Al-depleted mantle, contamination of SNC's by a Rb-enriched mantle or crustal source is required to explain the different REE characteristics of SNC rocks. Thus, there are indications of an old crustal rocktype on Mars, and this rock does not appear to have been sampled. This paper focuses primarily on the composition of the SNC basalts, however, and on the compositions of rocks which could be derived from SNC basaltic melt by magmatic processes. In particular, we consider the possible compositions which could be achieved through accumulation of early-formed crystals in the SNC primitive magma. Through a set of experiments we have determined (1) melt (magma) compositions which could be produced by melt evolution as crystals are removed from batches of this magma cooling at depth, and (2) which evolved (Si02enriched, MgO-depleted) rock compositions could be produced from the SNC magma, and how these compare with the Pathfinder andesite composition. Finally, we compare the SNC magma compositions to the Mars soil composition in order to determine whether any source other than SNC is required.

Rutherford, M. J.↗

NASA NTRS1999

Cyclic Oxidation of FeCrAlY/Al2O3 Composites

Three-ply FeCrAlY/Al2O3 composites and FeCrAlY matrix-only samples were cyclically oxidized at 1000 C and 1100 C for up to 1000 1-hr cycles. Fiber ends were exposed at the ends of the composite samples. Following cyclic oxidation, cracks running parallel to and perpendicular to the fibers were observed on the large surface of the composite. In addition, there was evidence of increased scale damage and spallation around the exposed fiber ends, particularly around the middle ply fibers. This damage was more pronounced at the higher temperature. The exposed fiber ends showed cracking between fibers in the outer plies, occasionally with Fe and Cr-rich oxides growing out of the cracks. Large gaps developed at the fiber/matrix interface around many of the fibers, especially those in the outer plies. Oxygen penetrated many of these gaps resulting in significant oxide formation at the fiber/matrix interface far within the composite sample. Around several fibers, the matrix was also internally oxidized showing Al2O3 precipitates in a radial band around the fibers. The results show that these composites have poor cyclic oxidation resistance due to the CTE mismatch and inadequate fiber/matrix bond strength at temperatures of 1000 C and above.

Nesbitt, James A.↗

NASA NTRS1998

Fluorescence of Pentavalent Chromium in SiO2 Sol-Gel Glasses

Chromium ions are very attractive to optical spectroscopy and laser physics. It is well known that the first laser in the history is a ruby laser activated with Cr(3+). It was found in early nineties that Cr(4+) was also an interesting lasing ion in the near infrared, and various Cr(4+) lasers have been developed. Very recently, it was reported that Cr(2+) doped in CdSe crystals showed lasing action in the infrared. The above achievement have stimulated an interest in searching for Cr(5+) and investigating its optical properties. Cr(5+) is isoelectronic with Ti(3+) and V(4+), having electron configuration 3d1. Ti(3+) is the active center of commercial cw and femtosecond sapphire lasers, tunable in the range 680-1100 nm. V(4+) doped in YAlO3 and Al2O3 showed broad band emission near 635 nm. Although EPR results of Cr(5+) were reported, the optical properties were less studied. Herren et al. reported an observation of luminescence from Cr doped in SiO2 sol-gel glass. The luminescence spectrum was assigned to pentavalent ions in their first paper, and later it was identified to be the emission from the charge transfer transition of Cr(6+). The first observation of photoluminescence from octahedrally coordinated Cr(5+) in BaCaMg aluminate glasses was reported very recently. In this work, we report luminescence results of Cr doped SiO2 sol-gel glasses. The fluorescence spectra are very different from Herrens' results, and we believe it originates from pentavalent Cr.

Jia, Weiyi↗

NASA NTRS1998

Raman and Infrared Spectroscopy of Yttrium Aluminum Borate Glasses and Glass-ceramics

Raman spectra of glasses and glass-ceramics in the Y2O3-Al2O3-B2O3 system are reported. Glasses with B2O3 contents ranging from 40 to 60 mole percent were prepared by melting 20 g of the appropriate oxide or carbonate powders in alumina crucibles at 1400 C for 45 minutes. Subsequent heat treatments of the glasses at temperatures ranging from 600 to 800 C were performed in order to induce nucleation and crystallization. It was found that Na2CO3 added to the melt served as a nucleating agent and resulted in uniform bulk crystallization. The Raman spectra of the glasses are interpreted primarily in terms of vibrations of boron - oxygen structural groups. Comparison of the Raman spectra of the glass-ceramic samples with spectra of aluminate and borate crystalline materials reveal that these glasses crystallize primarily as yttrium aluminum borate, YAl3(BO3)4.

Bradley, J.↗

NASA NTRS1997

Design for Oxidation Resistance

Alloys intended for use in high-temperature environment rely on the formation of a continuous, compact, slow-growing oxide layer for oxidation and hot corrosion resistance. To be protective, this oxide layer must be chemically, thermodynamically stable. Successful alloy design for oxidative environment is best achieved by developing alloys that are capable of forming adherent scales of either alumina (Al2O3), chromia (Cr2O3), or silica (SiO2). In this article, emphasis has been placed on the issue related to high-temperature oxidation of superalloys used in gas turbine engine application. Despite the complexity of these alloys, optimal performance has been associated with protective alumina scale formation. As will be described below, both compositional makeup and protective coatings play key role in providing oxidation protection. Other high-temperature materials described include nickel and titanium aluminide intermetallics, refractory metal, and ceramics.

Smialek, James L.↗

NASA NTRS1995

Design of a Three-Layer Antireflection Coating for High Efficiency Indium Phosphide Solar Cells Using a Chemical Oxide as First Layer

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 microns of the illuminated surface of the cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with the p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally, a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown, thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3- layer AR coating for thermally diffused p(+)n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p(+) emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as a fairly efficient antireflective layer yielding a measured record high AM0, 25 C, open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3, MgF2 or ZnS, MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductor materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating, should work well for essentially all III-V compound-based solar cells.

Moulot, Jacques↗

NASA NTRS2000

The Effect of Hydrogen Annealing on the Impurity Content of Alumina-Forming Alloys

Previously, the effect of hydrogen annealing on increasing the adhesion of Al2O3 scales had been related to the effective desulfurization that occurred during this process. The simultaneous reduction of other impurities has now been re-examined for up to 20 impurity elements in the case of five different alloys (NiCrAl, FeCrAl, PWA 1480, Rene'142, and Rene'N5). Hydrogen annealing produced measurable reductions in elemental concentration for B, C, Na, Mg, P, K, Sr, or Sn in varying degrees for at least one and up to three of these alloys. No single element was reduced by hydrogen annealing for all the alloys except sulfur. In many cases spalling occurred at low levels of these other impurities, while in other cases the scales were adherent at high levels of the impurities. No impurity besides sulfur was strongly correlated with adhesion.

Smialek, James L.↗

NASA NTRS2000

Crystallography of Alumina-YAG-Eutectic

Multiple descriptions of the alumina-YAG eutectic crystallography appear in the ceramic literature. The orientation between two phases in a eutectic system has direct impact on residual stress, morphology, microstructural stability, and high temperature mechanical properties. A study to demonstrate that the different crystallographic relationships can be correlated with different growth constraints was undertaken. Fibers produced by Laser-Heated Float Zone (LHFZ) and Edge-defined Film-fed Growth (EFG) were examined. A map of the orientation relationship between Al2O3 and Y3Al5O12 and their relationship to the fiber growth axis as a function of pull rate are presented. Regions in which a single orientation predominates are identified.

Farmer, Serene C.↗

NASA NTRS1999

Cyclic Oxidation of Single-Crystal NiAl-X Alloys

Several single-crystal NiAl-X alloys (X = Hf, Ti, Cr, Ga) were cyclically oxidized at 1000 C for up to 1000 1-hr cycles. The alloys all showed protective, adherent alpha-Al2O3 scale formation with positive weight change behavior throughout the test. There was no clear correlation between the composition of the various alloys and the specific weight gain although the ranking by weight change was relatively consistent for two duplicate series of samples. The presence of Hf (0.5 - 0.8 at.%) resulted in the internal formation of Al2O3/HfO2 "stringers." Diffusion of Hf to the growing oxide stringers resulted in the development of a near-surface layer depleted of these precipitates.

Nesbitt, James A.↗

NASA NTRS2000

Reliable, Low-Cost, Low-Weight, Non-Hermetic Coating for MCM Applications

Through an Air Force Research Laboratory sponsored STM program, reliable, low-cost, low-weight, non-hermetic coatings for multi-chip-module(MCK applications were developed. Using the combination of Sandia Laboratory ATC-01 test chips, AvanTeco's moisture sensor chips(MSC's), and silicon slices, we have shown that organic and organic/inorganic overcoatings are reliable and practical non-hermetic moisture and oxidation barriers. The use of the MSC and unpassivated ATC-01 test chips provided rapid test results and comparison of moisture barrier quality of the overcoatings. The organic coatings studied were Parylene and Cyclotene. The inorganic coatings were Al2O3 and SiO2. The choice of coating(s) is dependent on the environment that the device(s) will be exposed to. We have defined four(4) classes of environments: Class I(moderate temperature/moderate humidity). Class H(high temperature/moderate humidity). Class III(moderate temperature/high humidity). Class IV(high temperature/high humidity). By subjecting the components to adhesion, FTIR, temperature-humidity(TH), pressure cooker(PCT), and electrical tests, we have determined that it is possible to reduce failures 50-70% for organic/inorganic coated components compared to organic coated components. All materials and equipment used are readily available commercially or are standard in most semiconductor fabrication lines. It is estimated that production cost for the developed technology would range from $1-10/module, compared to $20-200 for hermetically sealed packages.

Jones, Eric W.↗