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Maturation of Additive Manufactured Aerospace Alloys and Development of Mechanical and Thermophysical Properties for Space Applications

The National Aeronautics and Space Administration (NASA) has been involved in the development and maturation of metal additive manufacturing (AM) for space applications since the late 2000’s. Several efforts have focused on the understanding of AM processes through design optimization, component fabrication, material characterization, testing, standards development, and infusion into propulsion development for flight applications. NASA and partners have matured commonly used aerospace alloys from various alloy families (Nickel, Steel, Iron, Aluminum, and Titanium) and AM processes. An extensive effort has been ongoing between NASA, industry partners, and academia to complete detailed AM process and heat treatment characterization, in addition to generating temperature-dependent mechanical and thermophysical properties. This presentation highlights the characterization and property results using laser powder bed fusion (L-PBF) and laser powder directed energy deposition (LP-DED) processes among various alloys. In addition to commonly used alloys, there is a need for ongoing AM optimized alloys using integrated computational materials engineering (ICME) and process development for high performance applications. The applications targeted are launch vehicles, liquid rocket engines, advanced propulsion systems, advanced power systems, and in-space propulsion with high heat fluxes, high pressure, and that utilize propellants such as hydrogen, which can degrade alloys. This presentation will also discuss some of the ongoing novel alloy development and maturation using AM for use in these harsh environments, such as GRCop-42, GRCop-84, NASA HR-1, and C-103. The results from these processes have demonstrated that AM can enable rapid development and new AM optimized alloys can yield higher performance. These alloys have undergone modeling, fundamental metallurgical evaluations, heat treatment studies, and microstructure characterization and mechanical testing campaigns. This, combined with direct application-specific component fabrication and hot-fire testing, can enable the increase of the Technology Readiness Level (TRL) through high duty-cycle testing. This presentation provides a background and overview of these various common and AM-enabled alloys and processing developments including the initial effort related to metallurgical, mechanical, and thermophysical property studies. It also covers the latest advancement in the parallel component development, hot-fire testing, and future developments for these alloys.

Additive Manufacturing↗

Syntrophus aciditrophicus sp. nov., a new anaerobic bacterium that degrades fatty acids and benzoate in syntrophic association with hydrogen-using microorganisms

Strain SBT is a new, strictly anaerobic, gram-negative, nonmotile, non-sporeforming, rod-shaped bacterium that degrades benzoate and certain fatty acids in syntrophic association with hydrogen/formate-using microorganisms. Strain SBT produced approximately 3 mol of acetate and 0.6 mol of methane per mol of benzoate in coculture with Methanospirillum hungatei strain JF1. Saturated fatty acids, some unsaturated fatty acids, and methyl esters of butyrate and hexanoate also supported growth of strain SBT in coculture with Desulfovibrio strain G11. Strain SBT grew in pure culture with crotonate, producing acetate, butyrate, caproate, and hydrogen. The molar growth yield was 17 +/- 1 g cell dry mass per mol of crotonate. Strain SBT did not grow with fumarate, iron(III), polysulfide, or oxyanions of sulfur or nitrogen as electron acceptors with benzoate as the electron donor. The DNA base composition of strain SBT was 43.1 mol% G+C. Analysis of the 16 S rRNA gene sequence placed strain SBT in the delta-subdivision of the Proteobacteria, with sulfate-reducing bacteria. Strain SBT was most closely related to members of the genus Syntrophus. The clear phenotypic and genotypic differences between strain SBT and the two described species in the genus Syntrophus justify the formation of a new species, Syntrophus aciditrophicus.

Non-NASA Center↗

Photovoltaic Hydrogen Sensor

Photovoltaic device senses hydrogen developed to test degradation of diodes with platinum flash gates on backs. Sensing element is p/n junction rather than conventional Schottky barrier or metal oxide/silicon field-effect transistor. Hydrogen-indicating electrical signal modulated optically rather than electrically. Layered structure of hydrogen detector and principle of operation resemble silicon solar photovoltaic cell. Hydrogen detector responds to hydrogen in atmosphere within minutes and recovers quickly when hydrogen removed.

Daud, Taher↗

Hydrogen Effects on GaAs Device Reliability

GaAs and InP devices in hermetically sealed packages have been observed to exhibit unacceptable degradation in both RF and DC characteristics. This degradation has been observed to occur at temperatures as low as 125oC. The source of the degradation has been linked to hydrogen gas that has been absorbed in the package's metals (Kovar, plating, etc.) and converted into atomic hydrogen within the Pt or Pd metallization of the gate structure. Subsequently, atomic hydrogen diffuses into the channel region of the FET structure and neutralizes the Si donors, resulting in a degradation of the device characteristics.

Gallium Arsenide↗

The resistance of selected high strength alloys to embrittlement by a hydrogen environment

Selected high strength iron base and cobalt base alloys were resistant to degradation of mechanical properties in a one atmosphere hydrogen environment at ambient temperature. These alloys were strengthened initially by cold working which produced strain induced martensite and fcc mechanical twins in an fcc matrix. Heat treatment of the cobalt base alloy after cold working produced carbide precipitates with retention of an hcp epsilon phase which increased the yield strength level. High strength alloys can be produced which have some resistance to degradation of mechanical properties by a hydrogen environment under certain conditions.

Benson, R. B., Jr.↗

Surface compositional variations of Mo-47Re alloy as a function of temperature

Molybdenum-rhenium alloys are candidate materials for the National Aero-Space Plane (NASP) as well as for other applications in generic hypersonics. These materials are expected to be subjected to high-temperature (above 1200 C) casual hydrogen (below 50 torr), which could potentially degrade the material strength. Since the uptake of hydrogen may be controlled by the contaminant surface barriers, a study of Mo-47Re was conducted to examine the variations in surface composition as a function of temperature from 25 C to 1000 C. Pure molybdenum and rhenium were also examined and the results compared with those for the alloy. The analytical techniques employed were Auger electron spectroscopy, electron energy loss spectroscopy, ion scattering spectroscopy, and x ray photoelectron spectroscopy. The native surface was rich in metallic oxides that disappeared at elevated temperatures. As the temperature increased, the carbon and oxygen disappeared by 800 C and the surface was subsequently populated by the segregation of silicon, presumably from the grain boundaries. The alloy readily chemisorbed oxygen, which disappeared with heating. The disappearance temperature progressively increased for successive dosings. When the alloy was exposed to 800 torr of hydrogen at 900 C for 1 hour, no hydrogen interaction was observed.

Hoekje, S. J.↗

Properties of materials in high pressure hydrogen at room and elevated temperatures

Experimental efforts in this program for this period. Mechanical property tests of wrought and cast nickel-base alloys and one wrought cobalt-base alloy were conducted in 34.5 MN/sq m (5000-psig) helium and hydrogen or hydrogen mixtures. Comparison of test results was made to determine degradation of properties due to the hydrogen environments. All testing was conducted on solid specimens exposed to external gaseous pressure. Specific mechanical properties determined and the testing methods used are summarized.

Harris, J. A., Jr.↗

Hot hydrogen testing of metallic turbo pump materials

The objectives of this investigation are to expose heat resistant alloys to hydrogen at elevated temperatures and to use various microstructural and analytical techniques to determine the chemical and rate process involved in degradation of these materials due to hydrogen environment. Inconel 718 and NASA-23 (wrought and cast) are candidate materials. The degradation of these materials in the presence of 1 to 5 atmospheric pressure of hydrogen from 450 C to 1100 C was examined. The hydrogen facility at Auburn University was used for this purpose. Control experiments were also conducted wherein the samples were exposed to vacuum so that a direct comparison of the results would separate the thermal contribution from the hydrogen effects. The samples were analyzed prior to and after exposure. A residual gas collection system was used to determine the gaseous species produced by any chemical reaction that may have occurred during the exposure. Analysis of this gas sample shows only the presence of H2 as expected. Analyses of the samples were conducted using optical microscopy, x-ray diffraction, scanning electron microscopy, and weight change. There appears to be no change in weight of the samples as a result of hydrogen exposure. In addition no visible change on the surface structure was detected. This indicates that the materials of interest do not have strong interaction with hot hydrogen. This is consistent with the microstructure results.

Zee, Ralph↗

Effect of Environment on the Stress- Rupture Behavior of a C/SiC Composite Studied

Advanced reusable launch vehicles will likely incorporate fiber-reinforced ceramic matrix composites (CMC's) in critical propulsion and airframe components. The use of CMC's is highly desirable to save weight, improve reuse capability, and increase performance. One of the candidate CMC materials is carbon-fiber-reinforced silicon carbide (C/SiC). In potential propulsion applications, such as turbopump rotors and nozzle exit ramps, C/SiC components will be subjected to a service cycle that includes mechanical loading under complex, high-pressure environments containing hydrogen, oxygen, and steam. Degradation of both the C fibers and the SiC matrix are possible in these environments. The objective of this effort was to evaluate the mechanical behavior of C/SiC in various environments relevant to reusable launch vehicle applications. Stress-rupture testing was conducted at the NASA Glenn Research Center on C/SiC specimens in air and steam-containing environments. Also, the oxidation kinetics of the carbon fibers that reinforce the composite were monitored by thermogravimetric analysis in the same environments and temperatures used for the stress-rupture tests of the C/SiC composite specimens. The stress-rupture lives obtained for C/SiC tested in air and in steam/argon mixtures are shown in the following bar chart. As is typical for most materials, lives obtained at the lower temperature (600 C) are longer than for the higher temperature (1200 C). The effect of environment was most pronounced at the lower temperature, where the average test duration in steam at 600 C was at least 30 times longer than the lives obtained in air. The 1200 C data revealed little difference between the lives of specimens tested in air and steam at atmospheric pressure.

Verrilli, Michael J.↗

Calibration of the Mid-Infrared Tully-Fisher Relation

Distance measures on a coherent scale around the sky are required to address the outstanding cosmological problemsof the Hubble constant and of departures from the mean cosmic flow. The correlation between galaxy luminositiesand rotation rates can be used to determine the distances to many thousands of galaxies in a wide range ofenvironments potentially out to 200 Mpc. Mid-infrared (3.6m) photometry with the Spitzer Space Telescope isparticularly valuable as a source of luminosities because it provides products of uniform quality across the sky.From a perch above the atmosphere, essentially the total magnitude of targets can be registered in exposures ofa few minutes. Extinction is minimal and the flux is dominated by the light from old stars, which is expected tocorrelate with the mass of the targets.In spite of the superior photometry, the correlation between mid-infrared luminosities and rotation rates extractedfrom neutral hydrogen profiles is slightly degraded from the correlation found with I-band luminosities. A colorcorrection recovers a correlation that provides comparable accuracy to that available at the I band (20 1in an individual distance) while retaining the advantages identified above. Without color correction, the relationbetween linewidth and [3.6] magnitudes is Mb,i,k,a [3.6] 20.34 9.74(logWimx 2.5). This description is foundwith a sample of 213 galaxies in 13 clusters that define the slope and 26 galaxies with Cepheid or tip of the red giant branch distances that define the zero point. A color-corrected parameter MC[3.6] is constructed that has reduced scatter: MC[3.6] 20.34 9.13(logWimx 2.5). Consideration of the seven calibration clusters beyond 50 Mpc, outside the domain of obvious peculiar velocities, provides a preliminary Hubble constant estimate of H0 74 4 km s1 Mpc1.

Mid-Infrared↗

The effect of hydrogen on the low cycle fatigue behavior of a single crystal superalloy

The present study compares the room temperature fatigue properties of PWA 1480 single crystals containing either normal or elevated hydrogen levels, giving attention to the effects of various levels of HIPing process-controlled porosity on hydrogen-trapping and fatigue life. Hydrogen charging is found to degrade the fatigue lives of alloy samples by an order of magnitude; the magnitude of this degradation is comparable at both high and low porosity. HIPing accomplished a small beneficial effect on the fatigue life of both the hydrogen-charged and uncharged PWA 1480 samples. Fatigue cracks are noted to have consistently initiated at large, near-surface pores. By reducing the size and frquency of the larger pores, HIPing apparently retarded fatigue-crack initiation.

Gayda, J.↗

Characteristics of a gelled liquid hyprogen polyphenylene oxide (PPO) foam open-cell insulation system, phase 1

A large scale gel production and storage facility and a small scale facility, the latter used for detailed visual examination of the gel/PPO foam interface, were developed. A subcontract was given to investigate techniques for the production of gelled liquid hydrogen, develop a process design for scale-up to a 1.89 cu m (500 gallon) gel production and storage facility, determine gel transfer characteristics, determine the solubility rate of gaseous helium in the gel, and investigate the gross gel/PPO foam interfacial phenomena. An inside-tank process for scaled-up production of gelled liquid hydrogen was selected. No detectable gel structure degradation occurred during repeated shearing. The viscosity of gelled liquid hydrogen at shear rates of 300/sec and higher is 2 to 5-fold greater than that of neat liquid hydrogen. No clogging problems were encountered during the transfer of gelled liquid hydrogen through warmed transfer lines. The solubility rate of helium in liquid hydrogen was significantly reduced by the presence of gel structure. The boil-off rates from gelled liquid hydrogen were reduced from 25 to 50 percent compared to those observed for the neat liquid hydrogen under compatible conditions. The polyphenylene oxide (PPO) foam insulation was found to be compatible with liquid ethane.

Source record↗

Ceramic composites portend long turbopump lives

Use of continuous fiber reinforced ceramic matrix composites (FRCMC) for turbopump hot section components offers a number of benefits. The performance benefits of incresed turbine inlet temperature are apparent and readily quantifiable. Perhaps less obvious are the potential benefits of incresed component life. At nominal turbopump operating conditions, FRCMC offer increased operating temperature margin relative to conventional materials. This results in potential for significant life enhancement. Other attributes (e.g., thermal shock resistance and high cycle fatigue endurance) of FRCMC provide even greater potential to improve life and reduce maintenance requirements. Silicon carbide (SiC0 matrix composites with carbon fibers (C/SiC) do not degrade when exposed to hydrogen-rich steam for 10 hours at 1200 C. This FRCMC is resistant to thermal shock transients far in excess of those anticipated for advanced, high temperature turbomachinery. Orthogonal, two-dimensional (2D0, plain woven, C/SiC also does not degrade when subjected to tensile-tensile fatigue at room temperature for 4 x 10(exp 5) cycles at 75% of the ultimate strength. Runout at greater than 10(exp 6) cycle occurs for axial specimens subjected to fully reversed strain controlled fatigue at ambient temperature and 0.3% strain.

Herbell, Tomas P.↗

An investigation of the kinetics for hydrogen chemisorption on iron metal surfaces

A quasi-isothermal approach was used to study the kinetics of hydrogen and hydrogen sulfide chemisorption onto iron film in an effort to understand the environmental degradation of steels. The coverage of chemisorbed hydrogen or chemisorbed sulfur was observed as a function of time for fixed conditions of substrate temperature. Auger electron spectroscopy was used to observe the sulfur and chemisorption-induced resistance change was employed to monitor hydrogen coverage. To compare the results obtained from studying the kinetics by two different techniques, the kinetics of oxygen chemisorption onto iron films was also studied. A reaction model utilized to interpret the H2/Fe2 chemisorption kinetics was applied to data from an earlier study on the desorption kinetics for H2 chemisorbed onto nicket films in the vicinity of the Curie temperature of the film. This analysis permitted a separation of the gross desorption process into individual components so that the influence of the magnetic phase transition on the rate constants could be determined.

Shanabarger, M. R.↗

Analysis of the thermal reaction products of para polyphenylene by combined gas chromatography-mass spectrometry

Analysis of the volatiles and sublimate produced when para-polyphenylene is pyrolyzed to constant weight under vacuum in the temperature range from 380 to 1000 C indicates that the polymer undergoes thermal degradation in two stages. The first stage involved dehydrohalogenation, which is essentially a curing reaction that produces crosslinking between polyphenylene chains resulting from the loss of chlorine from the polymer in the form of hydrogen chloride. The second stage of the thermal degradation is dehydrogenation because hydrogen is the major volatile species. Increasing amounts of polycyclic aromatic hydrocarbons (phenanthrene and 9, 10 benzphenanthrene) in the sublimate, concomitant with increasing C/H ratios of the polymeric residue with pyrolysis temperature, is consistent with the buildup of polynuclear structures in the polymer matrix.

Fewell, L. L.↗

The resistance of selected high strength alloys to embrittlement by a hydrogen environment

Selected high strength iron base and cobalt base alloys with yield strengths in the range from 1233 to 2129 MN per sq m (179 to 309 KSI) were resistant to degradation of mechanical properties in a one atmosphere hydrogen environment at ambient temperature. These alloys were strengthened initially by cold working which produced strain induced epsilon prime-hcp martensite and fcc mechanical twins in an fcc matrix. Heat treatment of the cobalt base alloy after cold working produced carbide precipitates with retention of an hcp epsilon phase which increased the yield strength level to a maximum of 2129 MN per sq m (309 KSI). High-strength alloys can be produced which have some resistance to degradation of mechanical properties by a hydrogen environment under certain conditions.

Benson, R. B., Jr.↗

Effects of Strain Rate and Surface Finish on Tensile Properties in High Pressure Hydrogen — A Case Study for LP-DED NASA HR-1

NASA has advanced NASA HR-1 as a solution for liquid rocket engine components that operate in hydrogen rich environments using various AM techniques. The NASA HR-1 for AM applications was specifically formulated for high ductility in high pressure gaseous hydrogen environment in addition to high strength and low cycle fatigue (LCF) resistance. NASA HR-1 meets materials requirements for liquid rocket engine components, including good hydrogen resistance, high conductivity, good LCF performance, and high elongation and strength for components in medium heat flux environments. NASA has completed fabrication of several subscale and full-scale channel wall nozzles in LP-DED NASA HR-1 and completed hot-fire testing. This includes refinement of the process to produce thin-walls and various channel geometries to meet the requirements for channel wall nozzle applications. The main objective of this investigation is to better understand the effects of tensile test strain rate and specimen surface finish on the amount of tensile ductility degradation in high pressure gaseous hydrogen environments. Performing smooth tensile tests in high pressure hydrogen and nitrogen environments can serve as a rapid and economical screening method to determine the relative susceptibility of materials to HEE. This paper presents the tensile test results for LP-DED NASA HR-1 in hydrogen and details the material evaluation on the effects of strain rate and surface finish condition on surface cracking behavior and fracture characteristics. The resistance to HEE for LP-DED NASA HR-1 and the wrought alloy is compared under the same testing conditions. Loss of tensile ductility is quantified in terms of changes in elongation at failure in hydrogen to compare HEE susceptibility. The most suitable strain rate and specimen surface finish condition for future HEE screening testing at MSFC are recommended.

Additive manufacturing↗

Analysis of the pyrolysis products of dimethyldichlorosilane in the chemical vapor deposition of silicon carbide in argon

A study of the products and reactions occurring during the chemical vapor deposition of silicon carbide from dimethyldichlorosilane in argon is presented. Reaction conditions were as follows: 700 to 1100 C, a contact time of about 1 min, and a pressure of 1 atm. At these conditions, the gases that formed were mainly methane, hydrogen, silicon tetrachloride, trichlorosilane, and methyltrichlorosilane. The silicon carbide solid that formed showed the presence of hydrogen and chloride as impurities, which might degrade the silicon carbide properties. These impurities were eliminated slowly, even at 1100 C, forming hydrogen, trichlorosilane, and silicon tetrachloride.

Cagliostro, Domenick E.↗