Oxide dispersed copper alloys by surface oxidation
Oxide dispersed Cu alloys preparation by surface oxidation of powders, considering structural stability and stress rupture properties
Grant, N. J.↗
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Development of dispersion-strengthened XD (trademark) Cu alloys for high heat-flux applications
In a previous effort sponsored by NASA LeRC, the XD(trademark) process was used to produce ZrB2 particulate reinforcements in Cu and the resulting extruded material was microstructurally characterized and evaluated in tension over a range of temperatures. A problem that was encountered in that study was microstructural inhomogeneity resulting from the frequent presence of 'ZrB2 agglomerates' that were several microns in size. The presence of these agglomerates was attributed to improper mixing of powders in the green compact used in the XD process for elemental boron powder segregation. In this program, several milling parameters were examined in an effort to optimize this processing step; two levels of ZrB2 reinforcements were considered (7 vol. percent and 15 vol. percent). Microstructures of the reacted powder mass were examined to verify the absence of these agglomerates. Larger bathes of powder were then mixed, reacted, machined to size, canned, and extruded. The microstructure and tensile properties of these extrusions were examined, and the measured properties were correlated with the observed microstructure. Large unreacted or partially reacted Zr particles were present. These particles affected the mechanical properties deleteriously, and their presence is attributed to insufficient heat of reaction during XD synthesis. Alternate processing routes are recommended.
Kumar, K. Sharvan↗
Expansion of Additive Manufacturing Capabilities Into in Situ Alloying of Dispersion Strengthened, High Temperature Cu Alloys
New alloys and materials are potentially possible through additive manufacturing’s unique thermal history. Current literature explores the fabrication of eutectic and solid solution strengthened alloys through in-situ alloying, to take advantage of AM’s unique thermal history. The resulting lessons learned by in-situ alloying currently available materials will likely lead to the development of novel materials solely possible through in-situ alloying. This work will expand the application of in-situ alloying via additive manufacturing to NASA’s GRCop-42 (Cu-4at% Cr-2at% Nb), a high temperature copper alloy which has shown success in additively manufactured combustion chambers from pre-alloyed powders. GRCop-42 is unique to literature because a reaction to form the Cr2Nb dispersoids is required during the in-situ alloying. Both reaction completion rate and how input energy from the AM process influences the reaction progress will be evaluated. Ultimately, expansion of in-situ alloying capabilities provides further insight to develop novel materials using AM.
David Steven Scannapieco↗
Property investigation and sputter deposition of dispersion-hardened copper for fatigue specimen fabrication
Sputter-deposited alloys of dispersion-hardenable Cu-0.25 vol% SiC and Cu-0.50 vol% SiC and precipitation-hardenable Cu-0.15 wt% Zr and Cu-0.05 wt% Mg-0.15 wt% Zr-0.40 wt% Cr were investigated for selection to evaluate fatigue specimen performance with potential application in fabricating regeneratively cooled rocket thrust chambers. Yield strengths in the 700 to 1000-MN/sq m range were observed with uniform elongation ranging from 0.5 to 1.5% and necking indicative of greater ductility. Electrical conductivity measured as an analog to thermal conductivity gave values 90% IACS for Cu-0.15 wt% Zr and Cu-0.05 wt% Mg-0.15 wt% Zr-0.40 wt% Cr. A 5500-g sputtered deposit of Cu-0.15 wt% Zr alloy, 12.29 mm (0.484 in.) average thickness in the fatigue specimen gage length, was provided to NASA on one of their substrates.
Mcclanahan, E. D.↗
Influence of gravity level and interfacial energies on dispersion-forming tendencies in hypermonotectic Cu-Pb-Al alloys
Results on the nondirectional solidification of several hypermonotectic Cu-Pb-Al alloys were obtained aboard NASA's KC-135 zero-gravity aircraft in order to determine the influence of interfacial energies and gravity levels on dispersion-forming tendencies. The Al content was systematially varied in the alloys. The dispersion-forming ability is correlated with gravity level during solidification, the interfacial energy between the immiscible phases, and the tendency for the minority immiscible phase to wet the walls of the crucible.
Andrews, J. B.↗
In situ deposits of copper and copper oxide containing condensation polyimide films
Novel copper-polyimide composites have been synthesized via simultaneous thermal decomposition of solid solutions of bis (trifluoroacetylacetonato) copper (II) and thermal cyclodehydration of polyimide acid. In contrast to conventional filled polymer composites which are prepared by dispersion of particles or fibers in a polymer matrix this study has yielded in general uniform Cu or CuO dispersions of very small particle size that reside near the film surface that was exposed to the atmosphere during curing. The nature of the copper deposit, the thickness of the copper deposit, and the polyimide overlayer which bonds the copper to the polymer substrate depend on the curing atmosphere used. A variety of analytical surface methods along with thermogravimetric analysis and variable temperature (surface and volume) electrical resistivity measurements have been used to characterize these thin, flexible copper doped polyimide films.
Porta, G. M.↗
Dispersion strengthening of precipitation hardened Al-Cu-Mg alloys prepared by rapid solidification and mechanical alloying
Several Al-4Cu-1Mg-1.5Fe-0.75Ce alloys have been processed from either rapidly solidified or mechanically alloyed powder using various vacuum degassing parameters and consolidation techniques. Strengthening by the fine subgrains, grains, and the dispersoids individually or in combination is more effective when the alloys contain shearable precipitates; consequently, the strength of the alloys is higher in the naturally aged rather than the artificially aged condition. The strengths of the mechanically alloyed variants are greater than those produced from prealloyed powder. Properties and microstructural features of these dispersion strengthened alloys are discussed in regards to their processing histories.
Gilman, P. S.↗
Oxidation-Reduction Resistance of Advanced Copper Alloys
Resistance to oxidation and blanching is a key issue for advanced copper alloys under development for NASA's next generation of reusable launch vehicles. Candidate alloys, including dispersion-strengthened Cu-Cr-Nb, solution-strengthened Cu-Ag-Zr, and ODS Cu-Al2O3, are being evaluated for oxidation resistance by static TGA exposures in low-p(O2) and cyclic oxidation in air, and by cyclic oxidation-reduction exposures (using air for oxidation and CO/CO2 or H2/Ar for reduction) to simulate expected service environments. The test protocol and results are presented.
Greenbauer-Seng, L.↗
Provenance of the K/T boundary layers
An array of chemical, physical and isotopic evidence indicates that an impact into oceanic crust terminated the Cretaceous Period. Approximately 1500 cu km of debris, dispersed by the impact fireball, fell out globally in marine and nonmarine environments producing a 2 to 4 mm thick layer (fireball layer). In North American locales, the fireball layer overlies a 15 to 25 mm thick layer of similar but distinct composition. This 15 to 25 mm layer (ejecta layer) may represent approximately 1000 cu km of lower energy ejecta from a nearby impact site. Isotopic and chemical evidence supports a mantle provenance for the bulk of the layers. The extraordinary REE pattern of the boundary clays was modelled as a mixture of oceanic crust, mantle, and approximately 10 percent continental material. The results are presented. If the siderophiles of the ejecta layer were derived solely from the mantle, a test may be available to see if the siderophile element anomaly of the fireball layer had an extraterrestrial origin. Radiogenic Os-187 is depleted in the mantle relative to an undifferentiated chondritic source. Os-187/Os-186 ratios of 1.049 and 1.108 were calculated for the ejecta and fireball layers, respectively.
Hildebrand, A. R.↗
The physical metallurgy of mechanically-alloyed, dispersion-strengthened Al-Li-Mg and Al-Li-Cu alloys
Powder processing of Al-Li-Mg and Al-Li-Cu alloys by mechanical alloying (MA) is described, with a discussion of physical and mechanical properties of early experimental alloys of these compositions. The experimental samples were mechanically alloyed in a Szegvari attritor, extruded at 343 and 427 C, and some were solution-treated at 520 and 566 C and naturally, as well as artificially, aged at 170, 190, and 210 C for times of up to 1000 hours. All alloys exhibited maximum hardness after being aged at 170 C; lower hardness corresponds to the solution treatment at 566 C than to that at 520 C. A comparison with ingot metallurgy alloys of the same composition shows the MA material to be stronger and more ductile. It is also noted that properly aged MA alloys can develop a better combination of yield strength and notched toughness at lower alloying levels.
Gilman, P. S.↗
Comparison of the Oxidation Rates of Some New Copper Alloys
Copper alloys were studied for oxidation resistance and mechanisms between 550 and 700 C, in reduced-oxygen environments expected in rocket engines, and their oxidation behaviors compared to that of pure copper. They included two dispersion-strengthened alloys (precipitation-strengthened and oxide-dispersion strengthened, respectively) and one solution-strengthened alloy. In all cases the main reaction was oxidation of Cu into Cu2O and CuO. The dispersion-strengthened alloys were superior to both Cu and the solution-strengthened alloy in oxidation resistance. However, factors retarding oxidation rates seemed to be different for the two dispersion-strengthened alloys.
Ogbuji, Linus U. J. Thomas↗
In-situ Mechanical Neutron Diffraction Loading Characteristics of GRCop-84 Fabricated by SLM
GRCop-84 is a precipitation strengthened alloy composed of Cu-8Cr-4Nb at % with Cr2Nb precipitates that provide dispersion and precipitation strengthening characteristics and limited solubility in the Cu matrix. The particle role of Cr2Nb(C15Laves) is unusual only contributing 1/3 of strengthening at high temperatures while the matrix provides the remainder. The particles mechanically and thermally stabilize the matrix retaining purity and preventing coarsening and loss of strength. At high temperatures (50-85%TmCu), GRCop-84 provides the best thermal and mechanical properties of available alloys. GRCop-84 is currently in development for reusable launch vehicles including the Space Launch System (SLS) with a focus on fabrication with additive manufacturing (AM) techniques. GRCop-84 is an optimal material for consolidating with AM. The base material is costly, the production times are long, and more geometry control can considerably improve cooling efficiency. Development of AMGR Cop-84 with selective laser melting (SLM) has rapidly progressed due to ease of printing and limited operator adjustment between builds, but the necessary knowledge-base of thermal history and stress state during builds is still under development.
Minneci, R.↗
I. THERMAL STABILITY OF CU-SIO SUB 2 AND CU-AL SUB 2 O SUB 3 ALLOYS. II. PREPARATION OF OXIDE DISPERSION STRENGTHENED NICKELMOLYBDENUM ALLOYS BY SELECTIVE REDUCTION. III. THE MECHANISM OF INTERNAL OXIDATION OF DILUTE NICKEL ALLOYS.
Thermostability of copper-oxide alloys, oxide strengthened alloys, oxidation of alloys
OXIDATION↗
A Simplified Test for Blanching Susceptibility of Copper Alloys
GRCop-84 (Cu-8Cr-4Nb) is a dispersion-strengthened alloy developed for space-launch rocket engine applications, as a liner for the combustion chamber and nozzle ramp. Its main advantage over rival alloys, particularly NARloy-Z (Cu-Ag-Zr), the current liner alloy, is in high temperature mechanical properties. Further validation required that the two alloys be compared with respect to service performance and durability. This has been done, under conditions resembling those expected in reusable launch engine applications. GRCop-84 was found to have a superior resistance to static and cyclic oxidation up to approx. 700 C. In order to improve its performance above 700 C, Cu-Cr coatings have also been developed and evaluated. The major oxidative issue with Cu alloys is blanching, a mode of degradation induced by oxidation-reduction fluctuations in hydrogen-fueled engines. That fluctuation cannot be addressed with conventional static or cyclic oxidation testing. Hence, a further evaluation of the alloy substrates and Cu-Cr coating material necessitated our devising a test protocol that involves oxidaton-reduction cycles. This paper describes the test protocols used and the results obtained.
Thomas-Ogbuji, Linus U.↗
Ultraviolet observations of cool stars. V - The local density of interstellar matter
A high-resolution Copernicus observation of the chromospheric Ly-alpha emission line of the nearby (3.3 pc) K dwarf epsilon Eri sets limits on the velocity, the velocity dispersion, and the density of atomic hydrogen in the local interstellar medium. Analysis shows that the interstellar Ly-alpha absorption is on the flat portion of the curve of growth. An upper limit of 0.12 per cu cm is derived for the atomic-hydrogen density. The value of this density is 0.08 (plus or minus 0.04 per cu cm if the velocity-dispersion parameter is 9 km/s, corresponding to a temperature of 5000 K. Also, the interstellar deuterium Ly-alpha line may be present in the spectrum.
Mcclintock, W.↗
A model for the kinetics of a solar-pumped long path laser experiment
A kinetic model for a solar-simulator pumped iodine laser system is developed and compared to an experiment in which the solar simulator output is dispersed over a large active volume (150 cu cm) with low simulator light intensity (approx. 200 solar constants). A trace foreign gas which quenches the upper level is introduced into the model. Furthermore, a constant representing optical absorption of the stimulated emission is introduced, in addition to a constant representing the scattering at each of the mirrors, via the optical cavity time constant. The non-uniform heating of the gas is treated as well as the pressure change as a function of time within the cavity. With these new phenomena introduced into the kinetic model, a best reasonable fit to the experimental data is found by adjusting the reaction rate coefficients within the range of known uncertainty by numerical methods giving a new bound within this range of uncertainty. The experimental parameters modeled are the lasing time, laser pulse energy, and time to laser threshold.
Stock, L. V.↗
Cu-Cr-Nb-Zr Alloy for Rocket Engines and Other High-Heat- Flux Applications
Rocket-engine main combustion chamber liners are used to contain the burning of fuel and oxidizer and provide a stream of high-velocity gas for propulsion. The liners in engines such as the Space Shuttle Main Engine are regeneratively cooled by flowing fuel, e.g., cryogenic hydrogen, through cooling channels in the back side of the liner. The heat gained by the liner from the flame and compression of the gas in the throat section is transferred to the fuel by the liner. As a result, the liner must either have a very high thermal conductivity or a very high operating temperature. In addition to the large heat flux (>10 MW/sq m), the liners experience a very large thermal gradient, typically more than 500 C over 1 mm. The gradient produces thermally induced stresses and strains that cause low cycle fatigue (LCF). Typically, a liner will experience a strain differential in excess of 1% between the cooling channel and the hot wall. Each time the engine is fired, the liner undergoes an LCF cycle. The number of cycles can be as few as one for an expendable booster engine, to as many as several thousand for a reusable launch vehicle or reaction control system. Finally, the liners undergo creep and a form of mechanical degradation called thermal ratcheting that results in the bowing out of the cooling channel into the combustion chamber, and eventual failure of the liner. GRCop-84, a Cu-Cr-Nb alloy, is generally recognized as the best liner material available at the time of this reporting. The alloy consists of 14% Cr2Nb precipitates in a pure copper matrix. Through experimental work, it has been established that the Zr will not participate in the formation of Laves phase precipitates with Cr and Nb, but will instead react with Cu to form the desired Cu-Zr compounds. It is believed that significant improvements in the mechanical properties of GRCop-84 will be realized by adding Zr. The innovation is a Cu-Cr-Nb-Zr alloy covering the composition range of 0.8 to 8.1 weight percent Cr, 0.7 to 7.2 weight percent Nb, 0.1 to 1.5 weight percent Zr, and balance Cu. The alloy combines two known strengthening mechanisms - dispersion strengthening by Cr2Nb precipitates (GRCop-84), and precipitation strengthening by CuxZr (AMZIRC) - to produce a synergistic increase in the capabilities of the alloy with the goal of achieving properties greater than either of the methods could achieve alone. The anticipated advantages of the alloy are higher strength at temperatures up to 700 C, improved creep strength, and significantly higher LCF lives relative to GRCop-84. The thermal expansion, thermal conductivity, and processing of the alloy are anticipated to remain largely unchanged relative to GRCop-84.
Ellis, David L.↗
Heavy metal toxicity as a kill mechanism in impact caused mass extinctions
Heavy metals that are known to be toxic exist in carbonaceous chrondrites at abundances considerably in excess to that of the terrestrial crust. An impactor of relatively undifferentiated cosmic matter would inject into the terrestrial environment large quantities of toxic elements. The abundances of toxic metals found in the Allende CV carbonaceous chondrite and the ratio of meteoritic abundance to crustal abundance are: Cr, 3630 PPM, 30X; Co, 662 PPM, 23X; ni, 13300 PPm, 134X; se, 8.2 PPM, 164X; Os, 0.828 PPM, 166X. The resulting areal density for global dispersal of impactor derived heavy metals and their dilution with terrestrial ejecta are important factors in the determination of the significance of impactor heavy metal toxicity as a kill mechanism in impact caused mass extinctions. A 10 km-diameter asteroid having a density of 3 gram per cu cm would yield a global areal density of impact dispersed chondritic material of 3 kg per square meter. The present areal density of living matter on the terrestrial land surface is 1 kg per square meter. Dilution of impactor material with terrestrial ejecta is determined by energetics, with the mass of ejecta estimated to be in the range of 10 to 100 times that of the mass of the impactor. Because a pelagic impact would be the most likely case, the result would be a heavy metal rainout.
Wdowiak, T. J.↗