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Upper critical field of copper molybdenum sulfide

The upper critical field of sintered and sputtered copper molybdenum sulfide Cu(x)Mo6S8 was measured and found to exceed the Werthamer, Helfand, and Hohenberg (1966) value for a type II superconductor characterized by dirty limit, weak isotropic electron phonon coupling, and no paramagnetic limiting. It is suggested that the enhancement results from anisotropy or clean limit or both. Other ternary molybdenum sulfides appear to show similar anomalies.

Alterovitz, S. A.↗

Critical Heat Flux in Pool Boiling on Metal-Graphite Composite Surfaces

A study is conducted on high heat-flux pool boiling of pentane on micro-configured composite surfaces. The boiling surfaces are copper-graphite (Cu-Gr) and aluminum-graphite (Al-Gr) composites with a fiber volume concentration of 50%. The micro-graphite fibers embedded in the matrix contribute to a substantial enhancement in boiling heat-transfer performance. Correlation equations are obtained for both the isolated and coalesced bubble regimes, utilizing a mathematical model based on a metal-graphite, two-tier configuration with the aid of experimental data. A new model to predict the critical heat flux (CHF) on the composites is proposed to explain the fundamental aspects of the boiling phenomena. Three different factors affecting the CHF are considered in the model. Two of them are expected to become the main agents driving vapor volume detachment under microgravity conditions, using the metal-graphite composite surfaces as the heating surface and using liquids with an unusual Marangoni effect as the working fluid.

Zhang, Nengli↗

Lightweight Chambers for Thrust Assemblies

The Marshall Space Flight Center (MSFC) of the National Aeronautics and Space Administration (NASA) has successfully applied new materials and fabrication techniques to create actively cooled thrust chambers that operate 200-400 degrees hotter and weigh 50% lighter than conventional designs. In some vehicles, thrust assemblies account for as much as 20% of the engine weight. So, reducing the weight of these components and increasing their operating range will benefit many engines and vehicle designs, including Reusable Launch Vehicle (RLV) concepts. Obviously, copper and steel alloys have been used successfully for many years in the chamber components of thrust assemblies. Yet, by replacing the steel alloys with Polymer Matrix Composite (PMC) and/or Metal Matrix Composite (MMC) materials, design weights can be drastically reduced. In addition, replacing the traditional copper alloys with a Ceramic Matrix Composite (CMC) or an advanced copper alloy (Cu-8Cr-4Nb, also known as GRCop-84) significantly increases allowable operating temperatures. Several small MMC and PMC demonstration chambers have recently been fabricated with promising results. Each of these designs included GRCop-84 for the cooled chamber liner. These units successfully verified that designs over 50% lighter are feasible. New fabrication processes, including advanced casting technology and a low cost vacuum plasma spray (VPS) process, were also demonstrated with these units. Hot-fire testing at MSFC is currently being conducted on the chambers to verify increased operating temperatures available with the GRCop-84 liner. Unique CMC chamber liners were also successfully fabricated and prepared for hot-fire testing. Yet, early results indicate these CMC liners need significantly more development in order to use them in required chamber designs. Based on the successful efforts with the MMC and PMC concepts, two full size "lightweight" chambers are currently being designed and fabricated for hot-fire testing at MSFC in 2001. These "full size" chambers will be similar in size to those used on the X33 engine (RS2200). One will be fabricated with a MMC structural jacket, while the other uses a PMC jacket. Each will be designed for thrust levels of 15,000 pounds in an oxygen/hydrogen environment with liquid hydrogen coolant. Both chambers will use GRCop-84 for its channel wall liner. Each unit is expected to be at least 60% lighter than a conventional design with traditional materials. Hot-fire testing on the full size units in late 2001 will directly compare performance results between a conventional chamber design and these "lightweight" alternatives. The technology developed and demonstrated by this effort will not only benefit next generation RLV programs, but it can be applied to other existing and future engine programs, as well. Efforts were sponsored by the Advanced Space Transportation Program for RLV Focused Technologies. The task team was led by MSFC with additional members from NASA-Glenn Research Center and the Rocketdyne Division of The Boeing Company. Specific materials development and fabrication processes were provided by Aerojet, Lockheed Martin Astronautics, Composite Optics, Inc., Hyper-Therm, Ceramic Composites, Inc., MSE Technology Applications, and Plasma Processes, Inc.

Elam, Sandra K.↗

Development of New Rocket Engine Liner Materials Based on Copper Alloys with Diamond Particle Additions

Novel copper-diamond materials containing particulate dispersions of diamond within a copper alloy matrix have been produced as next-generation rocket engine combustion chamber liner materials. These Copper-Diamond (Cu-D) composite materials have significantly higher thermal conductivity than conventional liner materials and have the potential to increase the engine performance significantly. Liner fabrication techniques include hot pressing and spark plasma sintering (SPS), which are capable of scale up to full-size production parts. The materials have been evaluated for thermal cycling resistance and ease of manufacturing. The results indicate great promise of these materials and associated economics to replace state-of-the-art combustion chamber liner materials such as GRCop-84 and NARloy-Z. Combustion chamber fabrication processes are also discussed, including SPS and additive manufacturing.

Bhat, Biliyar N.↗

Comparison of GRCop-84 to Other High Thermal Conductive Cu Alloys

The mechanical properties of five copper alloys (GRCop-84, AMZIRC, GlidCop Al-15, Cu-1Cr-0.1Zr, Cu-0.9Cr) competing in high temperature, high heat flux applications such as rocket nozzles, were compared. Tensile, creep, thermal expansion, and compression tests are presented. Tests were done on as-received material, and on material which received a simulated brazing heat treatment at 935 C. The 935 C heat treatment weakened AMZIRC, Cu-1Cr-0.1Zr, and Cu-0.9Cr, and the strength of as-received AMZIRC dropped precipitously as test temperatures exceeded 500 C. The properties of GlidCop Al-15 and GRCop-84 were not significantly affected by the 935 C heat treatment. Thus GRCop-84 is better than AMZIRC, Cu-1Cr-0.1Zr, and Cu-0.9Cr at temperatures greater than 500 C. Ductility was lowest in GlidCop Al-15 and Cu-0.9Cr. The creep properties of GRCop-84 were superior to those of brazed AMZIRC, Cu-1Cr-0.1Zr, and Cu-0.9Cr. At equivalent rupture life and stress, GRCop-84 had a 150 C temperature advantage over brazed AMZIRC; for equivalent rupture life and temperature GRCop-84 was two times stronger. The advantages of GRCop-84 over GlidCop Al-15 associated with ease of processing were confirmed by GlidCop s marginal ductility. In the post brazed condition, GRCop-84 was found to be superior to the other alloys due to its greater strength and creep resistance (compared to AMZIRC, Cu-1Cr-0.1Zr, and Cu-0.9Cr) and ductility (compared to GlidCop Al-15)

deGroh, Henry C., III↗

Characteristics of Pool Boiling on Graphite-Copper Composite Surfaces

Nucleate pool boiling performance of different liquids on graphite-copper composite (Gr-Cu) surfaces has been experimentally studied and modeled. Both highly wetting fluids, such as freon-113 and pentane, and a moderately wetting fluid (water) were tested on the Gr-Cu surfaces with different graphite-fiber volume fractions to reveal the enhancement effects of the composite surfaces on the nucleate pool boiling. Results of the experiments show that the graphite-fiber volume fraction has an optimum value. The Gr-Cu composite surface with 25 percent graphite-fiber volume (f=0.25) has a maximum enhancement effect on the nucleate boiling heat transfer comparing to the pure copper surface. For the highly wetting fluid, the nucleate boiling heat transfer is generally enhanced on the Gr- Cu composite surfaces by 3 to 6 times shown. In the low heat flux region, the enhancement is over 6 times, but in the high heat flux region, the enhancement is reduced to about 40%. For the moderately wetting fluid (water), stronger enhancement of nucleate boiling heat transfer is achieved on the composite surface. It shown the experimental results in which one observes the nucleate boiling heat transfer enhancement of 5 to 10 times in the low heat flux region and an enhancement of 3 to 5 times in the high heat flux region. Photographs of bubble departure during the initial stage of nucleate boiling indicate that the bubbles detached from the composite surface are much smaller in diameter than those detached from the pure copper surface. Typical photographs are presented.It shows that the bubbles departed from the composite surface have diameters of only O(0.1) mm, while those departed from the pure copper surface have diameters of O(1) mm. It is also found that the bubbles depart from the composite surface at a much higher frequency, thus forming vapor columns. These two phenomena combined with high thermal conductivity of the graphite fiber are considered the mechanisms for such a significant augmentation in nucleate boiling heat transfer on the composite surfaces. A physical model is developed to describe the phenomenon of bubble departure from the composite surface: The preferred site of bubble nucleation is the fiber tip because of higher tip temperature than the surrounding copper base and poor wettability of the graphite tip compared with that of the base material (copper). The high evaporation rate near the contact line produces the vapor cutback due to the vapor recoil pushing the three-phase line outwards from the fiber tip, and so a neck of the bubble is formed near the bubble bottom. Evaporation and surface tension accelerate the necking process and finally result in the bubble departure while a new small bubble is formed at the tip when the surface tension pushes the three-phase line back to the tip. The process is schematically shown. The proposed model is based on and confirmed by experimental results.

Zhang, Nengli↗

The influence of Ag+Mg additions on the nucleation of strengthening precipitates in a non-cold-worked Al-Cu-Li alloy

Aluminum-copper-lithium alloys generally require cold work to attain their highest strengths in artificially aged tempers. These alloys are usually strengthened by a combination of the metastable delta prime (Al3Li) and theta prime (Al2Cu) phases and the equilibrium T sub 1 (Al2CuLi) phase, and where the T sub 1 phase is a more potent strengthener than the delta prime. Various investigators have shown that the high strengths obtained after artificial aging associated with cold work result from the heterogeneous precipitation of T sub 1 on matrix dislocations. The objective here is to elucidate the mechanism by which the Ag+Mg additions stimulate the precipitation of T sub 1 type precipitates without cold work. To accomplish this, the microstructure of an Al-6.3Cu-1.3Li-0.14Zr model alloy was evaluated in a T6 type temper with and without the Ag+Mg addition.

Source record↗

Synthesis and structural chemistry of Au(III)-substituted Ba2YCu3O(7-delta)

Gold-substituted superconductors, Ba2Y(Au(x)Cu(1-x))3O(7-delta) (x = 0-0.1) were synthesized. For x = 0.1, there was no change in the a and b lattice parameters (a = 3.826 A and b = 3.889 A) but a 0.06 A c axis expansion to 11.75 A was observed. Substituted gold is found to be trivalent by XPS. Replacing Cu(1) in the copper oxide chain with a slight reordering of oxygen is consistent with c axis expansion. The formal charge of the site remains trivalent; remaining Cu in the chains may be reduced resulting in an oxygen stoichiometry is less than or equal to 7. A small effect on T(sub c)(89 K for x = 0.10) is observed upon gold substitution.

Hepp, A. F.↗

Structural chemistry of Au(III)-substituted Ba2YCu3O(7-delta)

A series of gold-substituted perovskite superconductors Ba2Y(Cu/1-x/Aux)3O(7-delta)(x = 0-0.1) was synthesized. For x = 0.1, there was no change in the a and b lattice parameters (a = 3.826 A and b = 3.889 A), but a 0.06 A c-axis expansion to 11.75 A was observed. Substituted gold was found to be trivalent by X-ray photoelectron spectroscopy. Replacing Cu(1) in the copper oxide chain with a slight reordering of oxygen is consistent with c-axis expansion. The formal charge of the site remains trivalent, while remaining Cu in the chains is reduced to Cu(I), resulting in an oxygen stoichiometry of less than 7. Finally, no large effect on Tc is observed (Tc = 89 K for x = 0.10), in contrast to the effect of a number of other metal ion dopants. These results are discussed relative to the chemistry of Au(III) and to the use of the metal in structures containing gold and ceramic superconductors.

Hepp, A. F.↗

Vanadium and copper in chondrites

V and Cu emission spectrographic analyses in chondrite types, noting distribution patterns between groups based on meteorite chemical fractionation mechanisms

Bingham, E.↗

Metallic copper in ordinary chondrites

Metallic Cu of moderately high purity (approximately 985 mg/g Cu, approximately 15 mg/g Ni) occurs in at least 66% of ordinary chondrites (OC) as heterogeneously distributed, small (typically less than or equal to 20 micrometers) rounded to irregular grains. The mean modal abundance of metallic Cu in H, L and LL chondrites is low: 1.0 to 1.4 x 10(exp -4) vol%, corresponding to only 4 - 5 % of the total Cu in OC whole rocks. In more than 75% of the metallic-Cu-bearing OC, at least some metallic Cu occurs at metallic-Fe-Ni-troilite grain boundaries. In some cases it also occurs within troilite, within metallic Fe-Ni, or at the boundaries these phases form with silicates or chromite. Ordinary chondrites that contain a relatively large number of occurrences of metallic Cu/sq mm have a tendency to have experienced moderately high degrees of shock. Shock processes can cause local melting and transportation of metallic Fe-Ni and troilte; because metallic Cu is mainly associated with these phases, it also gets redistributed during shock events. In the most common petrographic assemblage containing metallic Cu, the Cu is adjacent to small irregular troilite grains surrounded by taenite plus tetrataenite; this assemblage resembles fizzed troilite and may have formed by localized shock melting or remelting of a metal-troilite assemblage.

Rubin, Alan E.↗

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.↗

The effect of copper, chromium, and zirconium on the microstructure and mechanical properties of Al-Zn-Mg-Cu alloys

The present study evaluates the effect of the systematic variation of copper, chromium, and zirconium contents on the microstructure and mechanical properties of a 7000-type aluminum alloy. Fracture toughness and tensile properties are evaluated for each alloy in both the peak aging, T8, and the overaging, T73, conditions. Results show that dimpled rupture essentially characterize the fracture process in these alloys. In the T8 condition, a significant loss of toughness is observed for alloys containing 2.5 pct Cu due to the increase in the quantity of Al-Cu-Mg-rich S-phase particles. An examination of T8 alloys at constant Cu levels shows that Zr-bearing alloys exhibit higher strength and toughness than the Cr-bearing alloys. In the T73 condition, Cr-bearing alloys are inherently tougher than Zr-bearing alloys. A void nucleation and growth mechanism accounts for the loss of toughness in these alloys with increasing copper content.

Wagner, John A.↗

Copper Nanowire Production for Interconnect Applications

A method of fabricating metallic Cu nanowires with lengths up to about 25 micrometers and diameters in a range 20-100 nanometers, or greater if desired. Vertically oriented or laterally oriented copper oxide structures (CuO and/or Cu2O) are grown on a Cu substrate. The copper oxide structures are reduced with 99+ percent H or H2, and in this reduction process the lengths decrease (to no more than about 25 micrometers), the density of surviving nanostructures on a substrate decreases, and the diameters of the surviving nanostructures have a range, of about 20-100 nanometers. The resulting nanowires are substantially pure Cu and can be oriented laterally (for local or global interconnects) or can be oriented vertically (for standard vertical interconnects).

Han, Jin-Woo↗

Oxidation Behavior of GRCop-84 Copper Alloy Assessed

NASA's goal of safe, affordable space transportation calls for increased reliability and lifetimes of launch vehicles, and significant reductions of launch costs. The areas targeted for enhanced performance in the next generation of reusable launch vehicles include combustion chambers and nozzle ramps; therefore, the search is on for suitable liner materials for these components. GRCop-84 (Cu-8Cr-4Nb), an advanced copper alloy developed at the NASA Glenn Research Center in conjunction with Case Western Reserve University, is a candidate. The current liner of the Space Shuttle Main Engine is another copper alloy, NARloy-Z (Cu-3Ag-0.1Zr). It provides a benchmark against which to compare the properties of candidate successors. The thermomechanical properties of GRCop-84 have been shown to be superior, and its physical properties comparable, to those of NARloy-Z. However, environmental durability issues control longevity in this application: because copper oxide scales are not highly protective, most copper alloys are quickly consumed in oxygen environments at elevated temperatures. In consequence, NARloy-Z and most other copper alloys are prone to blanching, a degradation process that occurs through cycles of oxidation-reduction as the oxide is repeatedly formed and removed because of microscale fluctuations in the oxygen-hydrogen fuel systems of rocket engines. The Space Shuttle Main Engine lining typically degraded by blanching-induced hot spots that lead to surface roughening, pore formation, and coolant leakage. Therefore, resistance to oxidation and blanching are key requirements for second-generation reusable launch vehicle liners. The rocket engine ambient includes H2 (fuel) and H2O (combustion product) and is, hence, under reduced oxygen partial pressures. Accordingly, our studies were expanded to include oxygen partial pressures as low as 322 parts per million (ppm) at the temperatures likely to be experienced in service. A comparison of 10-hr weight gains of GRCop-84, NARloy-Z, and pure copper in 0.032, 2.2, and 100 percent oxygen from 550 to 750 C is shown. In 2.2 vol% and higher oxygen content, GRCop-84 oxidation was slower than that of NARloy-Z or Cu, but that advantage was lost or diminished in 322-ppm O2. Over longer (50-hr) exposures in 1.0 atm O2, however, the advantage of GRCop-84 increased significantly, its oxidation rate becoming approximately 10 times slower than those of Cu and NARloy-Z from 500 to 700 C. Weight gains were moderate and the kinetics parabolic for all three materials in 2.2 vol% and higher oxygen content; however, in 322-ppm O2, the scales were nonprotective below about 650 C, as reflected in linear kinetics and large weight gains. The superior oxidation resistance of GRCop-84 is likely related to the kinetics of extra oxygen consumption to form the additional oxides of Cr and Nb detected beneath the GRCop-84 oxide layer. While we continue to evaluate the blanching resistance of GRCop-84 in other tests, these oxidation results indicate that GRCop-84 is suitable as a reusable launch vehicle liner, and in applications where it is desired to use a copper alloy but without the risk of oxidative failure. Three bar charts comparing overall specific weight gains by each of the three materials studied. The top chart is for oxidation in 1.0 atm of oxygen, the middle is for 2.2% oxygen (balance argon), and the bottom is for 0.0322% oxygen. GRCop-84 outperforms the other two materials, showing the least weight gain in nearly all cases.

Thomas-Ogbuji, Linus U.↗

Spectra and energy levels of Cu XXII, Cu XXIII, Cu XXIV, and Cu XXV

Transitions in highly ionized copper in the wavelength range 65-121 A have been identified in spectra recorded at the University of Rochester's 24-beam Omega laser facility. Wavelengths and energy levels are presented for oxygenlike Cu XXII, nitrogenlike Cu XXII, carbonlike Cu XXIV, and boronlike Cu XXV. The wavelengths of magnetic dipole transitions within the ground configurations are predicted from the energy levels.

Ekberg, J. O.↗

GRCop-84 Rolling Parameter Study

This report is a section of the final report on the GRCop-84 task of the Constellation Program and incorporates the results obtained between October 2000 and September 2005, when the program ended. NASA Glenn Research Center (GRC) has developed a new copper alloy, GRCop-84 (Cu-8 at.% Cr-4 at.% Nb), for rocket engine main combustion chamber components that will improve rocket engine life and performance. This work examines the sensitivity of GRCop-84 mechanical properties to rolling parameters as a means to better define rolling parameters for commercial warm rolling. Experiment variables studied were total reduction, rolling temperature, rolling speed, and post rolling annealing heat treatment. The responses were tensile properties measured at 23 and 500 C, hardness, and creep at three stress-temperature combinations. Understanding these relationships will better define boundaries for a robust commercial warm rolling process. The four processing parameters were varied within limits consistent with typical commercial production processes. Testing revealed that the rolling-related variables selected have a minimal influence on tensile, hardness, and creep properties over the range of values tested. Annealing had the expected result of lowering room temperature hardness and strength while increasing room temperature elongations with 600 C (1112 F) having the most effect. These results indicate that the process conditions to warm roll plate and sheet for these variables can range over wide levels without negatively impacting mechanical properties. Incorporating broader process ranges in future rolling campaigns should lower commercial rolling costs through increased productivity.

Loewenthal, William S.↗