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Microsample Characterization of Coatings for GRCop-84 for High Temperature High Heat Flux Application

NASA's Glenn Research Center has developed GRCop-84 (Cu-8at.%Cr-4% Nb), a high conductivity, high strength copper alloy for use as liners in rocket engine combustion chambers, nozzle ramps and other actively-cooled components subject to high heat fluxes. Two metallic coatings, NiCrAlY and Cu-26%Cr, are being considered for preventing blanching, reducing 'dog- house' failures and providing better environmental resistance to the GRCop-84 liners. This presentation will outline a study of coating-substrate interactions that occur as a result of thermal cycling and coating specific properties at different temperatures. A furnace has been built to thermally cycle the samples under argon. The microsample testing approach is being used to measure the coating-substrate interfacial strength. Cu-26Cr/GRCop-84 samples did not show any obvious interdiffusion after 300 thermal cycles. Interfacial strength tests of these samples were affected by porosity present in the samples. A complete set of observations and results for Cu-26Cr and NiCrAlY coatings will be presented.

Jain, Piyush↗

Full-Scale GRCop-84 Combustion Chamber Liner Preform Fabricated Successfully

GRCop-84 (Cu-8 at.% Cr-4 at.% Nb) has been under development at the NASA Glenn Research Center for several years. The alloy possesses a unique combination of good thermal conductivity, high elevated temperature strength, long creep life, and long low-cycle- fatigue. The alloy is also more oxidation resistant than pure copper and most competitive alloys. The combination of properties has attracted attention from major rocket engine manufacturers who are interested in the alloy for the combustion chamber liner in their next generation of regeneratively cooled engines. Before GRCop-84 can be used in a main combustion chamber application, it must be demonstrated that the alloy can be made successfully to the large sizes and proper shape needed and that it retain useful properties. Recent efforts have successfully demonstrated the ability to fabricate a liner preform via metal spinning that retains the alloy s strength even in the welded sections.

Ellis, David L.↗

Quick Access Rocket Exhaust Rig Testing of Coated GRCop-84 Sheets Used to Aid Coating Selection for Reusable Launch Vehicles

The design of the next generation of reusable launch vehicles calls for using GRCop-84 copper alloy liners based on a composition1 invented at the NASA Glenn Research Center: Cu-8(at.%)Cr-4%Nb. Many of the properties of this alloy have been shown to be far superior to those of other conventional copper alloys, such as NARloy-Z. Despite this considerable advantage, it is expected that GRCop-84 will suffer from some type of environmental degradation depending on the type of rocket fuel utilized. In a liquid hydrogen (LH2), liquid oxygen (LO2) booster engine, copper alloys undergo repeated cycles of oxidation of the copper matrix and subsequent reduction of the copper oxide, a process termed "blanching". Blanching results in increased surface roughness and poor heat-transfer capabilities, local hot spots, decreased engine performance, and premature failure of the liner material. This environmental degradation coupled with the effects of thermomechanical stresses, creep, and high thermal gradients can distort the cooling channel severely, ultimately leading to its failure.

Raj, Sai V.↗

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.↗

Residual Stresses in Thermal Barrier Coatings for a Cu-8Cr-4Nb Substrate System

Analytical calculations were conducted to determine the thermal stresses developed in a coated copper-based alloy, Cu-8%(at.%)Cr-4%Nb (designated as GRCop-84), after plasma spraying and during heat-up in a simulated rocket engine environment. Finite element analyses were conducted for two coating systems consisting of a metallic top coat, a pure copper bond coat and the GRCop-84. The through thickness temperature variations were determined as a function of coating thickness for two metallic coatings, a Ni-17%(wt%)Cr-6%Al-0.5%Y alloy and a Ni-50%(at.%)Al alloy. The residual stresses after low-pressure plasma spraying of the NiCrAlY and NiAl coatings on GRCop-84 substrate were also evaluated. These analyses took into consideration a 50.8 mm copper bond coat and the effects of an interface coating roughness. The through the thickness thermal stresses developed in coated liners were also calculated after 15 minutes of exposure in a rocket environment with and without an interfacial roughness.

Ghosn, Louis J.↗

An Assessment of the Residual Stresses in Low Pressure Plasma Sprayed Coatings on an Advanced Copper Alloy

Modeling studies were conducted on low pressure plasma sprayed (LPPS) NiAl top coat applied to an advanced Cu-8(at.%)Cr-4%Nb alloy (GRCop-84) substrate using Ni as a bond coat. A thermal analysis suggested that the NiAl and Ni top and bond coats, respectively, would provide adequate thermal protection to the GRCop-84 substrate in a rocket engine operating under high heat flux conditions. Residual stress measurements were conducted at different depths from the free surface on coated and uncoated GRCop-84 specimens by x-ray diffraction. These data are compared with theoretically estimated values assessed by a finite element analysis simulating the development of these stresses as the coated substrate cools down from the plasma spraying temperature to room temperature.

Raj, S. V.↗

Conductivity of GRCop-42 Alloy Enhanced

GRCop-84, a material developed at the NASA Glenn Research Center, has shown considerable promise for staged combustion rocket engine cycles such as the Space Shuttle Main Engine. However, for an expander cycle rocket engine, the transfer of heat to the fuel is a paramount factor in determining the efficiency of the engine. Examples of current and potential future expander cycle rocket engines are the Pratt & Whitney RL-10, RL-60, and RLX engines. Development of a higher conductivity version of GRCop-84 was undertaken to meet these needs. All expander cycle engines need a main combustion chamber liner with the maximum possible thermal conductivity. In an effort at Glenn to trade some of the greatly increased mechanical properties of GRCop-84 for improved thermal conductivity, the amounts of chromium and niobium were halved. The new Cu-4 at.% Cr-2 at.% Nb alloy was designated GRCop-42.

Ellis, David L.↗

High Conductivity Materials for High Heat Flux Applications in Space Propulsion Systems

GRCop-84 is a new copper base alloy with an excellent combination of strength and conductivity and has been developed to the point that it is a strong candidate for near term rocket engine applications. This work sought to establish the feasibility of new alloys with capabilities beyond GRCop-84. The use of coatings as environmental and thermal barriers adds further capability into the Copper base structure. Finally, Nickel-Aluminum based systems have also been explored.

Nathal, M. V.↗

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.↗

Friction Stir Welding of GR-Cop 84 for Combustion Chamber Liners

GRCop-84 is a copper-chromium-niobium alloy developed by the Glenn Research Center for liquid rocket engine combustion chamber liners. GRCop-84 exhibits superior properties over conventional copper-base alloys in a liquid hydrogen-oxygen operating environment. The Next Generation Launch Technology program has funded a program to demonstrate scale-up production capabilities of GR-Cop 84 to levels suitable for main combustion chamber production for the prototype rocket engine. This paper describes a novel method of manufacturing the main combustion chamber liner. The process consists of several steps: extrude the GR-Cop 84 powder into billets, roll the billets into plates, bump form the plates into cylinder halves and friction stir weld the halves into a cylinder. The cylinder is then metal spun formed to near net liner dimensions followed by finish machining to the final configuration. This paper describes the friction stir weld process development including tooling and non-destructive inspection techniques, culminating in the successful production of a liner preform completed through spin forming.

Russell, Carolyn K.↗

Vacuum Plasma Spray Forming of Copper Alloy Liners for Regeneratively Cooled Liquid Rocket Combustion Chambers

Vacuum plasma spray (VPS) has been demonstrated as a method to form combustion chambers from copper alloys NARloy-Z and GRCop-84. Vacuum plasma spray forming is of particular interest in the forming of CuCrNb alloys such as GRCop-84, developed by NASA s Glenn Research Center, because the alloy cannot be formed using conventional casting and forging methods. This limitation is related to the levels of chromium and niobium in the alloy, which exceed the solubility limit in copper. Until recently, the only forming process that maintained the required microstructure of CrNb intermetallics was powder metallurgy formation of a billet from powder stock, followed by extrusion. This severely limits its usefulness in structural applications, particularly the complex shapes required for combustion chamber liners. This paper discusses the techniques used to form combustion chambers from CuCrNb and NARloy-Z, which will be used in regeneratively cooled liquid rocket combustion chambers.

Zimmerman, Frank↗

VPS Process for Copper Components in Thrust Chamber Assemblies

For several years, NASA's Marshall Space Flight Center (MSFC) has been working with Plasma Processes, Inc., (PPI) to fabricate thrust chamber liners with GRCop-84. Using the vacuum plasma spray (VPS) process, chamber liners of a variety of shapes and sizes have been created. Each has been formed as a functional gradient material (FGM) that creates a unique protective layer of NiCrAlY on the GRCop-84 liner s hot wall surface. Hot-fire testing was successfully conducted on a subscale unit to demonstrate the liner's durability and performance. Similar VPS technology has also been applied to create functional gradient coatings (FGC) on copper injector faceplates. Protective layers of NiCrAlY and zirconia were applied to both coaxial and impinging faceplate designs. Hot-fire testing is planned for these coated injectors in April 2005. The resulting material systems for both copper alloy components allows them to operate at higher temperatures with improved durability and operating margins.

Elam, Sandra↗

Chemical and Chemical-Mechanical Polishing of Surface Roughness on L-PBF/GRCop-42 Cu-Cr-Nb Additive Manufactured 10-GHz RF Structures

Laser-based powder bed fusion (L-PBF) allows additive manufacture (AM) of lower hybrid current drive (LHCD) radio-frequency (RF) launchers from Glenn Research Copper, a Cr 2 Nb precipitation-hardened alloy (GRCop-42) in configurations unachievable with conventional machining. Rough surfaces in AM components increase RF losses and lead to arcing in high-power vacuum RF applications. Chemical polishing, chemical-mechanical polishing, or a combination of both were utilized to planarize the internal surfaces of RF structures, resulting in surface roughness as low as R a = 0.2 µm. Refinement in polishing techniques now enables GRCop-42 alloys (4 at. % Cr, 2 at. % Nb) to achieve similar surface roughness to GRCop-84 (8 at. % Cr, 4 at. % Nb) and equivalent cavity losses to extruded oxygen-free copper waveguides at 10 GHz.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

2nd Generation Reusable Launch Vehicle NASA Led Propulsion Tasks

Design, development and test of a 2nd generation Reusable Launch Vehicle (RLV) is presented. This current paper discusses the following: 2nd Generation RLV Propulsion Project, Overview of NASA Led Tasks in Propulsion, Gen2 Turbo Machinery Technology Demonstrator, and Combustion Devices Test Bed, GRCop-84 Sheet For Combustion Chambers, Nozzles and Large Actively Cooled Structures

Richards, Steve↗

Oxidation Behavior of Copper Alloy Candidates for Rocket Engine Applications (Technical Poster)

A rocket engine's combustion chamber is lined with material that is highly conductive to heat in order to dissipate the huge thermal load (evident in a white-hot exhaust plume). Because of its thermal conductivity copper is the best choice of liner material. However, the mechanical properties of pure copper are inadequate to withstand the high stresses, hence, copper alloys are needed in this application. But copper and its alloys are prone to oxidation and related damage, especially "blanching" (an oxidation-reduction mode of degradation). The space shuttle main engine combustion chamber is lined with a Cu-Ag-Zr alloy, "NARloy-Z", which exhibits blanching. A superior liner is being sought for the next generation of RLVs (Reusable Launch Vehicles) It should have improved mechanical properties and higher resistance to oxidation and blanching, but without substantial penalty in thermal conductivity. GRCop84, a Cu-8Cr-4Nb alloy (Cr2Nb in Cu matrix), developed by NASA Glenn Research Center (GRC) and Case Western Reserve University, is a prime contender for RLV liner material. In this study, the oxidation resistance of GRCop-84 and other related/candidate copper alloys are investigated and compared

Ogbuji, Linus U. J.↗

RP-1 Thermal Stability and Copper Based Materials Compatibility Study

A series of electrically heated tube tests was performed at the NASA Glenn Research Center s Heated Tube Facility to investigate the effect that sulfur content, test duration, and tube material play in the overall thermal stability and materials compatibility characteristics of RP-1. Scanning-electron microscopic (SEM) analysis in conjunction with energy dispersive spectroscopy (EDS) were used to characterize the condition of the tube inner wall surface and any carbon deposition or corrosion formed during these runs. Results of the parametric study indicate that tests with standard RP-1 (total sulfur -23 ppm) and pure copper tubing are characterized by a depostion/deposit shedding process producing local wall temperature swings as high as 500 F. The effect of this shedding is to keep total carbon deposition levels relatively constant for run times from 20 minutes up to 5 hours, though increasing tube pressure drops were observed in all runs. Reduction in the total sulfur content of the fuel from 23 ppm to less than 0.1 ppm resulted in the elimination of deposit shedding, local wall temperature variation, and the tube pressure drop increases that were observed in standard sulfur level RP-1 tests. The copper alloy GRCop-84, a copper alloy developed specifically for high heat flux applications, was found to exhibit higher carbon deposition levels compared to identical tests performed in pure copper tubes. Results of the study are consistent with previously published heated tube data which indicates that small changes in fuel total sulfur content can lead to significant differences in the thermal stability of kerosene type fuels and their compatibility with copper based materials. In conjunction with the existing thermal stability database, these findings give insight into the feasibility of cooling a long life, high performance, high-pressure liquid rocket combustor and nozzle with RP-1.

Stiegemeier, B. R.↗

Oxidation of Copper Alloy Candidates for Rocket Engine Applications

The gateway to affordable and reliable space transportation in the near future remains long-lived rocket-based propulsion systems; and because of their high conductivities, copper alloys remain the best materials for lining rocket engines and dissipating their enormous thermal loads. However, Cu and its alloys are prone to oxidative degradation -- especially via the ratcheting phenomenon of blanching, which occurs in situations where the local ambient can oscillate between oxidation and reduction, as it does in a H2/02- fuelled rocket engine. Accordingly, resistance to blanching degradation is one of the key requirements for the next generation of reusable launch vehicle (RLV) liner materials. Candidate copper alloys have been studied with a view to comparing their oxidation behavior, and hence resistance to blanching, in ambients corresponding to conditions expected in rocket engine service. These candidate materials include GRCop-84 and GRCop-42 (Cu - Cr-8 - Nb-4 and Cu - Cr-4 - Nb-2 respectively); NARloy-Z (Cu-3%Ag-0.5%Y), and GlidCop (Cu-O.l5%Al2O3 ODS alloy); they represent different approaches to improving the mechanical properties of Cu without incurring a large drop in thermal conductivity. Pure Cu (OFHC-Cu) was included in the study to provide a baseline for comparison. The samples were exposed for 10 hours in the TGA to oxygen partial pressures ranging from 322 ppm to 1.0 atmosphere and at temperatures of up to 700 C, and examined by SEM-EDS and other techniques of metallography. This paper will summarize the results obtained.

Ogbuji, Linus U. Thomas↗

NiAl Coatings Investigated for Use in Reusable Launch Vehicles

As part of its major investment in the area of advanced space transportation, NASA is developing new technologies for use in the second- and third-generation designs of reusable launch vehicles. Among the prototype rocket engines being considered for these launch vehicles are those designed to use liquid hydrogen as the fuel and liquid oxygen as the oxidizer. Advanced copper alloys, such as copper-chromium-niobium (Cu-8(at.%)Cr- 4(at.%)Nb, also referred to as GRCop-84), which was invented at the NASA Glenn Research Center, are being considered for use as liner materials in the combustion chambers and nozzle ramps of these engines. However, previous experience has shown that, in rocket engines using liquid hydrogen and liquid oxygen, copper alloys are subject to a process called blanching, where the material undergoes environmental attack under the action of the combustion gases. In addition, the copper alloy liners undergo thermomechanical fatigue, which often results in an initially square cooling channel deforming into a dog-house shape. Clearly, there is an urgent need to develop new coatings to protect copper liners from environmental attack inside rocket chambers and to lower the temperature of the liners to reduce the probability of deformation and failure by thermomechanical fatigue.

Raj, Sai V.↗