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Viewgraphs and explanations on laser diagnostics for nuclear thermal propulsion (NTP) fuel corrosion studies are presented. Topics covered include: NTP fuels; U-Zr-C system corrosion products; planar laser-induced fluorescence (PLIF); utilization of PLIF for corrosion product characterization of nuclear thermal rocket fuel elements under test; ZrC emission spectrum; and PLIF imaging of ZrC plume.
Corrosion (mass loss) of carbide nuclear fuels due to their exposure to hot hydrogen in nuclear thermal propulsion engine systems greatly impacts the performance, thrust-to-weight and life of such systems. This report provides an overview of key issues and processes associated with the corrosion of carbide materials. Additionally, past pertinent development reactor test observations, as well as related experimental work and analysis modeling efforts are reviewed. At the conclusion, recommendations are presented, which provide the foundation for future corrosion modeling and verification efforts.
Corrosion problems with simulated fuel in launch vehicle models
Literature synthesized to develop corrosion predictions for unconventional fuels. Report presents studies of probable corrosive effects of such unconventional fuels as liquefied coal. Report prepared by analyzing probable composition of fuels when they come into wide use, identifying important compounds, and searching literature for information about corrosion problems associated with compounds in environments like those in industrial and commercial boilers and furnaces.
Four cast superalloys (one cobalt-base and three nickel-base) were tested at 900 C for 100 h in Mach 0.3 combustion gases. 5 ppm of synthetic sea salt were added to the gases in the combustion chamber. Several types of thermal cycle and washing procedures were employed. Similar tests were made with the addition of 300 ppm of a chromium-containing fuel additive. In both sets of tests the extent of hot corrosion was evaluated by specific weight change and metal recession. In general, the chromium additive in the fuel reduced the extent of hot (salt) corrosion but did not eliminate it. The percentage reduction of hot corrosion attack was similar for all four alloys. As great a reduction of hot corrosion was achieved by reducing the number of thermal cycles during the test from 100 to 5 or 6. The effect of washing the alloys every ten cycles as opposed to the end of the test was erratic; some alloys were attacked slightly more, others somewhat less. A NiCrAlY coating was found to be more effective in reducing hot corrosion than either the fuel additive or the washing schedule.
Four superalloys were tested at 900 C in high velocity combustion gases containing synthetic sea salt and, in some cases, a chromium containing fuel additive. While the additive reduced hot corrosion of the alloys over the 100 hour test period, the attack was not eliminated nor was the mode of attack changed. Reduction of the number of thermal cycles had as large a beneficial effect as the Cr additive. Intermittent washing during testing had either small beneficial or adverse effects depending on the alloy.
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In recent years there has been increased interest in the development of a new generation of high performance boost rocket engines. These efforts, which will represent a substantial advancement in boost engine technology over that developed for the Space Shuttle Main Engines in the early 1970s, are being pursued both at NASA and the United States Air Force. NASA, under its Space Launch Initiative s Next Generation Launch Technology Program, is investigating the feasibility of developing a highly reliable, long-life, liquid oxygen/kerosene (RP-1) rocket engine for launch vehicles. One of the top technical risks to any engine program employing hydrocarbon fuels is the potential for fuel thermal stability and material compatibility problems to occur under the high-pressure, high-temperature conditions required for regenerative fuel cooling of the engine combustion chamber and nozzle. Decreased heat transfer due to carbon deposits forming on wetted fuel components, corrosion of materials common in engine construction (copper based alloys), and corrosion induced pressure drop increases have all been observed in laboratory tests simulating rocket engine cooling channels. To mitigate these risks, the knowledge of how these fuels behave in high temperature environments must be obtained. Currently, due to the complexity of the physical and chemical process occurring, the only way to accomplish this is empirically. Heated tube testing is a well-established method of experimentally determining the thermal stability and heat transfer characteristics of hydrocarbon fuels. The popularity of this method stems from the low cost incurred in testing when compared to hot fire engine tests, the ability to have greater control over experimental conditions, and the accessibility of the test section, facilitating easy instrumentation. These benefits make heated tube testing the best alternative to hot fire engine testing for thermal stability and heat transfer research. This investigation used the Heated Tube Facility at the NASA Glenn Research Center to perform a thermal stability and heat transfer characterization of RP-1 in an environment simulating that of a high chamber pressure, regenerative cooled rocket engine. The first step in the research was to investigate the carbon deposition process of previous heated tube experiments by performing scanning electron microscopic analysis in conjunction with energy dispersive spectroscopy on the tube sections. This analysis gave insight into the carbon deposition process and the effect that test conditions played in the formation of deleterious coke. Furthermore, several different formations were observed and noted. One other crucial finding of this investigation was that in sulfur containing hydrocarbon fuels, the interaction of the sulfur components with copper based wall materials presented a significant corrosion problem. This problem in many cases was more life limiting than those posed by the carbon deposition process. The results of this microscopic analysis was detailed and presented at the December 2003 JANNAF Air-Breathing Propulsion Meeting as a Materials Compatibility and Thermal Stability Analysis of common Hydrocarbon Fuels (reference 1).
It is desirable to employ a corrosion screening test for catalyst or support candidates for the fuel cell cathode before entering upon optimization of the candidate or of the catalytic electrode. To this end, corrosion test electrodes, intended for complete immersion and maximum wetting, have been made with 30 to 40 vol. pct Teflon; with perovskites this is about 10 to 15 pct. The candidates were synthesized by methods intended for single-phase product without special emphasis on high surface area, although the substances tested were no coarser than 2 m squared/g. A typical loading was 25 mg/cm sq of the pure substance, usually on gold screen, a few mm squared of which were left bare for contacting. Contact to the gold lead wire was made by welding with a micro-torch or a spot-welder. Corrosion testing consisted of obtaining current-voltage data under flowing inert gas in the potential region for reduction of O2. The electrode was immersed in 30 pct KOH. Observations were made at 20 C and 80 C, and the results compared with data from gold standards. Results with some perovskites, pyrochlores, spinels, and interstitial compounds will be discussed.
Current/voltage data was obtained for specially made corrosion electrodes of some oxides and of gold materials for the purpose of developing a screening test of catalysts and supports for use at the cathode of the alkaline fuel cell. The data consists of measurements of current at fixed potentials and cyclic voltammograms. These data will have to be correlated with longtime performance data in order to fully evaluate this approach to corrosion screening. Corrosion test screening of candidates for the oxygen reduction electrode of the alkaline fuel cell was applied to two substances, the pyrochlore Pb2Ru2O6.5 and the spinel NiCo2O4. The substrate gold screen and a sample of the IFC Orbiter Pt-Au performance electrode were included as blanks. The pyrochlore data indicate relative stability, although nothing yet can be said about long term stability. The spinel was plainly unstable. For this type of testing to be validated, comparisons will have to be made with long term performance tests.
Current/voltage data have been obtained for specially made corrosion electrodes of some oxides and of gold materials for the purpose of developing a screening test of catalysts and supports for use at the cathode of the alkaline fuel cell. The data consist of measurements of current at fixed potentials and cyclic voltammograms. These data will have to be correlated with longtime performance data in order to evaluate fully this approach to corrosion screening.
Methods of preparing suspensions of a hydrocarbon in slush hydrogen for nuclear fuel element corrosion inhibition in rocket engines were investigated. Suspensions were prepared using approximately 5000 ppm by mass of methane, ethane, or cyclopropane in slush hydrogen. The suspensions were stable in the slush, but the hydrocarbons settled out of the liquid melt.
Two-layer thermal barrier coating, consisting of metal-CrA1Y bond coating and calcium silicate ceramic outer layer, greatly improves resistance of turbine parts to hot corrosion from fuel and air impurities. Both layers can be plasma sprayed, and ceramic layer may be polished to reduce frictional losses. Ceramic provides thermal barrier, so parts operate cooler metal temperatures, coolant flow can be reduced, or gas temperatures increased. Lower grade fuels also can be used.
A comprehensive NASA-Lewis program of coating development for aircraft gas turbine blades and vanes is presented. Improved ceramic layer compositions are investigated, along the MCrAlY bond films and the methods of uniform deposition of the coatings; the thermomechanical and fuel impurity tolerance limits of the coatings are being studied. Materials include the ZrO2-Y2O3/NiCrAlY system; the effects of the bond coat and zirconia composition on coating life and Mach 1 burner rig test results are discussed. It is concluded that Diesel engines can also utilize thermal barrier coatings; they have been used successfully on piston crowns and exhaust valves of shipboard engines to combat lower grade fuel combustion corrosion.
A multihundred kilowatt Regenerative Fuel Cell for use in a space station is envisioned. Three 0.508 sq ft (471.9 cm) active area multicell stacks were assembled and endurance tested. The long term performance stability of the platinum on carbon catalyst configuration suitability of the lightweight graphite electrolyte reservoir plate, the stability of the free standing butyl bonded potassium titanate matrix structure, and the long life potential of a hybrid polysulfone cell edge frame construction were demonstrated. A 18,000 hour demonstration test of multicell stack to a continuous cyclical load profile was conducted. A total of 12,000 cycles was completed, confirming the ability of the alkaline fuel cell to operate to a load profile simulating Regenerative Fuel Cell operation. An orbiter production hydrogen recirculation pump employed in support of the cyclical load profile test completed 13,000 hours of maintenance free operation. Laboratory endurance tests demonstrated the suitability of the butyl bonded potassium matrix, perforated nickel foil electrode substrates, and carbon ribbed substrate anode for use in the alkaline fuel cell. Corrosion testing of materials at 250 F (121.1 C) in 42% wgt. potassium identified ceria, zirconia, strontium titanate, strontium zirconate and lithium cobaltate as candidate matrix materials.
Nuclear Thermal Propulsion (NTP) was started in ~1955 under the Atomic Energy Commission as project Rover and was assigned to Los Alamos National Laboratory. The Nevada Test Site was selected in 1956 and facility construction began in 1957. The KIWI-A was tested on July 1, 1959 for 5 minutes at 70MW. KIWI-A1 was tested on July 8, 1960 for 6 minutes at 85MW. KIWI-A3 was tested on October 10, 1960 for 5 minutes at 100MW. The National Aeronautics and Space Administration (NASA) was formed in 1958. On August 31, 1960 the AEC and NASA established the Space Nuclear Propulsion Office and named Harold Finger as Director. Immediately following the formation of SNPO, contracts were awarded for the Reactor In Flight Test (RIFT), master plan for the Nuclear Rocket Engine Development Station (NRDS), and the Nuclear Engine for Rocket Vehicle Application (NERVA). From December 7, 1961 to November 30, 1962, the KIWI-B1A, KIWI-B1B, and KIWI-B4A were tested at test cell A. The last two engines were only tested for several seconds before noticeable failure of the fuel elements. Harold Finger called a stop to any further hot fire testing until the problem was well understood. The KIWI-B4A cold flow test showed the problem to be related to fluid dynamics of hydrogen interstitial flow causing fuel element vibrations. President Kennedy visited the NTS one week after the KIWI-B4A failure and got to see the engine starting to be disassembled in the maintenance facility. The KIWI-B4D and KIWI-B4E were modified to not have the vibration problems and were tested in test cell C. The NERVA NRX program started testing in early 1964 with NRX-A1 cold flow test series (unfueled graphite core), NRX-A2 and NRX-A3 power test series up to 1122 MW for 13 minutes. In March 1966, the NRX-EST (Engine System Test) was the first breadboard using flight functional relationship and total operating time of 116 minutes. The NRX-EST demonstrated the feasibility of a hot bleed cycle. The NRX-A5 had multiple start-ups in May-June 1966 with 30.75 minutes accumulative operating time at or above 1GW. The NRX-A6 was tested in December 1969 and ran for 62 minutes at 1100 MW. Each engine had post-test examination and found various structure anomalies which were identified for correction and the fuel element corrosion rate was reduced. The Phoebus series of research reactors began testing at test cell C, in June 1965 with Phoebus 1A. Phoebus 1A operated for 10.5 minutes at 1100 MW before unexpected loss of propellant and leading to an engine breakdown. Phoebus 1B ran for 30 minutes in February of 1967. Phoebus 2A was the highest steady state reactor built at 5GW. Phoebus 2A ran for 12 minutes at 4100 MW demonstrating sufficient power is available. The Peewee test bed reactor was tested November- December 1968 in test cell C for 40 minutes at 500MW with overall performance close to pre-run predictions. The XE' engine was the only engine tested with close to a flight configuration and fired downward into a diffuser at the Engine Test Stand (ETS) in 1969. The XE' was 1100 MW and had ~28 start-ups. The nuclear furnace NF-1 was operated at 44 MW with multiple test runs at 90 minutes in the summer of 1972. The NF-1 was the last NTP reactor tested. The Rover/NERVA program was cancelled in 1973. However, before cancellation, a lot of other engineering work was conducted by Aerojet on a 75, 000 lbf prototype flight engine and by Los Alamos on a ~16,000 lbf "Small Engine" nuclear rocket design. The ground test history of NTP at the NRDS also offers many lessons learned on how best to setup, operate, emergency shutdown, and post-test examine NTP engines. The reactor and engine maintenance and disassembly facilities were used for assembly and inspection of radioactive engines after testing. Most reactor/ engines were run at test cell A or test cell C with open air exhaust. The Rover/NERVA program became aware of a new environmental regulation that would restrict the amount of radioactive particulates allowed to be release in open air and successfully demonstrated a scrubber concept with the NF-1. The ETS stand was the only one with a high altitude test chamber used for XE'. The ETS and other test cells showed the effects the engine's radiation had on the facility materials and instrumentation as well as side effects the ground test facility has back on the engine operation. The breakdown of Phoebus 1A at test cell C showed how the site was cleaned up and back to operation for five more engines before the program was cancelled.
An evaluation is made of combustion product/combustion chamber compatibility in the case of a LOX/liquid hydrocarbon booster engine based on copper-alloy thrust chamber which is regeneratively cooled by the fuel. It is found that sulfur impurities in the fuel are the primary causes of copper corrosion, through formation of Cu2S; sulfur levels as low as 1 ppm can result in sufficiently severe copper corrosion to degrade cooling channel performance. This corrosion can be completely eliminated, however, through the incorporation of an electrodeposited gold coating on the copper cooling-channel walls.
Based on an analysis of the interaction of fuel physical and chemical properties with combustion characteristics and indicators, a ranking of the importance of various fuel properties with respect to the combustion process was established. This ranking was used to define a suite of specific experiments whose objective is the development of an alternative fuels design data base. Combustion characteristics and indicators examined include droplet and spray formation, droplet vaporization and burning, ignition and flame stabilization, flame temperature, laminar flame speed, combustion completion, soot emissions, NOx and SOx emissions, and the fuels' thermal and oxidative stability and fouling and corrosion characteristics. Key fuel property data is found to include composition, thermochemical data, chemical kinetic rate information, and certain physical properties.