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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1981

Cell and method for electrolysis of water and anode

An electrolytic cell for converting water vapor to oxygen and hydrogen include an anode comprising a foraminous conductive metal substrate with a 65-85 weight percent iridium oxide coating and 15-35 weight percent of a high temperature resin binder. A matrix member contains an electrolyte to which a cathode substantially inert. The foraminous metal member is most desirably expanded tantalum mesh, and the cell desirably includes reservoir elements of porous sintered metal in contact with the anode to receive and discharge electrolyte to the matrix member as required. Upon entry of a water vapor containing airstream into contact with the outer surface of the anode and thence into contact with iridium oxide coating, the water vapor is electrolytically converted to hydrogen ions and oxygen with the hydrogen ions migrating through the matrix to the cathode and the oxygen gas produced at the anode to enrich the air stream passing by the anode.

Aylward, J. R.↗
NASA NTRS2010

Electrochemical Detection of Multiple Bioprocess Analytes

An apparatus that includes highly miniaturized thin-film electrochemical sensor array has been demonstrated as a prototype of instruments for simultaneous detection of multiple substances of interest (analytes) and measurement of acidity or alkalinity in bioprocess streams. Measurements of pH and of concentrations of nutrients and wastes in cell-culture media, made by use of these instruments, are to be used as feedback for optimizing the growth of cells or the production of desired substances by the cultured cells. The apparatus is designed to utilize samples of minimal volume so as to minimize any perturbation of monitored processes. The apparatus can function in a potentiometric mode (for measuring pH), an amperometric mode (detecting analytes via oxidation/reduction reactions), or both. The sensor array is planar and includes multiple thin-film microelectrodes covered with hydrous iridium oxide. The oxide layer on each electrode serves as both a protective and electrochemical transducing layer. In its transducing role, the oxide provides electrical conductivity for amperometric measurement or pH response for potentiometric measurement. The oxide on an electrode can also serve as a matrix for one or more enzymes that render the electrode sensitive to a specific analyte. In addition to transducing electrodes, the array includes electrodes for potential control. The array can be fabricated by techniques familiar to the microelectronics industry. The sensor array is housed in a thin-film liquid-flow cell that has a total volume of about 100 mL. The flow cell is connected to a computer-controlled subsystem that periodically draws samples from the bioprocess stream to be monitored. Before entering the cell, each 100-mL sample is subjected to tangential-flow filtration to remove particles. In the present version of the apparatus, the electrodes are operated under control by a potentiostat and are used to simultaneously measure the pH and the concentration of glucose. It is anticipated that development of procedures for trapping more enzymes into hydrous iridium oxide (and possibly into other electroactive metal oxides) and of means for imparting long-term stability to the transducer layers should make it possible to monitor concentrations of products of many enzyme reactions for example, such key bioprocess analytes as amino acids, vitamins, lactose, and acetate.

Rauh, R. David↗
NASA NTRS2011

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Valdez, Thomas I.↗
NASA NTRS1981

Improved cell for water-vapor electrolysis

Continuous-flow electrolytic cells decompose water vapor in steam and room air into hydrogen and oxygen. Sintered iridium oxide catalytic anode coating yields dissociation rates hundredfold greater than those obtained using platinum black. Cell consists of two mirror-image cells, with dual cathode sandwiched between two anodes. Gas traverses serpentine channels within cell and is dissociated at anode. Oxygen mingles with gas stream, while hydrogen migrates through porous matrix and is liberated as gas at cathode.

Aylward, J. R.↗
NASA NTRS1997

A Rocket Engine for Mars Sample Return Using In Situ Propellants

Recent studies for the planned Mars sample return mission were reviewed and modified to utilize carbon monoxide and oxygen as potential in situ propellants. Based on these studies a representative full scale engine thrust of 2225 N (500 lbf) was selected as appropriate to demonstrate performance, and the design for that engine is presented. Previous experimental results combined with parametric analyses were used to define the geometry for the engine which operates on liquid carbon monoxide and liquid oxygen. The engine was constructed using a combination of high-temperature alloys and lightweight ceramics. The materials selected were hafnium oxide, iridium, rhenium, and carbon-carbon.

Linne, Diane L.↗
NASA NTRS2015

Low-Cost, High-Performance Combustion Chamber

Ultramet designed and fabricated a lightweight, high-temperature combustion chamber for use with cryogenic LOX/CH4 propellants that can deliver a specific impulse of approx.355 seconds. This increase over the current 320-second baseline of nitrogen tetroxide/monomethylhydrazine (NTO/MMH) will result in a propellant mass decrease of 55 lb for a typical lunar mission. The material system was based on Ultramet's proven oxide-iridium/rhenium architecture, which has been hot-fire tested with stoichiometric oxygen/hydrogen for hours. Instead of rhenium, however, the structural material was a niobium or tantalum alloy that has excellent yield strength at both ambient and elevated temperatures. Phase I demonstrated alloys with yield strength-to-weight ratios more than three times that of rhenium, which will significantly reduce chamber weight. The starting materials were also two orders of magnitude less expensive than rhenium and were less expensive than the C103 niobium alloy commonly used in low-performance engines. Phase II focused on the design, fabrication, and hot-fire testing of a 12-lbf thrust class chamber with LOX/CH4, and a 100-lbf chamber for LOX/CH4. A 5-lbf chamber for NTO/MMH also was designed and fabricated.

Fortini, Arthur J.↗
NASA NTRSDate not supplied

Autonomous Measurement of Electrochemical Redox Couples for In-Situ Characterization of Enceladus Plume Samples

A 3D-printed microfluidic electrochemical cell with integrated electrodes was developed to demonstrate autonomous in-situ electrochemical characterization of terrestrial seawater samples. The system is designed to extend the capabilities of the 2008 Phoenix Lander’s Wet Chemistry Laboratory (WCL) that analyzed the soluble chemistry of the Martian soil, by miniaturizing its fluidic architecture for analysis of µL-volume samples as expected from an Enceladus fly-by mission. The microfluidic device has a total fluid volume of 48 µL and includes dual channels each populated with 7 electrodes. Measurement of pH was measured using an iridium oxide electrode. Cyclic voltammetry with Au, Pt, and glassy carbon working electrodes was used to measure redox couples in synthetic seawater that contained inorganic and bio-organic molecules. Glassy carbon was found to have minimal risk of interference from constituents of synthetic seawater when measuring molecular organic redox species; however, care must be used to prevent interference due to potential oxidation or dissolution in the case of Au working electrodes. A completely autonomous end-to-end run including sample delivery was performed, to demonstrate the feasibility of microfluidic-based cyclic voltammetry measurements for in-situ characterization of redox couples in Ocean World samples.

Planetary Instruments↗
NASA NTRS1994

Evaluation of oxide-coated iridium-rhenium chambers

Iridium-coated rhenium (Ir-Re) provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase Ir-Re rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated Ir-Re, 22-N rocket chambers were tested with gaseous hydrogen/gaseous oxygen (GHz/G02) propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia (HfO2) or zirconia (ZrO2). Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of ZrO2 infiltrated with sol gel HfO2. The other chamber had a coating composed of an Ir-oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. Testing the Ir-oxide composite-coated chamber included over 29 min at mixture ratio 16. The thicker walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner walled coatings did not experience the macrocracking and chipping of the chambers that was seen with the thick, monolithic coatings. However, burn-throughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stoichiometric. The burn-throughs were probably the result of oxygen diffusion through the oxide coating that allowed the underlying Ir and Re layers to be oxidized. The results of this test program indicated that the thin-walled oxide coatings are better suited for repeated thermal cycling than the thick-walled coating, while thicker coatings may be required for operation in aggressively oxidizing environments.

Reed, Brian D.↗
NASA NTRS2010

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Shchetkovskiy, Anatoliy↗
NASA NTRS2010

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Shchetkovskiy, Anatoliy↗
NASA NTRS1995

High-Temperature Oxidation Behavior of Iridium-Rhenium Alloys

The life-limiting mechanism for radiation-cooled rockets made from iridium-coated rhenium (Ir/Re) is the diffusion of Re into the Ir layer and the subsequent oxidation of the resulting Ir-Re alloy from the inner surface. In a previous study, a life model for Ir/Re rockets was developed. It incorporated Ir-Re diffusion and oxidation data to predict chamber lifetimes as a function of temperature and oxygen partial pressure. Oxidation testing at 1540 deg C suggested that a 20-wt percent Re concentration at the inner wall surface should be established as the failure criterion. The present study was performed to better define Ir-oxidation behavior as a function of Re concentration and to supplement the data base for the life model. Samples ranging from pure Ir to Ir-40 wt percent Re (Ir-40Re) were tested at 1500 deg C, in two different oxygen environments. There were indications that the oxidation rate of the Ir-Re alloy increased significantly when it went from a single-phase solid solution to a two-phase mixture, as was suggested in previous work. However, because of testing anomalies in this study, there were not enough dependable oxidation data to definitively raise the Ir/Re rocket failure criterion from 20-wt percent Re to a Re concentration corresponding to entry into the two-phase region.

Reed, Brian D.↗
NASA NTRS1993

Design, analysis, and fabrication of oxide-coated iridium/rhenium combustion chambers

Iridium-coated rhenium (Ir/Re) combustion chambers provide high temperature, oxidation-resistant operation for radiation-cooled liquid-fueled rocket engines. A 22-N (5-lb(sub f)) chamber has been operated for 15 hours at 2200 C (4000 F) using nitrogen tetroxide/monomethyl hydrazine (NTO/MMH) propellant, with negligible internal erosion. The oxidation resistance of these chambers could be further increased by the addition of refractory oxide coatings, providing longer life and/or operation in more oxidizing and higher temperature environments. The oxide coatings would serve as a thermal and diffusion barrier for the iridium coating, lowering the temperature of the iridium layer while also preventing the ingress of oxygen and egress of iridium oxides. This would serve to slow the failure mechanisms of Ir/Re chambers, namely the diffusion of rhenium to the inner surface and the oxidation of iridium. Such protection could extend chamber lifetimes by tens or perhaps hundreds of hours, and allow chamber operation on stoichiometric or higher mixture ratio oxygen/hydrogen (O2/H2) propellant. Extensive thermomechanical, thermochemical, and mass transport modeling was performed as a key material/structure design tool. Based on the results of these analyses, several 22-N oxide-coated Ir/Re chambers were fabricated and delivered to NASA Lewis Research Center for hot-fire testing.

Jang, Q.↗
NASA NTRS1960

Oxidation Behavior of Binary Niobium Alloys

This investigation concludes a study to determine the effects of up to 25 atomic percent of 55 alloying additions on the oxidation characteristics of niobium. The alloys were evaluated by oxidizing in an air atmosphere for 4 hours at 1000 C and 2 hours at 1200 C. Titanium and chromium improved oxidation resistance at both evaluation conditions. Vanadium and aluminum improved oxidation resistance at 1000 C, even though the V scale tended to liquefy and the Al specimens became brittle and the scale powdery. Copper, cobalt, iron, and iridium improved oxidation resistance at 1200 C. Other investigations report tungsten and molybdenum are protective up to about 1000 C, and tantalum at 1100 C. The most important factor influencing the rate of oxidation was the ion size of the alloy additions. Ions slightly smaller than the Nb(5+) ion are soluble in the oxide lattice and tend to lower the compressive stresses in the bulk scale that lead to cracking. The solubility of the alloying addition also depends on the valence to some extent. All of the elements mentioned that improve the oxidation resistance of Nb fit this size criterion with the possible exception of Al, whose extremely small size in large concentrations would probably lead to the formation of a powdery scale. Maintenance of a crack-free bulk scale for as long as possible may contribute to the formation of a dark subscale that ultimately is rate- controlling in the oxidation process. The platinum-group metals, especially Ir, appear to protect by entrapment of the finely dispersed alloying element by the incoming Nb2O5 metal-oxide interface. This inert metallic Ir when alloyed in a sufficient amount with Yb appears to give a ductile phase dispersed in the brittle oxide. This scale would then flow more easily to relieve the large compressive stresses to delay cracking. Complex oxide formation (which both Ti and Zr tend to initiate) and valence effects, which probably change the vacancy concentration in the scale, are masked by the overriding tendency for a porous scale.

Barrett, Charles A.↗
NASA NTRS1976

Studies of noble-metal thermocouple stability at high temperatures

Two investigatory studies on performance characteristics of noble-metal thermocouples are described. (1) thermoelectric stability as affected by preferential oxidation of iridium in the system iridium-40% rhodium versus iridium, and (2) the effects of temperature gradients on the emf stability of the systems platinum-13% rhodium versus platinum and iridium-40% rhodium versus iridium, operating in air. The stability investigation was carried out at three temperatures - 1700, 1850, and 2000 C - by comparing the output of the test thermocouple in air with the output of an identically constructed reference thermocouple in nitrogen. The results show that no calibration shift was observed producing a change in output greater than that corresponding to a 2.0% change in the indicated temperature for all samples tested. The investigation of gradient effects was carried out by subjecting test thermocouples to both severe and mild gradients for periods up to 200 hours. For the platinum system, the operating temperature was 1500 C with gradients of 1475 and 700 C/cm; for the iridium system, 2000 C with gradients of 700, 1500, and 1975 C/cm. Exposure to temperature gradients was found to introduce significant changes in calibration for both systems. In both investigations, the thermoelements were examined by means of electron-probe analysis and by metallographic methods to detect chemical and structural changes. Data and micrographs are presented.

Freeze, P.↗
NASA NTRS1992

Low thrust chemical rocket technology

An on-going technology program to improve the performance of low thrust chemical rockets for spacecraft on-board propulsion applications is reviewed. Improved performance and lifetime is sought by the development of new predictive tools to understand the combustion and flow physics, introduction of high temperature materials and improved component designs to optimize performance, and use of higher performance propellants. Improved predictive technology is sought through the comparison of both local and global predictions with experimental data. Predictions are based on both the RPLUS Navier-Stokes code with finite rate kinetics and the JANNAF methodology. Data were obtained with laser-based diagnostics along with global performance measurements. Results indicate that the modeling of the injector and the combustion process needs improvement in these codes and flow visualization with a technique such as 2-D laser induced fluorescence (LIF) would aid in resolving issues of flow symmetry and shear layer combustion processes. High temperature material fabrication processes are under development and small rockets are being designed, fabricated, and tested using these new materials. Rhenium coated with iridium for oxidation protection was produced by the Chemical Vapor Deposition (CVD) process and enabled an 800 K increase in rocket operating temperature. Performance gains with this material in rockets using Earth storable propellants (nitrogen tetroxide and monomethylhydrazine or hydrazine) were obtained through component redesign to eliminate fuel film cooling and its associated combustion inefficiency while managing head end thermal soakback. Material interdiffusion and oxidation characteristics indicated that the requisite lifetimes of tens of hours were available for thruster applications. Rockets were designed, fabricated, and tested with thrusts of 22, 62, 440 and 550 N. Performance improvements of 10 to 20 seconds specific impulse were demonstrated. Higher performance propellants were evaluated: Space storable propellants, including liquid oxygen (LOX) as the oxidizer with nitrogen hydrides or hydrocarbon as fuels. Specifically, a LOX/hydrazine engine was designed, fabricated, and shown to have a 95 pct theoretical c-star which translates into a projected vacuum specific impulse of 345 seconds at an area ratio of 204:1. Further performance improvment can be obtained by the use of LOX/hydrogen propellants, especially for manned spacecraft applications, and specific designs must be developed and advanced through flight qualification.

Schneider, Steven J.↗
NASA NTRS1993

Testing and evaluation of oxide-coated iridium/rhenium chambers

Iridium-coated rhenium provides long life operation of radiation-cooled rockets at temperatures up to 2200 C. Ceramic oxide coatings could be used to increase iridium/rhenium rocket lifetimes and allow operation in highly oxidizing environments. Ceramic oxide coatings promise to serve as both thermal and diffusion barriers for the iridium layer. Seven ceramic oxide-coated iridium/rhenium, 22 N rocket chambers were tested on gaseous hydrogen/gaseous oxygen propellants. Five chambers had thick (over 10 mils), monolithic coatings of either hafnia or zirconia. Two chambers had coatings with thicknesses less than 5 mils. One of these chambers had a thin-walled coating of zirconia infiltrated with sol gel hafnia. The other chamber had a coating composed of an iridium/oxide composite. The purpose of this test program was to assess the ability of the oxide coatings to withstand the thermal shock of combustion initiation, adhere under repeated thermal cycling, and operate in aggressively oxidizing environments. All of the coatings survived the thermal shock of combustion and demonstrated operation at mixture ratios up to 11. The iridium/oxide composite coated chamber included testing for over 29 minutes at mixture ratio 16. The thicker-walled coatings provided the larger temperature drops across the oxide layer (up to 570 C), but were susceptible to macrocracking and eventual chipping at a stress concentrator. The cracks apparently resealed during firing, under compression of the oxide layer. The thinner-walled coatings did not experience the macrocracking and chipping of the chambers seen with the thick, monolithic coatings. However, burnthroughs in the throat region did occur in both of the thin-walled chambers at mixture ratios well above stochiometric. The burn-throughs were probably the result of oxygen-diffusion through the oxide coating that allowed the underlying iridium and rhenium layers to be oxidized. The results of this test program indicated that the thin-walled oxide coatings are better suited for repeated thermal cycling than the thick-walled coating, while thicker coatings may be required for operation in aggressively oxidizing environments.

Reed, Brian D.↗
NASA NTRS1999

High-Performance Bipropellant Engine

TRW, under contract to the NASA Lewis Research Center, has successfully completed over 10 000 sec of testing of a rhenium thrust chamber manufactured via a new-generation powder metallurgy. High performance was achieved for two different propellants, N2O4- N2H4 and N2O4 -MMH. TRW conducted 44 tests with N2O4-N2H4, accumulating 5230 sec of operating time with maximum burn times of 600 sec and a specific impulse Isp of 333 sec. Seventeen tests were conducted with N2O4-MMH for an additional 4789 sec and a maximum Isp of 324 sec, with a maximum firing duration of 700 sec. Together, the 61 tests totalled 10 019 sec of operating time, with the chamber remaining in excellent condition. Of these tests, 11 lasted 600 to 700 sec. The performance of radiation-cooled rocket engines is limited by their operating temperature. For the past two to three decades, the majority of radiation-cooled rockets were composed of a high-temperature niobium alloy (C103) with a disilicide oxide coating (R512) for oxidation resistance. The R512 coating practically limits the operating temperature to 1370 C. For the Earth-storable bipropellants commonly used in satellite and spacecraft propulsion systems, a significant amount of fuel film cooling is needed. The large film-cooling requirement extracts a large penalty in performance from incomplete mixing and combustion. A material system with a higher temperature capability has been matured to the point where engines are being readied for flight, particularly the 100-lb-thrust class engine. This system has powder rhenium (Re) as a substrate material with an iridium (Ir) oxidation-resistant coating. Again, the operating temperature is limited by the coating; however, Ir is capable of long-life operation at 2200 C. For Earth-storable bipropellants, this allows for the virtual elimination of fuel film cooling (some film cooling is used for thermal control of the head end). This has resulted in significant increases in specific impulse performance (15 to 20 sec). To determine the merits of a powder rhenium thrust chamber, Lewis On-Board Propulsion Branch directed TRW (under the Space Storable Rocket Technology Program and the High Pressure Earth Storable Rocket Technology Program) to design, fabricate, and test an engineering model to serve as a technology demonstrator.

Biaglow, James A.↗