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At least 19 records

Promoted Metals Combustion at Ambient and Elevated Temperatures

Promoted combustion testing of materials, Test 17 of NASA STD-6001, has been used to assess metal propensity to burn in oxygen rich environments. An igniter is used at the bottom end of a rod to promote ignition, and if combustion is sustained, the burning progresses from the bottom to the top of the rod. The physical mechanisms are very similar to the upward flammability test, Test 1 of NASA STD-6001. The differences are in the normal environmental range of pressures, oxygen content, and sample geometry. Upward flammability testing of organic materials can exhibit a significant transitional region between no burning to complete quasi-state burning. In this transitional region, the burn process exhibits a probabilistic nature. This transitional region has been identified for metals using the promoted combustion testing method at ambient initial temperatures. The work given here is focused on examining the transitional region and the quasi-steady burning region both at conventional ambient testing conditions and at elevated temperatures. A new heated promoted combustion facility and equipment at Marshall Space Flight Center have just been completed to provide the basic data regarding the metals operating temperature limits in contact with oxygen rich atmospheres at high pressures. Initial data have been obtained for Stainless Steel 304L, Stainless Steel 321, Haynes 214, and Inconel 718 at elevated temperatures in 100-percent oxygen atmospheres. These data along with an extended data set at ambient initial temperature test conditions are examined. The pressure boundaries of acceptable, non-burning usage is found to be lowered at elevated temperature.

Engel, Carl D.↗

Development of an Ultra High-Pressure Metals Promoted Combustion in Oxygen Test Apparatus

Materials flammability data is needed at pressures higher than ever tested before (greater than 10,000 psi). WSTF has designed and is currently building a metals flammability apparatus that can test metals up to 30,000 psi. Solid progress was achieved on the chamber in terms of system build up and fulfilling requirements to perform a NASA Test Readiness Review. Understanding metals flammability data at extreme pressure opens the doors for higher pressure and higher performance oxygen systems. Proposed systems include more reliable/higher performance propulsion systems and more reliable/lighter Environmental Control Life Support Systems (ECLSS). The test system needed for this testing required significant research and development to select a pressurization method and eliminate contact with potentially flammable materials back to the chamber. No additional promoted combustion data was collected in FY21. This International Research & Development (IRAD) proposal was critical to getting the system very close to operational status. This capability is critical to collect forward leaning material flammability data for future spacecraft and ground systems. Forward work has been identified and funding is being sought outside of the Center Innovation Fund (CIF) process for late FY23/FY24.

promoted combustion↗

Applications of low temperature CO-oxidation catalysts to breathable gases

Modifications of tin oxide/precious metal catalysts described for use in CO2 lasers have also been developed for use in other applications; namely, as low temperature CO oxidation components in fire escape hoods/masks for mines, aircrafts, hotels, and offices and in sealed environments, such as hyperbaric chambers and submarines. Tin oxide/precious metal catalysts have been prepared on a variety of high surface area cloth substrates for application in fire escape hoods. These show high and stable CO oxidation capability (10 to the 4th power ppm CO reduced to 10 to the 1st power ppm CO) at GHSV of 37,000 h(-1) with water saturated inlet gas at body heat (37 C) and below. Water vapor plays an important role in the surface state/performance of tin oxide catalyst. Water-resistant formulations have been produced by the introduction of transition metal promoters. Tin oxide/precious metal catalysts have also been developed for CO oxidation in the North Sea diving environment. These are currently in use in a variety of hyperbaric chambers and diving vehicles. Ambient temperature operation and resistance to atmospheric water vapor have been demonstrated, and as a result, they offer a viable alternative to hopcalite or heated catalyst systems. A new range of non-tin oxide based low temperature CO oxidation catalysts is described. They are based on reducible metal oxides promoted with previous metals. Preliminary data on selected materials in the form of both cloth artifacts and shaped pellets are presented. They are expected to be applicable both to the breathable gas application area and to CO2 lasers.

Noordally, Ehsan↗

Flammability testing conducted in support of Apollo 13

In support of the Apollo 13 investigation of the oxygen tank failure, flame propagation rates were determined for Teflon insulation in cryogenic and ambient temperature oxygen for upward, downward, and zero g burns. The propagation rates depended heavily on configuration and varied from 4.8 to 10.9 cm/sec for upward one g burns to 0.48 cm/sec for zero g burns. In addition to the flame propagation rates, tests were conducted to determine if Teflon burning in cryogenic oxygen could ignite metals (promoted ignition) with which it came in contact. Tests conducted on various metal alloys used in the oxygen tank indicated that most of the alloys could be ignited by burning Teflon in certain configurations. After the propagation rates and promoted metal ignitions had been evaluated, a test was conducted on a quantity gauge and wire harness used in the oxygen tank to determine if flame propagation to the tank wall was possible. Propagation of the wire bundle after ignition resulted in a catastrophic failure of the test vessel in the area of the quantity gauge.

Leger, L. J.↗

Relating FTS Catalyst Properties to Performance

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of γ-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature than in the unpromoted catalyst. Nevertheless, the Co clusters remained slightly larger, on average, in comparison with the unpromoted 15%Co/Al2O3 reference catalyst. None of the promoted catalysts (i.e., with Cd, In, or Sn) exhibited surface Co0 site densities higher than that of the unpromoted catalyst. In activity testing, the activities were even much lower than what was expected from the H2-TPD results. Two possible explanations were proposed: (1) the promoters may be located on the surfaces of cobalt particles, blocking surface Co0 but being able to desorb hydrogen or (2) the promoters may facilitate Co oxidation during FTS, as previously observed by Huffman and coworkers when K was added to cobalt catalysts.

Zirconia↗

Analysis of Additively Manufactured Inconel 718 Combustion Behavior in Promoted Oxygen Environments

Promoted combustion testing is a vital tool for engineers to establish the combustion and flammability characteristics of materials (metallic or otherwise) in oxygen enriched environments. Historically, much of the established data for metallic promoted combustion has been with regards to cast and wrought forms. However, with the emergence of additive manufacturing as a preferred method of fabrication, the need exists to evaluate how metals in that form behave. This paper will serve as a review of the work that has been done and an analysis of the nickel-based superalloy Inconel 718, a material popular for aerospace applications such as liquid fueled rocket components and turbine engines. Promoted combustion testing (per the ASTM G124 standard) was conducted on samples of both wrought and selective laser melted fabrication, to provide comparison of flammability response between materials produced by each manufacturing method. Additionally, post-build treatments were applied to test samples to identify any effects on performance provided by hot isostatic pressing, oxygen-getting wrap during HIP, stress relieving, and solutionizing/aging heat treatments. This study will utilize optical and scanning electron microscopy, energy dispersive spectroscopy, x-ray diffraction, and metallography to identify the differences in behavior of additively manufactured and wrought Inconel 718.

Additively Manufactured↗

Polyimide/metal composite films via in situ decomposition of inorganic additives - Soluble polyimide versus polyimide precursor

Polyimide-metal oxide (Co3O4 or CuO) composite films have been prepared via in situ thermal decomposition of cobalt (II) chloride or bis(trifluoroacetylacetonato)copper(II). A soluble polyimide (XU-218) and its corresponding prepolymer (polyamide acid) were individually employed as the reaction matrix. The resulting composites exhibited a greater metal oxide concentration at the air interface with polyamide acid as the reaction matrix. The water of imidization that is released during the concurrent polyamide acid cure and additive decomposition is believed to promote metal migration and oxide formation. In contrast, XU-218 doped with either HAuCl4.3H2O or AgNO3 yields surface gold or silver when thermolyzed (300 C).

Rancourt, J. D.↗

Thermal oxidative degradation reactions of linear perfluoroalky lethers

Thermal and thermal oxidative stability studies were performed on linear perfluoro alkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors are reported. The liner perfluoro alkylethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoro alkylether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating.

Jones, W. R., Jr.↗

Thermal oxidative degradation reactions of linear perfluoroalkyl ethers

Thermal and thermal oxidative stability studies were performed on linear perfluoroalkyl ether fluids. The effect on degradation by metal catalysts and degradation inhibitors is reported. The linear perfluoroalkyl ethers are inherently unstable at 316 C in an oxidizing atmosphere. The metal catalysts greatly increased the rate of degradation in oxidizing atmospheres. In the presence of these metals in an oxidizing atmosphere, the degradation inhibitors were highly effective in arresting degradation at 288 C. However, the inhibitors had only limited effectiveness at 316 C. The metals promote degradation by chain scission. Based on elemental analysis and oxygen consumption data, the linear perfluoroalkyl ether fluids have a structural arrangement based on difluoroformyl and tetrafluoroethylene oxide units, with the former predominating. Previously announced in STAR as N82-26468

Jones, W. R., Jr.↗

Effect of Metal Alloys, Degradation Inhibitors, Temperatures, and Exposure Duration on the Stability of Poly(hexafluoropropene oxide) Fluid

Results of the action of 440C steel, Ti(4Al,4Mn), and Ti(6Al,4V) alloys on poly(hexafluoropropene oxide) fluid and the degradation inhibition by phosphate esters, phosphine, and monophospha-s-triazine are reported. The effects of temperature, exposure duration, and metal surface area are discussed. The studies show clearly the autocatalytic nature of the metal-promoted degradation, which explains the effectiveness of the degradation-arresting additives, even in the case of the highly detrimental titanium alloys.

Paciorek, Kazimiera J. L.↗

Promoted Combustion of Metals in a High-Pressure, Flowing Oxygen Environment

Traditional promoted combustion testing has used 0.125 inch diameter samples that are ignited in a pressurized, oxygen-enriched environment. Many years of testing this sample size have yielded useful data regarding threshold pressure, or the minimum oxygen pressure required to support self-sustained combustion. However, when a material is tested in a flowing system, the threshold pressure changes. White Sands Test Facility has developed a test system to burn samples in flowing gaseous oxygen. Current sample configurations are 0.5 inch diameter rods and 1.25 inch diameter pipes with pressures ranging up to 2000 psi and gas velocities reaching 200 ft/s. This paper describes the test apparatus, modifications made as the result of a fire, and a description of the tests currently being performed.

Maes, M. J.↗

Fischer-Tropsch Catalyst for Aviation Fuel Production

As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to non-petroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

deLaRee, Ana B.↗

Fischer-Tropsch Catalyst for Aviation Fuel Production

As the oil supply declines, there is a greater need for cleaner alternative fuels. There will undoubtedly be a shift from crude oil to nonpetroleum sources as a feedstock for aviation (and other transportation) fuels. The Fischer-Tropsch process uses a gas mixture of carbon monoxide and hydrogen which is converted into various liquid hydrocarbons; this versatile gas-to-liquid technology produces a complex product stream of paraffins, olefins, and oxygenated compounds such as alcohols and aldehydes. The Fischer-Tropsch process can produce a cleaner diesel oil fraction with a high cetane number (typically above 70) without any sulfur and aromatic compounds. It is most commonly catalyzed by cobalt supported on alumina, silica, or titania or unsupported alloyed iron powders. Cobalt is typically used more often than iron, in that cobalt is a longer-active catalyst, has lower water-gas shift activity, and lower yield of modified products. Promoters are valuable in improving Fischer-Tropsch catalyst as they can increase cobalt oxide dispersion, enhance the reduction of cobalt oxide to the active metal phase, stabilize a high metal surface area, and improve mechanical properties. Our goal is to build up the specificity of the Fischer-Tropsch catalyst while adding less-costly transition metals as promoters; the more common promoters used in Fischer-Tropsch synthesis are rhenium, platinum, and ruthenium. In this report we will describe our preliminary efforts to design and produce catalyst materials to achieve our goal of preferentially producing C8 to C18 paraffin compounds in the NASA Glenn Research Center Gas-To-Liquid processing plant. Efforts at NASA Glenn Research Center for producing green fuels using non-petroleum feedstocks support both the Sub-sonic Fixed Wing program of Fundamental Aeronautics and the In Situ Resource Utilization program of the Exploration Technology Development and Demonstration program.

DeLaRee, Ana B.↗

Promoted combustion of nine structural metals in high-pressure gaseous oxygen - A comparison of ranking methods

The 316, 321, 440C, and 17-4 PH stainless steels, as well as Inconel 600, Inconel 718, Waspaloy, Monel 400, and Al 2219, have been evaluated for relative nonflammability in a high-pressure oxygen environment with a view to the comparative advantages of four different flammability-ranking methods. The effects of changes in test pressure, sample diameter, promoter type, and sample configuration on ranking method results are evaluated; ranking methods employing velocity as the primary ranking criterion are limited by diameter effects, while those which use extinguishing pressure are nonselective for metals with similar flammabilities.

Steinberg, Theodore A.↗

Formation of nucleoside 5'-polyphosphates under potentially prebiological conditions

The characteristics and efficiencies of biochemical reactions involving nucleoside 5'-diphosphates and -triphosphates (important substrates of RNA and DNA synthesis) under conditions corresponding to the primitive prebiotic earth are investigated. Urea catalysis of the formation of linear inorganic polyphosphates and metal ions promoting the reactions are discussed. Linear polyphosphate was incubated with Mg(++) in the presence of a nucleoside 5'-phosphate, to yield nucleoside 5'-polyphosphates when products are dried, while Mg(++) prompts depolymerization to trimetaphosphate in aqueous solutions. Plausible biogenetic pathways are examined.

Lohrmann, R.↗

Phillips CO-oxidation catalyts for long-lived CO2 lasers: Activity and initial characterization studies

Four different catalysts have been developed specifically for use in sealed carbon dioxide lasers. The catalysts have been designed to be low dusting, stable to shock and vibration, have high activity at low temperatures and have long active lifetimes. Measured global CO oxidation rates range from 1.4 to 2.2 cc CO converted per minute per gram of catalyst at ambient temperature. The catalysts also retain substantial activity at temperatures as low as -35 C. The Phillips laser catalysts are prepared in a variety of different shapes to meet the different pressure drop and gas flow profiles present in the many different styles of lasers. Each catalyst has been tested in sealed TEA lasers and has been shown to substantially increase the sealed life of the laser. Activity measurements made on the precious metal catalysts which were prepared with and without activity promoters showed that the promoter materials increase catalyst CO oxidation activity at least an order of magnitude at ambient temperature. Initial studies using H2 and CO chemisorption, X ray diffraction (XRD) and X ray photoelectron spectroscopy (XPS) have shown that the activity promoters do not significantly affect the precious metal crystallite size or the electronic structure around the precious metal. In addition, the formation or lack of formation of solid solutions between the precious metal and promoters has also been shown not to affect the activity of the promoted catalyst.

Kolts, J. H.↗

Thermal Model of the Promoted Combustion Test

Flammability of metals in high pressure, pure oxygen environments, such as rocket engine turbopumps, is commonly evaluated using the Promoted Combustion Test (PCT). The PCT emphasizes the ability of an ignited material to sustain combustion, as opposed to evaluating the sample's propensity to ignite in the first place. A common arrangement is a rod of the sample material hanging in a chamber in which a high pressure, pure oxygen environment is maintained. An igniter of some energetically combusting material is fixed to the bottom of the rod and fired. This initiates combustion, and the sample burns and melts at its bottom tip. A ball of molten material forms, and this ball detaches when it grows too large to be supported by surface tension with the rod. In materials which do not sustain combustion, the combustion then extinguishes. In materials which do sustain combustion, combustion re-initiates from molten residue left on the bottom of the rod, and the melt ball burns and grows until it detaches again. The purpose of this work is development of a PCT thermal simulation model, detailing phase change, melt detachment, and the several heat transfer modes. Combustion is modeled by a summary rate equation, whose parameters are identified by comparison to PCT results. The sensitivity of PCT results to various physical and geometrical parameters is evaluated. The identified combustion parameters may be used in design of new PCT arrangements, as might be used for flammability assessment in flow-dominated environments. The Haynes 214 nickel-based superalloy, whose PCT results are applied here, burns heterogeneously (fuel and oxidizer are of different phases; combustion takes place on the fuel surface). Heterogeneous combustion is not well understood. (In homogeneous combustion, the metal vaporizes, and combustion takes place in an analytically treatable cloud above the surface). Thermal modeling in heterogeneous combustion settings provides a means for linking test results more directly to detailed combustion mechanics, leading to improved data analysis, and improved understanding of heterogeneous combustion phenomena.

Jones, Peter D.↗