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At least 19 records

Refractory Oxidative-Resistant Ceramic Carbon Insulation

High-temperature, lightweight, ceramic carbon insulation is prepared by coating or impregnating a porous carbon substrate with a siloxane gel derived from the reaction of an organodialkoxy silane and an organotrialkoxy silane in an acid or base medium in the presence of the carbon substrate. The siloxane gel is subsequently dried on the carbon substrate to form a ceramic carbon precursor. The carbon precursor is pyrolyzed, in an inert atmosphere, to form the ceramic insulation containing carbon, silicon, and oxygen. The carbon insulation is characterized as a porous, fibrous, carbon ceramic tile which is particularly useful as lightweight tiles for spacecraft.

Leiser, Daniel B.↗

Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

Hung, Ching-Chen↗

Sustaining PICA TPS for Future NASA Robotic Science Missions

Phenolic Impregnated Carbon Ablator (PICA), invented in the mid 1990's, is a low-density ablative thermal protection material proven capable of meeting sample return mission needs from the moon, asteroids, comets and other "unrestricted class V destinations" as well as for Mars. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flagship class missions. It is important that NASA maintain this TPS material capability and ensure its availability for future NASA use. The rayon based carbon precursor raw material used in PICA preform manufacturing required replacement and requalification at least twice in the past 25 years and a third substitution is now needed. The carbon precursor replacement challenge is twofold – the first involves finding a long-term replacement for the current rayon and the second is to assess its future availability periodically to ensure it is sustainable and be alerted if additional replacement efforts need to be initiated. Rayon is no longer a viable process in the US and Europe due to environmental concerns. In the early 80's rayon producers began investigating a new method of producing a cellulosic fiber through a more environmentally responsible process. This cellulosic fiber, lyocell, is a viable replacement precursor for PICA fiberform. This presentation reviews current SMD-PSD funded PICA sustainability activities in ensuring a rayon replacement for the long term is identified and in establishing that the capability of the new PICA derived from an alternative precursor is in family with previous versions of the so called "heritage" PICA.State of the Art Low Density Carbon Phenolic AblatorsStardust SRC post flight withPICA forebody heat shield(0.8m max. diameter)PICA Processing StepsRole of Rayon/Lyocellin PICA.

Stackpoole, Mairead↗

Sustaining PICA for Future NASA Robotic Science Missions Including NF-4 and Discovery

Phenolic Impregnated Carbon Ablator (PICA), invented in the mid 1990's, is a low-density ablative thermal protection material proven capable of meeting sample return mission needs from the moon, asteroids, comets and other unrestricted class V destinations as well as for Mars. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flag-ship class missions. It is important that NASA maintain this thermal protection material capability and ensure its availability for future NASA use. The rayon based carbon precursor raw material used in PICA preform manufacturing has experienced multiple supply chain issues and required replacement and requalification at least twice in the past 25 years and a third substitution is now needed. The carbon precursor replacement challenge is twofold - the first involves finding a long-term replacement for the current rayon and the second is to assess its future availability periodically to ensure it is sustainable and be alerted if additional replacement efforts need to be initiated. This paper reviews current PICA sustainability activities to identify a rayon replacement and to establish that the capability of the new PICA derived from an alternative precursor is in family with previous versions.

Stackpoole, Mairead↗

Sustaining PICA for Future NASA Robotic Science Missions Including NF-4 and Discovery

Phenolic Impregnated Carbon Ablator (PICA), invented in the mid 1990's, is a low-density ablative thermal protection material proven capable of meeting sample return mission needs from the moon, asteroids, comets and other unrestricted class V destinations as well as for Mars. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flag-ship class missions. It is important that NASA maintain this thermal protection material capability and ensure its availability for future NASA use. The rayon based carbon precursor raw material used in PICA preform manufacturing has experienced multiple supply chain issues and required replacement and requalification at least twice in the past 25 years and a third substitution is now needed. The carbon precursor replacement challenge is twofold - the first involves finding a long-term replacement for the current rayon and the second is to assess its future availability periodically to ensure it is sustainable and be alerted if additional replacement efforts need to be initiated. This paper reviews current PICA sustainability activities to identify a rayon replacement and to establish that the capability of the new PICA derived from an alternative precursor is in family with previous versions.

Stackpoole, Mairead↗

Non-noble electrocatalysts for alkaline fuel cells

Carbons activated with macrocyclics have attracted increasing attention as alternative electrocatalysts for oxygen reduction. Initial activity of these catalysts is good, but performance declines rapidly. Pyrolyzing the macrocyclic on the carbon support leads to enhanced stability and the catalysts retain good activity. The approach described is designed to develop bulk doped catalysts with similar structures to pyrolyzed macrocyclic catalysts. The transition metal and coordinated ligands are dispersed throughout the bulk of the conductive carbon skeleton. Two approaches to realizing this concept are being pursued, both involving the doping of carbon precursors. In one approach, the precursor is a solid phase carbon-containing ion-exchange resin. The precursor is doped with a transition metal and/or nitrogen, and the resulting mixture is pyrolyzed. In the other approach, the precursor is a gas-phase hydrocarbon. This is introduced with a transition metal species and nitrogen species into a reactor and pyrolyzed. Several studies have been conducted to determine if there is a synergistic effect between the transition metal and nitrogen and the effect of different methods of introducing the metal-nitrogen (M-N) coordination on performance. One approach was to introduce the metal and nitrogen separately, for example, by sequentially doping FeCl3 and NH4OH into the resin. Catalysts were prepared from an undoped ion-exchange resin, a resin doped only with N, a resin doped only with Fe, and a resin doped with both Fe and N. Introduction of nitrogen alone has no beneficial effect on the performance of the catalysts. The introduction of the Fe alone significantly improves the performance in both the high and low current density regions. When both Fe and N are introduced, the performance at lower current densities (catalytic activity) is increased beyond that of the Fe-doped carbon, but the performance at higher current densities is similar to the carbon containing only Fe. Catalysts prepared from resins-Fe(bipy)3SO4 precursors have performance that is only slightly less then CoTMPP adsorbed and pyroloyzed on Vulcan XC-72. Their performance is much better than carbons which have had the N and Fe introduced separately.

Sarangapani, S.↗

Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

Cooper, George W.↗

Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions

Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems. Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid. Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones. The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO. Both carbon sources yield the same lipid classes with essentially the same ranges of compounds. The synthesis reactions were confirmed by using 13C labeled precursor acids.

Non-NASA Center↗

Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate

The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

Non-NASA Center↗

Qualification of Domestic Lyocell Based Phenolic Impregnated Carbon Ablator (PICA-D) for NASA Missions

Phenolic Impregnated Carbon Ablator (PICA) is a low-density ablator that has been used as the planetary entry heatshield for several NASA missions since the late 90’s. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flag-ship class missions, from Sample Return missions such as Stardust, OSIRIS-REx to large Mars Lander missions such as Mars Science Lab (MSL) and Mars 2020. The rayon-based carbon precursor raw material used in PICA preform manufacturing has experienced multiple supply chain issues. The challenge involved in finding a replacement fiber source is in processing as well as in the final performance of the ablator. Each replacement necessitates the requalification of the PICA. This has happened at least twice in the past 25 years, and a third substitution is now needed. Due to the obsolescence of the input foreign rayon fiber source, a new variant of PICA has been developed using a domestic rayon-like fiber source, Lyocell. Due to its flight heritage and proven capability, PICA is baselined as the Thermal Protection System (TPS) for Dragonfly and Mars Sample Return Sample Retrieval Lander mission and is being considered for the backshell of the Mars Sample Return Earth Entry System. All three missions are due to be launched between 2026 and 2028. The challenge this time is to ensure the PICA made with domestic material is a suitable replacement to the heritage PICA used in MSL and Mars 2020 so that the design of the heatshield can be matured without much risk. Results are presented from the recent efforts of 22 PICA-D billets that were Lot Acceptance Tested. Thermal, mechanical, and representative environment arc-jet tests have been conducted. Testing of PICA-Domestic (PICA-D) indicates very comparable performance with respect to “heritage” PICA materials and thus PICA-D is expected to be a sustainable and nearly a “drop-in” replacement solution for future NASA missions.

PICA↗

Amino acids of the Murchison meteorite. II - Five carbon acyclic primary beta-, gamma-, and delta-amino alkanoic acids

The five-carbon acyclic primary beta, gamma, and delta amino alkanoic acids of the Murchison meteorite are studied using gas chromatography-mass spectrometry and ion exchange chromatography. The chromatograms reveal that alpha is the most abundant monoamino alkanoic acid followed by gamma and beta, and an exponential increase in the amount of amino acid is observed as the carbon number increases in the homologous series. The influence of frictional heating, spontaneous thermal decomposition, and radiation of the synthesis of amino acids is examined. The data obtained support an amino acid synthesis process involving random combination of single-carbon precursors.

Cronin, J. R.↗

Application of Chlorine-Assisted Chemical Vapor Deposition of Diamond at Low Temperatures

Low temperature deposition of diamond has been achieved by a chlorine-assisted diamond chemical vapor deposition (CA-CVD) process. This method begins with the thermal dissociation of molecular chlorine into atomic chlorine in a resistively heated graphite furnace at temperatures between 1300 and 1500 deg. C. The atomic chlorine, upon mixing, subsequently reacts with molecular hydrogen and hydrocarbons. The rapid exchange reactions between the atomic chlorine, molecular hydrogen, and hydrocarbons give rise to the atomic hydrogen and carbon precursors required for diamond deposition. Homoepitaxial diamond growth on diamond substrates has been studied over the substrate temperature range of 100-950 C. It was found that the diamond growth rates are approximately 0.2 microns/hr in the temperature range between 102 and 300 C and that the growth rates do not decrease significantly with a decrease in substrate temperature. This is unique because the traditional diamond deposition using H2/CH4 systems usually disappears at substrate temperatures below approx. 500 deg. C. This opens up a possible route to the deposition of diamond on low-melting point materials such as aluminum and its alloys.

Pan, Chenyu↗

Elemental Metals or Oxides Distributed on a Carbon Substrate or Self-Supported and the Manufacturing Process Using Graphite Oxide as Template

A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a percursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be further processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

Hung, Ching-Chen↗

Development of Domestic Lyocell Based Phenolic Impregnated Carbon Ablator (PICA-D) for Future NASA Missions

Phenolic Impregnated Carbon Ablator (PICA) is a low-density ablator that has been used as the planetary entry heatshield for several NASA missions since the late 90's. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flag-ship class missions. The rayon-based carbon precursor raw material used in PICA preform manufacturing has experienced multiple supply chain issues and required replacement and requalification at least twice in the past 25 years, and a third substitution is now needed. Due to the obsolescence of the input foreign rayon fiber source, a new variant of PICA has been developed using a domestic rayon-like fiber source, Lyocell. Results are presented from this effort including fiber conversion, fabrication of tile component and near net shaped heatshield preforms, and conversion to PICA materials. Thermal, mechanical, and representative environment arc-jet tests have been conducted. Initial testing of PICA-Domestic (PICA-D) indicates comparable performance with respect to "heritage" PICA materials and thus PICA-D is expected to be a sustainable solution for future NASA missions.

Drop-In Replacement↗

Development of Domestic Lyocell Based Phenolic Impregnated Carbon Ablator (PICA-D) for Future NASA Missions

Phenolic Impregnated Carbon Ablator (PICA) is a low-density ablator that has been used as the planetary entry heatshield for several NASA missions since the late 90's. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flag-ship class missions. The rayon-based carbon precursor raw material used in PICA preform manufacturing has experienced multiple supply chain issues and required replacement and requalification at least twice in the past 25 years, and a third substitution is now needed. Due to the obsolescence of the input foreign rayon fiber source, a new variant of PICA has been developed using a domestic rayon-like fiber source, Lyocell. Results are presented from this effort including fiber conversion, fabrication of tile component and near net shaped heatshield preforms, and conversion to PICA materials. Thermal, mechanical, and representative environment arc-jet tests have been conducted. Initial testing of PICA-Domestic (PICA-D) indicates comparable performance with respect to "heritage" PICA materials and thus PICA-D is expected to be a sustainable solution for future NASA missions.

Drop-In Replacement↗

Sensitivity of Tropospheric Ozone Over the Southeast USA to Dry Deposition

Dry deposition (DD) is a major loss process for tropospheric ozone and some reactive nitrogen and carbon precursors. We investigate the response of summertime ozone and its production chemistry over the Southeast United States (USA) to variability in this sink. Turning off DD of oxidized nitrogen, ozone, or all species over the United States in the Geophysical Fluid Dynamics Laboratory AM3 model increases regional mean surface ozone by 5, 18, or 25 ppb, respectively. Additional sensitivity simulations demonstrate that, assuming linearity, surface ozone has a similar sensitivity to ozone DD as to NOx emissions. Trends in ozone production efficiency derived from observed relationships between ozone and precursor oxidation products may not solely reflect precursor emission changes if ozone DD varies (e.g., with meteorology). We conclude that DD variability merits consideration when interpreting observed ozone trends. Quantifying the impact of changes in sinks versus sources will require long‐term DD measurements across the region of interest.

dry deposition↗

Qualification of Domestic Lyocell Based Phenolic Impregnated Carbon Ablator (PICA-D) for NASA Missions

Phenolic Impregnated Carbon Ablator (PICA) is a low-density ablator that has been used as the planetary entry heatshield for several NASA missions since the late 90’s. Its low density and efficient performance characteristics have proven effective for use from Discovery to Flag-ship class missions, from Sample Return missions such as Stardust, OSIRIS-REx to large Mars Lander missions such as Mars Science Lab (MSL) and Mars 2020. The rayon-based carbon precursor raw material used in PICA preform manufacturing has experienced multiple supply chain issues. The challenge involved in finding a replacement fiber source is in processing as well as in the final performance of the ablator. Each replacement necessitates the requalification of the PICA. This has happened at least twice in the past 25 years, and a third substitution is now needed. Due to the obsolescence of the input foreign rayon fiber source, a new variant of PICA has been developed using a domestic rayon-like fiber source, Lyocell. Due to its flight heritage and proven capability, PICA is baselined as the Thermal Protection System (TPS) for Dragonfly and Mars Sample Return Sample Retrieval Lander mission and is being considered for the backshell of the Mars Sample Return Earth Entry System. All three missions are due to be launched between 2026 and 2028. The challenge this time is to ensure the PICA made with domestic material is a suitable replacement to the heritage PICA used in MSL and Mars 2020 so that the design of the heatshield can be matured without much risk. Results are presented from the recent efforts of 22 PICA-D billets that were Lot Acceptance Tested. Thermal, mechanical, and representative environment arc-jet tests have been conducted. Testing of PICA-Domestic (PICA-D) indicates very comparable performance with respect to “heritage” PICA materials and thus PICA-D is expected to be a sustainable and nearly a “drop-in” replacement solution for future NASA missions.

Matt Gasch↗

Nozzle designs with pitch precursor ablatives

Recent developments in carbon phenolic ablatives for solid rocket motor nozzles have yielded a pitch precursor carbon fiber offering significant raw material availability and cost saving advantages as compared to conventional rayon precursor material. This paper discusses the results of an experimental program conducted to assess the thermal performance and characterize the thermal properties of pitch precursor carbon phenolic ablatives. The end result of this program is the complete thermal characterization of pitch fabric, pitch mat, hybrid pitch/rayon fabric and pitch mat molding compound. With these properties determined an analytic capability now exists for predicting the thermal performance of these materials in rocket nozzle liner applications. Further planned efforts to verify material performance and analytical prediction procedures through actual rocket motor firings are also discussed.

Blevins, H. R.↗