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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

Carbon fibers derived from commodity polymers: A review

Carbon fiber composites are prohibitively expensive for a wide array of applications that would greatly benefit from their superior specific strength and specific stiffness. Replacing the market-dominant carbon fiber precursor material, polyacrylonitrile, with a low-cost alternative would significantly reduce the cost of carbon fiber production. Commodity polymers may provide such an alternative thanks to their abundance and ease of production into fibers. Furthermore, this review presents state-of-the-art carbon fiber production from polyacrylonitrile, an overview of melt-spinnable alternative precursors broadly, and an in-depth review of the latest advances in the synthesis of carbon fibers from low-cost, commodity thermoplastics such as polyethylene, polyamide, polystyrene, polyester, and poly(vinyl chloride).

36 MATERIALS SCIENCE↗

Fischer-Tropsch Synthesis: The Characterization and Testing of Pt-Co/SiO 2 Catalysts Prepared with Alternative Cobalt Precursors

Different low-cost cobalt precursors (acetate, chloride) and thermal treatments (air calcination/H 2 reduction versus direct H 2 -activation) were investigated to alter the interaction between cobalt and silica. H 2 -activated catalysts prepared from cobalt chloride had large Co 0 particles (XRD, chemisorption) formed by weak interactions between cobalt chloride and silica (temperature programmed reduction (TPR), TPR with mass spectrometry (TPR-MS), TPR with extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge spectroscopy (XANES) techniques) and retained Cl-blocked active sites, resulting in poor activity. In contrast, unpromoted Co/SiO 2 catalysts derived from cobalt acetate had strong interactions between Co species and silica (TPR/TPR-MS, TPR-EXAFS/XANES); adding Pt increased the extent of the Co reduction. For these Pt-promoted catalysts, the reduction of uncalcined catalysts was faster, resulting in larger Co 0 clusters (19.5 nm) in comparison with the air-calcined/H 2 -activated catalyst (7.8 nm). Both catalysts had CO conversions 25% higher than that of the Pt-promoted catalyst prepared in the traditional manner (air calcination/H 2 reduction using cobalt nitrate) and three times higher than that of the traditional unpromoted Co/silica catalyst. The retention of residual cobalt carbide (observed in XANES) from cobalt acetate decomposition impacted performance, resulting in a higher C 1 –C 4 selectivity (32.2% for air-calcined and 38.7% for uncalcined) than that of traditional catalysts (17.5–18.6%). The residual carbide also lowered the α-value and olefin/paraffin ratio. Future work will focus on improving selectivity through oxidation–reduction cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of tension during sulfonation stabilization for UHMWPE-derived carbon fibers

Polyethylene is a promising low-cost alternative precursor material for carbon fiber production, but it has yet to show mechanical properties near or surpassing polyacrylonitrile-derived carbon fibers. The high molecular weight and order of ultra-high molecular weight polyethylene (UHMWPE) may offer a pathway to realizing this promise by enabling long-range graphitic structure formation and superior mechanical properties. The tension applied during the precursor stabilization process is crucial to maintaining the shape of the fibers during the conversion process, but no published study has yet probed the relationship between sulfonation tension and carbon fiber microstructure and mechanical properties. In this work, a logarithmic sweep of tensile stress was applied to UHMWPE fibers during the stabilization process followed by carbonization. Increasing tension significantly reduced fiber shrinkage, resulted in straighter fibers with less severe kink bands, and greatly improved the mechanical properties of the fibers. Raman spectroscopy and X-ray diffraction revealed that in all cases the carbon fibers were largely amorphous, but increasing tension resulted in increased size and alignment of the turbostratic crystallites with the fiber axis. Large voids were present in the sample fibers, so the Griffith-Irwin relation was employed to predict the potential ultimate tensile strength of the fibers with voids reduced to sizes comparable to commercially produced fibers. Furthermore, this work demonstrates the importance of tension applied during the stabilization of polyethylene fibers for carbon fiber production and establishes a framework for achieving high mechanical properties from these precursors.

36 MATERIALS SCIENCE↗

Low-Cost, High-Performance Carbon Fiber for Compressed Natural Gas Storage Tanks (Final Technical Report – Down Select Report)

The aim of this project is to reduce the cost of Type IV, carbon fiber (CF) composite overwrap compressed gas storage tanks by reducing the cost of CF and CF composites. The project team worked to reduce the cost of CF by exploring and testing opportunities for a low-cost alternative precursor material for CF production to supplant market-dominant and costly polyacrylonitrile (PAN). Concurrently, the team aimed to reduce the cost of the tanks at the composite level by improving the interfacial adhesion between the fibers and the matrix resin through the incorporation of low-cost nanoparticles recycled from waste materials, which would reduce the volume of costly CF required to achieve the same tank performance. At the end of the first year, the project team selected mesophase pitch as the primary precursor candidate from a field of materials based on the superior mechanical performance and cost-saving potential. During the second year, the team produced CFs derived from mesophase pitch achieving an average tensile strength of 365.6 ksi and average tensile modulus of 40.74 Msi. Facility availability for spinning and converting these fibers at greater scale has hindered scale-up demonstration, but the team has identified opportunities to conduct this work in the near term. Cost modeling shows that these mesophase pitch-derived CFs can be up to 40% less expensive than PAN-derived CFs due to the lower cost of the feedstock material, higher throughput, greater conversion yield, and lower cost spinning method and compared to PAN. Additionally, the team has demonstrated at lab-scale that nanoparticle coating CFs can significantly increase the interfacial shear strength and load transfer efficiency of CFs in a matrix. Single filament pull-out testing showed a 27% average increase in max interfacial shear strength due to this coating. A continuous method of applying these coatings to a tow of CF has been developed for scale-up. 26 m tows of coated CFs were produced using this system and formed into composite ring samples for ASTM ring burst testing. Issues with the testing protocol have limited assessment of these results. A prototype Type IV tank was designed to meet ANSI HGV2 standards, and the design criteria set out by DOE, using the CF properties developed by the team paired with a proprietary resin matrix, a polyamide liner, and aluminum end bosses. The tank weighs 153.1 kg and with a total capacity of 5.8 kg H2 (5.6 kg usable), which yields a gravimetric capacity of 1.17 kWh/kg. Cost modeling predicts that the tank will have a projected cost of $15.73/kWh. Tank performance modeling does not include considerations for fiber-matrix load transfer efficiency improvements offered by nanoparticle coating method.

08 HYDROGEN↗

In-situ resource utilization for the human exploration of Mars : a Bayesian approach to valuation of precursor missions

The need for sufficient quantities of oxygen, water, and fuel resources to support a crew on the surface of Mars presents a critical logistical issue of whether to transport such resources from Earth or manufacture them on Mars. An approach based on the classical Wildcat Drilling Problem of Bayesian decision theory was applied to the problem of finding water in order to compute the expected value of precursor mission sample information. An implicit (required) probability of finding water on Mars was derived from the value of sample information using the expected mass savings of alternative precursor missions.

water↗

Low-latency Science Exploration of Planetary Bodies: a Demonstration Using ISS in Support of Mars Human Exploration

We summarize a proposed experiment to use the International Space Station to formally examine the application and validation of low-latency telepresence for surface exploration from space as an alternative, precursor, or potentially as an adjunct to astronaut "boots on the ground." The approach is to develop and propose controlled experiments, which build upon previous field studies and which will assess the effects of different latencies (0 to 500 msec), task complexity, and alternate forms of feedback to the operator. These experiments serve as an example of a pathfinder for NASA's roadmap of missions to Mars with low-latency telerobotic exploration as a precursor to astronaut's landing on the surface to conduct geological tasks.

ISS in Support↗

Low-Latency Science Exploration of Planetary Bodies: How ISS Might Be Used as Part of a Low-Latency Analog Campaign for Human Exploration

We suggest that the International Space Station be used to examine the application and validation of low-latency telepresence for surface exploration from space as an alternative, precursor, or potentially as an adjunct to astronaut "boots on the ground." To this end, controlled experiments that build upon and complement ground-based analog field studies will be critical for assessing the effects of different latencies (0 to 500 milliseconds), task complexity, and alternate forms of feedback to the operator. These experiments serve as an example of a pathfinder for NASA's roadmap of missions to Mars with low-latency telerobotic exploration as a precursor to astronaut's landing on the surface to conduct geological tasks.

robotic space exploration↗

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↗

Sintering effects on NpO 2 grain size and morphology: The role of precursor Np phase

Neptunium dioxide (NpO 2 ) is a key phase in nuclear material processing as a target material for the production of plutonium-238 ( 238 Pu) and has been historically synthesized via the calcination of a Np oxalate precursor. Alternative synthesis methods for NpO 2 are now more prevalent, necessitating their study and comparison with the more common oxalate route. The purpose of this work was to investigate the microstructural properties of NpO 2 synthesized from a nitrate-based Np precursor phase via the assessment of NpO 2 particle size and morphology as a function of calcination temperature and time. Scanning electron microscopy (SEM) was used to probe the primary grain size and morphology of NpO 2 after calcination at temperatures ranging from 700 to 1100 °C and hold times ranging from 1 to 10 h. Post-image analysis using ImageJ software enabled the quantification of mean particle diameter. This analysis indicated that particle diameter increases with both increasing calcination temperature and hold time. Primary particles were shown to be clumped in irregular patterns into the overall rough, blocky aggregates, but this macroscopic morphology was not affected by calcination time or temperature. Although trends in primary grain size of NpO 2 were consistent with available literature from other Np precursor phases, the macroscopic morphology of the NpO 2 aggregates was quite different than reported for other precursors. Through comparison with historical literature on Np oxalate, this work emphasizes the importance of Np precursor on the physical properties of NpO 2 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

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↗

Data for A Consolidated Bioprocess Design to Produce Multiple High-Value Platform Chemicals from Lignocellulosic Biomass and Its Technoeconomic Feasibility

5-hydroxymethyl furfural (HMF) and furfurals are DOE-listed platform chemicals that can be derived from the renewable carbon in the lignocellulosic biomasses and have the potential to replace petroleum-derived alternatives. High substrate cost and use of expensive solvents limit the economic feasibility of bio-based HMF production on an industrially relevant scale. The study presents an experimental optimized condition that maximizes the chemical-free production of HMF and furfurals without lowering the yield of total fermentable sugars from Saccharum bagasse. Hydrothermal pretreatment at 210 °C for 15 min yielded approximately 10%, 12%, and 46% of HMF, furfurals, and fermentable sugars per gram of dry biomass, respectively. Additionally, the study proposes a consolidated bioprocess model to produce and recover four high-value bioproducts i.e., HMF, furfurals, ethanol, and acetic acid based on the experimental results and evaluates its technoeconomic feasibility considering HMF as the main product. The minimum selling price (MSP) of HMF was estimated to be 930.6 USD/t which is competitive with its petroleum-derived precursor alternative p-xylene (1,113 USD/t). The sensitivity analysis performed for the process parameters suggests that pretreatment cost and revenues from coproducts immensely influence the MSP of HMF. The preliminary technoeconomic analysis performed on the consolidated bioprocess design indicates that additional revenue streams from diversified coproducts in biorefineries aid in lowering the MSP of high-value bioproducts.

Conversion↗

A consolidated bioprocess design to produce multiple high-value platform chemicals from lignocellulosic biomass and its technoeconomic feasibility

5-Hydroxymethyl furfural (HMF) and furfurals are DOE-listed platform chemicals that can be derived from the renewable carbon in the lignocellulosic biomasses and have the potential to replace petroleum-derived alter- natives. High substrate cost and use of expensive solvents limit the economic feasibility of bio-based HMF production on an industrially relevant scale. The study presents an experimental optimized condition that maximizes the chemical-free production of HMF and furfurals without lowering the yield of total fermentable sugars from Saccharum bagasse. Hydrothermal pretreatment at 210 °C for 15 min yielded approximately 10%, 12%, and 46% of HMF, furfurals, and fermentable sugars per gram of dry biomass, respectively. Additionally, the study proposes a consolidated bioprocess model to produce and recover four high-value bioproducts i.e., HMF, furfurals, ethanol, and acetic acid based on the experimental results and evaluates its technoeconomic feasibility considering HMF as the main product. The minimum selling price (MSP) of HMF was estimated to be 930.6 USD/ t which is competitive with its petroleum-derived precursor alternative p-xylene (1,113 USD/t). The sensitivity analysis performed for the process parameters suggests that pretreatment cost and revenues from coproducts immensely influence the MSP of HMF. The preliminary technoeconomic analysis performed on the consolidated bioprocess design indicates that additional revenue streams from diversified coproducts in biorefineries aid in lowering the MSP of high-value bioproducts.

09 BIOMASS FUELS↗

Trimethyltriazacyclohexane coordination chemistry of simple rare-earth metal salts

Reactions of 1,3,5-trimethyl-triazacyclohexane (Me 3 tach) with common rare-earth metal iodide, chloride, and triflate salts were examined to determine the capacity of this inexpensive chelate to provide alternative precursors for THF-free reactions. The reaction of LaI 3 (THF) 4 and CeI 3 (THF) 4 with 1,3,5-trimethyl-triazacyclohexane in THF generated toluene soluble (Me 3 tach) 2 LnI 3 , 1-Ln , in which the Ln center has a tri-capped trigonal prismatic geometry with two eclipsed Me 3 tach rings. Reaction with NdI 3 (THF) 3.5 forms the analogous 1-Nd , but a different structure with one outer sphere iodide, [(Me 3 tach) 2 NdI 2 ][I], 2-Nd , is also accessible and has a structure reminiscent of bent metallocenes. The reaction of LaCl 3 and Me 3 tach forms the less soluble (Me 3 tach) 2 LaCl 3 , which has a structure analogous to 1-Ln with eclipsed Me 3 tach rings. The mono-ring yttrium complex, (Me 3 tach)YCl 3 (THF) 2 , could be isolated from the reaction of YCl 3 with Me 3 tach. Reactions of La(OTf) 3 with Me 3 tach were sensitive to the presence of residual proton sources as exemplified by the isolation of {[(Me 3 tach)La(μ-OH)(μ-OTf)] 2 (μ-OTf) 2 } 2 , 5-La , and [HMe 3 tach][(Me 3 tach) 2 La-(OTf) 4 ], 6-La . SmI 2 reacts with Me 3 tach to produce the Sm( II ) complex, (Me 3 tach) 2 SmI 2 (THF), 7-Sm , but 2-Sm can also form in this reaction. Complexes of the larger 1,4,7-trimethyltriazacyclononane (Me 3 tacn) ligand, namely (Me 3 tacn)LaI 3 (THF), (Me 3 tacn)YCl 3 , and (Me 3 tacn)SmI 2 (THF) were synthesized for comparison. Several examples of the protonated ligands with simple counteranions, [HMe 3 tach][X] (X = Cl, Br, I) and [HMe 3 tacn][OTf], were identified in the course of these studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analyzing the effect of misalignment on single-filament carbon fiber tensile testing via stereoscopic computer vision imaging

An understanding of the constitutive properties of carbon fibers (CF) is critical to the accuracy of high-resolution composite simulations and to the development of CF derived from low-cost alternative precursor materials. Single-fiber tensile testing is a capable tool to measure CF properties and is well suited to research efforts where only a small number of fibers may be available. However, single-fiber tensile tests are challenging to conduct due to the difficulty in handling small diameter fibers (5-15 μm), the brittleness of single fibers, and the required nanoscale/microscale resolution of testing equipment. The accuracy of the measured properties depends on several factors, but a critical factor is fiber misalignment, especially at short gauge lengths. Current standards do not address the effect of tensile specimen misalignment on measured properties. Furthermore, this work presents a robust method of fiber alignment using stereoscopic computer vision that enables users to align fibers vertically for tensile testing to improve the accuracy of resulting mechanical properties. Additionally, an analytical relationship between fiber misalignment angle and measured properties is developed and validated against the experimental results. As a result, new best practices for single-fiber tensile testing of CF are recommended.

47 OTHER INSTRUMENTATION↗

Lightweight Materials - Carbon Fiber and Polymer Composites, Integrated Computational Materials Engineering (ICME) Predictive Tools Development for Low-Cost Carbon Fiber for Lightweight Vehicles (University of Virginia) (Final Report)

This project aimed to develop low-cost alternative precursors and processing techniques through the implementation of an integrated computational materials engineering (ICME) framework to evaluate precursor conversion kinetics. Once established, this framework was then used to down-select precursors for laboratory- and pilot-scale production to validate resulting carbon fiber (CF) material properties and process cost-savings. The two most promising approaches to reduce the cost of CFs were to (1) use new low-cost precursors and (2) reduce the energy requirements of CF processing. These approaches were investigated over the course of three phases of work, spanning 3.5 years. This report describes the overall project objectives, approach, and the key accomplishments in each phase.

36 MATERIALS SCIENCE↗

Comment on the Predicted Size of Cycle 23 Based on the Inferred Three-Cycle Quasi-Periodicity of the Planetary Index Ap

Recently, Ahluwalia [1998] reviewed the solar and geomagnetic data for the last 6 decades and remarked that these data "indicate the existence of a three-solar-activity-cycle quasi-periodicity in them." Futhermore, on the basis of this inferred quasi-periodicity, he asserted that cycle 23 represents the initial cycle in a new 3-cycle string, implying that it "will be more modest (a la cycle 17) with an annual mean sunspot number count of 119.3 +/- 30 at the maximum," a prediction that is considerably below the consensus prediction of 160 +/- 30 by Joselyn et al. [1997] and of similar predictions by others based on a variety of predictive techniques. Several major sticking points of Ahluwalia's presentation, however, must be redressed, and these issues form the basis of this comment. In particular, it is shown that Ahluwalia used inappropriate values of the Ap index in his analysis, that the inferred 3-cycle relationship which Ahluwalia claims for both Ap and SSN does not exist for the previous 6-cycle interval (prior to cycle 17) for SSN, that his inferred fit is only of marginal statistical significance (having r = 0.81), and that two alternative precursor fits (both with r = 0.96 or greater) exist which strongly suggest that R max for cycle 23 will be much larger than forecast by Ahluwalia (namely, about 168-187). Thus, caution must be exercised in accepting Ahluwalia's findings.

Hathaway, David H.↗