Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “carbonaceous materials”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

947 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Biochar Nanocomposite as an Inexpensive and Highly Efficient Carbonaceous Adsorbent for Hexavalent Chromium Removal

Biochar is commonly used for soil amendment, due to its excellent water-holding capacity. The Cr(VI) contamination of water is a current environmental issue in industrial regions. Here, we evaluated the effects of two-step modifications on boosting biochar’s performance in terms of the removal of aqueous hexavalent chromium (Cr(VI)), along with investigating the alterations to its surface properties. The first modification step was heat treatment under air at 300 °C, producing hydrophilic biochar (HBC). The resulting HBC was then impregnated with zero-valent iron nanoparticles (nZVI), creating an HBC/nZVI composite, adding a chemical reduction capability to the physical sorption mechanism. Unmodified biochar (BC), HBC, and HBC/nZVI were characterized for their physicochemical properties, including surface morphology and elemental composition, by SEM/EDS, while functional groups were ascertained by FTIR and surface charge by zeta potential. Cr(VI) removal kinetic studies revealed the four-time greater sorption capacity of HBC than BC. Although unmodified BC showed faster initial Cr(VI) uptake, it rapidly worsened and started desorption. After nZVI impregnation, the Cr(VI) removal rate of HBC increased by a factor of 10. FTIR analysis of biochars after Cr(VI) adsorption showed the presence of Cr(III) oxide only on the used HBC/nZVI and demonstrated that the carbonyl and carboxyl groups were the main groups involved in Cr(VI) sorption. Modified biochars could be considered an economical substitute for conventional methods.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effect of Surface Temperature on the Distribution and Reactivity of Rh Active Sites for CO Oxidation

Single–atom catalysts are a fast–emerging area in which late–transition metal atoms are supported on oxides, metals, and carbonaceous supports. They show great promise for selective chemical reactions due to their well–defined active sites, and significantly reduce precious metal loading. However, oxide–supported single–atom catalysts have drawbacks such as deactivation due to sintering, and there are on–going debates about the exact nature of the active sites. Herein we report a model system where the surface temperature during Rh deposition on a copper oxide support dictates the Rh size distribution. Here our temperature–programmed desorption experiments reveal that Rh clusters perform CO oxidation at lower temperature than single atoms, and isotopic labelling demonstrates differences in the mechanism in that the C–O bond is broken and reformed on clusters, as opposed to a pure Mars van Krevelen mechanism for CO oxidation at the single–atom Rh sites. We further examine the cluster size distributions with scanning tunneling microscopy and X–ray photoelectron spectroscopy which confirm the presence of both clusters and single atoms for the lower temperature deposition and only single atoms for the higher temperature deposition. Together, these results provide a fundamental understanding of the differences in the CO oxidation mechanism on Rh atoms and clusters.

36 MATERIALS SCIENCE↗
NASA NTRS1997

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Schuraytz, B. C.↗
NASA NTRS2006

Comets, Asteroids, Meteorites, and the Origin of the Biosphere

During the past few decades, the delivery of water, organics, and prebiotic chemicals to the Biosphere of Earth during the Hadean (4.5-3.8 Ga) period of heavy bombardment by comets and asteroids has become more widely accepted. Comets are still largely regarded as frigid, pristine bodies of protosolar nebula material that are devoid of liquid water and therefore unsuitable for life. Complex organic compounds have been observed in comets and on the water-rich asteroid 1998 KY26 and near IR observations have indicated the presence of crystalline water ice and ammonia hydrate on the large Kuiper Belt object (50000) Quaoar that has resurfacing suggesting cryovolcanic outgassing. Spacecraft observations of the chemical compositions and characteristics of the nuclei of several comets (Halley, Borrelly, Wild 2, and Tempel 1) have shown that comets contain complex organic chemicals; that water is the predominant volatile; and that extremely high temperatures (approx. 350-400 K) can be reached on the surfae of the very black (albedo approx. 0.03) nuclei of comets when they approach the Sun. Impact craters and pinnacles observed on comet Wild 2 suggest a thick crust. Episodic outbursts and jets from the nuclei of several comets indicate that localized regimes of liquid water and water vapor can periodically exist beneath the comet crust. The Deep Impact mission found the temperature of the nucleus of comet Tempel 1 at 1.5 AU varied from a minimum of 280 plus or minus 8 K the 330K (57 C) on the sunlit side. In this paper it is argued that that pools and films of liquid water exist (within a wide range of temperatures) in cavities and voids just beneath the hot, black crust. The possibility of liquid water existing over a wide range of temperatures significantly enhances the possibility that comets might contain niches suitable for the growth of microbial communities and ecosystems. These regimes would be ideal for the growth of psychrophilic, mesophilic, and thermophilic photoautotrophs and chemolithotrophs such as the motile filamentous cyanobacteria (e.g., Calothrix, Oscillatoria, Phormidium, and Spirulina) that grow in geothermal springs and geysers of Earth at temperatures ranging fiom 320K to 345K and are also found growing in cold polar desert soils. The mineralized remains of morphotypes of all of these cyanobacteria have also been found in the Orgueil CI1 and the Murchison CN2 carbonaceous meteorites that may derive from cometary parent bodies. Observational results that support the hypothesis that liquid water can in active regions just beneath the surface of comets and that comets, carbonaceous meteorites, and asteroids may have played a significant role in the origin and evolution of the Biosphere and in the distribution of microbial life throughout the Solar System.

Hoover, Richard B.↗
DOE OSTI2021

Non-Solvent Induced Phase Separation Enables Designer Redox Flow Battery Electrodes

Porous carbonaceous electrodes are performance-defining components in redox flow batteries (RFBs), where their properties impact the efficiency, cost, and durability of the system. The overarching challenge is to simultaneously fulfill multiple seemingly contradictory requirements—i.e., high surface area, low pressure drop, and facile mass transport—without sacrificing scalability or manufacturability. Here, non-solvent induced phase separation (NIPS) is proposed as a versatile method to synthesize tunable porous structures suitable for use as RFB electrodes. The variation of the relative concentration of scaffold-forming polyacrylonitrile to pore-forming poly(vinylpyrrolidone) is demonstrated to result in electrodes with distinct microstructure and porosity. Tomographic microscopy, porosimetry, and spectroscopy are used to characterize the 3D structure and surface chemistry. Flow cell studies with two common redox species (i.e., all-vanadium and Fe2+/3+) reveal that the novel electrodes can outperform traditional carbon fiber electrodes. It is posited that the bimodal porous structure, with interconnected large (>50 µm) macrovoids in the through-plane direction and smaller (<5 µm) pores throughout, provides a favorable balance between offsetting traits. Although nascent, the NIPS synthesis approach has the potential to serve as a technology platform for the development of porous electrodes specifically designed to enable electrochemical flow technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Using multimodal X-ray computed tomography to advance 3D petrography: A non-destructive investigation of olivine inside a carbonaceous chondrite

Rocks form in three dimensions through time and studying them provides information from inside dynamic systems we cannot otherwise observe. Yet how we typically access the interior of the rocks themselves to gain that information may limit our understanding and influence how we reconstruct the processes that formed them. Here, we demonstrate combined non-destructive 3D X-ray imaging techniques that produce quantitative densitometric and crystallographic maps of entire individual grains inside a rock. Olivine grains throughout a sample of the carbonaceous chondrite Northwest Africa (NWA) 11346 were each characterized by size, shape, composition, zoning intensity, and crystallographic orientation. The addition of 3D crystallographic mapping to calibrated 3D densitometric analysis—used to calculate chemical composition—demonstrates a fully non-destructive petrographic method and provides unique insight. For instance, in our case, using crystallographic data to delineate individual grains and then measuring the 3D size, shape, and composition of each distinguishes variably reset relict grains from those later crystallized after a melting event. Intersection in a 2D slice could not have led to this interpretation because the integration of three-dimensional size, rounding, composition, location, and crystallographic orientation measured from each grain forms the key patterns. Multimodal laboratory X-ray imaging has strong potential to advance 3D petrography.

36 MATERIALS SCIENCE↗
NASA NTRS2016

40 Years of Processing Pieces of Space

This year marks the 40th year anniversary for the Antarctic Search for Meteorite (ANSMET) program. In 1976, the ANSMET program led the first expedition to Antarctica. The ANSMET program is a US-led field-based science project that recovers meteorite samples from Antarctica. Once a year from late November to late January, a field team consisting of 8 to 12 people, spends 6-8 weeks camping on the ice and collecting meteorites. Since 1976, more than 22,000 meteorite samples have been recovered. These meteorites come from asteroids, planets and other bodies of the solar system. Once collected, the Antarctic meteorites are shipped to NASA/Johnson Space Center (JSC) Houston, TX. in a refrigerated truck and are kept frozen to minimize oxidation until they are ready for initial processing. In Antarctica each meteorite is given a field tag which consists of numbers, once in the lab, this is replaced by an official tag, consisting of the Antarctic field location and year collected. The types and numbers of meteorites that have been classified include 849 carbonaceous chondrites, 135 enstatites, 512 achondrites, 64 stony, 115 irons, 48 others (27 R chondrites, 7 ungrouped), 6,161 H chondrites, 7,668 L chondrites, and 4,589 LL chondrites. Although 80-85 percent of the collected meteorites fall in the ordinary chondrite group, the other approximately 15 percent represent rare types of achondrites and carbonaceous chondrites. These rare meteorites include 25 lunar meteorites, 15 Martian meteorites, scores of various types of carbonaceous chondrites, and unique achondrites. The Antarctic meteorites that have been collected are processed in the Meteorite Processing Lab at JSC in Houston, TX. Initial processing of the meteorites begins with thawing/drying the meteorites in a nitrogen glove box for 24 to 48 hours. The meteorites are then photographed, measured, weighed and a description of the interior and exterior of each meteorite is written. The meteorite is broken and a representative sample, either a 1-3 gram chip or thin section is sent to the Smithsonian Institution for classification. After Antarctic meteorites have been classified and approved by the Nomenclature Committee of the Meteoritical Society, they are announced in the Antarctic Meteorite Newsletter, which is published twice per year (fall and spring) so that scientists may review which meteorites are available to study. Requests for Antarctic Meteorite samples are welcomed from research scientists, regardless of their current state of funding for meteorite studies. Since its inception over 3,300 requests have been made for pieces of these meteorites and over 400 investigators worldwide are active in the study of meteorites.. Research on these samples has been published in more than1500 peer reviewed articles; a listing of papers for any meteorite sample can be generated by accessing http://curator.jsc.nasa.gov/antmet/referencesearch.cfm. Antarctic meteorite samples requested by scientists are prepared several different ways. Most samples are prepared as chips, either using a rock splitter or using a chisel and chipping bowl. In special situations, a researcher may request a meteorite slab in which case the samples are cut using a diamond-bladed bandsaw inside of a dry nitrogen glove box. The meteorites are always cut in a 100 percent liquid-free environment. Additionally, thin/thick sections of Antarctic meteorites are also prepared at JSC. The meteorite thin section lab at JSC can prepare standard 30-micron thin sections, thick sections of variable thickness (100 to 200 microns), or demountable sections using superglue, all section are prepared without using water. Although many of the techniques used back in the '70's are still used today, advances in computers, software, databases, available tools and instrumentation have helped to streamline and shorten the duration of the classification process. In conjunction with present day missions to asteroids and other planets, meteorite studies have not only led to a better understanding of the complex histories of these bodies but have also tied certain meteorite groups to particular asteroid bodies. New meteorite discoveries by the ANSMET program provide a cost effective method for obtaining samples of previously unsampled bodies, allowing scientists to learn more about the origin, composition, and evolution of the solar system. Preservation in our cleanrooms at NASA allows material to be archived for future generations and advances in instrumentation and analysis.

Satterwhite, C. E.↗
NASA NTRS2012

Analysis of Direct Samples of Early Solar System Aqueous Fluids

Over the past three decades we have become increasingly aware of the fundamental importance of water, and aqueous alteration, on primitive solar-system bodies. Some carbonaceous and ordinary chondrites have been altered by interactions with liquid water within the first 10 million years after formation of their parent asteroids. Millimeter to centimeter-sized aggregates of purple halite containing aqueous fluid inclusions were found in the matrix of two freshly-fallen brecciated H chondrite falls, Monahans (1998, hereafter simply "Monahans") (H5) and Zag (H3-6) (Zolensky et al., 1999; Whitby et al., 2000; Bogard et al., 2001) In order to understand origin and evolution of the aqueous fluids inside these inclusions we much measure the actual fluid composition, and also learn the O and H isotopic composition of the water. It has taken a decade for laboratory analytical techniques to catch up to these particular nanomole-sized aqueous samples. We have recently been successful in (1) measuring the isotopic composition of H and O in the water in a few fluid inclusions from the Zag and Monahans halite, (2) mineralogical characterization of the solid mineral phases associated with the aqueous fluids within the halite, and (3) the first minor element analyses of the fluid itself. A Cameca ims-1270 equipped with a cryo-sample-stage of Hokkaido University was specially prepared for the O and H isotopic measurements. The cryo-sample-stage (Techno. I. S. Corp.) was cooled down to c.a. -190 C using liquid nitrogen at which the aqueous fluid in inclusions was frozen. We excavated the salt crystal surfaces to expose the frozen fluids using a 15 keV Cs+ beam and measured negative secondary ions. The secondary ions from deep craters of approximately 10 m in depth emitted stably but the intensities changed gradually during measurement cycles because of shifting states of charge compensation, resulting in rather poor reproducibility of multiple measurements of standard fluid inclusions of +/- 90 0/00(2 sigma) for delta D, and +/- 29 0/00 (2 sigma) for delta O-18. On the other hand, the reproducibility of Delta O-17 is plus or minus 8 /00 (2 sigma ) because the observed variations of isotope ratios follow a mass dependent fractionation law. Variations of delta D of the aqueous fluids range over sog,a 330(90; 2 sigma ) to +1200(90) 0/00 for Monahans and delta 300(96) 0/00 to +90(98)0/00 for Zag. Delta O-17 of aqueous fluids range over delta 16(22) 0/00 to +18(10) 0/00 for Monahans and +3(10) 0/00 to +27(11) 0/00 for Zag. These variations are larger than the reproducibility of standard analyses and suggest that isotope equilibria were under way in the fluids before trapping into halite. The mean values of delta D and Delta O-17 are +290 0/00 and +9 0/00, respectively. The mean values and the variations of these fluids are different from the representative values of ordinary chondrites, verifying our working hypothesis that the fluid inclusion-bearing halites were not indigenous to the H chondrite parent-asteroid but rather represent exogenous material delivered onto the asteroid from a separate cryovolcanically-active body. This initial isotopic work has demonstrated the feasibility of the measurements, but also revealed sample processing and analytical shortcomings that are now being addressed. Examination of solid mineral inclusions within Monahans and Zag halite grains by confocal Raman spectroscopy at the Carnegie Geophysical Laboratory has revealed them to be metal, magnetite, forsteritic olivine (Fo.98), macromolecular carbon (MMC), pyroxenes, feldspar with Raman spectral affinity to anorthoclase and, probably, fine-grained lepidocrocite (FeO(OH)). In addition, one inclusion features aliphatic material with Raman spectral features consistent with a mixture of short-chain aliphatic compounds. We have initiated analyses of the bulk composition of the fluids within the inclusions in Zag and Monahans halites at Virginia Tech by LA ICPMS using angilent 7500ce quadrupole ICPMS and a Lambda Physik GeoLas 193 nm excimer laser ablation system. Preliminary results reveal that the inclusion aqueous fluids contain highly charged cations of Ca, Mg and Fe. The minerals and compounds discovered thus far within Monahans/Zag halites are indicative of an originating body at least partly composed of unequilibrated anhydrous materials (high Fo olivine, pyroxenes, feldspars, possibly the metal) which were subjected to aqueous alteration (the halite parent brine) and containing a light organic component (the short-chain aliphatic compounds). This material was ejected from the originating body with little or no disruption, as evidenced with the presence of fluid inclusions. An actively geysering body similar to modern Enceladus (Postberg et al., 2011) may be a reasonable analogue in this respect. Also, the originating body should have been within close proximity to the H chondrite parent in order to generate the number of halite grains seen in Monahans and Zag. Other candidates for Monahans/Zag halite parent bodie(s) may include a young Ceres with its possible liquid ocean, or Main Belt comets.

Zolensky, Michael E.↗
DOE OSTI2022

Nickel-rich, volatile depleted iron meteorites: Relationships and formation processes

Ungrouped iron meteorites Tishomingo, Willow Grove, and Chinga, and group IVB iron meteorites, are Ni-rich. Similarities include enrichments of 10–100 × CI for some refractory siderophile elements, and equivalent depletions in more volatile siderophile elements. Superimposed on the overall enrichment/depletion trend, certain siderophile elements (P, W, Fe, Mo) are depleted relative to elements of similar volatility. All three ungrouped irons derive from parent bodies formed in the early Solar System. Willow Grove and Chinga are characterized by cosmic ray exposure corrected 182 W/ 184 W consistent with metal-silicate segregation on their parent bodies within 1–3 Myr of Solar System formation, within the age range determined for segregation of magmatic iron meteorite parent bodies, including group IVB irons. Tishomingo is characterized by a younger model age 4–5 Myr subsequent to Solar System formation, reflecting either late stage melting resulting from 26 Al decay, or an impact resetting. The discovery of stishovite in Tishomingo, indicating exposure to a minimum shock pressure of 8–9 GPa, is consistent with the latter. Stishovite in Tishomingo and chromite included in troilite-daubréelite in IVB irons allows oxygen isotopic composition comparison between these meteorites. Different mass independent oxygen isotopic compositions of IVB irons and Tishomingo indicate genetically distinct parent bodies. By contrast, mass independent Mo isotopic compositions overlap within analytical uncertainties, indicating a similar, carbonaceous chondrite (CC) type genetic heritage. Molybdenum and 183 W isotopic data for Chinga and Willow Grove indicate derivation from CC type parent bodies. Willow Grove shares Mo and 183 W isotopic compositions with the Ni-rich South Byron Trio (SBT) grouplet and the Milton pallasite. These Ni-rich meteorites likely formed in the same general nebular environment as other CC planetesimals, likely the outer Solar System. Highly siderophile element (HSE) abundances of Willow Grove and Tishomingo are similar to some IVB meteorites, consistent with formation by moderate degrees of fractional crystallization from initial metallic melts with low S and P, and modestly fractionated HSE. The comparable HSE abundances of Tishomingo and Willow Grove to some IVB irons, yet substantially higher Ni concentrations, indicate formation on parent bodies with lower bulk HSE abundances or HSE concentration in proportionally smaller volumes of metal. HSE abundances in Chinga are considerably lower than in IVB irons, highly fractionated, and processes responsible for these remain elusive. For IVB irons and these ungrouped irons, high temperature condensation likely dominated the enrichment and depletion of the refractory and volatile siderophile elements, respectively. Parent body degassing may have also played a role. Relative depletion of volatile siderophile elements is not, however, a universal feature of high-Ni meteorites. The SBT and Milton pallasite are Ni-rich, but less depleted in the more volatile siderophile elements. Nickel enrichment was likely driven by oxidation of Fe metal during parent body accretion or core segregation. Oxidation of the Tishomingo and Willow Grove parent bodies may have occurred at ~ IW + 1, indicated by relative Mo and W depletions due to metal/water reaction during differentiation. Late-stage reduction, indicated by the presence of Cr-bearing sulfides in Tishomingo and IVB irons, may have resulted from exhaustion of the oxidant.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Iraq/Afghanistan war lung injury reflects burn pits exposure

This descriptive case series retrospectively reviewed medical records from thirty-one previously healthy, war-fighting veterans who self-reported exposure to airborne hazards while serving in Iraq and Afghanistan between 2003 and the present. They all noted new-onset dyspnea, which began during deployment or as a military contractor. Twenty-one subjects underwent non-invasive pulmonary diagnostic testing, including maximum expiratory pressure (MEP) and impulse oscillometry (IOS). In addition, five soldiers received a lung biopsy; tissue results were compared to a previously published sample from a soldier in our Iraq Afghanistan War Lung Injury database and others in our database with similar exposures, including burn pits. We also reviewed civilian control samples (5) from the Stony Brook University database. Military personnel were referred to our International Center of Excellence in Deployment Health and Medical Geosciences, Donald and Barbara Zucker School of Medicine at Hofstra/Northwell under the auspices of Northwell IRB: 17-0140-FIMR Feinstein Institution for Medical Research “Clinicopathologic characteristics of Iraq Afghanistan War Lung Injury.” We retrospectively examined medical records, including exposure data, radiologic imaging, and non-invasive pulmonary function testing (MGC Diagnostic Platinum Elite Plethysmograph) using the American Thoracic Society (ATS) standard interpretation based on Morgan et al., and for a limited cohort, biopsy data. Lung tissue, when available, was examined for carbonaceous particles, polycyclic aromatic hydrocarbons (Raman spectroscopy), metals, titanium connected to iron (Brookhaven National Laboratory, National Synchrotron Light Source II, Beamline 5-ID), oxidized metals, combustion temperature, inflammatory cell accumulation and fibrosis, neutrophil extracellular traps, Sirius red, Prussian Blue, as well as polarizable crystals/particulate matter/dust. Among twenty-one previously healthy, deployable soldiers with non-invasive pulmonary diagnostic tests, post-deployment, all had severely decreased MEP values, averaging 42% predicted. These same patients concurrently demonstrated abnormal airways reactance (X5Hz) and peripheral/distal airways resistance (D5–D20%) via IOS, averaging – 1369% and 23% predicted, respectively. These tests support the concept of airways hyperresponsiveness and distal airways narrowing, respectively. Among the five soldiers biopsied, all had constrictive bronchiolitis. We detected the presence of polycyclic aromatic hydrocarbons (PAH)—which are products of incomplete combustion—in the lung tissue of all five warfighters. All also had detectable titanium and iron in the lungs. Metals were all oxidized, supporting the concept of inhaling burned metals. Combustion temperature was consistent with that of burned petrol rather than higher temperatures noted with cigarettes. All were nonsmokers. Neutrophil extracellular traps were reported in two biopsies. Compared to our prior biopsies in our Middle East deployment database, these histopathologic results are similar, since all database biopsies have constrictive bronchiolitis, one has lung fibrosis with titanium bound to iron in fixed mathematical ratios of 1:7 and demonstrated polarizable crystals. These results, particularly constrictive bronchiolitis and polarizable crystals, support the prior data of King et al. (N. Engl. J. Med. 365:222–230, 2011) Soldiers in this cohort deployed to Iraq and Afghanistan since 2003, with exposure to airborne hazards, including sandstorms, burn pits, and improvised explosive devices, are at high risk for developing chronic clinical respiratory problems, including: (1) reduction in respiratory muscle strength; (2) airways hyperresponsiveness; and (3) distal airway narrowing, which may be associated with histopathologic evidence of lung damage, reflecting inhalation of burned particles from burn pits along with particulate matter/dust. Non-invasive pulmonary diagnostic tests are a predictor of burn pit-induced lung injury

36 MATERIALS SCIENCE↗
DOE OSTI2025

Coal to Carbon Fiber (C2CF) Continuous Processing for High Value Composites (Final Report)

Coal tar is a condensed and recovered by-product of the coking of metallurgical coal for steel production. The heaviest fraction of distilled coal tar is an isotropic pitch largely used as a binder in the manufacturing of carbonaceous electrodes for primary aluminum smelting and in electric arc furnaces. Coal tar pitch offers high carbon yield upon carbonization. In this project, a process to convert the domestically sourced isotropic coal tar pitch, containing very low particulates (QI = 0.32 wt.%), to form flow-domain mesophase pitch amenable for melt spinning into precursor (green) fibers for carbon fiber, was developed and optimized. The final reproducible processing developed is reviewed in this report, along with several characterizations of the mesophase pitch. A final definition of the characteristics of a ‘spinnable’ mesophase pitch is presented. With this mesophase pitch, reproducible and stable multifilament melt spinning was developed, producing green fiber tows with filament diameters of approximately 20 m. The multifilament melt spinning was the most challenging aspect of the project and required the most effort. The best practices learned from this project for melt spinning are reviewed in this report. Once spun, the green fibers were oxidatively stabilized, carbonized and graphitized under inert gas atmosphere to form the final carbon fibers. Given the relatively high softening point of the mesophase pitch, no issues of interfilament fusion were observed during batch oxidation, and subsequent batch carbonization and graphitization went smoothly in all cases. An ~ 80 wt.% conversion of the green fiber mass to final carbon fiber was achieved. After graphitization, the carbon fibers showed high tensile moduli (most were ~ 600 GPa, or 87 Msi) consistent with commercially-available high-performance pitch-based carbon fiber. However, tensile strength and strain to failure were comparatively low. Further work to reduce defects in and on the fiber surfaces would increase these properties. SEM imaging of the graphitic fiber textures is presented herein. Rudimentary composites were fabricated from the carbon fibers and characterized showing similar modulus to baseline composites fabricated with commercial carbon fiber. Finally, a basic economic analysis was done showing the potential to increase the value of the isotropic coal tar pitch by up to 13.6 to 136 times based on a carbon fiber value of $\$$5/lb to $\$$50/lb, respectively. Moreover, the site case study suggests that the coal tar from the single integrated steel mill could supply production of up to 16 kt/yr of carbon fiber. Finally, a technological gap analysis was done which shed light on remaining technical challenges. These challenges included: recovery and utilization of condensates from the mesophase pitch processing, further advancing and increasing stability of the multifilament melt spinning processing, optimization of the oxidation processing, defect reduction for increased carbon fiber strength, and the development of a weaving process towards carbon fiber fabrics. To maximize the coal value chain, the primary objectives of this project were to (a) develop and scale efficient processing technology for producing melt-spinnable mesophase pitch from isotropic coal tar pitch, (b) clarify and simplify tedious continuous fiber processing technologies (particularly multifilament melt spinning of mesophase pitch) towards the efficient production of high performance carbon fiber, and (c) demonstrate and characterize representative composite parts derived from the final carbon fiber. Immense progress was made on all 3 objectives and is detailed in this report.

01 COAL, LIGNITE, AND PEAT↗