Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “nodulation”

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.

At least 145 records · Page 8

Laser Ablation Increases PEM/Catalyst Interfacial Area

An investigational method of improving the performance of a fuel cell that contains a polymer-electrolyte membrane (PEM) is based on the concept of roughening the surface of the PEM, prior to deposition of a thin layer of catalyst, in order to increase the PEM/catalyst interfacial area and thereby increase the degree of utilization of the catalyst. The roughening is done by means of laser ablation under carefully controlled conditions. Next, the roughened membrane surface is coated with the thin layer of catalyst (which is typically platinum), then sandwiched between two electrode/catalyst structures to form a membrane/ele c t - rode assembly. The feasibility of the roughening technique was demonstrated in experiments in which proton-conducting membranes made of a perfluorosulfonic acid-based hydrophilic, protonconducting polymer were ablated by use of femtosecond laser pulses. It was found that when proper combinations of the pulse intensity, pulse-repetition rate, and number of repetitions was chosen, the initially flat, smooth membrane surfaces became roughened to such an extent as to be converted to networks of nodules interconnected by filaments (see Figure 1). In further experiments, electrochemical impedance spectroscopy (EIS) was performed on a pristine (smooth) membrane and on two laser-roughened membranes after the membranes were coated with platinum on both sides. Some preliminary EIS data were interpreted as showing that notwithstanding the potential for laser-induced damage, the bulk conductivities of the membranes were not diminished in the roughening process. Other preliminary EIS data (see Figure 2) were interpreted as signifying that the surface areas of the laser-roughened membranes were significantly greater than those of the smooth membrane. Moreover, elemental analyses showed that the sulfur-containing molecular groups necessary for proton conduction remained intact, even near the laser-roughened surfaces. These preliminary results can be taken as indications that laser-roughened PEMs should function well in fuel cells and, in particular, should exhibit current and power densities greater than those attainable by use of smooth membranes.

Whitacre, Jay↗

The Mineralogical and Chemical Case for Habitability at Yellowknife Bay, Gale Crater, Mars

Sediments of the Yellowknife Bay formation (Gale crater) include the Sheepbed member, a mudstone cut by light-toned veins. Two drill samples, John Klein and Cumberland, were collected and analyzed by the CheMin XRD/XRF instrument and the Sample Analysis at Mars (SAM) evolved gas and isotopic analysis suite of instruments. Drill cuttings were also analyzed by the Alpha Particle X-ray Spectrometer (APXS) for bulk composition. The CheMin XRD analysis shows that the mudstone contains basaltic minerals (Fe-forsterite, augite, pigeonite, plagioclase), as well as Fe-oxide/hydroxides, Fe-sulfides, amorphous materials, and trioctahedral phyllosilicates. SAM evolved gas analysis of higher-temperature OH matches the CheMin XRD estimate of ~20% clay minerals in the mudstone. The light-toned veins contain Ca-sulfates; anhydrite and bassanite are detected by XRD but gypsum is also indicated from Mastcam spectral mapping. These sulfates appear to be almost entirely restricted to late-diagenetic veins. The sulfate content of the mudstone matrix itself is lower than other sediments analyzed on Mars. The presence of phyllosilicates indicates that the activity of water was high during their formation and/or transport and deposition (should they have been detrital). Lack of chlorite places limits on the maximum temperature of alteration (likely <100 C). The presence of Ca-sulfates rather than Mg- or Fe-sulfates suggests that the pore water pH was near-neutral and of relatively low ionic strength (although x-ray amorphous Mg-and Fe- sulfates could be present and undetectable by CheMin). The presence of Fe and S in both reduced and oxidized states represents chemical disequilibria that could have been utilized by chemolithoautotrophic biota, if present. When compared to the nearby Rocknest sand shadow mineralogy or the normative mineralogy of Martian soil, both John Klein and Cumberland exhibit a near-absence of olivine and a surplus of magnetite (7-9% of the crystalline component). The magnetite is interpreted as an authigenic product formed when olivine was altered to phyllosilicate. Saponitization of olivine (a process analogous to serpentinization) could have produced H2 in situ. Indeed, early diagenetic hollow nodules ("minibowls") present in the Cumberland mudstone are interpreted by some as forming when gas bubbles accumulated in the unconsolidated mudstone. Lastly, all of these early diagenetic features appear to have been preserved with minimal alteration since their formation, as indicated by the ease of drilling (weak lithification, lack of cementing phases), the presence of 20-30% amorphous material, and the late-stage fracturing with emplacement of calcium sulfate veins and minibowl infills, where they were intersected by veins. A rough estimate of the minimum duration of the lacustrine environment is provided by the minimum thickness of the Sheepbed member. Given 1.5 meters, and applying a mean sediment accumulation rate for lacustrine strata of 1 m/1000 yrs yields a duration of 1,500 years. If the aqueous environments represented by overlying strata are considered, such as Gillespie Lake and Shaler, then this duration increases. The Sheepbed mudstone meets all the requirements of a habitable environment: Aqueous deposition at clement conditions of P, T, pH, Eh and ionic strength, plus the availability of sources of chemical energy.

Blake, David Frederick↗

Constraining the Texture and Composition of Pore-Filling Cements at Gale Crater, Mars

The Mars Science Laboratory (MSL) rover Curiosity has encountered a wide variety of sedimentary rocks deposited in fluvio-lacuestrine sequences at the base of Gale Crater. The presence of sedimentary rocks requires that initial sediments underwent diagenesis and were lithified. Lithification involves sediment compaction, cementation, and re-crystallization (or authigenic) processes. Analysis of the texture and composition of the cement can reveal the environmental conditions when the cements were deposited, enabling better understanding of early environments present within Gale Crater. The first step in lithification is sediment compaction. The Gale crater sediments do not show evidence for extensive compaction prior to cementation; the Sheepbed mudstone in Yellowknife Bay (YKB) has preserved void spaces ("hollow nodules"), indicating that sediments were cemented around the hollow prior to compaction, and conglomerates show imbrication, indicating minimal grain reorganization prior to lithification. Furthermore, assuming the maximum burial depth of these sediments is equivalent to the depth of Gale Crater, the sediments were never under more than 1 kb of pressure, and assuming a 15 C/km thermal gradient in the late Noachian, the maximum temperature of diagenesis would have been approximately 75 C. This is comparable to shallow burial diagenetic conditions on Earth. The cementation and recrystallization components of lithification are closely intertwined. Cementation describes the precipitation of minerals between grains from pore fluids, and recrystallization (or authigenesis) is when the original sedimentary mineral grains are altered into secondary minerals. The presence of authigenic smectites and magnetite in the YKB formation suggests that some recrystallization has taken place. The relatively high percentage of XRD-amorphous material (25-40%) detected by CheMin suggests that this recrystallization may be limited in scope, and therefore may not contribute significantly to the cementing material. However, relatively persistent amorphous components could exist in the Martian environment (e.g. amorphous MgSO4), so recrystallization, including loss of crystallinity, cannot yet be excluded as a method of cementation. In order to describe the rock cementation, both the rock textures and their composition must be considered. Here, we attempt to summarize the current understanding of the textural and compositional aspects of the cement across the rocks analyzed by Curiosity to this point.

Siebach, K. L.↗

Diagenetic Mineralogy at Gale Crater, Mars

Three years into exploration of sediments in Gale crater on Mars, the Mars Science Laboratory rover Curiosity has provided data on several modes and episodes of diagenetic mineral formation. Curiosity determines mineralogy principally by X-ray diffraction (XRD), but with supporting data from thermal-release profiles of volatiles, bulk chemistry, passive spectroscopy, and laser-induced breakdown spectra of targeted spots. Mudstones at Yellowknife Bay, within the landing ellipse, contain approximately 20% phyllosilicate that we interpret as authigenic smectite formed by basalt weathering in relatively dilute water, with associated formation of authigenic magnetite as in experiments by Tosca and Hurowitz [Goldschmidt 2014]. Varied interlayer spacing of the smectite, collapsed at approximately 10 A or expanded at approximately 13.2 A, is evidence of localized diagenesis that may include partial intercalation of metal-hydroxyl groups in the approximately 13.2 A material. Subsequent sampling of stratigraphically higher Windjana sandstone revealed sediment with multiple sources, possible concentration of detrital magnetite, and minimal abundance of diagenetic minerals. Most recent sampling has been of lower strata at Mount Sharp, where diagenesis is widespread and varied. Here XRD shows that hematite first becomes abundant and products of diagenesis include jarosite and cristobalite. In addition, bulk chemistry identifies Mg-sulfate concretions that may be amorphous or crystalline. Throughout Curiosity's traverse, later diagenetic fractures (and rarer nodules) of mm to dm scale are common and surprisingly constant and simple in Ca-sulfate composition. Other sulfates (Mg,Fe) appear to be absent in this later diagenetic cycle, and circumneutral solutions are indicated. Equally surprising is the rarity of gypsum and common occurrence of bassanite and anhydrite. Bassanite, rare on Earth, plays a major role at this location on Mars. Dehydration of gypsum to bassanite in the dry atmosphere of Mars has been proposed but considered unlikely based on lab studies of dehydration kinetics in powdered samples. Dehydration is even less likely for bulk vein samples, as lab data show dehydration rates one to two orders of magnitude slower in bulk samples than in powders. On Mars, exposure ages of 100 Ma or more may be a significant factor in dehydration of hydrous phases.

Vaniman, David↗

Modeling of Sulfide Microenvironments on Mars

Yellowknife Bay (YKB; sol 124-198) is the second site that the Mars Science Laboratory Rover Curiosity investigated in detail on its mission in Gale Crater. YKB represents lake bed sediments from an overall neutral pH, low salinity environment, with a mineralogical composition which includes Ca-sulfates, Fe oxide/hydroxides, Fe-sulfides, amorphous material, and trioctahedral phyllosilicates. We investigate whether sulfide alteration could be associated with ancient habitable microenvironments in the Gale mudstones. Some textural evidence for such alteration may be pre-sent in the nodules present in the mudstone.

Schwenzer, S. P.↗

Fine-Gained CAIs in Comet Samples: Moderate Refractory Character and Comparison to Small Refractory Inclusions in Chondrites

Examination of >200 comet Wild 2 particles collected by the Stardust (SD) mission shows that the CAI abundance of comet Wild 2's rocky material is near 1% and that nearly 50% of all bulbous tracks will contain at least one recognizable CAI fragment. A similar abundance to Wild 2 is found in a giant cluster IDP thought to be of cometary origin. The properties of these CAIs and their comparison with meteoritic CAIs provide important clues on the role of CAIs in the early Solar System (SS) and how they were transported to the edge of the solar nebula where Kuiper Belt comets formed. Previously, only two CAIs in comet Wild 2 had been identified and studied in detail. Here we present 2 new Wild 2 CAIs and 2 from a giant cluster cometary IDP, describe their mineralogical characteristics and show that they are most analogous to nodules in spinel-rich, fine-grained inclusions (FGIs) observed in CV3 and other chondrites. Additionally, we present new O isotope measurements from one CAI from comet Wild 2 and show that its oxygen isotopic composition is similar to some FGIs. This is only the second CAI from Wild 2 in which O isotopes have been measured.

Joswiak, D. J.↗

CDKN1a/p21 Plays a Critical Role in Suppressing Stem Cell Regenerative Potential During Aging

Unloading during spaceflight is known to adversely affect mammalian physiology. Mechanical stimulation is required for repair and regeneration by stem cell lineages to maintain tissue health and mass. CDKN1a/p21 functions as a potent cell cycle arrest molecule and we previously found that CDKN1a/p21 was overexpressed in mouse bone during 15-days of spaceflight on STS-131 and localized to osteoprecursor cells in the femur. Therefore, we hypothesized that altered expression of CDKN1a/p21 leads to an arrest of bone formation during spaceflight in response to altered load. To study CDKN1a/p21 and its role in stem cell-based tissue regeneration, we use a CDKN1a/p21 knockout (KO) mouse to investigate the impact on bone structure, osteoprogenitor proliferation, and mineralized nodule formation. We have shown that bone marrow stem cells isolated from juvenile (11-week-old) and skeletally mature (18-week-old) KO mice have an increased bone formation potential as evidenced by increased proliferation and mineralization rates. In addition, we have shown that juvenile KO mice display significantly increased bone volume fraction (BV/TV) relative to wildtype (WT) mice, but not in skeletally mature KO mice, indicating increased resorption and bone turnover in adult mice. To more closely examine age differences in the KO mouse, we will study a wider spectrum of mice ranging from 4 weeks to 12 months in age. To do this, we will analyze differences in bone morphometric parameters using MicroCT and osteoblastogenesis assays. The pelvis, femur, and tibia are key in distributing weight and we expect to see altered remodeling and stem cell potential with age. In combination with histomorphometry, these results will help elucidate the complex mechanisms underlying bone tissue maintenance and stem cell regeneration.

stem cells↗

Fine-Grained, Spinel-Rich Ca-Al-Rich Inclusions From The Reduced CV3 Chondrite Efremovka: A Genetic Link To Wark-Lovering Rims?

Fine-grained, spinel-rich Ca-Al-rich inclusions (FGIs) in carbonaceous chondrites, mostly CV3 chondrites, are interpreted as aggregates of nebular gas-solid condensates that escaped significant melting [1]. Multiple lines of evidence suggest a condensation origin for FGIs, including their layered structures and irregular shapes and the fine grain size of numerous spinel-cored nodules [e.g., 2,3], and the distinctive volatility-fractionated group II rare earth element patterns of bulk inclusions and their mineral constituents [e.g., 4,5]. The origin and nature of FGIs are poorly constrained because of their fine grain sizes and intimate intergrowths of refractory phases, combined with their susceptibility to secondary parent body alteration processes, making detailed mineralogical and petrologic characterizations difficult using scanning electron microscope (SEM) and electron microprobe techniques. In this study, we present preliminary transmission electron microscope (TEM) analyses of pristine FGIs from the reduced CV3 chondrite Efremovka in order to provide the detailed characterization of their micrometer- to nanometer-scale textures and chemical compositions. Our goals are to better understand the formation processes and conditions of FGIs in the early solar nebula and to explore their possible genetic relationship with other early-formed refractory inclusions and their rims.

Keller, L. P.↗

Primary Nanocrystalline Anhydrous Chondrule Mesostasis: Limited Evidence of Secondary Alteration in Most CR Chondrites

The chondrule regions generally regarded to be most susceptible to aqueous alteration are mesostasis and Fe-Ni metal nodules. In CMs, studies of mesostasis have successfully placed contraints into their asteroidal histories. Unlike CM mesostasis, only a few studies of CR mesostasis are currently available [e.g. 1-4]. Here we study the effects aqueous alteration can have on the texture, composition, and mineralogy of CR chondrule mesostasis from 9 Antarctic CR chondrites: EET 92062,5, EET 96259,13, GRA 95229,77, GRO 95577,61 LAP 02342,44, LAP 04516,4, LAP 04720,16 and MIL 07525,7 and MIL 090001,2, generously provided by the U.S. Antarctic Meteorite Collection. To our knowledge, this is the first detailed TEM and compositional study of differences between chondrule setting in CR mesostasis. Based on these data, we place constraints on the degree to which these CRs record aqueous alteration.

Abreu, N. M.↗

Modulation of Bone Marrow Primary Cell Osteoblastogenesis and Cell Senescence by Mechanical Stimulation

Cell and animal studies conducted onboard the International Space Station and formerly the Shuttle flights have provided groundbreaking data illuminating the deleterious biological response of bone to mechanical unloading. Specifically CDKN1A/p-21 a cell senescence protein, was found to be upregulated in osteoprecursor cells of the femur during 15-day spaceflight, leading to the working hypothesis that CDKN1A/p-21 plays a role in inhibition of bone formation via mechanical regulation. To evaluate this hypothesis, utilizing a p-21 knockout mouse-line and relevant wildtype control, we cultured femoral bone marrow primary cells under unloaded (static) and cyclically stretched loading through a 30 day osteoblastogenesis protocol. Morphologic evaluation of the cultures demonstrated that mechanical stretching aligned the cells and increased the presence of defined focal adhesion expressing talin, integrin αvβ3, and PTK2 protein tyrosine kinase 2, also known as focal adhesion kinase (FAK) in both mouse strains. In corroboration with previous investigations of cell survival signals relation to FAK, our study found that with greater concentration of focal adhesions via stretch stimulation the live cell percentage was significantly higher than the unloaded controls (p-21 knockout line: +49.70%, p*=0.009, wildtype control: +18.14%, p*=.01). Also evaluated was the mineralization and ECM secretion capability of the differentiating cells. Von Kossa staining has shown that in the p-21 knockout cells unloaded cells produce more matrix that the stretch stimulated, however the matrix is unorganized presenting in sporadic nodules covering approximately 30% of the culture area at day 14 (n=6 wells) while the stretch stimulated cultures have less mineralization content the surface area containing mineralized matrix is greater (~68% at day 14). Q-PCR evaluation of the p-21 knockout cells revealed that canonical (β-catenin cascade) and non-canonical wnt11 and downstream planar cell polarity (wnt/PCP) pathway molecule RAC1 are prevalently upregulated with mechanical stimulation. Immunofluorescence for β-catenin and RAC1 showed co-localization at the nuclear membrane of the p-21 knockout cells but not the wildtype (n=1) suggesting that molecular communication via the canonical and wnt/PCP pathway are initiated by mechanical loading and experience regulation along the signaling cascade by CDKN1A/p-21. Future investigations will further elucidate this relationship and provide causal data demonstrating mechanical loading’s modulatory effect on p-21 expression change.

Juran, Cassandra M.↗

Microstructural Record of Evolving Condensation Processes in Fine-Grained Ca-Al-Rich Inclusions from the Reduced CV3 Chondrites

Fine-grained, spinel-rich Ca-Al-rich inclusions (FGIs) in carbonaceous chondrites consist of numerous layered nodules having cores of spinel, hibonite, and/or perovskite surrounded by multiple thin layers of melilite, anorthite, diopside, and/or olivine. They are interpreted as aggregates of direct high-temperature condensates from an 16O-rich nebular gas that escaped significant melting. However, FGIs are very complex objects composed of intimate intergrowths of fine-grained refractory phases and show extremely large variations in mineralogy, modal abundance, and textures. Thus, detailed FIB/TEM analyses of FGIs are required to fully characterize their micro-to-nanometer scale textures, mineralogy, and chemical compositions and hence elucidate their formation processes and conditions in the early solar nebula. Here, we present our on-going study of pristine FGIs from the reduced CV3 chondrites Efremovka and Thiel Mountains (TIL) 07003 and 07007 that have minimal evidence for secondary parent body alteration.

Han, J.↗

The Effects of CDKN1a/p21 on Oxidative Stress and Mitochondrial Function During Long Duration Spaceflight

Broad tissue degeneration and the failure of normal tissue regenerative processes in microgravity because of mechanical unloading are increasing concerns for sustaining life in space as the duration of future flight missions increases. Work in our laboratory has identified normal adult stem cell-based tissue regenerative processes, such as the formation of new bone, cartilage, and immune cells, as being particularly sensitive to the stresses of mechanical unloading in microgravity. Our studies have also identified the inhibition of differentiation of marrow mesenchymal stem cells and activation of CDKN1ap21-mediated cell cycle arrest in proliferative osteoprecursor cells on the bone surface as potential mechanisms for spaceflight-induced skeletal changes. This finding, in combination with the role of CDKN1ap21 as a suppressor of mammalian tissue regeneration, suggests that this gene could be responsible for suppressing stem cell-based tissue regeneration in response to disuse. In this work, we hypothesized that CDKN1ap21 regulates regenerative bone formation in response to alterations in mechanical load and tested this hypothesis by studying the skeletal phenotype and stem cell regenerative ability of juvenile (4-11 weeks old) and adult (18 weeks-12 months old) p21 (--) knockout (KO) mice. Additionally, we analyzed bone micro-architectural properties, bone formation rates and differentiation capacity of bone marrow stem cells (BMSCs) from male and female KO mice exposed to hindlimb unloading (HU) for 15-30 days. We found that juvenile KO mice exhibited increased femoral trabecular and cortical bone formation, whilst three-point bending of the tibias from KO mice showed decreased bone stiffness. Conversely, adult KO mice exhibited no significant differences in micro-architectural properties compared to WT (wild-type) but woven bone structure was indicative of rapid bone remodeling. Furthermore, cortical bone properties showed similar characteristics to aged bone, including increased cross-sectional area and perimeter, whilst three-point bending showed increased stiffness and toughness. Interestingly, in-vitro, KO mice exhibited increased differentiation and mineralized nodule formation in osteoblastogenesis assays compared to WT. Preliminary results from CDKN1ap21 KO mice subjected to HU suggest altered sensitivity to mechanical unloading resulting in decreased cortical thickness compared to WT mice. However, KO mice subjected to short and long-duration HU show increased in-vitro differentiation potential of BMSCs to from form mature, mineral-forming osteoblasts, indicating maintenance of regenerative potential. Analysis of bone formation rates, cell proliferation rates and key genes of interest are currently underway. These results indicate a novel role for CDKN1ap21 in load-dependent osteoprogenitor proliferation and differentiation and that deletion of CDKN1ap21 results in an age-dependent release of osteoblast proliferation inhibition and increased bone formation and turnover.

Stem Cells↗

Durability of YSZ Coated Ti2AlC in 1300°C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300°C for 500 h. A 160 µm thick YSZ coating was applied to a Ti2AlC MAX phase sample by PS-PVD and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No TBC spallation or recession was observed, only a 2.4 mg/sq. cm mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111) flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21-23 m under the heated YSZ face and ~13-15 m on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and etching of the underlying Al2O3 scale by volatile hydroxides in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample due to creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions.

Smialek, J.↗

Durability of YSZ Coated Ti2AlC in 1300 °C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300 °C for 500 h. A 160 µm thick yttria stabilized zirconia (YSZ) coating was applied to a Ti2AlC MAX phase bar sample by plasma spray physical vapor deposition (PS-PVD) and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No thermal barrier coating (TBC) spallation or recession was observed, only a 2.4 mg/cm2 mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111)flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to equilibrium teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21 to 23 μm under the heated YSZ face and ~13 to 15 μm on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and partial etching of the underlying Al2O3 scale by volatile hydroxides formed in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample via creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions, with thermal expansion matching playing a key role. The purpose of this study was to demonstrate long term durability of YSZ/MAX phase system in aggressive high temperature burner rig testing. MAX phases have been keenly studied because of their unique crystal structure and intriguing properties (Refs. 1 and 2). Having Mn+1(Al,Si)(C,N)n general composition, they are defined as ceramics, but possess unusual desirable attributes such as high conductivity, thermal shock resistance, easy machinability, and deformation tolerance. The mechanical properties derive from weak M-(Al,Si) bonding in the basal plane that leads to sliding and kinking in preference to catastrophic crack growth. Like most ceramics they are phase stable at high temperatures, generally up to 1500 °C. High temperature oxidation resistance is excellent for alumina-forming Ti3AlC2, Ti2AlC, and Cr2AlC, as reviewed by Tallman, et al. (Ref. 3). Compatibility with α-Al2O3 scales is further enhanced in cyclic exposures by a close matching of thermal expansion coefficients, (Ref. 4) i.e., (~9.3, 10.2, 11.3×10–6/K for Al2O3, Ti2AlC, and YSZ, to be discussed). Turbine environments generally contain 10 percent water vapor in the combustion gases, therefore moisture effects can be a concern for some materials (Ref. 5). Furnace tests of MAX phases in high temperature steam generally showed little effect on Al2O3 scale growth (Ref. 6). However, high velocity and high pressure gas can influence scale losses by the formation of volatile reaction products, such as TiO(OH)2 and Al(OH)3 (Refs. 7 to 10). This phenomenon had been discussed for 1100 to 1300 °C high pressure burner rig tests of Ti2AlC (Ref. 11). A single cubic growth rate parameter kcubic was measurably lower than comparable furnace TGA data, but it could be matched reasonably well if corrected for a slight volatility term. In general, a two-parameter cubic-linear growth-volatility law was believed to apply. Corresponding scale volatility loss rates, directly measured at 1300 °C on a pre-oxidized sample, were moderate (0.012 mg/cm2/h) and largely attributed to removal of the initial TiO2 transient scale. A related CH4 burner study of high purity Cr2AlC MAX phase demonstrated 1200 °C durability after 500 rapid (5 min. heat and 2 min. cool) thermal shock cycling (29 h hot time) (Ref. 12). Heating and cooling rates were ~1000 and 500 °C per minute, with a gas velocity of 5 m/s, producing a 75 °C/mm gradient. A 7 μm Al2O3 surface scale and a 13 μm Cr7C3 depletion zone formed with no signs of failure. No evidence of scale volatility was evident, although weight change was not provided, the velocity was moderate, and the total hot time was not extensive. The same high gradient BRT was used to produce 1400 °C surface temperatures for a YSZ/Cr2AlC/IN738 system in the first study of MAX phases used as bond coats for thermal barrier coatings (TBC) (Ref. 25). Here TBC failure was reported after 745 cycles, with only a 1.5 μm Al2O3 scale entrained within a porous, Cr7C3 bondcoat depletion phase. YSZ thermal barrier coatings have been considered to be a compatible complement to Al-MAX phases because of thermal expansion matching and extremely low volatility in water vapor. Initial studies showed superior oxidative stability up to 1300 °C, for long times (at least 500 h) for Ti2AlC substrates and less (268 h) for Cr2AlC, while withstanding large alumina TGO scale thickness (~35 to 40 μm) (Refs. 13 and 14). By comparison, typical superalloy systems can only survive 1150 °C maximum interface temperatures for extended periods, with a maximum sustained TGO below 10 μm (Ref. 15). High temperature SiC based systems are known to form slow-growing SiO2 scales. But these are subject to rate enhancement and volatile Si(OH)4 products in the presence of water vapor, as described comprehensively by Opila, et al. (Refs. 5, 16 to 19). Net weight losses are generally observed in high velocity, high pressure burner rig studies (e.g., 0.084 mg/cm2/h at 1300 °C) (Ref. 20). Furthermore, the loss rates have been shown from chemical physics to scale with v1/2 and pH2O 2 (Ref. 16). Low activity, moisture-resistant environmental barrier coatings (EBC), such as rare earth silicates, are needed to prevent substrate recession under turbine conditions (Refs. 21 to 23).

Smialek, James L.↗

Durability of YSZ coated Ti2AlC in 1300°C high velocity burner rig tests

A thermal barrier coating system survived 500 h in cyclic burner rig tests at 1300°C, exceeding the life of all previous systems. An yttria stabilized zirconia (7YSZ) thermal barrier coating (TBC) was plasma sprayed on the oxidation resistant Ti2AlC MAX phase and tested in a jet fuel burner. No coating spallation or recession was observed, only a 2.4 mg/sq.cm mass gain due to typical cubic Al2O3 oxidation kinetics. The modest weight gain contrasted with large TBC spallation or oxide volatility losses that might occur under cyclic, high velocity (~100 m/s) burner conditions. The coating surface exhibited colonies of [111]flourite fiber-textured columns separated by craze crack patterns, but with no visible moisture attack. The thickness of the alumina scale under the YSZ face was >20 μm, more than twice that formed on TBC/superalloy systems at failure. TiO2 nodules, initially formed on the uncoated backside, were then removed as volatile hydroxides formed in high temperature, high velocity water vapor (~10%). Overall, the test indicated the exceptional stability of the YSZ/Ti2AlC system under turbine conditions, due in large part to good thermal expansion matching.

alumina, MAX phases, thermal barrier coatings (TBC↗

Assessing Organic Preservation and the Implications for Potential Biosignatures in the Bastide Member of the Séítah Formation, Jezero Crater

Introduction: Olivine has the highest CO2 trapping potential of ultramafic minerals, due to its rapid rate of dissolution and high percentage of divalent cations/unpolymerized silicate tetrahedra [1]. It generates divalent carbonates from CO2 and sequesters CO2 into the mineral matrix of the target lithology. The co-occurrence of olivine and carbonate within abraded targets from the Bastide Member of the Séítah Formation (Fm) of the Jezero crater floor [2] suggests the carbonation of olivine occurred within the mineral matrix hosted in a subsurface system. Hydrothermal origins for the subsurface system are hypothesized from orbital data [3]. This is supported by the detection of hydration features within the rock as well as the carbonate features are solely detected within the abrasion patch but not the rock’s surface. Organic preservation potential of abrasion patches: We incorporated the SHERLOC/WATSON results acquired from the Dourbes, Garde, and Quartier abrasion patches in the Séítah Fm to investigate the organomineral associations, and determine the biosignature preservation potential of these rocks. Dourbes is dominated by olivine and has minor amounts of carbonate, hydrated Ca-sulfate, and amorphous or microcrystalline silicate. Fluorescence features (330-340 nm) are detected in discrete locales and could be consistent with double ring aromatic organic molecules; yet, these features do not appear to be associated with an identified mineral phase. Dark subhedral to euhedral olivine grains within the Garde abrasion patch often co-occur with carbonate-consistent spectral signatures in all analyzed scans. The availability of Fe2+ is a known influence on olivine dissolution rates [1] and SuperCam estimates of the olivine composition (Forsterite-60 average for Sols 202-234) may thereby provide a constraint on the carbonation extent. Carbonated olivine phenocrysts within the matrix may be due to aqueous alteration, as the carbonation of nodules is consistent with observations in other hydrothermal systems and within Martian meteorites (ALH84001) [4]. In comparison, the Quartier abrasion patch represents an extensively altered endmember within the Bastide Member of the Séítah Fm. It contains a fluorescence doublet at 305/325 nm that coexists with multiple species of Na-sulfate and Mg-sulfate, Mg-carbonates, olivine [5]. Aqueous alteration and implications for habitability: The identification of primary and secondary mineral phases observed in the Bastide Member suggests the release of cations from primary ultramafic minerals through aqueous alteration. Within Garde, the carbonate detected appears to be Mg-rich and likely formed from the in situ alteration of Mg-rich olivine within the region as carbonate has only been detected within the rock via in situ analysis. Carbonates derived from abiotic and biotic reactions preserve biosignatures (i.e. indices of habitability) on Earth. The detected carbonate phase found in association with fluorescent features within the rock matrix may also indicate potential organic compounds preserved in a putative hydrothermal system. Fluorescent features (~330 nm) are unique to Garde and Dourbes, though they are co-located to carbonate signatures solely within Garde, and between the light toned minerals. Identification of these fluorescent features may be consistent with 1-2 ring aromatic compounds. The limit of detection for Raman is multiple orders of magnitude greater than the limit of detection required for fluorescence [6]. Implications for provenance: Hydrothermal systems represent disequilibrium chemical conditions that are hypothesized to have supported the emergence of life and also preserve ancient carbon within precipitated carbonates [7]. Hydrothermal system associated carbonates are capable of preserving biosignatures up to an estimated ~3.77 – 4.28 Gya [8]. Thus, carbonated olivine found within the Séítah Fm may represent a high-potential biosignature preserving environment on Mars. The formation of carbonates by an aqueous alteration process, such as carbonation of olivine is also consistent with hypotheses for carbonate within the greater regional-olivine bearing unit [2,3], which contains Garde, Dourbes, and Quartier. Acknowledgments: This work was carried out at the Jet Propulsion Laboratory, The California Institute of Technology under a contract from NASA. References: [1] Wood et al., (2019) ES&T, 6, 10. [2] Stack, K. et al., (2020) Space Sci Rev, 216, 127. [3] Tarnas, J. et al., (2021) JGR: Planets, 126, 11. [4] Steele et al., (2007) Meteorit. Planet. Sci., 42, 9. [5] Murphy, A.E. et al., (2022) LPSC [6] Bhartia et al., (2021) Space Sci Rev, 217, 58. [7] Luther (2021) GRL, 48, e2021GL094869. [8] Dodd et al., (2017) Nature, 543, 60-64

E L Cardarelli↗

The CheMin X-ray Diffractometer on MSL Curiosity: A Decade of Mineralogical Observations from Gale Crater, Mars

For more than a decade, the CheMin X-ray Diffraction instrument on the Mars Science Laboratory rover Curiosity has been returning quantitative mineralogical data from Gale crater, Mars. CheMin receives and analyzes sieved soil and powdered rock samples from Curiosity’s Sample Acquisition / Sample Processing and Handling (SA/SPaH) system. To date, 38 samples have been analyzed over the course of a 28 km transit. These samples document more than 600 vertical meters of flat-lying lacustrine, fluvial and aeolian sediments that comprise the lower part of the central mound of Gale crater (commonly called Mt. Sharp).The principal mineralogy of the sediments is basaltic, with evidence of early and late-stage diagenetic overprinting. The rocks in many cases preserve most of their primary mineralogy and sedimentary features, suggesting that they were never strongly heated or deformed. Using aeolian soil composition as a proxy for the composition of the deposited and lithified sediment, it appears that in many cases the diagenetic changes observed are principally isochemical. Exceptions to this include secondary nodules, calcium sulfate veining and rare alteration halos. A striking hematite-rich feature in lower Mt. Sharp called Vera Rubin Ridge is interpreted to be lake sediment diagenetically altered by silica-poor fluids. A surprising and as yet poorly understood observation is that nearly all of the 3.7 Gyr old sedimentary rocks analyzed to date are comprised of 25-50% X-ray amorphous material. Overall, this 600 m vertical section of sedimentary rock explored in lower Mt. Sharp documents a perennial shallow lake environment grading upward into alternating lacustrine/fluvial and aeolian environments. The mineralogical changes observed going up-section include a transition from trioctahedral to dioctahedral clay minerals and a transition from magnetite to hematite. More recently, in the last 150 m of section, CheMin has documented an overall decrease in clay minerals and increase in Fe3+ oxides and oxyhydroxides. The mineralogical changes observed in Gale crater may document the gradual drying out and oxidation of the martian hydrosphere.

CHEMIN↗

Importance of Sulfur for Phosphorus Mobility on the Martian Surface

Sulfur and phosphorus were mobile on the martian surface, and we present evidence that sulfate was likely a control on phosphate mobility. Mobility of the two elements on the martian surface is crucial for the habitability of Mars because their availability for biochemical reactions and biological structures is a major constraint on life. In the sedimentary rocks of Gale crater, the rover Curiosity has discovered evidence of mobile S and P with the alpha particle X-ray spectrometer (APXS). Sulfur-rich fluids are evident in ubiquitous Ca-sulfate veins that crosscut the bedrock. Compelling evidence of P mobility is in nodules, veins, crusts, and haloes with P2O5 enrichments (1.5-7.5 wt%) relative to the median bedrock (0.9-1.2 wt%) and average basaltic crust (~0.9 wt%). We have investigated phosphorus mobility in Hawaiian analogues, where the primary P2O5 (0.2-2.1 wt%) is contained in Ca-apatite. Four relevant processes have emerged: (1) In open-system, circumneutral regolith weathering profiles, we found up to 40% of the P was leached over 10s-100s ka. (2) Natural acid-sulfate alteration at the Maunakea summit resulted in the dissolution of apatite and mobilization of phosphate 10s-1000s µm to rock surfaces where it formed Al-phosphates and substituted into crystalline sulfates (alunite and jarosite). (3) Experimental results indicate that basaltic sediment chemisorbs phosphate (pH < 7). (4) In experimental systems containing water, basaltic sediment, and a starting pH = 2-7, phosphate has higher solubility in chloride-rich fluids, but significantly lower solubility in sulfate-rich fluids. For example, in water doped with phosphate (~100-500 mg/L), ~60-80% of the PO43- was removed from the sulfate-rich fluid, whereas ~20% of the PO43- was removed from the Cl-rich and pure water fluids (likely via adsorption). Gypsum precipitated from the sulfate-rich fluids; the fate of phosphate in the solid residue is unconfirmed. The potential for phosphate incorporation in martian sulfates is reflected in the enrichment of P2O5 in Gale Ca-sulfate veins, based on preliminary analyses of APXS data. Models for the mobility of phosphorus in Gale crater should consider these conflicting P characteristics: (1) P solubility may have been inhibited by sulfate and (2) P¬ is enriched in diagenetic features and was therefore mobile.

Jeff A. Berger↗