Search NASA⌕ Search

SEARCH · Search NASA

Results for “Cell Parameters”

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 127 records · Page 7

Crystallization and Preliminary X-ray analysis of Human Recombinant Acid beta-glucocerebrosidase, a treatment for Gaucher's Disease

Acid beta-glucocerebrosidase (N-acylsphingosyl - O - beta-D - glucoside:glucohydrolase) is a lysosomal glycoprotein that catalyzes the hydrolysis of the glycolipid glucocerebroside to glucose and ceramide. Inadequate levels of this enzyme underly the pathophysiology of Gaucher's disease. Cerezyme(R) (Genzyme Corporation, Cambridge, MA) is a partially deglycosylated form of recombinant human acid beta-glucocerebrosidase that is commercially available for the treatment of Gaucher patients. Although acid beta-glucocerebrosidase belongs to a large family of glycosidases, relatively little is known regarding its structural biology. We report the crystallization and the initial diffraction analysis of Cerezyme(R). The crystals are C-centered orthorhombic, with unit-cell parameters of a = 285.0 A, b = 110.2 A, and c = 91.7 A. A 99.9 A complete data set has been collected to 2.75 A with an R(sub sym) of 8.8 %.

Roeber, Dana F.↗

Crystallization and Preliminary X-ray Analysis of Der f 2, a Potent Allergen Derived from the House Dust Mite

Although a number of allergens have been identified and isolated, the underlying molecular basis for the potent immune response is poorly understood. House dust mites (Dermatophugoides sp.) are particularly ubiquitous contributors to atopy in developed countries. The rhinitis, dermatitis, and asthma associated with allergic reactions to these arthropods are often caused by relatively small (125-129 amino acids) mite proteins of unclear biological function. Der f 2, a major allergen from the mite Dermatophagoides farinae, has been recombinantly expressed and characterized. The Der f 2 protein has been crystallized in our laboratory and a native data set collected at a synchrotron source. The crystals belong to the orthorhombic space group I422 with unit cell parameters of a = 95.2 Angstroms, b = 95.2 Angstroms, and c = 103.3 Angstroms. An essentially complete (97.2%) data set has been collected to 2.4 Angstroms. Attempts to solve the crystal structure of Der f 2 by molecular replacement using the available NMR coordinates for either Der f 2 or Der p 2 (the homologous protein from D. pterovssinus) failed to reveal a creditable solution.

Roeber, Dana↗

Curve Fitting Solar Cell Degradation Due to Hard Particle Radiation

This paper investigates the suitability of the equation for accurately defining solar cell parameter degradation as a function of hard particle radiation. Y = Y/sub o/ + C/sub 1/ * Log(1 + /spl phi///spl phi//sub x/) + C/sub 2/ * Log(1 + /spl phi///spl phi//sub y/) The paper also provides methods for determining the constants in the equation and compares results from this equation to those obtained by the more traditionally used. Y = /spl Sigma/(a/sub i/ * [In(/spl phi/)]/sup i/)

Edward M. Gaddy↗

Mineralogical and chemical characterization of iron-, manganese-, and copper-containing synthetic hydroxyapatites

The National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program is evaluating the use of Fe-, Mn-, and Cu-containing synthetic hydroxyapatite (SHA) as a slow release fertilizer for crops that might be grown on the International Space Station or at Lunar and Martian outposts. Separate Fe-, Mn-, and Cu-containing SHA materials along with a transition-metal free SHA (pure-SHA) were synthesized using a precipitation method. Chemical and mineralogical analyses determined if and how Fe, Mn, and Cu were incorporated into the SHA structure. X-ray diffraction (XRD), Rietveld refinement, and transmission electron microscopy (TEM) confirmed that SHA materials with the apatite structure were produced. Chemical analyses indicated that the metal containing SHA materials were deficient in Ca relative to pure-SHA. The shift in the infrared PO4-mu 3 vibrations, smaller unit cell parameters, smaller particle size, and greater structural strain for Fe-, Mn-, and Cu-containing SHA compared with pure-SHA suggested that Fe, Mn, and Cu were incorporated into SHA structure. Rietveld analyses revealed that Fe, Mn, and Cu substituted into the Ca2 site of SHA. An Fe-rich phase was detected by TEM analyses and backscattered electron microscopy in the Fe-containing SHA material with the greatest Fe content. The substitution of metals into SHA suggests that metal-SHA materials are potential slow-release sources of micronutrients for plant uptake in addition to Ca and P.

NASA Center JSC↗

Stereology techniques in radiation biology

Clinicians involved in conventional radiation therapy are very concerned about the dose-response relationships of normal tissues. Before proceeding to new clinical protocols, radiation biologists involved with conformal proton therapy believe it is necessary to quantify the dose response and tolerance of the organs and tissues that will be irradiated. An important focus is on the vasculature. This presentation reviews the methodology and format of using confocal microscopy and stereological methods to quantify tissue parameters, cell number, tissue volume and surface area, and vessel length using the microvasculature as a model tissue. Stereological methods and their concepts are illustrated using an ongoing study of the dose response of the microvessels in proton-irradiated hemibrain. Methods for estimating the volume of the brain and the brain cortex, the total number of endothelial cells in cortical microvessels, the length of cortical microvessels, and the total surface area of cortical microvessel walls are presented step by step in a way understandable for readers with little mathematical background. It is shown that stereological techniques, based on a sound theoretical basis, are powerful and reliable and have been used successfully.

Non-NASA Center↗

Crystallization and preliminary X-ray analysis of Der f 2, a potent allergen derived from the house dust mite (Dermatophagoides farinae)

Although a number of allergens have been identified and isolated, the underlying molecular basis for the potent immune response is poorly understood. House dust mites (Dermatophagoides sp.) are ubiquitous contributors to atopy in developed countries. The rhinitis, dermatitis and asthma associated with allergic reactions to these arthropods are frequently caused by relatively small (125-129 amino acids) mite proteins of unknown biological function. Der f 2, a major allergen from the mite D. farinae, has been recombinantly expressed, characterized and crystallized. The crystals belong to the tetragonal space group I4(1)22, with unit-cell parameters a = b = 95.2, c = 103.3 A. An essentially complete (97.2%) data set has been collected to 2.4 A at a synchrotron source. Attempts to solve the crystal structure of Der f 2 by molecular replacement using the NMR coordinates for either Der f 2 or Der p 2 (the homologous protein from D. pteronyssinus) failed, but preliminary searches using the crystalline Der p 2 atomic coordinates appear to be promising.

Pyroglyphidae/chemistry/immunology↗

Crystallization and preliminary X-ray analysis of recombinant human acid beta-glucocerebrosidase, a treatment for Gaucher's disease

Acid beta-glucocerebrosidase (N-acylsphingosyl-1-O-beta-D-glucoside:glucohydrolase) is a lysosomal glycoprotein that catalyzes the hydrolysis of the glycolipid glucocerebroside to glucose and ceramide. Inadequate levels of this enzyme underly the pathophysiology of Gaucher's disease. Cerezyme (Genzyme Corporation, Cambridge, MA, USA) is a partially deglycosylated form of recombinant human acid beta-glucocerebrosidase that is used in the treatment of Gaucher patients. Although acid beta-glucocerebrosidase belongs to a large family of glycosidases, relatively little is known regarding its structural biology. Here, the crystallization and the initial diffraction analysis of Cerezyme are reported. The crystals are C-centered orthorhombic, with unit-cell parameters a = 285.0, b = 110.2, c = 91.7 A. A 99.9% complete data set has been collected to 2.75 A with an R(sym) of 8.8%.

Glucosylceramidase/chemistry↗

Crystallization and initial X-ray diffraction analysis of human pyruvate dehydrogenase

Human pyruvate dehydrogenase (E1) is a component enzyme of the pyruvate dehydrogenase complex. The enzyme catalyzes the irreversible decarboxylation of pyruvic acid and the rate-limiting reductive acetylation of the lipoyl moiety linked to the dihydrolipoamide acetyltransferase component of the pyruvate dehydrogenase complex. E1 is an alpha(2)beta(2) tetramer ( approximately 154 kDa). Crystals of this recombinant enzyme have been grown in polyethylene glycol 3350 using a vapor-diffusion method at 295 K. The crystals are characterized as orthorhombic, space group P2(1)2(1)2(1), with unit-cell parameters a = 64.2, b = 126.9, c = 190.2 A. Crystals diffracted to a minimum d spacing of 2.5 A. The asymmetric unit contains one alpha(2)beta(2) tetrameric E1 assembly; self-rotation function analysis showed a pseudo-twofold symmetry relating the two alphabeta dimers.

Pyruvate Dehydrogenase Complex/chemistry↗

Crystallization and preliminary X-ray diffraction analysis of restriction endonuclease EcoRII

Crystals of the restriction endonuclease EcoRII have been obtained by the vapor-diffusion technique in the presence of ammonium sulfate or polyethylene glycol. The best crystals were grown with ammonium sulfate as a precipitant. Crystals with dimensions of up to 0.6 x 0. 6 x 0.6 mm have been observed. The crystals diffract to about 4.0 A resolution at a cryo-temperature of 100 K using a rotating-anode X-ray source and a Rigaku R-AXIS IV imaging-plate detector. The space group has been determined to be either I23 or I2(1)3, with unit-cell parameters a = b = c = 160.3 A, alpha = beta = gamma = 90 degrees. The crystal asymmetric unit contains two protein molecules, and self-rotation function analysis shows a pseudo-twofold symmetry relating the two monomers. Attempts to improve the resolution of crystal diffraction and to search for heavy-atom derivatives are under way.

Deoxyribonucleases, Type II Site-Specific/chemistr↗

The XRD Amorphous Component in John Klein Drill Fines at Yellowknife Bay, Gale Crater, Mars

Drill fines of mudstone (targets John Klein and Cumberland) from the Sheepbed unit at Yel-lowknife Bay were analyzed by MSL payload elements including the Chemistry and Mineralogy (CheMin), APXS (Alpha Particle X-Ray Spectrometer), and Sample Analysis at Mars (SAM) instruments. CheMin XRD results show a variety of crystalline phases including feldspar, pyroxene, olivine, oxides, oxyhydroxides, sulfates, sulfides, a tri-octahedral smectite, and XRD amorphous material. The drill fines are distinctly different from corresponding analyses of the global soil (target Rocknest) in that the mudstone samples contained detectable phyllosilicate. Here we focus on John Klein and combine CheMin and APXS data to calculate the chemical composition and concentration of the amorphous component. The chemical composition of the amorphous plus smectite component for John Klein was calculated by subtracting the abundance-weighted chemical composition of the individual XRD crystalline components from the bulk composition of John Kline as measured by APXS. The chemical composition of individual crystalline components was determined either by stoichiometry (e.g., hematite and magnetite) or from their unit cell parameters (e.g., feldspar, olivine, and pyroxene). The chemical composition of the amorphous + smectite component (approx 71 wt.% of bulk sample) and bulk chemical composition are similar. In order to calculate the chemical composition of the amorphous component, a chemical composition for the tri-octahedral smectite must be assumed. We selected two tri-octahedral smectites with very different MgO/(FeO + Fe2O3) ratios (34 and 1.3 for SapCa1 and Griffithite, respectively). Relative to bulk sample, the concentration of amorphous and smectite components are 40 and 29 wt.% for SapCa1 and 33 and 36 wt.% for Griffithite. The amount of smectite was calculated by requiring the MgO concentration to be approx 0 wt.% in the amorphous component. Griffithite is the preferred smectite because the position of its 021 diffraction peak is similar to that reported for John Klein. In both cases, the amorphous component has low SiO2 and MgO and high FeO + Fe2O3, P2O5, and SO3 concentrations relative to bulk sample. The chemical composition of the bulk drill fines and XRD crystalline, smectite, and amorphous components implies alteration of an initially basaltic material under near neutral conditions (not acid sulfate), with the sulfate incorporated later as veins of CaSO4 injected into the mudstone.

Morris, Richard V.↗

Amorphous Analogs of Martian Global Soil: Pair Distribution Function Analyses and Implications for Scattering Models of Chemin X-ray Diffraction Data

Soils on Mars have been analyzed by the Mars Exploration Rovers (MER) and most recently by the Mars Science Laboratory (MSL) rover. Chemical analyses from a majority of soil samples suggest that there is a relatively uniform global soil composition across much of the planet. A soil site, Rocknest, was sampled by the MSL science payload including the CheMin X-ray diffractometer and the Alpha Particle X-ray Spectrometer (APXS). Che- Min X-ray diffraction (XRD) data revealed crystalline phases and a broad, elevated background, indicating the presence of amorphous or poorly ordered materials (Fig 1). Based on the chemical composition of the bulk soil measured by APXS and the composition of crystalline phases derived from unit-cell parameters determined with CheMin data, the percentages of crystalline and amorphous phases were calculated at 51% and 49%, respectively. Attempts to model the amorphous contribution to CheMin XRD patterns were made using amorphous standards and full-pattern fitting methods and show that the broad, elevated background region can be fitted by basaltic glass, allophane, and palagonite. However, the modeling shows only that these phases have scattering patterns similar to that for the soil, not that they represent unique solutions. Here, we use pair distribution function (PDF) analysis to determine the short-range order of amorphous analogs in martian soils and better constrain the amorphous material detected by CheMin.

Achilles, C. N.↗

Update on the Chemical Composition Of Crystalline, Smectite, and Amorphous Components for Rocknest Soil and John Klein and Cumberland Mudstone Drill Fines at Gale Crater, Mars

We have previously calculated the chemical compositions of the X-ray-diffraction (XRD) amorphous component of three solid samples (Rocknest (RN) soil, John Klein (JK) drill fines, and Cumberland (CB) drill fines) using major-element chemistry (APXS), volatile-element chemistry (SAM), and crystalline- phase mineralogy (CheMin) obtained by the Curiosity rover as a part of the ongoing Mars Science Laboratory mission in Gale Crater. According to CheMin analysis, the RN and the JK and CB samples are mineralogically distinct in that RN has no detectable clay minerals and both JK and CB have significant concentrations of high-Fe saponite. The chemical composition of the XRD amorphous component is the composition remaining after mathematical removal of the compositions of crystalline components, including phyllosilicates if present. Subsequent to, we have improved the unit cell parameters for Fe-forsterite, augite, and pigeonite, resulting in revised chemical compositions for the XRD-derived crystalline component (excluding clay minerals). We update here the calculated compositions of amorphous components using these revised mineral compositions.

Morris, R. V.↗

Diagenesis in the Murray Formation, Gale Crater, Mars

The Mars Science Laboratory (MSL) Curiosity rover began investigating the rocks of Mt. Sharp in September 2014. The Murray formation is the lowermost unit, which is mostly comprised of finely laminated mudstones, suggesting these sediments were deposited in a lacustrine environment. It is important to characterize the geochemical and mineralogical trends throughout the Murray Fm to interpret the aqueous conditions of the ancient lake, the sources of the lake sediments, and post-depositional alteration processes. Four samples have been drilled from the Murray Fm so far: Confidence Hills, Mojave 2, and Telegraph Peak were collected from the Pahrump Hills member - the basal portion of the Murray Fm, and Buckskin was collected in the Marias Pass region (Fig. 1). The drill fines were delivered to the instruments inside the rover, including the CheMin instrument, a combination X-ray diffractometer and X-ray fluorescence spectrometer. Rietveld refinements and FULLPAT analyses of 1D CheMin XRD patterns were performed to determine quantitative abundances of minerals and amor-phous phases and the unit cell parameters of minerals present in abundances greater than 4-5 wt.%.

Rampe, E. B.↗

High-Temperature, Perhaps Silicic, Volcanism on Mars Evidenced by Tridymite Detection in High-SiO2 Sedimentary Rock at Gale Crater, Mars

The Mars Science Laboratory (MSL) rover, Curiosity, has been exploring sedimentary rocks within Gale crater since landing in August, 2012. On the lower slopes of Aeolis Mons (a.k.a. Mount Sharp), drill powder was collected from a high-silica (74 wt% SiO2) outcrop named Buckskin (BK). It was a surprise to find that the Buckskin sample contained significant amounts of the relatively rare silica polymorph tridymite. We describe the setting of the Buckskin sample, the detection of tridymite by the MSL Chemistry and Mineralogy (CheMin) X-ray diffraction instrument, and detection implications. Geologic setting: The Buckskin outcrop is part of the Murray formation exposed in the Marias Pass area. The formation was previously studied by CheMin in the Pahrump Hills member [1] where three samples of drill fines were analyzed (Confidence Hills (CH), Mojave2 (MJ) and Telegraph Peak (TP) [2]). Assuming approximately horizontal bedding, the Buckskin outcrop is approx.15 m stratigraphically above the bottom of the Pahrump Hills member. Mudstone, generally characterized by fine lamination, is the dominant depositional facies [1]. Buckskin Mineralogical and Chemical Composition: The CheMin instrument and XRD pattern analysis procedures have been previously discussed [3-6]. The diffraction pattern used for quantitative XRD analysis (Fig. 1) is the sum of the first 4 of 45 diffraction images. The remaining images are all characterized by both on-ring and off-ring diffraction spots that we attributed to poor grain motion and particle clumping. Coincident with particle clumping was a significant decrease in the intensity of the tridymite diffraction peaks (Fig. 2a). The derived mineralogical composition of the crystalline component (derived from the first 4 diffraction images) is given in Table 1. The tridymite is well-crystalline and its pattern is refined as monoclinic tridymite (Fig 1). Mineral chemical compositions were derived from XRD unit cell parameters or obtained from stoichiometry. The XRD-calculated amorphous component was 50 +/- 15 wt%. We constrained the value to 60 wt% because it is the minimum value necessary to give a positive Al2O3 concentration for the amorphous component using APXS data for the post-sieve dump pile (Table 2). The amorphous component has high SiO2 (approx.77 wt%) and high anion (SO3+P2O5+Cl ~10 wt%) concentrations. Calculation shows that a cation-anion balance is achieved if the cations in the amorphous component except SiO2 and TiO2, which do not readily form salts, are assumed to be present as amorphous mixed-cation sulfates, phosphates, and chlorides (or perchlorates/ chlorates).

Morris, R. V.↗

Mineralogy of Mudstone at Gale Crater, Mars: Evidence for Dynamic Lacustrine Environments

The Mars Science Laboratory Curiosity rover landed in Gale crater in August 2012 to assess the habitability of sedimentary deposits that show orbital evidence for diverse ancient aqueous environments. Gale crater contains a 5 km high mound of layered sedimentary rocks in its center, informally named Mount Sharp. The lowermost rocks of Mount Sharp contain minerals that are consistent with a dramatic climate change during Mars' early history. During the rover's traverse across the Gale crater plains to the base of Mount Sharp, Curiosity discovered sedimentary rocks consistent with a fluviolacustrine sequence. Curiosity studied ancient lacustrine deposits at Yellowknife Bay on the plains of Gale crater and continues to study ancient lacustrine deposits in the Murray formation, the lowermost unit of Mount Sharp. These investigations include drilling into the mudstone and delivering the sieved less than 150 micrometers fraction to the CheMin XRD/XRF instrument inside the rover. Rietveld refinement of XRD patterns measured by CheMin generates mineral abundances with a detection limit of 1-2 wt.% and refined unit-cell parameters of minerals present in abundances greater than approximately 5 wt.%. FULLPAT analyses of CheMin XRD patterns provide the abundance of X-ray amorphous materials and constrain the identity of these phases (e.g., opal-A vs. opal-CT). At the time of writing, CheMin has analyzed 14 samples, seven of which were drilled from lacustrine deposits. The mineralogy from CheMin, combined with in-situ geochemical measurements and sedimentological observations, suggest an evolution in the lake waters through time, including changes in pH and salinity and transitions between oxic and anoxic conditions. In addition to a geochemically dynamic lake environment, the igneous minerals discovered in the lake sediments indicate changes in source region through time, with input from mafic and silicic igneous sources. The Murray formation is predominantly comprised of lacustrine mudstone and is 150-200 m thick, suggesting long history of lake environments in Gale crater. Curiosity has traversed through the lowermost approximately 30 m of the Murray formation, and each additional sample provides clues about the climate on early Mars.

Rampe, E. B.↗

New Perspectives of Ancient Mars: Mineral Diversity and Crystal Chemistry at Gale Crater, Mars from the CheMin X-Ray Diffractometer

The Mars Science Laboratory Curiosity rover arrived at Mars in August 2012 with a primary goal of characterizing the habitability of ancient and modern environments. Curiosity landed in Gale crater to study a sequence of ~3.5 Ga old sedimentary rocks that, based on orbital visible/near-infrared reflectance spectra, contain secondary minerals that suggest deposition and/or alteration in liquid water. The sedimentary sequence that comprises the lower slopes of Mount Sharp within Gale crater may preserve a dramatic shift on early Mars from a relatively warm and wet climate to a cold and dry climate based on a transition from smectite-bearing strata to sulfate-bearing strata. The rover is equipped with cameras and geochemical and mineralogical instruments to examine the sedimentology and identify compositional changes within the stratigraphy. These observations provide information about variations in depositional and diagenetic environments over time. The Chemistry and Mineralogy (CheMin) instrument is one of two internal laboratories on Curiosity and includes a transmission X-ray diffractometer (XRD) and X-ray fluorescence (XRF) spectrometer with a Co-K source. CheMin measures loose sediment samples scooped from the surface and drilled rock powders. The XRD provides quantitative mineralogy of scooped and drilled samples to a detection limit of ~1 wt.%. Curiosity has traversed >20 km since landing and has primarily been exploring the site of a predominantly ancient lake environment fed by groundwater and streams emanating from the crater rim. Results from CheMin demonstrate an incredible diversity in the mineralogy of fluvio-lacustrine rocks that signify variations in source rock composition, sediment transport mechanisms, and depositional and diagenetic fluid chemistry. Abundant trioctahedral smectite and magnetite at the base of the section may have formed from low-salinity pore waters with a circumneutral pH within lake sediments. A transition to dioctahedral smectite, hematite, and Ca-sulfate going up section suggests a change to more saline and oxidative aqueous conditions within the lake waters themselves and/or within diagenetic fluids. The primary minerals detected in fluvio-lacustrine samples by CheMin also suggest diversity in the igneous source regions for the sediments, where abundant pyroxene and plagioclase in most samples suggest a basaltic protolith, but sanidine and pyroxene in one sample may have been sourced from a potassic trachyte, and tridymite and sanidine in another sample may have been transported from a rhyolitic source. Crystal chemistry of major phases in each sample have been calculated from refined unit-cell parameters, providing further constraints on aqueous alteration processes and igneous protoliths for the sediments. Perhaps one of the biggest mysteries revealed by the CheMin instrument is the high abundance of X-ray amorphous materials (15 to 73 wt.%) in all samples measured to date. X-ray amorphous materials were detected by CheMin based on the observation of broad humps in XRD patterns. How these materials formed, their composition, and why they persist near the martian surface remain a topic of debate. The sedimentology and composition of the rocks analyzed by Curiosity demonstrate that habitable environments persisted intermittently on the surface or in the subsurface of Gale crater for perhaps more than a billion years.

Rampe, E. B.↗

Investigation of Magmatic Activities on Early Mars Using Igneous Mineral Chemistry in Gale Crater, Mars

One objective of rover missions is exploring the geological context of the surroundings. Over the years, igneous petrology and sedimentology have been disconnected, the first investigating magmatic processes and volcanic activities, and the second seeking environmental conditions in the past and assessing the habitability of the planet. Although different, one is related to the other: igneous rocks are altered and broken down, leading to the formation of sedimentary rocks, which can in turn be used to back out the nature of their magmatic source. The Curiosity rover that landed in the 3.7 Gyr old impact crater Gale is traveling through sedimentary rocks. About fifty float rocks have been observed, and several of them with ambiguous texture and composition have been classified as igneous or sedimentary depending on studies such as Jake_M. The composition of several unambiguous igneous rocks has been analyzed [4- 6] but their heterogeneity at a larger instrumental (measurement size < 2 cm) scale prevents the measurement of a bulk composition as performed on Earth. An original approach avoiding these two last issues is to consider igneous mineral chemistry analyzed within igneous and sedimentary rocks to assess magmatic processes that could have formed them. Most Curiosity data are used to explore ancient environmental conditions, and a significant number of compositional analyses are under-explored for constraining magmatic activities. We will present how we can make use of sedimentary data for investigating igneous processes in the vicinity of Gale crater. Geological Context: We focus on the first 750 martian days, corresponding to measurements in a coherent lacustrine sedimentary unit called Bradbury, because all sedimentary rocks were sourced from the same watershed and appear to have a consistent source with minimal alteration [2-3]. Igneous detrital minerals including feldspar and pyroxene, are observed in sedimentary rocks. Monte Carlo models showed that minimal cation loss is observed based on the composition of all Bradbury rocks, implying negligible weathering [3]. Although clay minerals are detected in few rocks [7], chemical compositions of rocks can be explained by a mixture of primary igneous minerals [3]. Variation of composition within Bradbury rocks can be explained by mineral sorting and one distinct source component. While a common magmatic source is suggested, Bradbury sediments likely come from several volcanic eruptions from a single magmatic chamber [9- 10]. The occurrence of alkali minerals like sanidine and K-rich rocks throughout Bradbury supports the presence of a potassic component, likely trachytic, while plagioclase and a mafic composition suggest a basaltic component [8-9]. Instruments: Mineral chemistry can be estimated by three instruments onboard Curiosity. The CheMin instrument enables detection of mineral assemblages using X-ray diffraction (XRD). Using Rietveld refinement, each mineral is identified according to their 1D XRD pattern [11]. Note that distinction between pyroxene minerals is challenging with the CheMin instrument due to overlapping peaks on XRD patterns and low angular resolution of the instrument [12]. Then, using least square regression and optimization algorithms based on unit-cell parameters, mineral chemistry has been estimated by [11]. Plagioclase composition has been estimated using the NaAlSi3O8- CaAl2Si2O8 system and alkali feldspar is based on the NaAlSi3O8-KAlSi3O8 system (stars in Fig.1). Two mudstone samples (John Klein and Cumberland) and one sandstone sample (Windjana) were analyzed by CheMin at Yellowknife Bay and Kimberley, respectively. Figure 1. Ternary diagrams of feldspars (top) and pyroxene (bottom) quadrilateral. Stars correspond to CheMin composition and the gray patches to ChemCam composition. The colored dots are the composition of feldspar and pyroxene that crystallized during fractional crystallization at FMQ+1 of a melt extracted at distinct melting degree during the adiabatic ascent of a primitive mantle composition, without any water (left panels) and with 0.5 wt.% of water (right panels) at distinct pressure. The ChemCam instrument enables the analysis of the chemical compositions of rocks at hundreds of micrometer scale (350-550 μm) using laser induced breakdown spectroscopy (LIBS), which may provide the composition of minerals when they are larger than the beam spot (>550 μm) [13]. Within >5000 LIBS points, we performed a typical stoichiometric filtering allowing us to distinguish 56 feldspar and 10 pyroxene mineral compositions (grey patches in Fig. 1). Finally, the Alpha Particle X-ray Spectrometer (APXS) analyzes the composition of rocks with a 1.6 cm diameter spot size. Monte Carlo mass balance modeling allowed [3] to decipher a feldspar range varying between An30 and An40 (Fig. 1). Discussion: Although there could be a more complex history and other ways to form the whole compositional range of igneous minerals analyzed within the Bradbury formation, we are presenting here simple magmatic pathways commonly occurring on Earth using the thermodynamical softwares pMELTS and rhyoliteMELTS [14]. The objective is to find reasonable igneous processes that produce minerals that parallel the compositions of feldspar and pyroxene analyzed by the Curiosity rover. As commonly observed for mid-ocean ridge basalts, the adiabatic ascent of a primitive mantle composition [15] partially melting at 2 GPa has been modeled, followed by the extraction of a liquid at distinct degrees of partial melting, which undergoes fractional crystallization at an oxygen fugacity +1 log unit above the fayalite-magnetite-quartz (FMQ) buffer within the crust (0.02-0.4 GPa) with H2O = 0- 0.5 wt. %. These latter conditions correspond to those recorded within igneous clasts from the Noachian martian breccia NWA 7034 and paired and within Gale igneous rocks (colored dots in Fig. 1) [16-17]. To check the reliability of these 2-step models, we also tested fractional crystallization at similar conditions (FMQ+1; P=0.02-0.4 GPa; H2O = 0-0.5 wt. %) of starting compositions corresponding to that of magmas with distinct melting degrees obtained from isobaric experiments at 2 GPa [18]. Mineral compositions obtained from both models are similar. As shown on Fig. 1, the whole range of observed feldspar compositions cannot be reproduced by fractionation of one magma only. Indeed, while alkali feldspar and Na-plagioclase likely crystallized from fractional crystallization of a low-degree melt (here <15%), plagioclase and pyroxene can only be formed by fractional crystallization of a higher degree melt (here >19%). The corresponding liquid descent lines are broadly in agreement with compositions estimated by ChemCam corresponding to float igneous rocks (Fig. 2) [4-6]. Figure 2. Silica versus alkali content. Lines show the liquid lines of descent from magmas with distinct degrees of melting. Gray patches represents the composition of Gale igneous rocks [4-6]. Trachytic to rhyolitic magmas crystallize alkali feldspar, and andesite to dacite magmas likely form plagioclase. Therefore, at least two starting magmas at distinct melting degrees, which could easily come from a single mantle source, are necessary to explain the whole compositional range of feldspar and pyroxene analyzed within Bradbury rocks. Conclusion: Because rocks from the Bradbury formation are likely originating from the same magmatic source with minimal weathering as supported by several studies using different approaches, igneous mineral chemistry analyzed by CheMin and ChemCam allows us to back out reasonable magmatic pathways that could have crystallized them. Fractional crystallization of at least two starting magmas originating from distinct melting degrees of a single mantle source can explain the whole range of feldspar and pyroxene composition. Both alkaline and sub-alkaline liquids can be produced, with compositions corresponding to those of the igneous rocks analyzed by ChemCam within the Bradbury formation, highlighting the complexity of Mars magmatism.

Payre, V.↗

Machine Learning Approaches for Rare-Earth Silicate Environmental Barrier Coating Thermochemical and Thermomechanical Property Predictions

Environmental barrier coatings (EBCs) are a necessary enabling technology for the transition from superalloys to silicon carbide (SiC) ceramic matrix composites (CMCs) in gas turbine engines for increased efficiency and decreased fuel costs. SiC-based CMCs are prone to oxidation-based degradation in the engine hot section, and rare-earth (RE) silicates are promising candidates for EBCs due to their close thermal expansion match to the composite substrate and oxidation resistance. However, the design of EBCs is hindered by the large chemical space of candidate materials and the difficulty in obtaining material properties for engineering optimization. This is especially difficult as research continues into mixed-cation or “high-entropy” RE silicates. First-principles computational methods such as density functional theory (DFT) are highly effective at calculating material properties to guide coating design but are limited by their computational cost. Atomistic simulations have the potential to both accelerate property calculations and expand the properties able to be calculated due to their lower computational compared to DFT. However, they require interatomic potentials (IAPs) specific to the material system of interest, and, to our knowledge, there are no suitable IAPs for RE silicates. Machine learning (ML) is a promising technique to accelerate material property predictions indirectly by generating IAPs for atomistic simulations or via direct prediction. In this work, we present two ML approaches to accelerate the calculation of RE silicate properties relevant to EBC design: 1) a ML-derived interatomic potential (IAP) for atomistic simulations of yttrium disilicate (Y2Si2O7) from DFT training data, and 2) a neural network (NN) model to directly predict thermochemical properties of RE silicates and oxides directly from easily obtainable unit cell parameters. Classical MD simulations using the IAP yield lattice properties and bond lengths in good agreement with both DFT and experimental results from x-ray diffraction. Thermodynamic properties calculated using the finite-displacement phonon method and quasi-harmonic approximation were orders of magnitude faster than DFT with good agreement to the DFT results. The IAP was also used to calculate properties such as coefficient of thermal expansion (CTE) that require large simulation supercells and are therefore difficult with DFT. The IAP correctly predicted the anisotropic nature of the CTE in three different phases of Y2Si2O7. The NN model predicts constant pressure heat capacity, Cp, orders of magnitude faster than DFT calculations, which can enable its use as a surrogate model for multiscale simulations. The two methods presented in this work demonstrate the utility of ML for accelerating the prediction of RE silicate properties, which can in turn accelerate EBC design and optimization.

machine learning↗