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Properties of Desert Sand and CMAS Glass

As-received desert sand from a Middle East country has been characterized for its phase composition and thermal stability. X-ray diffraction analysis showed the presence of quartz (SiO2), calcite (CaCO3), gypsum (CaSO4.2H2O), and NaAlSi3O8 phases in as-received desert sand and showed weight loss of approx. 35 percent due to decomposition of CaCO3 and CaSO4.2H2O when heated to 1400 C. A batch of as-received desert sand was melted into calcium magnesium aluminosilicate (CMAS) glass at approx. 1500 C. From inductively coupled plasma-atomic emission spectrometry, chemical composition of the CMAS glass was analyzed to be 27.8CaO-4MgO-5Al2O3-61.6SiO2-0.6Fe2O3-1K2O (mole percent). Various physical, thermal and mechanical properties of the glass have been evaluated. Bulk density of CMAS glass was 2.69 g/cc, Young's modulus 92 GPa, Shear modulus 36 GPa, Poisson's ratio 0.28, dilatometric glass transition temperature (T (sub g)) 706 C, softening point (T (sub d)) 764 C, Vickers microhardness 6.3 +/- 0.4 GPa, indentation fracture toughness 0.75 +/- 0.15 MPa.m (sup 1/2), and coefficient of thermal expansion (CTE) 9.8 x 10 (exp -6)/degC in the temperature range 25 to 700 C. Temperature dependence of viscosity has also been estimated from various reference points of the CMAS glass using the Vogel-Fulcher-Tamman (VFT) equation. The glass remained amorphous after heat treating at 850 C for 10 hr but crystallized into CaSiO3 and Ca-Mg-Al silicate phases at 900 C or higher temperatures. Crystallization kinetics of the CMAS glass has also been investigated by differential thermal analysis (DTA). Activation energies for the crystallization of two different phases in the glass were calculated to be 403 and 483 kJ/mol, respectively.

Desert sand↗

Thermochemistry of Rare Earth Silicates for Environmental Barrier Coatings

Rare earth silicates are promising candidates as environmental protective coatings (EBCs) for silica-forming ceramics and composites in combustion environments since they are predicted to have lower reactivity with the water vapor combustion products. The reactivity of rare earth silicates is assessed by the thermodynamic activity of the silica component which is best measured by Knudsen effusion mass spectrometry (KEMS). Here, we discuss a novel method based on a reducing agent to increase the partial pressure of SiO(g) which is then used to calculate thermodynamic activity of silica in Y2O3-SiO2 and Yb2O3-SiO2 systems. After the KEMS measurements, samples were probed by X-ray diffraction and their phase content was calculated from Rietveld refinement.

Rare Earth Silicates↗

Thermochemistry of Silicates

The thermodynamic properties of vapor and condensed phases of silicates are crucial in many fields of science. These quantities address fundamental questions on the formation, stability, transformation, and physical properties of silicate minerals and silicate coating compositions. Here the thermodynamic activities of silica and other species in solid solution have been measured by the analysis of the corresponding high temperature vapors using Knudsen Effusion Mass Spectrometry (KEMS). In first set of experiments KEMS has been used to examine the volatility sequence of species (Fe, SiO, Mg, O2 and O) present in the vapor phase during heating of fosterite-rich olivine (Fo93Fa7) up to 2400 C and to measure the Fe, SiO and Mg activities in its solid solution. The data of fosterite-rich olivine are essential for thermochemical equilibrium models to predict the atmospheric and surface composition of hot, rocky exoplanets (Lava Planets). In the second set of experiments the measured thermodynamic activities of the silica in Y2O3-SiO2 and Yb2O3-SiO2 systems are used to assess their reactivity and degradation recession as environmental barrier coatings (EBCs) in combustion environments (e.g. non-moveable parts of gas turbine engine).

Silicates↗

Distinct Igneous APXS Rock Compositions on Mars from Pathfinder, MER and MSL

The alpha particle x-ray spectrometer (APXS) on all four Mars Rovers returned geochemical data from about 1000 rocks and soils along the combined traverses of over 50 kilometers. Here we discuss rocks likely of igneous origin, which might represent source materials for the soils and sediments identified along the traverses. Adirondack-type basalts, abundant in the plains of Gusev Crater, are primitive, olivine bearing basalts. They resemble in composition the basaltic soils encountered at all landing sites, except the ubiquitous elevated S, Cl and Zn in soils. They have been postulated to represent closely the average Martian crust composition. The recently identified new Martian meteorite Black Beauty has similar overall geochemical composition, very distinct from the earlier established SNC meteorites. The rim of the Noachian crater Endeavour, predating the sulfate-bearing Burns formation at Meridiani Planum, also resembles closely the composition of Adirondack basalts. At Gale Crater, the MSL Curiosity rover identified a felsic rock type exemplified by the mugearitic float rock JakeM, which is widespread along the traverse at Gale. While a surprise at that time, possibly related more evolved, alkaline rocks had been previously identified on Mars. Spirit encountered the Wishstone rocks in the Columbia Hills with approx. 6% Na2O+K2O, 15 % Al2O3 and low 12% FeO. Pathfinder rocks with elevated K and Na and >50% SiO2 were postulated to be andesitic. Recently Opportunity encountered the rock JeanBaptisteCharbonneau with >15% Al2O3, >50% SiO2 and approx. 10% FeO. A common characteristic all these rocks is the very low abundance of Cr, Ni and Zn, and an Fe/Mn ratio of about 50, indicating an unaltered Fe mineralogy. Beside these likely igneous rock types, which occurred always in several rocks, a few unique rocks were encountered, e.g. Bounce Rock, a pyroxene-bearing ejecta rock fragment resembling the Shergottite EETA 79001B meteorite. The APXS data can be used to relate the findings of all 4 landing sites, constrain the water to rock ratio of sediments or imply source rock provenance. Beyond that the capability to quantify important volatile elements like P, S, Cl, and Br have provided new insights into the chemistry and the environment present during the formation of the sediments.

Gellert, Ralf↗

Igneous and Sedimentary Compositions from Four Landing Sites on Mars from the Alpha Particle X-Ray Spectrometer (APXS)

The APXS - supported and promoted strongly by Heinrich Waenke - on all four Mars Rovers has returned compositional data from about 1000 rocks and soil targets along the combined traverses of over 60 kilometers. Providing precise and accurate bulk chemistry with typically 16 quantified elements, the APXS is a powerful and versatile tool that when combined with the ability to traverse to key rocks and soils has provided critical information needed to understand the geologic evolution of Mars. APXS data allow comparisons among landing sites, provide ground truth for orbiters and connections back to SNC meteorites. The soils and dust are basaltic in character and represent the average Mars composition similar to Adirondack basalts from Gusev crater but with unambiguous elevated and correlated S, Cl and Zn contents. At all four landing sites the APXS found several rocks with a felsic composition. The similarity is best assessed in a logarithmic ratio plot of rock normalized to the average soil composition (Fig.1). High alkaline, Al, and low Mg, Fe, low S, Cl and Ni, Zn as well as an Fe/Mn ratio of approximately 50 indicate a likely unaltered and igneous origin. Sediments, e.g. the Burns formation, with approximately 25 wt% SO3 at Meridiani Planum have been documented over 10s of kilometers (Fig. 2). This formation is compositionally homogeneous, but showing the removal of MgSO4 and a threefold increase in Cl downhill in 2 craters. The degraded rim of the Noachian crater Endeavour resembles average Mars crust, with local Ca, Mg and Fe sulfate alteration and elevated Mn, some felsic rocks, and high Al, Si and low Fe rocks, possibly indicating clays. Unusual soils at Gusev crater in the area surrounding Home Plate include some very rich in ferric sulfate salts (up to 35 wt% SO3) and some with 90% wt% SiO2, possibly indicating fumerolic activities. Rocks in the Columbia Hills show significant signs of alteration including elevated S, Cl and Br in the abraded interior. At Gale Crater, mudstones with approximately 20% clay, less than 1% SO3 and overall average Mars composition indicate a former habitable environment with low acidity. A remarkable diversity of compositions was found during Curiosity's traverses, which likely stems from material influx from the northern Gale rim. At Pahrump, the base of Mount Sharp, a homogeneous mudstone with lower Mg and Ca was encountered. The composition of this Murray unit can be traced over several kilometers with smooth trends of higher Fe/Mn and lower soluble trace elements Ni and Zn at higher elevation. The likely aeolian Stimson formation with average Mars crustal composition intersects in several places in sharp contact with the Murray formation. Both units show local alteration halos with highly elevated SiO2 of up to 75%, usually correlated with increase in Ti and often P.

Gellert, R.↗

Silicon Chemistry in the Mesosphere and Lower Thermosphere

Silicon is one of the most abundant elements in cosmic dust, and meteoric ablation injects a significant amount of Si into the atmosphere above 80 km. In this study, a new model for silicon chemistry in the mesosphere lower thermosphere is described, based on recent laboratory kinetic studies of Si, SiO,SiO2, and S(exp +). Electronic structure calculations and statistical rate theory are used to show that the likely fate of SiO2 is a two-step hydration to silicic acid (Si(OH)4), which then polymerizes with metal oxides and hydroxides to form meteoric smoke particles. This chemistry is then incorporated into a whole atmosphere chemistry-climate model. The vertical profiles of Si+ and the Si(exp +)Fe(exp +) ratio are shown to be in good agreement with rocket-borne mass spectrometric measurements between 90 and 110 km. Si(exp +) has consistently been observed to be the major meteoric ion around 110 km; this implies that the relative injection rate of Si from meteoric ablation, compared to metals such as Fe and Mg, is significantly larger than expected based on the irrelative chondritic abundances. Finally, the global abundances of SiO and Si(OH)4 show clear evidence of the seasonal meteoric input function, which is much less pronounced in the case of other meteoric species.

Plane, John M. C.↗

Monte Carlo Computational Modeling of Atomic Oxygen Interactions

Computational modeling of the erosion of polymers caused by atomic oxygen in low Earth orbit (LEO) is useful for determining areas of concern for spacecraft environment durability. Successful modeling requires that the characteristics of the environment such as atomic oxygen energy distribution, flux, and angular distribution be properly represented in the model. Thus whether the atomic oxygen is arriving normal to or inclined to a surface and whether it arrives in a consistent direction or is sweeping across the surface such as in the case of polymeric solar array blankets is important to determine durability. When atomic oxygen impacts a polymer surface it can react removing a certain volume per incident atom (called the erosion yield), recombine, or be ejected as an active oxygen atom to potentially either react with other polymer atoms or exit into space. Scattered atoms can also have a lower energy as a result of partial or total thermal accommodation. Many solutions to polymer durability in LEO involve protective thin films of metal oxides such as SiO2 to prevent atomic oxygen erosion. Such protective films also have their own interaction characteristics. A Monte Carlo computational model has been developed which takes into account the various types of atomic oxygen arrival and how it reacts with a representative polymer (polyimide Kapton H) and how it reacts at defect sites in an oxide protective coating, such as SiO2 on that polymer. Although this model was initially intended to determine atomic oxygen erosion behavior at defect sites for the International Space Station solar arrays, it has been used to predict atomic oxygen erosion or oxidation behavior on many other spacecraft components including erosion of polymeric joints, durability of solar array blanket box covers, and scattering of atomic oxygen into telescopes and microwave cavities where oxidation of critical component surfaces can take place. The computational model is a two dimensional model which has the capability to tune the interactions of how the atomic oxygen reacts, scatters, or recombines on polymer or nonreactive surfaces. In addition to the specification of atomic oxygen arrival details, a total of 15 atomic oxygen interaction parameters have been identified as necessary to properly simulate observed interactions and resulting polymer erosion that have been observed in LEO. The tuning of the Monte Carlo model has been accomplished by adjusting interaction parameters so the erosion patterns produced by the model match those from several actual LEO space experiments. Surface texturing in LEO can also be predicted by the model. Such comparison of space tests with ground laboratory experiments have enabled confidence in ground laboratory lifetime prediction of protected polymers. Results of Monte Carlo tuning, examples of surface texturing and undercutting erosion prediction, and several examples of how the model can be used to predict other LEO and Mars orbital space results are presented.

Monte Carlo Modeling↗

Monte Carlo Computational Modeling of Atomic Oxygen Interactions

Computational modeling of the erosion of polymers caused by atomic oxygen in low Earth orbit (LEO) is useful for determining areas of concern for spacecraft environment durability. Successful modeling requires that the characteristics of the environment such as atomic oxygen energy distribution, flux, and angular distribution be properly represented in the model. Thus whether the atomic oxygen is arriving normal to or inclined to a surface and whether it arrives in a consistent direction or is sweeping across the surface such as in the case of polymeric solar array blankets is important to determine durability. When atomic oxygen impacts a polymer surface it can react removing a certain volume per incident atom (called the erosion yield), recombine, or be ejected as an active oxygen atom to potentially either react with other polymer atoms or exit into space. Scattered atoms can also have a lower energy as a result of partial or total thermal accommodation. Many solutions to polymer durability in LEO involve protective thin films of metal oxides such as SiO2 to prevent atomic oxygen erosion. Such protective films also have their own interaction characteristics. A Monte Carlo computational model has been developed which takes into account the various types of atomic oxygen arrival and how it reacts with a representative polymer (polyimide Kapton H) and how it reacts at defect sites in an oxide protective coating, such as SiO2 on that polymer. Although this model was initially intended to determine atomic oxygen erosion behavior at defect sites for the International Space Station solar arrays, it has been used to predict atomic oxygen erosion or oxidation behavior on many other spacecraft components including erosion of polymeric joints, durability of solar array blanket box covers, and scattering of atomic oxygen into telescopes and microwave cavities where oxidation of critical component surfaces can take place. The computational model is a two dimensional model which has the capability to tune the interactions of how the atomic oxygen reacts, scatters, or recombines on polymer or nonreactive surfaces. In addition to the specification of atomic oxygen arrival details, a total of 15 atomic oxygen interaction parameters have been identified as necessary to properly simulate observed interactions and resulting polymer erosion that have been observed in LEO. The tuning of the Monte Carlo model has been accomplished by adjusting interaction parameters so the erosion patterns produced by the model match those from several actual LEO space experiments. Surface texturing in LEO can also be predicted by the model. Such comparison of space tests with ground laboratory experiments have enabled confidence in ground laboratory lifetime prediction of protected polymers. Results of Monte Carlo tuning, examples of surface texturing and undercutting erosion prediction, and several examples of how the model can be used to predict other LEO and Mars orbital space results are presented.

Atomic Oxygen↗

High Temperature Vaporization into Different Environments

Materials in extreme environments are often negatively affected by the process of vaporization. The maximum vaporization rate is determined by calculating a flux from the equilibrium vapor pressure(s) of each component. However, this maximum vaporization flux is decreased by the vaporization coefficient and the atmosphere above the material. This paper discusses each of these factors for common oxides, using SiO2 as an example. Vaporization into a vacuum is an ideal starting point, as the basic mechanisms for vaporization have been derived from these studies. Imposing an over-pressure of a static gas changes the vaporization rates from both a thermodynamic and kinetic aspect. Finally, a flowing gas is the most common situation encountered in many extreme environments. Laminar and turbulent flow effects are be treated with both analytical transport expressions and computational fluid dynamics (CFD). The example of a vaporizing SiO2 coupon in a laboratory furnace is examined with both the analytical expressions and with CFD.

Jacobson, Nathan↗

Dissolution Rates of Allophane with Variable Fe Contents: Implications for Aqueous Alteration and the Preservation of X-ray Amorphous Materials on Mars

Recent measurements from Mars document X-ray amorphous/nano-crystalline materials in multiple locations across the planet. However, despite their prevalence, little is known about these materials or what their presence implies for the history of Mars. The X-ray amorphous component of the martian soil in Gale crater has an X-ray diffraction pattern that can be partially fit with allophane (approximately Al2O3•(SiO2)1.3-2•(H2O)2.5-3), and the low-temperature water release data are consistent with allophane. The chemical data from Gale crater suggest that other silicate materials similar to allophane, such as Fe-substituted allophane (approximately (Fe2O3)0.01-0.5(Al2O3)0.5-0.99•(SiO2)2•3H2O), may also be present. In order to investigate the properties of these potential poorly crystalline components of the martian soil, Fe-free allophane (Fe:Al = 0), Fe-poor allophane (Fe:Al = 1:99), and Fe-rich allophane (Fe:Al = 1:1) were synthesized and then characterized using electron microscopy and Mars-relevant techniques, including infrared spectroscopy, X-ray diffraction, and evolved gas analysis. Dissolution experiments were performed at acidic (initial pH values pH0 = 3.01, pH0 = 5.04), near-neutral (pH0 = 6.99), and alkaline (pH0 = 10.4) conditions in order to determine dissolution kinetics and alteration phases for these poorly crystalline materials. Dissolution rates (rdiss), based on the rate of Si release into solution, show that these poorly crystalline materials dissolve approximately an order of magnitude faster than crystalline phases with similar compositions at all pH conditions. For Fe-free allophane, logrdiss = -10.65 – 0.15 × pH; for Fe-poor allophane, logrdiss = -10.35 – 0.22 × pH; and for Fe-rich allophane, logrdiss = -11.46 – 0.042 × pH at 25°C, where rdiss has the units of mol m-2 s-1. The formation of incipient phyllosilicate-like phases was detected in Fe-free and Fe-rich allophane reacted in aqueous solutions with pH0 = 10.4 (steady-state pH ≈ 8). Mars-analog instrument analyses demonstrate that Fe-free allophane, Fe-poor allophane, and Fe-rich allophane are appropriate analogs for silicate phases in the martian amorphous soil component. Therefore, similar materials on Mars must have had limited interaction with liquid water since their formation. Combined with chemical changes expected from weathering, such as phyllosilicate formation, the rapid alteration of these poorly crystalline materials may be a useful tool for evaluating the extent of aqueous alteration in returned samples of martian soils.

S J Ralston↗

Zircon, Baddeleyite, and Reidite Found in Ries Crater Suevite

Introduction: Impact events can generate superheated impact melts and even vapor [1]. In the past decade, evidence of the high temperatures and high pressures of the impact process has been found in the impact melt from terrestrial craters (e.g., Mistastin Lake [2], Meteor Crater [3]) and even on the Moon [4–5]. Often, these studies involve zircon or zirconium-bearing phases. Zircon is a particularly useful mineral, due to its robustness and durability against weathering. It is used principally for chronology, but it has a multitude of geologic applications, including geothermometry and fingerprinting magma sources. Here we focus on its capability of recording impact conditions. Grains of zircon (ZrSiO4) are converted at high temperature and/or pressure during an impact event to reidite (a high-pressure polymorph of ZrSiO4) or to tetragonal-ZrO2 + SiO2 [6]. Reidite and tertragonal-ZrO2 leave identifying relicts in the rocks, markers of the high pressures and/or temperatures these rocks underwent. Ries Crater is a 26-km-diameter peak ring crater in southern Germany that formed approximately 15 Ma [7–9]. Ries is the type locality of the polymict impact breccia known as suevite. Here, we report a microanalytical study of suevite from the Ries impact structure. These analyses are used to inform our understanding of the pressure and temperature conditions involved in creating a polymict impact breccia such as suevite in a peak ring crater. Sample Description: The sample, denoted 16RS08, originates from Otting Quarry, at 48.8777° N, 10.7921° E, approximately 17 km from the center of the Ries Crater in Germany (approximately 4 km outside the crater rim). The material recorded in sample 16RS08 is therefore considered an outer suevite. The outer suevite is a discontinuous layer of polymict impact breccia that occurs outside the central ring of Ries, up to 22 km from the center of the crater [9]. Lithic clasts in the outer suevite consist primarily of crystalline basement rocks (gneiss, granite, amphibolite), with less than 5% of lithic clasts being overlying sedimentary rocks (limestone, sandstone, shale) [9]. The thin section studied contains variably shocked lithic and mineral clasts, impact glass, and interstitial minerals that make up the matrix of the breccia (Fig. 1) [9]. Methods: We used a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona to obtain 15 elemental X-ray maps of 16RS08. We next used the JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC) to obtain electron backscatter diffraction (EBSD) maps and energy dispersive X-ray spectroscopy (EDS) maps of select portions of the section. The EBSD data were collected under beam conditions of 20 kV, and ~9 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We used the elemental X-ray maps to identify the areas of interest in the section, particularly phosphates and Zr-bearing grains. These areas of interest were then targeted for follow up EBSD and EDS analyses. We have identified, through combined EBSD and EDS analysis, the presence of zircon, reidite, and monoclinic-ZrO2 (baddeleyite) in 16RS08. In 16RS08, we have found singular grains of zircon, zircon with a vermicular baddeleyite halo (Fig. 2a), and granular zircon with reidite (Fig. 2b). The different Zr-rich phases and their corresponding textures signifies that this sample underwent a broad spectrum of pressure and temperature conditions during the impact event. For example, zircons surrounded by a vermicular baddeleyite and SiO2 intergrowth (i.e., Fig. 2a) have been shown to preserve evidence of the extremely high temperatures of impact melt, upwards of 2370 °C [2, 6]. Similarly, reidite and granular zircon (i.e., Fig. 2b) have been shown to preserve evidence of high pressure, as the transition to reidite occurs >30 GPa [3, 6]. Future Work: Next, we will process the EBSD and EDS data for these Zr-rich grains, specifically looking for indicators of cubic- or tetragonal-ZrO2 in the baddeleyite remnants and of shock-precursors to the reidite. To further inform our work, we will also obtain BSE images of these grains using a Hitachi S-4800 SEM in KMICF at the University of Arizona, as well as geochemical spot analyses via EPMA. The data collected will be used to constrain the formation conditions of the Ries Crater outer suevite. Acknowledgments: We thank Ken Domanik and Jerry Chang for their support with data collection. This work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. TME thanks A. Cavosie and N. Timms for assistance during field sampling. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Melosh H. J. (1989) Oxf. U. Press. [2] Timms et al. (2017) EPSL 477, 52–58. [3] Cavosie et al. (2016) Geology 44:9, 703–706. [4] White et al. (2020) Nature Astr. 4, 974–978. [5] Crow C. A. et al. (2017) GCA 202, 264–284. [6] Timms et al. (2017) Earth-Sci. Rev. 165, 185–202. [7] Schmieder M. et al. (2018) GCA 220, 146–157. [8] Schwarz W. H. et al. (2020) M&PS 55:2, 312–325. [9] Stöffler et al. (2013) M&PS 43:4, 515–589.

Zircon↗

Development of New Lunar Highland Regolith Simulant, NUW-LHT-5M

Introduction: NASA has a need for large quantities of lunar simulants that closely match future manned lunar missions at landing sites near the Lunar South Pole. The current simulant was designed to approximate NU-LHT-2M, and -4M, except using natural minerals and a fully synthetic, non-basaltic, high calcium glass. Washington Mills in Niagara Falls, NY was contracted to produce this new simulant due to their electric arc furnace (EAF) fusion technology and capabilities for crushing and sizing ceramics. The primary objectives of this work were: (1) to create a commercially produced simulant that contains a high fidelity, high calcium (An90+), low Mg/Fe glass without basaltic constituents; (2) to create a simulant that uses existing, terrestrially mined, and readily available minerals blended with a synthetic glass, and (3) accomplish objectives (1) and (2) using conventional processing methods capable of production levels that can meet substantial current and future demands of NASA projects. Another consideration was that highland simulants closest to meeting these requirements, NU-LHT-2M and -4M types, are out of production and largely out of stock. Design: The design chosen for development and production for this work is NU-LHT-2M, de-signed by Doug Stoeser and Douglas Rickman, which uses Stillwater anorthosite and norite rocks and synthetic glass. The composition targeted the average composition, glass content and particle size distribution of Apollo 16 samples [1]. The design utilizes two Stillwater minerals, anorthosite (37.7 wt.%), norite (17.6 wt.%), a commercially sourced olivine (4.7 wt.%), and a synthetic glass (40 wt.%). Processing: Stillwater rocks were hand collected and initially crushed by the USGS. Further crushing and milling was performed at Washing-ton Mills. For the glass, oxides were blended in the ap-propriate ratios, blended in a v-blender, and placed in a graphite lined, water cooled pot. The mixture was fused in Washington Mills’ pilot scale, 500 kW EAF. The molten glass was then poured into water and quenched to inhibit crystallization. Several pour/quench cycles were required to produce the total quantity of glass needed. Anorthosite, norite and olivine were milled together to the target particle size in a ball mill. The glass was ball milled separately. The complete simulant was produced by blending the milled materials. Particle size distribution, phase and chemical analyses of the materials was were per-formed at Washington Mills. Results: The glass composition was found to match the Apollo 16 oxide content average [1] quite well, with the exception of SiO2 and Fe2O3. The deviation of SiO2 and Fe2O3 from batched content was believed to be due to limitations inherent in the use of the arc furnace technique for these types of materials. A particle size distribution of the full simulant formulation closely matching the average for the Apollo 16 samples was also achieved. Fig. 1 shows the morphology of the final simulant particles. The size distribution is compared to the target in Fig. 2. Conclusions: A new lunar highlands type simulant containing a high-quality synthetic glass, closely matching an average composition of the Apollo 16 regolith was produced. Processing utilized easily scalable mineral and glass making methods.

simulant↗

Photonic near infrared heater

A multilayer photonic stack comprising a lower plurality of alternating layers comprising at least A and B and an upper plurality of alternating layers comprising at least C and D, layer A comprises at least one of Al, Au, W, Ag, Ni, Ti, Pt, and Cr, layer B comprises at least one of Al2O3, AlN, MgO, SiO2, TiO2, Si3N4, MgF2, Ta2O5, SiC, Si, Ge, and Indium Tin Oxide (ITO), and layers C and D comprise at least one of Al2O3, AlN, MgO, SiO2, TiO2, Si3N4, MgF2, Ta2O5, SiC, Si, Ge, and Indium Tin Oxide (ITO).

Prasher, Ravi Shankar↗

Oxidation-resistant reflective surfaces for solar dynamic power generation in near Earth orbit

Reflective surfaces for space station power generation systems are required to withstand the atomic oxygen-dominated environment of near Earth orbit. Thin films of platinum and rhodium, which are corrosion resistant reflective metals, have been deposited by ion beam sputter deposition onto various substrate materials. Solar reflectances were then measured as a function of time of exposure to a RF-generated air plasma. Similarly, various protective coating materials, including MgF2, SiO2, Al2O3, and Si3N4, were deposited onto silver-coated substrates and then exposed to the plasma. Analysis of the films both before and after exposure by both ESCA and Auger spectroscopy was also performed. The results indicate that Pt and Rh do not suffer any loss in reflectance over the duration of the tests. Also, each of the coating materials survived the plasma environment. The ESCA and Auger analyses are discussed as well.

Gulino, D. A.↗

Understanding the Origin of Negative Temperature Dependence and Activity of N-Coordinated Cobalt Sites During Ethylene Dimerization

The on-demand production of short-chain linear alpha olefins (LAOs; C4-C8) via C2H4 dimerization and oligomerization is industrially attractive, prompting extensive research on designing active, selective, and stable catalysts for industrial use. Cobalt supported on ammoniated carbon (Co(NH3)x/C) catalysts have shown remarkable activity and selectivity in this process. However, critical aspects such as the active phase, active site structure, the role of the catalyst support, cobalt loading effects, and the inverse correlation of the reaction rate with temperature remain inadequately understood. This study systematically explores these factors using a combination of steady-state differential catalytic tests, in situ molecular characterization including diffuse reflectance UV-Vis (DR-UV-Vis), Infrared, and Raman spectroscopies, and ex situ X-ray diffraction (XRD) and high annular aberration-corrected dark field transmission electron microscopy (HAADF-STEM). Various supports (SiO2, Al2O3, NH4-ZSM-5, g-C3N4, and C) and cobalt loadings (1.0-3.0 Co nm-2) were studied to determine the optimal catalyst composition and identify the active phase and sites. Carbon-supported catalysts uniquely produce C4-8 LAOs during C2H4 dimerization, with site-time-yield remaining constant (~10-3 s-1) for 1.0-4.0 Co nm-2 at prolonged reaction times (24-48?h time-on-stream). At higher loadings of 6.0 Co nm-2, the formation of crystalline CoO and Co3O4 phases reduces catalytic activity and LAO selectivity. Our findings show that active catalysts lack crystalline cobalt oxides and instead feature dispersed Co2+ sites, tetra-coordinated to a mix of N/NH3 and O/H2O ligands, which catalyze C2H4 dimerization via the Cossee-Arlman mechanism, exhibiting 1st order dependence on C2H4 concentration. The observed inverse rate-temperature correlation is attributed to compensation effects (i.e., presence of Cremer-Constable relationship) linked to changes in adsorption enthalpic and entropic factors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystalline Loading of Lipophilic Coenzyme Q10 Pharmaceuticals within Conjugated Carbon Aerogel Derivatives

Low-density aerogel materials currently are being considered for applications in controlling the rate of release for small-molecule pharmaceuticals in vivo. In particular, silica (SiO2) aerogels are an intriguing platform for controlling both the absolute amount of drug loading, but also the crystalline state of small molecule pharmaceuticals has been shown to affect drug release kinetics. To date, loading silica aerogel materials with crystalline pharmaceuticals typically require dissolving small molecules in a supercritical solvent (i.e., CO2) before drying to recover the aerogel/drug composite. Here we demonstrate a simple and low-cost method for controlling the crystallinity of the model drug coenzyme Q10 (CoQ10) within carbon aerogel materials by rationally controlling the chemical microstructure of the aerogel to exhibit ?-conjugated (sp2) chemical bonding. In particular, both pyrolyzed graphene and nanodiamond aerogels exhibit enhanced intrinsic drug loading capacity and CoQ10 crystallinity over a broad range of sp2 surface-curvature. In contrast, amorphous carbon aerogel materials are observed to load CoQ10 pharmaceuticals with strictly amorphous microstructure.

Lim, Mathew↗

Toward Rational Design of Supported Vanadia Catalysts of Lignin Conversion to Phenol

In sustainable chemical engineering, catalytic upgrading of lignocellulosic biomass has recently gained attention for producing renewable platform chemicals. To achieve maximal biomass utilization, upgrading the underutilized lignin components is essential. Among various catalysts for lignin upgrading, supported vanadia (V2O5) catalysts are promising because of their cost-effectiveness and tunability of either dopant metals or catalyst supports. Here, computational studies are conducted to derive rational design guidelines of supported V2O5 catalysts for accomplishing the high catalytic activity of lignin upgrading to phenol, a key compound for producing bioplastics and biofuel blendstocks. Guaiacol was used as the model compound since it comprises the highest portion of depolymerized lignin. Computational mechanistic studies for the catalytic guaiacol conversion to phenol were performed for the V2O5 catalysts on Titania (TiO2) and silica (SiO2) to explain higher experimental phenol yields on V2O5/SiO2 than V2O5/TiO2. The hydrogen migration from the methoxy group to the aryl ring was identified as a rate-determining step, and the overall activation energies on the two catalysts were compared. A structural analysis was carried out for the catalysts and rate-determining transition states to gain further insights from mechanistic studies. It was concluded that the tilt angle of the aryl group in the hydrogen migration transition state is a key descriptor determining the catalytic activity of phenol formation. These features correlate well with activation energies and experimental phenol yields, indicating that they provide design guidelines for supported metal catalysts for lignin upgrading before experiments.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Computer simulation of reaction and transport of core-scale serpentinization of Fe-bearing olivine and evolution of geological hydrogen

We present reactive flow and transport simulations of core-scale serpentinization of forsteritic, Fe-bearing olivine under hydrothermal conditions. The model captures fluid flow, evolving porosity–permeability, and redox-controlled H 2 production in a cylindrical core over 55 days at 245 °C and 37 bar. Key processes include olivine dissolution, precipitation of serpentine and magnetite, and oxidation of Fe2+ to Fe 3+ . Here, results show strong coupling among flow velocity, alteration front propagation, and spatially heterogeneous H 2 generation. Elevated H2 concentrations align with inlet-localized magnetite precipitation, consistent with experiments. Secondary mineral formation reduces porosity and permeability, altering transport pathways. Reactive flow at the fluid–solid interface governs H 2 generation rates and distribution. Dissolved SiO2 promotes serpentine and talc formation by suppressing brucite, while bicarbonate extends reaction duration and moderates surface complexation effects.

Geologic hydrogen↗