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Studies of Lubricating Materials in Vacuum

Lubricating materials for use in a vacuum environment have been the subject of a series of experimental investigations. Evaporation properties were evaluated for solid polymeric compositions. Friction and wear studies explored the behavior during sliding contact for series of polymeric compositions, binary alloys containing soft film-forming phases, complex alloys with film-forming materials, and a burnished MoS2 film. Friction and wear experiments were conducted at 10(exp-9)mm Hg with a 3/16-inch-radius-hemisphere rider specimen sliding on the flat surface of a rotating 2-1/2-inch-diameter disk specimen with materials that had low rates of evaporation. The influence of fillers in polytetrafluoroethylene (PTFE) on decomposition during vacuum friction studies was determined with a mass spectrometer. A real advantage in reducing decomposition and improving friction wear properties is gained by adding fillers (e.g., copper) that improve thermal conductivity through the composite materials. A polyimide and an epoxy-MoS2 composition material were found to have better friction and wear properties than PTFE compositions. A series of alloys (cast binary as well as more complex alloys) that contained microinclusions of potential film-forming material was studied. These materials replaced the normal surface oxides as they were worn away on sliding contact. Iron sulfide, nickel oxide, and tin are typical film-forming materials employed and were demonstrated to be effective in inhibiting surface welding and reducing friction. A burnished MoS2 film applied to type 440-C stainless steel in argon with a rotating soft wire brush had good endurance properties but somewhat higher friction than commercially available bonded films. An oil film applied to the burnished MoS2 markedly reduced its endurance life.

WEAR↗

Manufacture and engine test of advanced oxide dispersion strengthened alloy turbine vanes

Oxide-Dispersion-strengthened (ODS) Ni-Cr-Al alloy systems were exploited for turbine engine vanes which would be used for the space shuttle thermal protection system. Available commercial and developmental advanced ODS alloys were evaluated, and three were selected based on established vane property goals and manufacturing criteria. The selected alloys were evaluated in an engine test. Candidate alloys were screened by strength, thermal fatigue resistance, oxidation and sulfidation resistance. The Ni-16Cr (3 to 5)Al-ThO2 system was identified as having attractive high temperature oxidation resistance. Subsequent work also indicated exceptional sulfidation resistance for these alloys.

Bailey, P. G.↗

Current Status and Future Directions of All-Solid-State Batteries with Lithium Metal Anodes, Sulfide Electrolytes, and Layered Ternary Oxide Cathodes

All-solid-state batteries (ASSBs) offer great promise as a next-generation energy storage technology with higher energy density, wider operating temperature range, and improved safety for electric vehicles. ASSBs employing lithium metal anodes (Li), sulfide-based solid-state electrolytes (SSE), and Ni-rich layered transition metal oxide cathodes (LiMO 2 , M = Ni, Mn, Co, Al) are particularly promising due to its superior electrochemical performance compared to other solid-electrolyte systems. However, the battery cycle life at high cathode mass loading and high current is still limited because the failure mechanism is not fully understood. Lithium dendrite growth at the anode or inside a solid electrolyte still represents as a serious risk of cell failure. Interfacial resistance increases attributed to electrolyte decomposition and interfacial void formation at both cathode–electrolyte and anode–electrolyte interfaces lead to gradual capacity fading. In this Review, we present the fundamental challenges and recent scientific understandings of each component in ASSBs. The novel diagnostic tools for these components, especially the interfaces buried under the surface that are often hard for characterization are mainly examined. Lastly, we offer a perspective for future research directions. We hope this Review will provide a timely snapshot of state-of-the-art research progress in ASSBs to accelerate the development of ASSBs.

25 ENERGY STORAGE↗

Chemistry in Retrieved Ryugu Asteroid Samples Revealed by Non-Invasive X-ray Microanalyses: Pink-Beam Fluorescence CT and Tender-Energy Absorption Spectroscopy

The Hayabusa2 space mission recently retrieved 5.4 g of material from asteroid Ryugu, providing the first direct access to pristine material from a carbonaceous asteroid. This study employs a novel combination of non-invasive synchrotron X-ray techniques to examine microscale chemistry (elemental distributions and element-specific chemical speciation and local structure) inside Ryugu grains without physically cutting the samples. Manganese primarily occurs in carbonate: Mn-bearing dolomite with minor earlier ankerite. Iron sulfides present as large single grains and as smaller particles in the finer-grained matrix are both predominantly pyrrhotite. At the 5 μm scale, Fe sulfides do not show the mineralogical heterogeneity seen in many carbonaceous meteorites but exhibit some heterogeneous localized oxidation. Iron is present often as intergrowths of oxide and sulfide, indicating incomplete replacement. Trace selenium substitutes for S in pyrrhotite. Copper is present as Fe-poor Cu sulfide. These results demonstrate multiple episodes of fluid alteration on the parent body, including partial oxidation, and help constrain the sequence or evolution of fluids and processes that resulted in the current grain-scale mineralogical composition of Ryugu materials.

36 MATERIALS SCIENCE↗

The Miniaturized Moessbauer Spectrometer MIMOS II of the Athena Payload for the 2003 MER Missions

A first-order requirement of spacecraft missions that land on Mars is instrumentation for in situ mineralogical analysis. Moessbauer Spectroscopy is a powerful tool for quantitative analysis of Fe-bearing materials. The Athena Moessbauer spectrometer MIMOS II on the martian surface will provide: (1) identification of iron-bearing phases (e.g., oxides, silicates, sulfides, sulfates, and carbonates), (2) quantitative measurement of the distribution of iron among its oxidation states (e.g., Fe(2+)/Fe(3+) ratio), and (3) quantitative measurement of the distribution of iron among iron-bearing phases (e.g., the relative proportions of iron in olivine, pyroxene, and magnetite in a basalt) in rocks and soils. Moessbauer data will also be highly complementary with chemical analyses from the APXS and the Mini-TES compositional data. Mars is a particularly good place to do Moessbauer mineralogy because its surface is iron rich (approx. 20% Fe as Fe2O3). Moessbauer spectrometers that are built with backscatter measurement geometry require no sample preparation, a factor important for in situ planetary measurements.

G Klingelhoefer↗

High-temperature oxidation/corrosion of iron-based superalloys

The oxidation and sulfidation of several novel iron-base superalloys were evaluated in high-temperature cyclic tests. The experimental austenitic alloys examined were modifications of NASAUT-4GA which were developed for Stirling-engine application. The weight gains and resulting surface scales were measured and analyzed. Mixed oxide scales were found to form on all specimens exposed above 871 C. The build-up of these scales led to a depletion of Mn and Cr in a zone adjacent to the oxides. In addition, the initial oxidation of the Fe-rich alloy was inhibited by a thin but tenacious Si layer which formed at the interface between oxides and the parent layer. Sulfidation tests using Na2SO4 coatings resulted in the formation of a protective spinel and alpha-Fe2O3 phases. Preferential attack of the carbide phase by hydrogen was not observed after 350 h at 871 C.

Lemkey, F. D.↗

A Review of Nanocarbon-Based Anode Materials for Lithium-Ion Batteries

Renewable and non-renewable energy harvesting and its storage are important components of our everyday economic processes. Lithium-ion batteries (LIBs), with their rechargeable features, high open-circuit voltage, and potential large energy capacities, are one of the ideal alternatives for addressing that endeavor. Despite their widespread use, improving LIBs’ performance, such as increasing energy density demand, stability, and safety, remains a significant problem. The anode is an important component in LIBs and determines battery performance. To achieve high-performance batteries, anode subsystems must have a high capacity for ion intercalation/adsorption, high efficiency during charging and discharging operations, minimal reactivity to the electrolyte, excellent cyclability, and non-toxic operation. Group IV elements (Si, Ge, and Sn), transition-metal oxides, nitrides, sulfides, and transition-metal carbonates have all been tested as LIB anode materials. However, these materials have low rate capability due to weak conductivity, dismal cyclability, and fast capacity fading owing to large volume expansion and severe electrode collapse during the cycle operations. Contrarily, carbon nanostructures (1D, 2D, and 3D) have the potential to be employed as anode materials for LIBs due to their large buffer space and Li-ion conductivity. However, their capacity is limited. Blending these two material types to create a conductive and flexible carbon supporting nanocomposite framework as an anode material for LIBs is regarded as one of the most beneficial techniques for improving stability, conductivity, and capacity. This review begins with a quick overview of LIB operations and performance measurement indexes. It then examines the recently reported synthesis methods of carbon-based nanostructured materials and the effects of their properties on high-performance anode materials for LIBs. These include composites made of 1D, 2D, and 3D nanocarbon structures and much higher Li storage-capacity nanostructured compounds (metals, transitional metal oxides, transition-metal sulfides, and other inorganic materials). The strategies employed to improve anode performance by leveraging the intrinsic features of individual constituents and their structural designs are examined. The review concludes with a summary and an outlook for future advancements in this research field.

25 ENERGY STORAGE↗

MoS2 interactions with 1.5 eV atomic oxygen

Exposures of MoS2 to 1.5-eV atomic oxygen in an anhydrous environment reveal that the degree of oxidation is essentially independent of crystallite orientation, and that the surface-adsorbed reaction products are MoO3 and MoO2. A mixture of oxides and sulfide exists over a depth of about 90 A, and this layer has a low diffusion rate for oxygen. It is concluded that a protective oxide layer forms on MoS2 on exposure to the atomic-oxygen-rich environment of LEO.

Martin, J. A.↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

T. Ramprasad↗

Chemical and Microstructural Changes in Metallic and Ceramic Materials Exposed to Venusian Surface Conditions

The chemical and microstructural behavior of steels (304, 310, 316, and 1018), nickel-based alloys (beta-NiAl, G30, and 625), gold, coatings (4YSZ, SilcoNert(TradeMark) 1040 (SilcoTek Co.), Dursan(TradeMark) (SilcoTek Co.), and porcelain), and bulk ceramics (alpha-Al2O3, fused quartz, beta-SiC, and alpha-Si3N4) were probed after exposure to supercritical fluid with temperature, pressure, and composition mimicking the Venus lower atmosphere. Exposures were carried out in the Glenn Extreme Environments Rig (GEER) chamber with the Venusian gas mixture (96.5% CO2, 3.5% N2, 30 ppm H2O, 150 ppm SO2, 28 ppm CO, 15 ppm OCS, 3 ppm H2S, 0.5 ppm HCl, and 5 ppb HF) at 92 bar (1330 psi) and 467 C (873 F) for durations of 10 and 42 days. An additional 21-day exposure was done to stainless steel uncoated and coated with SilcoNert(TradeMark) and Dursan(TradeMark). Samples were characterized before and after the experiment by gravimetric analysis, X-ray diffraction, X-ray photoelectron and Auger electron spectroscopies, and cross section electron microscopy analysis. All steels exposed for 10 and 42 days formed double-layered scales consisting mainly of metal (Cr, Fe, Ni) oxides and sulfides showing different chemistry, microstructure, and crystalline phases. The alloys G30 and 625 formed double-layered scales consisting mainly of nickel sulfides. After 10 days, the beta-NiAl exhibited no detectable scale, suggesting only a very thin film was formed. The 304 and 316 stainless steels coated with 4YSZ that were exposed for 10 and 42 days exhibited no significant oxidation. Steel 1018 coated with 4YSZ exhibited a corrosion scale of iron and/or chromium oxide formed at the base of the alloy. The 304 steel coated with porcelain did not exhibit corrosion, although the coating exhibited recession. SilcoNert(TradeMark) exposed for 10 and 42 days exhibited recession, although no oxidation was found to occur at the base of the alloy. Stainless steel 316 coated with Dursan(TradeMark)  exhibited corrosion at the base of the alloy. All ceramics tested showed no clear evidence of reaction. The weight-gain-per-area performance of the materials exposed in the GEER for 10 and 42 days are reported from the lowest to the highest weight gain per area as follows: gold did not exhibit any weight change; nickel-based alloys: beta- NiAl < G30 < 625; steels: 304 < 310 < 316 < 1018; ceramics: considering the experimental uncertainties, no weight change was observed for all ceramics of this work (alpha-Al2O3, Si3N4, SiC, and amorphous SiO2).

Costa, Gustavo C. C.↗

Review of Multifunctional Separators: Stabilizing the Cathode and the Anode for Alkali (Li, Na, and K) Metal–Sulfur and Selenium Batteries

Alkali metal batteries based on lithium, sodium, and potassium anodes and sulfur-based cathodes are regarded as key for next-generation energy storage due to their high theoretical energy and potential cost effectiveness. However, metal–sulfur batteries remain challenged by several factors, including polysulfides’ (PSs) dissolution, sluggish sulfur redox kinetics at the cathode, and metallic dendrite growth at the anode. Functional separators and interlayers are an innovative approach to remedying these drawbacks. Here we critically review the state-of-the-art in separators/interlayers for cathode and anode protection, covering the Li–S and the emerging Na–S and K–S systems. The approaches for improving electrochemical performance may be categorized as one or a combination of the following: Immobilization of polysulfides (cathode); catalyzing sulfur redox kinetics (cathode); introduction of protective layers to serve as an artificial solid electrolyte interphase (SEI) (anode); and combined improvement in electrolyte wetting and homogenization of ion flux (anode and cathode). It is demonstrated that while the advances in Li–S are relatively mature, less progress has been made with Na–S and K–S due to the more challenging redox chemistry at the cathode and increased electrochemical instability at the anode. Throughout these sections there is a complementary discussion of functional separators for emerging alkali metal systems based on metal–selenium and the metal–selenium sulfide. The focus then shifts to interlayers and artificial SEI/cathode electrolyte interphase (CEI) layers employed to stabilize solid-state electrolytes (SSEs) in metal–sulfur solid-state batteries (SSBs). The discussion of SSEs focuses on inorganic electrolytes based on Li- and Na-based oxides and sulfides but also touches on some hybrid systems with an inorganic matrix and a minority polymer phase. The review then moves to practical considerations for functional separators, including scaleup issues and Li–S technoeconomics. The review concludes with an outlook section, where we discuss emerging mechanics, spectroscopy, and advanced electron microscopy (e.g. cryo-transmission electron microscopy (cryo-TEM) and cryo-focused ion beam (cryo-FIB))-based approaches for analysis of functional separator structure–battery electrochemical performance interrelations. Finally, throughout the review we identify the outstanding open scientific and technological questions while providing recommendations for future research topics.

25 ENERGY STORAGE↗

Electrochemical Proton Insertion Modulates the Hydrogen Evolution Reaction on Tungsten Oxides

Development of new electrocatalysts for the hydrogen evolution reaction (HER) could reduce dependence on Pt and other rare metals and enable large-scale production of hydrogen with near-zero carbon emissions. Mechanistic insight into the electrocatalytic activity of a material helps to accelerate the development of new electrocatalysts. Alternative electrocatalyst materials such as transition metal oxides and sulfides can undergo insertion reactions that change their properties. Recent reports indicate that the presence of inserted ions can influence electrocatalytic activity. In this work, we utilized a materials chemistry approach to understand the role of proton insertion on the HER activity of layered tungsten oxide hydrates (WO 3 ∙xH 2 O, x = 1, 2). We synthesized a series of tungsten oxide hydrates along with an octylamine-pillared tungsten oxide (OA-WO 3 ). We used cyclic voltammetry to study the electrochemical reactivity of each material and performed ex situ X-ray diffraction and Raman spectroscopy to understand bulk and surface structural changes during electrochemical cycling. We show an inverse relationship between the degree of proton insertion and HER overpotential in tungsten oxides: the lack of proton insertion leads to a high overpotential for the HER. We discuss three hypotheses for how proton insertion leads to HER activity in WO 3 ∙xH 2 O: 1) proton insertion changes the electronic band structure of WO 3 ∙xH 2 O, 2) the presence of bulk protons can influence ΔG H,ads at the surface sites, and 3) inserted protons may participate in the HER mechanism on WO 3 ∙xH 2 O. Overall, this work shows the critical role of proton insertion in enabling high HER activity in tungsten oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State Products

Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.

microscopy↗

RIO Tinto Faulted Volcanosedimentary Deposits as Analog Habitats for Extant Subsurface Biospheres on Mars: A Synthesis of the MARTE Drilling Project Geobiology Results

Geochemistry and mineralogy on Mars surface characterized by the MER Opportunity Rover suggest that early Mars hosted acidic environments in the Meridiani Planum region [1, 2]. Such extreme paleoenvironments have been suggested to be a regional expression of the global Mars geological cycle that induced acidic conditions by sulfur complexation and iron buffering of aqueous solutions [3]. Under these assumptions, underground reservoirs of acidic brines and, thereby, putative acidic cryptobiospheres, may be expected. The MARTE project [4, 5] has performed a drilling campaign to search for acidic and anaerobic biospheres in R o Tinto basement [6] that may be analogs of these hypothetical communities occurring in cryptic habitats of Mars. This Rio Tinto geological region is characterized by the occurrence of huge metallic deposits of iron sulfides [7]. Late intensive diagenesis of rocks driven by a compressive regimen [8] largely reduced the porosity of rocks and induced a cortical thickening through thrusting and inverse faulting and folding. Such structures play an essential role in transporting and storing water underground as any other aquifers do in the Earth. Once the underground water reservoirs of the Ro Tinto basement contact the hydrothermal pyrite deposits, acidic brines are produced by the release of sulfates and iron through the oxidation of sulfides [9].

Fernandez-Remolar, D. C.↗

Synthesis of cerium precursors with alkoxide ligands for degradation to cerium oxide nanoparticles

Lanthanide oxide and sulfide nanoparticles present intriguing theoretical questions regarding their electronic structures, alongside numerous potential applications in material science and catalysis. Although these materials can be formed through hydrolysis, their synthesis via thermolysis is crucial for nanoscale materials and practical applications. This research aims to enhance our understanding of the decomposition mechanisms by focusing on cerium compounds, which are analogous to those studied previously. Currently, our knowledge of the decomposition mechanisms of cerium alkoxide precursors is limited. The objective of this project is to develop a mechanistic understanding of the formation of cerium oxide nanoparticles from cerium alkoxide precursors, employing a variety of techniques. These techniques include collision-induced dissociation in an ion-trap mass spectrometer, nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC), and gas chromatography-mass spectrometry (GC-MS) to investigate the decomposition mechanisms of the synthesized precursors.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Structure analysis of supported disordered molybdenum oxides using pair distribution function analysis and automated cluster modelling

Molybdenum oxides and sulfides on various low-cost high-surface-area supports are excellent catalysts for several industrially relevant reactions. The surface layer structure of these materials is, however, difficult to characterize due to small and disordered MoO x domains. Here, it is shown how X-ray total scattering can be applied to gain insights into the structure through differential pair distribution function (d-PDF) analysis, where the scattering signal from the support material is subtracted to obtain structural information on the supported structure. MoO x catalysts supported on alumina nanoparticles and on zeolites are investigated, and it is shown that the structure of the hydrated molybdenum oxide layer is closely related to that of disordered and polydisperse polyoxometalates. By analysing the PDFs with a large number of automatically generated cluster structures, which are constructed in an iterative manner from known polyoxometalate clusters, information is derived on the structural motifs in supported MoO x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Utilizing metal cation reactions with carbonyl sulfide to remove isobaric interferences in tandem inductively coupled plasma mass spectrometry analyses

Carbonyl sulfide (OCS) was used as a reaction gas to investigate gas phase metal (M + ) ion-molecule reactions using the Agilent 8900 inductively coupled plasma tandem mass spectrometer (ICP-MS/MS) to yield insight on how this gas may be used to remove isobaric interferences in analytical measurements. The experimental work was paired with density functional theory (DFT) calculations of the reaction enthalpy to predict whether M + will react with OCS. A multi-element standard containing 46 elements ranging from 9 to 208 u was analyzed in the presence and absence of OCS. When a reaction was observed, the dominant product was the sulfide (MS + ). Oxide products were also observed for many M + but formation was less efficient with OCS than previously observed with other reaction gases. This is likely due to the weaker OC-S bond that makes MS + formation more favorable. Increasing the flow rate from 0.1 to 0.2 mL/min (corresponding to a change in reaction gas pressure from 0.35 to 0.53 Pa (2.6 to 4.0 mTorr)) generally resulted in greater MS + production, including the secondary product MS 2 + for a few cations. The early lanthanide series ions (La + , Ce + , Pr + and Nd + ) produced greater quantities of MO + at the higher pressure, although MS + products were still the dominant product. The DFT-predicted reaction enthalpies were consistent with the observed sulfide formation, with an accuracy >90%; however, model predictions were less accurate for the minor and higher order products (< 77% for MO + ). Finally, the work presented here continues a systematic study of ion-molecule reactions in ICP-MS/MS to understand and develop new and novel ways to analyze complex mixtures with minimal pre-analysis treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distinguishing Indigenous from Contaminating Microorganisms in Rock Samples from a Deep Au Mine in South Africa

The concentration and distribution of microbial biomass within deep subsurface rock strata is not well known To date, most analyses are from water samples and a few cores. Hand samples, block samples and cores from an actively mined Carbon Leader ore zone at 3.2 kilometers depth were collected for microbial analyses. The Carbon Leader was comprised of quartz, S-bearing aromatic hydrocarbons, Fe(III) oxyhydroxides, sulfides, uraninite, Au and minor amounts of sulfate. The porosity of the ore was 1% and the maximum pore throat diameter was less than 0.1 microns; whereas, the porosity of the adjacent quartzite was .02 to .9% with a maximum pore throat diameter of 0.9 microns. Rhodamine dye, fluorescent microspheres, microbial enrichments, autoradiography, phospholipid fatty acid (PLEA) and 16S rDNA analyses were performed on these rock samples and the mining water. The date indicate that the levels of solute contamination less than 0.01% for pared rock samples. Despite this low level of contamination, PLEA, microbial enrichment, DNA and tracer analyses and calculations indicate that most of the viable microorganisms in the Carbon Leader represent gram negative aerobic heterotrophs and ammonia oxidizers that are phylogenetically identical or closely related to service water microorganisms. These microbial contaminants probably infiltrated the low permeability rock through mining-induced microfractures. Geochemical data also detected drilling water in a fault zone approx. 1 meter behind the rock face encountered during coring. The mining induced macrofractures that are common at these great depths act as pathways for the drilling water borne microorganisms into the lower temperature zone that extends several meters into rock strata from the rock face. Combined PLEA and T- RFLP analyses of the service water and Carbon Leader samples indicate that the concentration of indigenous microorganisms was less than 10(exp 2) cells/gram. Such a low concentrations result from the submicron pore throat diameters. PLFA. SO4-35 autoradiography and tracer analyses indicate that the bounding quartzite contains thermophilic sulfate reducing bacteria at 10(exp 3) cells/gram that are not attributable to drilling water contamination. The microorganisms may be surviving on sulfate generated by oxidation of sulfide by radiolytic reactions resulting from the high U concentration in the ore zone. The presence of up to 8,000 ppm of Fe(III) oxyhydroxides in the host rock will also act to recycle sulfide generated by the sulfate reducing bacteria into sulfate. The activity of these sulfate-reducing bacteria may be enhanced by mining induced fracturing which can propagate up to 40 meters into virgin rock where the temperatures are ca. 50 C, and decrepitate of sulfate rich fluid inclusions. In ultra deep mines, judicious application of tracers and multiple microbial characterization techniques can distinguish microbial contamination caused by the near field fracturing and drilling water migration from the indigenous microbial communities in rock strata. The importance of far field fracturing on indigenous microbial communities, however, remains unknown.

Onstott, T. C.↗