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Breakdown characteristics and conditioning of carbon and refractory metal electrodes

High voltage carbon and refractory metal electrodes employed in devices used in space, such as ion thrusters and traveling wave tubes, can be easily damaged by electrical breakdown and arcing events. Modification of the electrode surfaces due to these events can impact the voltage hold off capability of the surfaces, which could lead to additional arcing, further damage, and the potential for device failure. On the cathode-potential surface, the arc energy is deposited by all of the processes at the surface ultimately responsible for net electron emission, such as melting, vapor and particulate formation, sputtering, ion bombardment, etc. On the anode-potential surface, the energy is deposited from the plasma or electron stream that crosses the gap, which causes surface damage by local heating. In spite of this energy dependence on the damage, many systems that use arc discharges characterize the amount of material removed from the surfaces and the lifetime of the device for voltage hold-off by the amount of current that passes through the arc, or the 'Coulomb-rating'. The results of a series of tests that were preformed on the boltage hold off capability and damage to carbon-carbon composite surfaces and molybdenum surfaces due to induced arcing will be presented and discussed. Damage to the surfaces was characterized by the field emission performance after the arc initiation and SEM photographs for the different energy and coulomb-transfer arc conditions. Both conditioning and damage to the surfaces were observed, and will be related to the characteristics of the electrical breakdown.

high voltage breakdown↗

Systematic investigations on iron cycling in phosphorus/siderophore systems: Synergism or antagonism?

Synergisms between microbial exudates on Fe (hydr)oxide dissolution as an effective Fe acquisition pathway have been recently addressed and vigorously debated. However, Fe liberation mechanisms and where siderophores and phosphorus (P) coexist received little attentions. Current study systematically investigated ferrihydrite dissolution in the presence of desferrioxamine B (DFOB) (a kind of fungally-derived siderophores) and inorganic/organic phosphorus (orthophosphate, Pi; myo-inositol hexaphosphate, IHP), as a function of solute pH, reaction time and reagent content. Reacted solids were characterized by N 2 -BET adsorption, zeta (ζ) potential analysis, sequential extraction analysis (SEDEX), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), micro Raman spectroscopy and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). Our results indicate that upon reaction with P-only or (DFOB + P) systems, interfacial complexation partially switched from monolayer bidentate-binuclear surface complexes to ternary complexes, or laterally transformed into amorphous Fe–P precipitates. The Fe-Pi complex precipitated more readily under acidic conditions, and Fe-IHP complex preferentially nucleated in neutral-alkaline environments. Phosphorus slightly promoted Fe release from minerals and fixation to the leached layer or interfacial liquid zone initially, but subsequently prevented further attacks from protons and DFOB. The co-effects of P and DFOB likely correspond to two successive scenarios: 1) DFOB is preferentially attracted toward ferrihydrite surfaces by negative electrical fields induced by adsorbed phosphorus and can act synergistically with labile P–Fe complexes, resulting in intensive temporal dissolution of Fh; 2) subsequent Fe shuttling to DFOB can be prohibited by stabilized, passive P/Fe–P layers. Finally, our results emphasize the antagonism between P compounds and siderophores (i.e., DFOB here) on ferrihydrite dissolution to improve understanding of the biologically-mediated Fe cycling in natural systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA Tech Briefs, September 2005

Topivs include: Diamond-Coated Carbon Nanotubes for Efficient Field Emission; Improved Anode Coatings for Direct Methanol Fuel Cells; Advanced Ablative Insulators and Methods of Making Them; PETIs as High-Temperature Resin-Transfer-Molding Materials; Stable Polyimides for Terrestrial and Space Uses; Low-Density, Aerogel-Filled Thermal-Insulation Tiles; High-Performance Polymers Having Low Melt Viscosities; Nonflammable, Hydrophobic Aerogel Composites for Insulation; Front-Side Microstrip Line Feeding a Raised Antenna Patch; Medium-Frequency Pseudonoise Georadar; Facilitating Navigation Through Large Archives; Program for Weibull Analysis of Fatigue Data; Comprehensive Micromechanics-Analysis Code - Version 4.0; Component-Based Visualization System; Software for Engineering Simulations of a Spacecraft; LabVIEW Interface for PCI-SpaceWire Interface Card; Path Following with Slip Compensation for a Mars Rover; International Space Station Electric Power System Performance Code-SPACE; Software for Automation of Real-Time Agents, Version 2; Software for Optimizing Plans Involving Interdependent Goals; Computing Gravitational Fields of Finite-Sized Bodies; Custom Sky-Image Mosaics from NASA's Information Power Grid; ANTLR Tree Grammar Generator and Extensions; Generic Kalman Filter Software; Alignment Stage for a Cryogenic Dilatometer; Rugged Iris Mechanism; Treatments To Produce Stabilized Aluminum Mirrors for Cryogenic Uses; Making AlNx Tunnel Barriers Using a Low-Energy Nitrogen-Ion Beam; Making Wide-IF SIS Mixers with Suspended Metal-Beam Leads; Sol-Gel Glass Holographic Light-Shaping Diffusers; Automated Counting of Particles To Quantify Cleanliness; Phase Correction for GPS Antenna with Nonunique Phase Center; Compact Infrasonic Windscreen; Broadband External-Cavity Diode Laser; High-Efficiency Solar Cells Using Photonic-Bandgap Materials; Generating Solid Models from Topographical Data; Computationally Lightweight Air-Traffic-Control Simulation; Spool Valve for Switching Air Flows Between Two Beds; Partial Model of Insulator/ Insulator Contact Charging; Asymmetric Electrostatic Radiation Shielding for Spacecraft; and Reusable Hybrid Propellant Modules for Outer-Space Transport.

Source record↗

Use of LEED, Auger emission spectroscopy and field ion microscopy in microstructural studies

Surface research tools such as LEED, Auger emission spectroscopy analysis, and field ion microscopy are discussed. Examples of their use in studying adhesion, friction, wear, and lubrication presented. These tools have provided considerable insight into the basic nature of solid surface interactions. The transfer of metals from one surface to another at the atomic level has been observed and studied with each of these devices. The field ion microscope has been used to study polymer-metal interactions and Auger analysis to study the mechanism of polymer adhesion to metals. LEED and Auger analysis have identified surface segregation of alloying elements and indicated the influence of these elements in metallic adhesion. LEED and Auger analysis have assisted in adsorption studies in determining the structural arrangement and quantity of adsorbed species present in making an understanding of the influence of these species on adhesion possible. These devices are assisting in the furtherance of understanding of the fundamental mechanism involved in the adhesion, friction, wear, and lubrication processes.

Ferrante, J.↗

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↗

Novel Concepts for High Gradient Acceleration (Final Technical Report)

We have conducted an intensive, pioneering program to demonstrate novel concepts for achieving high gradient acceleration at frequencies from the conventional microwave bands up to the millimeter wave /THz bands. High gradient accelerators hold the promise of smaller and less costly accelerators for applications ranging from the largest scale accelerators used for discovery science down to the smallest accelerators used for industrial, homeland security and medical applications. The research consisted of two major research thrusts: 1.) Structure-based wakefield accelerator (SWFA) research in collaboration with the Argonne Wakefield Accelerator research group and 2.) Millimeter Wave / THz high gradient acceleration in collaboration with SLAC. The specific goals of the research program were: Design novel metallic metamaterial structures that increase the beam-wave coupling for the accelerator mode and reduce the effect of high order modes; test novel metamaterial structures to achieve higher output power, > 1 GW at X-Band (11.7 GHz), in test at the Argonne Wakefield Accelerator (AWA); determine the experimental breakdown threshold for nanosecond-scale pulses at X-Band in testing at the AWA; test a 110 GHz accelerator structure with a field emission electron gun, built at SLAC, using pulses from a 1 MW, 110 GHz gyrotron; design, build and test a 110 GHz quasi-optical, resonant-ring pulse compressor to compress microsecond pulses from the 1 MW gyrotron into > 20 MW, 5 ns output pulses for accelerator structure testing. The proposed research program built on our successes in our research program including: Generation of 510 MW, 2.1 ns (FWHM) pulses at 11.7 GHz from a metallic metamaterial structure in test at the Argonne Wakefield Accelerator using a train of eight 65 MeV electron bunches spaced at 1.3 GHz with a total charge of 280 nC. The metamaterial structure consisted of 100 copper unit cells each consisting of a “wagon-wheel” plate and a spacer plate with a total structure length of 0.2 m. The 510 MW pulse generated an on-axis wakefield of 130 MV/m that could be used to accelerate a trailing witness bunch. Demonstration of coupling of an unprecedented rf power level of 575kW into a 110 GHz accelerator structure using a quasi-optical setup. The standing structure consisted of a central copper cavity located between two matching cavities fed by a TM01 mode. The 6 ns input pulses were sliced from 3 microsecond pulses from the gyrotron using a laser-driven silicon switch. We obtained an unprecedented high gradient up to 230MV/m corresponding to a peak surface electric field of more than 520 MV/m.

43 PARTICLE ACCELERATORS↗

Fast and Scalable Synthesis of LiNi 0.5 Mn 1.5 O 4 Cathode by Sol–Gel-Assisted Microwave Sintering

High-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) is a promising cathode material for high-energy-density and high-power-density lithium-ion batteries (LIBs). The high cost of the currently available LIBs needs to be addressed urgently for wide application in the transport sector (electric vehicles, buses) and large-scale energy storage systems (ESS). Of significance, herein, novel fast and scalable microwave-assisted synthesis of LNMO is reported, which leads to a production cost cut. X-ray diffraction (XRD) analysis confirms the formation of the desired phase with high crystallinity. Field emission scanning (FE-SEM) and transmission electron microscopy (TEM) analyses indicate that the synthesized phase is of nanometric size (50–150 nm) due to an extremely short sintering time (20 min). The material synthesized at 750 °C shows a higher initial discharge capacity (130 mA h g -1 ) than that synthesized at 650 °C (115 mA h g -1 ). The materials heat treated at higher temperatures show better electrochemical performance in terms of initial capacity, rate capability, and improved cycling. The improved electrochemical performance of LNMO at 750 °C is attributed to the formation of a stable crystal structure, low charge transfer resistance at the electrode/electrolyte interface, high electrical conductivity due to the presence of a disorder structure, and improved ionic diffusivity.

25 ENERGY STORAGE↗

Corrosion evaluation of Ti–6Al–4V manufactured by electron beam melting in Ringer’s physiological solution: an in vitro study of the passive film

We report that electrochemical characteristics and semiconducting behavior of additively manufactured electron beam melted (EBM) and wrought (WR) Ti–6Al–4V (Ti-G5) are compared in Ringer’s physiological solution. X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) confirmed the α+β structure of the tested materials, with two different microstructure types of “bimodal” and “basket-weave” for WR and EBM, respectively. Potentiodynamic polarization (PDP) revealed that the corrosion current density for EBM (i corr =0.27±0.06 μA cm -2 ) is less than the WR (i corr =0.70±0.05 μA cm -2 ). Moreover, potentiostatic polarization (PS) that was employed to form the passive layers at three different potentials of 300, 500, and 700 mV Ag/AgCl , showed that the passive films on the EBM sample are thinner. This finding was confirmed by electrochemical impedance spectroscopy (EIS). Furthermore, through Mott–Schottky (M–S) analysis, donor densities on WR passive films were found to be ~1.5 times larger than EBM. Although PS and EIS confirmed that the passive layer on EBM is thinner, it provides higher corrosion resistance than WR. The passive layer on both samples were found to have n-type characteristics with a duplex structure.

36 MATERIALS SCIENCE↗

Electron beam irradiation effects on bulk metals: a comparative study of polycrystalline versus single-crystalline structures

This study investigates the effects of electron beam (e-beam) irradiation on the mechanical and structural properties of eight bulk metallic samples, comprising both polycrystalline (PC) and single-crystalline (SC) forms of Ni, Cr, V, and Ti. These metals were evaluated as potential candidates for beam exit windows in high-power (MW-class) particle accelerators. The primary objective is to identify metals capable of withstanding the conditions of high-power/MW-class e-beam accelerators and serve effectively as exit windows. Selection criteria were based on each metal’s intrinsic properties, power dissipation capability, and irradiation-induced changes in mechanical behavior, including hardness, elastic modulus, and defect density. Comprehensive characterization was conducted using field-emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM–EDS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and nanoindentation, performed both before and after exposure to a ~¿66 kGy dose from a 10 MeV e-beam accelerator. Results revealed that e-beam irradiation induced hardening in PC Ni, whereas PC Ti, commonly used in beam exit windows, exhibited softening. The observed softening in PC Ti is attributed to grain coarsening, elongation, and the formation of twins and twin boundaries, in contrast to the smaller, compressed grains in the pristine (Pr) PC Ti samples, consistent with the Hall–Petch relationship. The stresses due to twinning are small and insignificant in influencing the overall hardening of the PC Ti irradiated sample when compared to the stresses due to the dislocation density. Conversely, SC Ti samples exhibited irradiation-induced hardening. The SC Ti irradiated samples developed additional irradiation-induced modifications in crystallographic texture of (100), (101), (110), (200), (112), (004), and (211) as evidenced from the XRD results, which could probably explain the hardening effect that is caused by irradiation.

36 MATERIALS SCIENCE↗

High performance graphene-like thinly layered graphite based visible light photodetector

In this work, the drop casting method is utilized to obtain a thin graphene-like graphite layer as a photodetection layer on a SiO{sub 2}/Si substrate, and its performance is characterized to determine its potential use in commercial applications. The thin layer is formed by first synthesizing graphite soot from a butane flame before being turned into a liquid solution and drop-casted onto the substrate to form a thin graphene-like graphite film. Field emission scanning electron microscope and Raman vibrational mode analyses indicate that the fabricated graphene-like graphite layer has characteristics similar to the graphene. The graphene-like graphite photodetector demonstrates a narrow photoresponse from 530 to 680 nm, covering visible sources from green to red. The responsivity and external quantum efficiency of the device under the illumination of red laser 660 nm is found to be around 148 mA W{sup −1} and 27.8% respectively and is faster than that reported for similar systems using graphene and reduced graphene oxide previously. A fast response time of 83.7 and 28 µs at a modulation frequency of 1.0 and 10000 Hz respectively from the graphene-like thinly layered graphite photodetector shows potential application for the development of low-cost carbon-based photodetectors in near future.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Statistical fracture behavior of doped UO 2 using a ball-on-ring equibiaxial flexure test method

Metal oxide dopants, such as titanium and chromium oxides, have garnered considerable attention for their potential to increase grain size (≥ 30 µm) in UO 2 fuel, purportedly enhancing fission gas retention during reactor operation. Fuel performance is significantly impacted by fuel fracture behavior, so it is important to understand the effects of enhanced grain size and dopant content on UO 2 fuel fracture. UO 2 pellets were doped with 0.1 wt% TiO 2 and 0.3 wt% Cr 2 O 3 to alter density and grain size. Inductively coupled plasma mass spectroscopy measured dopant levels pre- and post-sintering. X-ray diffraction revealed lattice changes and microstrain via Rietveld refinement. Field emission scanning electron microscopy determined grain sizes of approximately 30 µm for TiO 2 doping and 7 µm for Cr 2 O 3 doping. Transverse rupture strength tests were performed on over 30 samples per dataset to obtain characteristic strength and Weibull modulus. Results indicate no statistical difference in fracture strength between 0.1 wt% TiO 2 doped UO 2 and undoped UO 2 , while 0.3 wt% Cr 2 O 3 doped UO 2 exhibited a 20% decrease in fracture strength. Doped UO 2 samples also showed reduced Weibull modulus compared to undoped UO 2 , suggesting increased scatter in fracture strength. This study's findings suggest that titanium and chromium oxide doping in UO 2 , regardless of grain size, induce residual stresses, decreasing fracture strength and increasing variability in fracture behavior.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Degradation of a Cr-Mo steel by carbide precipitation over long-term service

Microstructure of the 40-year service-exposed 1Cr-0.5Mo steel extracted from pressure vessels through the boat sampling technique was characterized using x-ray diffraction, field-emission scanning electron microscopy, energy dispersive spectrometry, electron backscatter diffraction, focused ion beam, and transmission electron microscopy. The microstructure degradation during long-term service was identified. Statistical crystal plastic ity models were developed to correlate the microstructure and mechanical properties quantitatively. The steel is found significantly strengthened but slightly embrittled. Nanoscale Mo 2 C carbides have nucleated within the ferrite matrix over the long-term service, resulting in significant strengthening of the matrix. The coarser grain boundary Cr 23 C 6 carbides, on the other hand, act as the damage accumulation sites and lead to the degradation.

36 MATERIALS SCIENCE↗

Development of an in situ ion irradiation scanning electron microscope

An in situ ion irradiation scanning electron microscope (I 3 SEM) has been developed, installed, and integrated into the Ion Beam Laboratory at Sandia National Laboratories. The I 3 SEM facility combines a field emission, variable pressure, scanning electron microscope, a 6 MV tandem accelerator, high flux low energy ion source, an 808 nm-wavelength laser, and multiple stages to control the thermal and mechanical state of the sample observed. The facility advances real-time understanding of materials evolution under combined environments at the mesoscale. As highlighted in multiple examples, this unique combination of tools is optimized for studying mesoscale material response in overlapping extreme environments, allowing for simultaneous ion irradiation, implantation, laser bombardment, conductive heating, cooling, and mechanical deformation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Characterizing mineralization on low carbon steel exposed to aerated and degassed synthetic hydraulic fracture fluids

This study investigates the mineralization occurring at the interface between injected hydraulic fracturing fluids and steel production casing during the shut-in period of unconventional shale wells. Mild steel coupons were reacted with synthetic hydraulic fracturing fluids with varying base fluid and dissolved gas concentrations. Experiments were carried out in an autoclave system set at 50 °C and 2000 PSI for 2 and 14 days. Physical and mineralogical changes to the steel coupons’ surface were characterized using an FEI Quanta 600 field emission gun (FEG) scanning electron microscope (SEM) and a PANalytical XPert Pro diffractometer. Barite precipitation occurred ubiquitously during the first 48 hours in all experimental scenarios. Sulfate radicals created from degradation and reduction of ammonium persulfate breakers facilitate barite formation. Concomitant barite and corrosion related precipitates on the sample surfaces suggest iron hydroxy salts act as nucleation sites for mineral scale growth. These results suggest hydraulic fracturing fluids may have deleterious effects on the wellbore before production of the well begins.

36 MATERIALS SCIENCE↗

Geochemical and Microstructural Characterization of Shale Rock: A Workflow for Site Evaluation for Energy–Fluids Storage

Shales are a central component of petroleum systems, as source, seal, and unconventional reservoir rocks. Unlike traditional unconventional shale, a newly emerging Caney Shale play is regarded as an unconventional of unconventional shales (UUS), due to its high content of fine-grained materials, lower reservoir porosity, dominance of nanopores, and a scarcity of visible natural fractures. Other developed unconventional shales such as the Woodford and Barnett have larger average pore size, higher porosity, and extensive natural fractures at core scale that contribute to reservoir quality. In this work, the Caney Shale was cored in entirety to characterize its interbedded ductile and reservoir intervals and establish criteria for their recognition. Representative ductile and reservoir intervals known as D2 and R3, respectively, were selected for detailed analysis including variations in elemental composition, mineralogy, facies, and the presence of natural fractures at well and core scales using X-ray fluorescence, X-ray diffraction, and thin section and core description. Characteristics of microstructure and microgeochemistry at nano- and microscales are compared using field emission scanning electron microscopy with energy dispersive spectroscopy and lowpressure nitrogen adsorption isotherms with fractal dimension analysis. The ductile (detrital clay-rich) member D2 is characterized by higher concentrations of Ti and Al and lower Si, while the reservoir R3 (possibly biogenic silica-accumulated) is characterized by lower Ti and Al and higher Si. Eight mixed carbonate–siliciclastic facies are recognized, and R3 shows a higher heterogeneity of facies stacking and average fracture abundance than D2. Further, R3 shows a more microscopically heterogeneous fabric/texture of matrix and a higher microporosity than D2 that has a higher pore surface heterogeneity. A fundamental understanding of the compositional and microstructural characteristics of UUS and further ductile/reservoir intervals will allow for a better assessment of reservoir quality, more effective production of hydrocarbons, and optimized selection of safe caprocks in carbon sequestration and subsurface hydrogen storage.

58 GEOSCIENCES↗

Directional Gateway to Metal Oxidation: 3D Chemical Mapping Unfolds Oxygen Diffusional Pathways in Rhodium Nanoparticles

The interaction of oxygen with a reactive metal is ubiquitous, yet the precise atomic-level mechanisms and pathways leading to the formation of a surface oxide are not well-understood. We report oxygen atom distributions inside Rh single nanoparticles using atom probe microscopy (APM) and demonstrate that mainly facets of the ?022¯? crystallographic directions act as oxygen-permeable gateways. The highly anisotropic spatial distribution of incorporated oxygen atoms is in agreement with video-field emission analyses according to which {113} facets of the ?022¯? zones act as portals for subsurface diffusion. In addition to providing a more fundamental understanding of the precursor states to metal corrosion, in particular for the case of nanosized metal particles, our studies are also relevant for heterogeneous catalysis where catalytic activity and selectivity conform to reaction-induced structural changes of metal nanoparticles.

Lambeets, Sten V M.↗

Iridium-Doped Nanosized Zn–Al Layered Double Hydroxides as Efficient Water Oxidation Catalysts

Layered double hydroxides (LDHs) are an ideal platform to host catalytic metal centers for water oxidation (WO) owing to the high accessibility of water to the interlayer region, which makes all centers potentially reachable and activated. In this paper, we report the syntheses of three iridium-doped zinc–aluminum LDHs (Ir-LDHs) nanomaterials (1–3, with about 80 nm of planar size and a thickness of 8 nm as derived by field emission scanning electron microscopy and powder X-ray diffraction studies, respectively), carried out in the confined aqueous environment of reverse micelles, through a very simple and versatile procedure. These materials exhibit excellent catalytic performances in WO driven by NaIO 4 at neutral pH and 25 °C, with an iridium content as low as 0.5 mol % (~0.8 wt %), leading to quantitative oxygen yields (based on utilized NaIO 4 , turnover number up to ~10,000). Nanomaterials 1–3 display the highest ever reported turnover frequency values (up to 402 min –1 ) for any heterogeneous and heterogenized catalyst, comparable only to those of the most efficient molecular iridium catalysts, tested under similar reaction conditions. The boost in activity can be traced to the increased surface area and pore volume (>5 times and 1 order of magnitude, respectively, higher than those of micrometric materials of size 0.3–1 μm) estimated for the nanosized particles, which guarantee higher noble metal accessibility. X-ray absorption spectroscopy (XAS) studies suggest that 1–3 nanomaterials, as-prepared and after catalysis, contain a mixture of isolated, single octahedral Ir(III) sites, with no evidence of Ir–Ir scattering from second-nearest neighbors, excluding the presence of IrO 2 nanoparticles. The combination of the results obtained from XAS, elemental analysis, and ionic chromatography strongly suggests that iridium is embedded in the brucite-like structure of LDHs, having four hydroxyls and two chlorides as first neighbors. These results demonstrate that nanometric LDHs can be successfully exploited to engineer efficient WOCs, minimizing the amount of iridium used, consistent with the principle of the noble-metal atom economy.

36 MATERIALS SCIENCE↗