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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Surface Pressure Fluctuations Induced by a Hypersonic Turbulent Boundary Layer on a Sharp Cone at Angle of Attack

High-fidelity simulations are performed to characterize the turbulence-induced wall pressure fluctuations on a sharp cone at a 5.5° angle-of-attack in a Mach 8 flow. Wall-resolved large-eddy simulation (LES) and wall-modeled large-eddy simulation (WMLES) results are compared to measurements at several locations on the cone body, where comparisons with high-frequency PCB sensors are good, while comparison with low-frequency kulite sensors varies depending on the location. For a given streamwise location, simulation results show significant azimuthal variation in the wall pressure fluctuation statistics. Comparisons between LES and WMLES results indicate that WMLES can accurately reproduce the low-frequency component of the autospectra quite well, while slight sensitivity is apparent in the coherence. A grid sensitivity study for WMLES further demonstrated sensitivity in the wall pressure fluctuation coherence, but not in the autospectra.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Using SWMM for emergency response planning: A case study evaluating biological agent transport under various rainfall scenarios and urban surfaces

To assist in emergency preparedness for a biological agent terrorist attack or accidental pathogen release, potential contaminant levels and migration pathways of spores spread by urban stormwater were evaluated using a Storm Water Management Model (SWMM) of U.S. Coast Guard Base Elizabeth City, North Carolina. The high temporal-spatial resolution SWMM model was built using spore concentrations in stormwater runoff from asphalt, grass, and concrete collected from a point-scale field study. The subsequent modeled contamination scenarios included a notional plume release and point releases mimicking the field study under three rainfall conditions. The rainfall scenarios included a 6-hour natural rainfall event on Dec. 8, 2021 and two design storms (2-year and 100-year events). The observed spore concentrations from asphalt and concrete from the actual field experiment were applied to calibrate the washoff parameters in the SWMM model, using an exponential washoff function. The calibrated washoff coefficient (c 1 ) and exponent (c 2 ) were 0.01 and 1.00 for asphalt, 0.05 and 1.45 for grass, and 2.45 and 1.00 for concrete, respectively. The calibrated SWMM model simulated spore concentrations in runoff at times and magnitudes similar to the field study data. In the point release modeled scenario, the concrete surface generated 55.6% higher average spore concentrations than asphalt. Similarly, in the field experiment, a 175% (p < 0.05) higher average spore concentration in surface runoff was observed from concrete than from asphalt. Here, this study demonstrates how SWMM may be used to evaluate spore washoff from urban surfaces under different precipitation amounts, intensities, and durations, and how visualized spatial migration pathways in stormwater runoff may be used for emergency planning and remediation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Pit Stability Predictions of Additively Manufactured SS316 Surfaces Using Finite Element Analysis

Stainless steels are susceptible to localized forms of corrosion attack, such as pitting. The size and lifetime of a nucleated pit can vary, depending on a critical potential or current density criterion, which determines if the pit repassivates or continues growing. This work uses finite element method (FEM) modeling to compare the critical pit radii predicted by thermodynamic and kinetic repassivation criteria. Experimental electrochemical boundary conditions are used to capture the active pit kinetics. Geometric and environmental parameters, such as the pit shape and size (analogous to additively manufactured lack-of-fusion pores), solution concentration, and water layer thickness were considered to assess their impact on the pit repassivation criterion. The critical pit radius (the transition point from stable growth to repassivation) predicted for a hemispherical pit was larger when using the repassivation potential (E rp ) criteria, as opposed to the current density criteria (pit stability product). Including both the pit stability product and E rp into its calculations, the analytical maximum pit model predicted a critical radius two times more conservative than the FEA approach, under the conditions studied herein. The complex pits representing lack-of-fusion pores were shown to have minimal impact on the critical radius in atmospheric conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

High-Order Wall-Modeled Large-Eddy Simulation of High-Lift Configuration

This paper presents the assessment of several recent enhancements for a high-order wall-modeled large-eddy simulation (WMLES) approach and demonstrates order independence with a fixed data exchange location in the wall model. The two enhancements include the use of isotropic tetrahedral elements to improve accuracy and an explicit subgrid-scale model, the Vreman model, to improve accuracy and robustness. The [Formula: see text] study focused on the high-lift Common Research Model (HL-CRM) at the angle of attack of 19.57 deg, a benchmark problem from the 4th AIAA High-Lift Prediction Workshop. Solution polynomial orders of [Formula: see text], and 5 were used in the study. The study demonstrated [Formula: see text] independence in integrated forces, pitch moment, velocity profile in the wall-normal direction, and surface flow topology. It also showed that a [Formula: see text] order of at least 3 ([Formula: see text]) was needed to correctly predict the external inviscid flow and the surface flow topology. Thereafter, [Formula: see text] simulations over several other angles of attack demonstrated that the high-order WMLES approach can correctly predict the maximum lift and flow separation regions for HL-CRM with about 40 million degrees of freedom (DOF) compared to at least 250 million DOF required by second-order methods.

Engineering↗
DOE OSTI2021

Mechanistic Similarities and Differences for Hydrogenation of Aromatic Heterocycles and Aliphatic Carbonyls on Sulfided Ru Nanoparticles

This study establishes the contrasting reactivity trends for the hydrogenation of aromatic hydrocarbons (AHCs = C n H m X, X = N, S, O, and C) and aliphatic carbonyls [R a C(O)R b ; R a = alkyl group, R b = CH 3 or H] on sulfided Ru clusters arising from the difference in the elementary proton and hydride attack catalytic sequence. Both reactions require sequential additions of a proton from either Ru n+ –(SH 2 ) or S 2 –(H δ+ ) species and a hydride from Ru n+ –(H δ– ) species to the unsaturated C=X bonds. For the five-membered-ring aromatic heterocycles (AHCs = pyrrole, thiophene, and furan), an initial proton addition limits the catalytic turnovers; thus, their hydrogenation reactivity increases with increasing gas-phase proton affinities of the AHCs. Pyridine as the more basic six-membered N-AHC is more susceptible to protonation; therefore, it is more reactive, and its initial proton addition is quasi-equilibrated, followed by the kinetically relevant hydride addition. Conversely, aliphatic carbonyls prefer to undergo hydrogen additions in a reverse sequence, where a Ru n+ –(H δ– ) hydride initially attacks the electron-deficient carbonyl C atom as the kinetically relevant step before a subsequent rapid S 2 –(H δ+ ) proton addition on the electron-rich O atom, as confirmed by isotopic exchange studies with butanal-D 2 and 1-butanol-D 2 mixtures and density functional theory calculations on S-deficient RuS 2 (100) surfaces. For these reasons, their hydrogenation reactivity increases with increasing gas-phase hydride affinities of the carbonyls. On metallic Ru surfaces without sulfur, hydrogen adatoms (H*) are the only reactive hydrogen species; the reactivity of their attack on aromatic heterocycles increases with increasing reactant proton affinities much more sensitively than that on sulfided Ru surfaces. This work illustrates the distinct catalytic roles of the diverse hydrogen species in hydrogenation—the interplay between proton and hydride additions has marked catalytic consequences in shaping the free energy landscape of the reactions, which in turn leads to the observed kinetic dependences, kinetic parameters, reactivity trends, and scaling relations between the measured barriers and the appropriate kinetic descriptors, that is, proton affinity of AHCs and hydride affinity of carbonyls in hydrogenation catalysis. Here, these mechanistic similarities and differences provide explanations of the observed reactivity trends and thus have profound implications for industrial hydrogenation and hydrotreating catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Progression to Compatibility Evaluations in Flowing Molten Salts

Molten salt compatibility with structural alloys has been identified as a key issue for the development of Generation 3 concentrating solar power (CSP) systems with thermal storage. To accelerate this evaluation to pumped systems, the goal of this project was to conduct thermal convection loop (TCL) experiments with a peak temperature of ≥700°C and a typical temperature gradient of ~100°C. The experiments indicated that conventional ~16wt.%Cr Ni-based alloys are compatible up to 700°C with purified (i.e. low O) or dried (low H₂O) industrial-sourced Mg-K-Na chloride salt with <10 μm/yr loss. This two-year project was conducted based on the experimental and mechanistic understanding developed more than 60 years ago at Oak Ridge National Laboratory (ORNL). The first TCL experiment met the <15 μm/yr corrosion metric for this project with specimens of Ni-based alloy 600 exposed at 580°-700°C for 1000 h and post-exposure room temperature tensile tests showed minimal degradation. The second TCL experiment successfully deployed an electrochemical sensor from Argonne National Laboratory and had a peak temperature of 750°C but only ran for ~110 h due to a furnace failure. Both experiments used highly purified industrial-sourced salt with an O content of ~3 μg O/g salt and a Mg addition of 0.04 wt.%. In the second year, the Chloride Collective developed a more economical drying procedure such that the O content was much higher (>20,000 μg O/g salt). A third TCL experiment was conducted with a sensor and a peak temperature of 700°C using dried salt from the same industrial source and increased NaCl content (~20 wt.%). In addition to a 0.05% Mg addition to the salt, a Mg coupon was added in the coldest part of the loop which dissolved during the experiment. Again, small mass changes were noted for specimens of alloys 600 and C276 but the values were slightly higher than those measured in purified salt with Mg. A thin non-continuous and non-adherent oxide layer was deposited on most specimens containing Mg, Si and Al but Cr depletion also was observed. Both years included facilities qualification crucible experiments and then capsule experiments to confirm a baseline isothermal reaction rate. The first year capsule experiment led to the conclusion that the two-stage ORNL purification process using NH₄Cl and CCl₄ left the salt with a high Cl potential and a Mg addition (~0.05wt.%) was needed to lower the potential. The second year capsule experiments at 600° and 700°C found little difference in depth of attack for 0-0.25%Mg additions. In general, the complex reactions where salt can be trapped in the porous surface layer of metal indicated that mass change is an unreliable metric and average depth of Cr depletion is a better metric for assessing the extent of attack. These results have created a new baseline that is contrary to the recent published literature for chloride salts where mass losses have been reported that can be extrapolated to very significant annual metal loss rates. Chloride salt corrosion can be controlled and the results also indicate that salt purification to low O levels may not be necessary. However, additional TCL experiments are needed at different times and temperatures to generate important engineering information such as temperature dependent corrosion rates and reaction rate laws for extrapolation to long-term behavior and isolate the effect of salt additives and impurities.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Corrosion characteristics of Mo and TZM alloy for plasma facing components in molten lithium at 623 K

Here, in this study, the corrosion behaviours of molybdenum (Mo) and a Mo-based alloy (TZM) were investigated using a static immersion corrosion technique. Weight loss, surface microstructure, and corrosion depth of Mo and the TZM alloy were correlated with elements. The compatibility of Mo and the TZM alloy in static liquid Li was suitable. Mo demonstrated uniform corrosion with a homogenous dissolution of free C and Mo, and TZM alloy exhibited a nonuniform corrosion behaviour with a preferential grain boundary attack caused by the selective dissolution of free C, Ti, and Zr. When the surface oxidation layer of the samples was consumed, free C from Mo and TZM diffused into molten Li to form Li 2 C 2 and then was captured by Zr, Ti, and Mo to form thermodynamically stable carbides, which resulted in the enrichment of the C layer near the sample surfaces. In addition, Ti and Zr acted as N-trappers in liquid Li; the formation of Zr and Ti nitrides resulted in the enrichment of N, Ti, and Zr elements on the surface and led to TZM corrosion increase. Thus, Zr and Ti depletion, pitting, and grain boundary corrosion were problematic for TZM under long-term exposure to liquid Li. Reducing the content of free C and nonmetallic N and increasing the amount of Ti and Zr carbides on the surface of and inside the raw TZM alloy helped improve the corrosion resistance of TZM in liquid Li.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Influence of native oxide film on corrosion behavior of additively manufactured stainless steel 316L

The influence of the native oxide film on passive film properties and localized corrosion of additively manufactured SS 316L was studied in 1 wt% HCl by XPS characterization, electrochemical polarization curves, and post-test morphology analysis by SEM. Increased Cr oxidation kinetics was observed in the as-polished sample with the native oxide film resulting in formation of an overall more protective and compact film compared to the cathodically-activated sample. Electrochemical analysis showed that corrosive attack varied between dislocation cell boundaries to cell interiors depending on the initial surface state and polarization conditions. In conclusion, a corrosion mechanism is proposed to explain this variation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A co-opted steroid synthesis gene, maintained in sorghum but not maize, is associated with a divergence in leaf wax chemistry

Significance Virtually all above-ground plant surfaces, such as leaf and stem exteriors, are covered in a cuticle: a wax-infused polyester. This waxy biocomposite is the largest interface between Earth’s biosphere and atmosphere. Its chemical composition is not only highly tuned to mediate nonstomatal water loss, but it also self-assembles to produce superhydrophobic surfaces, protects against UV radiation, and contains bioactive compounds that help resist microbial attack. Developing fundamental knowledge of waxy biocomposites, particularly those on crop species, is a prerequisite for an understanding of their structure–function relationships. Here, we uncover a likely genetic basis for the presence and absence, respectively, of triterpenoids in the leaf waxes of sorghum and maize—compounds previously associated with creating heat-tolerant cuticular water barriers.

09 BIOMASS FUELS↗
DOE OSTI2022

Influence of copper and aluminum substitution on high-temperature oxidation of the FeCoCrNiMn “Cantor” alloy

In this study, the oxidation behavior of FeCoCrNiMn (HEA + Mn) is compared to three modified HEAs manufactured by substituting Mn with Al, Cu, or Al + Cu. Oxidation tests were conducted between 600°C and 800°C for up to 500 h in synthetic air. Substitution of Mn leads to a significant improvement in the oxidation resistance for the three modified HEAs. For FeCoCrNiCu (HEA + Cu), a local attack of a Cu-rich phase was observed, leading to the formation of CuO blisters on the surface. The FeCoCrNiAl (HEA + Al) alloy was characterized by the formation of a thin Al 2 O 3 surface layer for all temperatures. However, for the HEA + Al alloy the formation of AlN was observed after 300 h at 800°C, leading to a partial breakdown of the protective scale. FeCoCrNiCuAl (HEA + Cu + Al) by far showed the best oxidation resistance, characterized by the formation of a highly protective Al 2 O 3 scale that effectively inhibited nitrogen penetration into the metal subsurface and local attack of the Cu-rich phase.

36 MATERIALS SCIENCE↗
DOE OSTI2024

PRISTINE: An Emulation Platform for PCB-Level Hardware Trojans

Printed circuit Boards (PCBs) are becoming increasingly vulnerable to malicious design alteration, also known as Trojan attacks, due to a distributed business model that often involves various untrusted parties. Such attacks can be mounted at various stages in the PCB life cycle. The relative ease of alteration of PCB hardware even after fabrication (due to physical access to surface-mounted critical components and traces) makes them attractive for an adversary to manipulate their functional/physical behavior for malicious intent. There is a growing need to explore viable Trojan attacks in a PCB, analyze their functional and physical characteristics (e.g., impact on power or delay), and study the effectiveness of countermeasures against these attacks. While simulation-based approaches for PCB Trojan insertion are effective at creating a large population of possible Trojans, they fail to provide functional feasibility analysis with a realistic workload for a trigger circuit. Also, they cannot estimate a Trojan’s side-channel footprint due to the unavailability of physical models of diverse PCB components. To address these deficiencies, in this paper, we present PRISTINE, a PCB-level emulation system for any integrity or physical tampering issues, specifically, hardware Trojan insertion. The need for building such an emulation platform to resolve PCB trust issues in the supply chain is also surveyed and discussed. Both custom Hardware Hacking (HaHa) boards and multiple commercial PCBs are then used to test the ability of the proposed system to emulate various hardware Trojans specially designed to exploit board-specific hardware characteristics. Experimental results on emulated board-level Trojans show that a wide range of Trojans can be successfully activated, thus enabling the expected payload effects on both types of boards to be studied and quantified. The resulting data are further analyzed to create PCB-level Trojan benchmarks. In particular, a comparative evaluation of the experimental results is used to propose a risk level metric that quantifies the probability of detection and degree of payload impact of each Trojan on a given commercial PCB.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Understanding the mechanisms of anisotropic dissolution in metal oxides by applying radiolysis simulations to liquid-phase TEM

Iron-based redox-active minerals are ubiquitous in soils, sediments, and aquatic systems. Their dissolution is of great importance for microbial impacts on carbon cycling and the biogeochemistry of the lithosphere and hydrosphere. Despite its widespread significance and extensive prior study, the atomic-to-nanoscale mechanisms of dissolution remain poorly understood, particularly the interplay between acidic and reductive processes. Here, we use in situ liquid-phase-transmission electron microscopy (LP-TEM) and simulations of radiolysis to probe and control acidic versus reductive dissolution of akaganeite (β–FeOOH) nanorods. Informed by crystal structure and surface chemistry, the balance between acidic dissolution at rod tips and reductive dissolution at rod sides was systematically varied using pH buffers, background chloride anions, and electron beam dose. We find that buffers, such as bis-tris, effectively inhibited dissolution by consuming radiolytic acidic and reducing species such as superoxides and aqueous electrons. In contrast, chloride anions simultaneously suppressed dissolution at rod tips by stabilizing structural elements while promoting dissolution at rod sides through surface complexation. Dissolution behaviors were systematically varied by shifting the balance between acidic and reductive attacks. The findings show LP-TEM combined with simulations of radiolysis effects can provide a unique and versatile platform for quantitatively investigating dissolution mechanisms, with implications for understanding metal cycling in natural environments and the development of tailored nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Water Energy Resource Innovation on the Cavitation Characteristics

The main purpose of this study is to numerically correlate the amount of generated vapor over a hydrofoil to the lift and drag coefficients acting on it. As such, cavitation characteristics were investigated of a hydrofoil in the cavitating, sub-cavitating, and non-cavitating flows for different angles of attacks (AoA) with the high upstream flow velocity. The hydrofoil was tested in a square water tunnel with water entering the tunnel at various velocities for each AoA ranges from 9.1 m/s to 12.2 m/s. It was found that lift and drag forces acting on the hydrofoil follow the trend of the experimental data quite closely. While the cavitation can be identified by a unique number (averaged vapor volume fraction), the work done created an inverse correlation between this number and the cavitation number at the same angle of attack. The lift force declines with the increase in the vapor content on the hydrofoil surface, meanwhile the drag force peaks at certain vapor volume fraction, and then, a huge reduction occurs with the considerable decrease in the corresponding cavitation number. A fourth-order correlation generated between the lift to drag (L/D) and the cavitation number (σ). It was found the lift-to-drag ratio decreases by the formation of the cavitation over the hydrofoil, thus causing a drop in the efficiency of the turbomachines.

42 ENGINEERING↗
DOE OSTI2025

Developing Machine Learning Interatomic Potential for Fe-Cr-Ni Alloys

Accurate prediction of creep and fatigue behavior of stainless steel at elevated temperatures in hydrogen environment requires fundamental understanding of alloy-hydrogen interaction at cross-scale including bulk lattice and key defects such as vacancies, grain boundaries, surfaces, stacking faults, dislocations, and precipitates. This project aims to predict creep behavior of 347H stainless steel with H using machine learning interatomic potentials based on first-principles density functional theory simulations. The Moment Tensor Potentials platform is adopted for this work since it demonstrates a fine balance between model accuracy and computational efficiency. The potential is well trained based on large amount of high-fidelity density functional theory calculations. The validation is carried out by comparing various important properties including short range order, coefficient of thermal expansion, elastic properties, stacking fault energy, grain boundary energy, and surface energy. This work lays the foundation for reliable atomistic simulation of high temperature hydrogen attack of stainless steel.

density functional theory (DFT)↗
DOE OSTI2023

Evolution of the Cellulose Microfibril through Gamma-Valerolactone-Assisted Co-Solvent and Enzymatic Hydrolysis

Biomass recalcitrance during deconstruction remains a key bottleneck to affordable biomass processing technologies. A clear connection between the cell wall structure and biomass deconstruction is necessary to understand how lignocellulosic material is broken down to valuable monomeric components. Here, we monitor changes in the cellulose microfibril domains of poplar, sorghum, and switchgrass throughout gamma-valerolactone (GVL)–water co-solvent pretreatment and enzymatic hydrolysis using solid-state 13 C cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy (CP/MAS 13 C-NMR) and wide-angle X-ray scattering (WAXS). Spectral fitting of NMR peaks corresponding to different cellulose microenvironments at the C 4 carbon center suggests that a mildly acidic GVL–water co-solvent pretreatment of poplar leads to nearly full removal of xylan–cellulose linkages, which primes the cellulose for enzymatic attack. The spectral fitting also suggests that the pretreatment causes significant depletion of the inaccessible fibril surface domains with an increase in more thermally stable crystalline resonances (I β ). WAXS confirmed a decrease in the lattice spacing between (200) crystalline planes with increasing co-solvent pretreatment severity. These results are interpreted as an opening of bound microfibril surfaces previously inaccessible to the co-solvent system, which leaves behind a more thermally stable, crystalline domain that is potentially prone to relaxation and recrystallization. Full conversion of residual GVL-pretreated biomass was achieved after the GVL co-solvent pretreatment at 140 °C using a commercial enzyme cocktail, CTec2, which contains different cellulases and other enzymes. Spectral fitting of enzymatically hydrolyzed samples by a single engineered cellulase, CelR, suggests that the residual cellulose recalcitrance is mainly due to the inability of CelR to digest the I β crystalline domain present in pretreated samples. This work helps to provide new information regarding the structure of the cell wall and recalcitrance throughout GVL–water mild acidolysis and CelR enzymatic biomass deconstruction by tracking the evolution of structural domains within the cellulose microfibril. This work further directs recommendations for improving the conversion and sugar yields in future studies. Finally, our findings inform inquiry into larger questions of cellulose recalcitrance through GVL pretreatment and CelR enzymatic hydrolysis and give insight into subsequent required steps for full cellulose conversion with attention to the most recalcitrant cellulose structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Plasma-assisted atomic layer etching of single-crystal diamond

Applications of near-surface nitrogen-vacancy (NV) centers in diamond are often limited by surface defects created during processing. Understanding and controlling plasma-induced surface damage is important for preserving the optical and spin properties of diamond NV centers. We report molecular dynamics simulations of a novel form of plasma-aided atomic layer etching of diamond. In this proposed scheme, the initial surface modification step consists of Ar + ion bombardment. This creates an amorphous layer at the surface, the thickness of which is controlled by the ion energy. Amorphization is known to help smooth the surface, at least locally, and would also serve to sputter clean an initially contaminated surface. A second step impacts the amorphous carbon layer with O + between about 1 and 5 eV. Simulations show that this energy range will remove the amorphous carbon but will not etch the underlying diamond. Though this energy range is not trivial to achieve in a conventional low-temperature plasma, potential methods for creating these low-energy O + ions are discussed. In addition to a-C etching, the O + impacts are predicted to remove any isolated (100) diamond terraces by selectively attacking the edges of the terraces. The proposed atomic layer etching (ALE) approach reverses the conventional ALE sequence in which the surface modification step is usually chemical modification (oxidation in this case), followed by a removal step using Ar + impacts. This plasma ALE procedure is predicted to create a diamond surface that is atomically flat and defect free.

Draney, J. S. [Princeton University, NJ (United St↗
DOE OSTI2021

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↗
DOE OSTI2022

Scalable Nano-Scaffold SOFC Anode Architecture Enabling Direct Hydrocarbon Utilization

This project is based on WVU’s pending patents, technology and aims to design and modify the internal surfaces of the Ni/YSZ anode from currently commercially viable Solid Oxide Fuel Cells (SOFCs) using the additive manufacturing process of Atomic Layer Deposition (ALD). The surface architecture/scaffold added onto the internal surface of the anode possesses an engineered nanostructure but it features only commonly-used oxide conductors and electro-catalyst materials. The surface layer possesses a minimum thickness of ~2-40 nm and is solely designed to control the surface reforming reactions and to increase catalytic activity. Three-dimensional (3D) nano scaffold architectures with the noble metal nano-catalyst, low-cost bimetallic catalytic alloys, and nano-scale ionic conducting oxide fully compatible with the state-of-the-art Ni/YSZ anode, were applied to the internal surface of the entire porous SOFC anode using ALD. In the present work, the surface scaffold architecture is essentially multi-functional at the nano-scale, facilitated by the multiple heterostructured interfaces. It will significantly enhance the power density and cell durability for direct hydrocarbon utilization by (1) increasing the number of electrochemical reaction sites to enhance the hydrogen/hydrocarbon oxidation reactions; (2) reducing carbon formation; (3) mitigating the coarsening of backbone Ni phase and the oxidation attack of Ni from oxidants (e.g., H2O, CO2); and (4) promoting the internal reforming capabilities, especially for natural gas applications. ALD is employed to generate stable anode surface architectures that are uniform, precisely controllable at the atomic scale, and accurately repeatable for processing. The engineered anode surface nano-scaffold architecture was cataloged and analyzed using High-resolution Transmission Electron Microscopy (TEM), and cell power/durability performance assessed via comprehensive electrochemical performance testing with commercial specimens and relevant environments using hydrocarbon fuels. To the best of our knowledge, this project is the First Report on ALD of Ni/YSZ. The actual achievement of this Project includes (1). Successful demonstration of 7 types of ALD layers on Ni/YSZ anode, including Co, Ni, Mn, Pt, Ru, ZrOx and multi-functional nano-composite. (1). Conformal coating and subsequently spontaneously pinning the discrete nano-catalyst, including the precious metal nano-catalyst and the Ni and Co catalysts, on the YSZ surface upon the electrochemical operation in the reduced atmosphere. Those nano-catalysts on the ionic-conducting YSZ provided excellent sites for promoting internal reforming; (2). Demonstrated ALD coating increased both catalytic activity and conductivity of Ni/YSZ. Conformal coating provided dopants and introduced additional electrical conducting pathways on the YSZ ionic conductor. The doped surface layer of YSZ with mixed conductivity thus further introduces the active triple phase boundaries adjacent to the ALD-coated nano-catalysts such as Pt, Co, and Ni that are pinned on the YSZ surface. The nano-composite ALD coating on Ni/YSZ anode has significantly increased cell durability; and (3). ALD coating of Ni/YSZ anode increased the power density of the entire cell by 300%. For a long time, the SOFC performance, such as the power density, was deemed hindered by the cathode. The sluggish oxygen reduction reaction (ORR) in the cathode was deemed as hindering the power density of the SOFCs. For the anode-supported commercial SOFCs, the cell performance is considered to be limited by the cathode's performance. For the first time in the field of SOFC, this project has demonstrated that (1). the performance of commercial SOFCs can be further increased by the ALD coating on Ni/YSZ anode backbone. (2). ALD coating on Ni/YSZ fuel electrodes results in the enhancement of power density, and increased reliability, robustness, and endurance of SOFCs, for their application using both hydrogen and hydrocarbon fuels over the entire operating temperature range of 650-800ºC for the inherently functional commercial cells. (3). ALD coating provides alternative approaches of exsolutions for introducing the stable catalyst onto the internal surface of the Ni/YSZ electrode. ALD coating could be much more versatile than exsolution in employing the catalysts with various chemistries onto the various backbones. (4). Due to the negligible amount of ALD materials coated onto the internal surface of the porous cathode of the as-fabricated cells, a peak power density increase up to 300 % induced by ALD coating was simultaneously achieved in terms of both power density and specific power. (5). The ALD coating developed through this project was applied to both the SOFC and Solid Oxide Electrolysis Cells (SOEC). SOEC’s face a similar but more demanding need to improve the fuel electrode's performance. It opens further research directions for electrocatalytic surface nanoionics with a wide range of chemistry. It will revolutionize our ability to render the formation of a nanostructured electrode that has been constantly pursued yet barely achieved for practical SOFC/SOEC applications. The research is also immediately transformative since both the preliminary data and the proposed work are on the direct implantation of nanoionics into the state-of-the-art inherently functional SOCs. It represents an immediate impact on the commercial sectors in SOC technology since the applied ALD processing is computer-controlled ALD coating using the commercial ALD systems, and it is scalable to both the single cells and SOC stacks.

36 MATERIALS SCIENCE↗