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All sources NASA NTRS DOE OSTI

DOE OSTI2023

Revealing atomic-to-nanoscale oxidation mechanisms of metallic materials

Oxidation and corrosion are the leading causes of degradation and failure of metallic materials. Future alloy development requires the incorporation of corrosion resistance into alloy design and processing, and this begins with attaining a fundamental insight into dynamic reaction mechanisms and kinetics between a metal and aggressive environments. With recent advances in environmental transmission electron microscopy, there have been increased efforts to apply this approach to atomically probe the microscopic mechanisms that govern the oxidation and corrosion behavior of metallic materials. Consequently, fundamental insights have been obtained in understanding the underlying processes of oxidation and passivation, including active sites, surface restructuring, oxide/metal interface dynamics, and microstructure and phase evolution. Additionally, we discuss on-going and future developments that are expected to significantly advance the field of high-temperature oxidation and corrosion.

25 ENERGY STORAGE↗

NASA NTRS2002

Analysis for the Progressive Failure Response of Textile Composite Fuselage Frames

A part of aviation accident mitigation is a crash worthy airframe structure, and an important measure of merit for a crash worthy structure is the amount of kinetic energy that can be absorbed in the crush of the structure. Prediction of the energy absorbed from finite element analyses requires modeling the progressive failure sequence. Progressive failure modes may include material degradation, fracture and crack growth, and buckling and collapse. The design of crash worthy airframe components will benefit from progressive failure analyses that have been validated by tests. The subject of this research is the development of a progressive failure analysis for textile composite. circumferential fuselage frames subjected to a quasi-static, crash-type load. The test data for these frames are reported, and these data, along with stub column test data, are to be used to develop and to validate methods for the progressive failure response.

Johnson, Eric R.↗

NASA NTRS2002

Analysis for the Progressive Failure Response of Textile Composite Fuselage Frames

A part of aviation accident mitigation is a crashworthy airframe structure, and an important measure of merit for a crashworthy structure is the amount of kinetic energy that can be absorbed in the crush of the structure. Prediction of the energy absorbed from finite element analyses requires modeling the progressive failure sequence. Progressive failure modes may include material degradation, fracture and crack growth, and buckling and collapse. The design of crashworthy airframe components will benefit from progressive failure analyses that have been validated by tests. The subject of this research is the development of a progressive failure analysis for a textile composite, circumferential fuselage frame subjected to a quasi-static, crash-type load. The test data for the frame are reported, and these data are used to develop and to validate methods for the progressive failure response.

Johnson, Eric R.↗

DOE OSTI2021

Position-specific isotope effects during alkaline hydrolysis of 2,4-dinitroanisole resolved by compound-specific isotope analysis, 13 C NMR, and density-functional theory

Compound-specific isotope analysis (CSIA), position-specific isotope analysis (PSIA), and computational modeling (e.g., quantum mechanical models; reactive-transport models) are increasingly being used to monitor and predict biotic and abiotic transformations of organic contaminants in the field. However, identifying the isotope effect(s) associated with a specific transformation remains challenging in many cases. We describe and interpret the position-specific isotope effects of C and N associated with a SN 2 Ar reaction mechanism by a combination of CSIA and PSIA using quantitative 13 C nuclear magnetic resonance spectrometry, and density-functional theory, using 2,4-dinitroanisole (DNAN) as a model compound. The position-specific 13 C enrichment factor of O–C 1 bond at the methoxy group attachment site (ε C1 ) was found to be approximately -41‰, a diagnostic value for transformation of DNAN to its reaction products 2,4-dinitrophenol and methanol. Theoretical kinetic isotope effects calculated for DNAN isotopologues agreed well with the position-specific isotope effects measured by CSIA and PSIA. This combination of measurements and theoretical predictions demonstrates a useful tool for evaluating degradation efficiencies and/or mechanisms of organic contaminants and may promote new and improved applications of isotope analysis in laboratory and field investigations.

13C NMR↗

DOE OSTI2023

Influence of electronic transport on electrochemical performance of (Cu,Mn) 3 O 4 solid oxide fuel cell cathodes

Alkaline Earth free spinel oxides provide a potential benefit over Sr-doped perovskite-based materials commonly used as electrodes in high-temperature electrochemical energy conversion devices, e.g., solid oxide fuel cells (SOFCs). Sr-segregation is a known issue leading to performance degradation. In this study, Cu x Mn 3-x O 4 (x = 1, 1.2, and 1.5) porous electrodes were examined as SOFC cathodes using electrochemical impedance spectroscopy to investigate the oxygen reduction reaction (ORR) kinetics in relation to the material's intrinsic conductivity, the extrinsic electrode structure, and the cell test design. Similar to the electronic conducting (La,Sr)MnO 3 SOFC cathodes, the ORR kinetics of Cu x Mn 3-x O 4 spinel electrodes was governed by the oxygen adsorption and diffusion at the particle surface as well as the charge transfer at the triple phase boundaries. The overall electrode polarization resistance was highly dependent on contact density with the metallic current collector, active material particle connectivity, electrode thickness, and the intrinsic electronic materials conductivity. Here, we describe the importance of effective electronic charge transport parallel to the electrode surface in maximizing the electrochemically active electrode volume and enhancing electrode performance. We discuss an approach to optimize cell and electrode design with respect to active materials properties. This aspect is critical to ensure reliable evaluation of new materials, since laboratory-scale button-cells typically exhibit a high degree of electrode microstructure (e.g. porosity, thickness) and electrical contact density variation from sample to sample.

(Cu,Mn)3O4↗

DOE OSTI2024

Simulated Start-Stop and the Impact of Catalyst Layer Redox on Degradation and Performance Loss in Low-Temperature Electrolysis

Stress tests are developed that focus on anode catalyst layer degradation in proton exchange membrane electrolysis due to simulated start-stop operation. Ex situ testing indicates that repeated redox cycling accelerates catalyst dissolution, due to near-surface reduction and the higher dissolution kinetics of metals when cycling to high potentials. Similar results occur in situ, where a large decrease in cell kinetics (>70%) is found along with iridium migrating from the anode catalyst layer into the membrane. Additional processes are observed, however, including changes in iridium oxidation, the formation of thinner and denser catalyst layers, and platinum migration from the transport layer. Increased interfacial weakening is also found, adding to both ohmic and kinetic loss by adding contact resistances and isolating portions of the catalyst layer. Repeated shutoffs of the water flow further accelerate performance loss and increase the frequency of tearing and delamination at interfaces and within catalyst layers. These tests were applied to several commercial catalysts, where higher loss rates were observed for catalysts that contained ruthenium or high metal content. These results demonstrate the need to understand how operational stops occur, to identify how loss mechanisms are accelerated, and to develop strategies to limit performance loss.

08 HYDROGEN↗

NASA NTRS1984

Electrical research on solar cells and photovoltaic materials

The flat-plate solar cell array program which increases the service lifetime of the photovoltaic modules used for terrestrial energy applications is discussed. The current-voltage response characteristics of the solar cells encapsulated in the modules degrade with service time and this degradation places a limitation on the useful lifetime of the modules. The most desirable flat-plate array system involves solar cells consisting of highly polarizable materials with similar electrochemical potentials where the cells are encapsulated in polymers in which ionic concentrations and mobilities are negligibly small. Another possible mechanism limiting the service lifetime of the photovoltaic modules is the gradual loss of the electrical insulation characteristics of the polymer pottant due to water absorption or due to polymer degradation from light or heat effects. The mechanical properties of various polymer pottant materials and of electrochemical corrosion mechanisms in solar cell material are as follows: (1) electrical and ionic resistivity; (2) water absorption kinetics and water solubility limits; and (3) corrosion characterization of various metallization systems used in solar cell construction.

Orehotsky, J.↗

NASA NTRS1990

Compatibility of Fe-40Al with various fibers

Chemical reaction can occur at the fiber/matrix interface of intermetallic matrix composites, leading to a degradation of mechanical properties. Fe-40Al matrix composites were fabricated using SiC, B, W, Mo-base, and Al2O3 fibers. Composite samples were heat treated up to 1500 K to study the reaction kinetics, and reaction rates were determined from reaction zone thickness measurements. The Al2O3 and W fibers were found to be compatible with the Fe-40Al matrix, while the Mo-based fibers reacted moderately and the B and SiC fibers reacted severely. Experimental results are compared to theoretical thermodynamic predictions.

Draper, S. L.↗

NASA NTRS1992

Effect of oxidation on the mechanical properties of a NbAl3 alloy at intermediate temperatures

The effect of environment on the mechanical properties of an Nb-67Al-7Cr-0.25W-0.5Y alloy was investigated experimentally in the temperature range 800-1200 K. It is found that the severity of environmental attack in the alloy is determined by both matrix plasticity and oxidation kinetics. The former determines the ability of the matrix to accommodate the localized stresses generated during deformation and oxidation, while the latter governs the rate of formation of a protective oxide scale. The environmental degradation of the alloy can thus be reduced or eliminated by increasing atomic mobility.

Raj, S. V.↗

NASA NTRS2002

C/sic Life Prediction for Propulsion Applications

Accurate life prediction is critical to successful use of ceramic matrix composites (CMC). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and process made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC. Issues such as oxidation, steam and hydrogen effects on material behavior are discussed. Preliminary tests indicate that steam will aggressively remove SiC seal coat and matrix in line with past experience. The kinetics of water vapor reaction with carbon fibers is negligible at 600 C, but comparable to air attack at 1200 C. The mitigating effect of steam observed in fiber oxidation studies has also been observed in stress rupture tests. Detailed microscopy of oxidized specimens is being carried out to develop the oxidation model. Carbon oxidation kinetics are reaction controlled at intermediate temperatures and diffusion controlled at high temperatures (approximately 1000 C). Activation energies for T-300 and interface pyrolytic carbon were determined as key inputs to the oxidation model. Crack opening as a function of temperature and stress was calculated. Mechanical property tests to develop and verify the probabilistic life model are very encouraging except for residual strength prediction. Gage width is a key variable governing edge oxidation of seal coated specimens. Future efforts will include architectural effects, enhanced coatings, biaxial tests, and LCF. Modeling will need to account for combined effects.

Levine, Stanley R.↗

NASA NTRS2002

C/SIC Life Prediction for Propulsion Applications

Accurate life prediction is critical to successful use of ceramic matrix composites (CMC). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and progress made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC. Issues such as oxidation, steam and hydrogen effects on material behavior are discussed. Preliminary tests indicate that stream will aggressively remove SiC seal coat and matrix in line with past experience. The kinetics of water vapor reaction with carbon fibers is negligible at 600 C, but comparable to air attack at 1200 C. The mitigating effect of steam observed in fiber oxidation studies has also been observed in stress rupture tests. Detailed microscopy of oxidized specimens is being carried out to develop the oxidation model. Carbon oxidation kinetics are reaction controlled at intermediate temperatures and diffusion controlled at high temperatures (approx. 1000 C). Activation energies for T-300 and interface pyrolytic carbon were determined as key inputs to the oxidation model. Crack opening as a function of temperature and stress was calculated. Mechanical property tests to develop and verify the probabilistic life model are very encouraging except for residual strength prediction. Gage width is a key variable governing edge oxidation of seal coated specimens. Future efforts will include architectural effects, enhanced coatings, biaxial tests, and LCF. Modeling will need to account for combined effects.

Levine, Stanley R.↗

DOE OSTI2020

Monte Carlo simulations of Cu/Ni–Si–Mn co-precipitation in duplex stainless steels

First-Passage Kinetic Monte Carlo (FPKMC) simulations of species migration in duplex stainless steels were performed in order to establish relationships between alloy content, segregation behavior, and the formation of Ni-Si-Mn rich particles in cast duplex stainless steels during thermal aging. The Ni-Si-Mn-rich second phase forms after extended aging at reactor operating temperatures and degrades alloy properties. Simulations of Ni-Si-Mn cluster formation were validated through comparison with experimental results obtained through Atom Probe Tomography (APT) on similar alloy compositions, identifying several trends. First, Cu promotes the formation of Ni-Si-Mn clusters, but only when Ni or Mn prefer segregation to the surface of Cu particles; without the segregation of these species, the critical composition for the clusters to form was not achieved. Second, the width of precipitate-denuded zones near ?/d interfaces increases with decreasing Cu content. This finding was in strong agreement with APT results, further validating our model. Finally, our model predicts that Ni-Si-Mn cluster formation will be the most extensive when the Si:Mn ratio is approximately 1:1 and the least extensive when one of these key elements is less concentrated (Mn = 0.5 at.% or Si = 0.5 at.%). The implications of these results on how to improve alloy properties are discussed.

Cu co-precipitation, Atom probe tomography (APT), ↗

NASA NTRS1985

Environmental Degradation of Materials: Surface Chemistry Related to Stress Corrosion Cracking

Parallel experiments have been performed in order to develop a comprehensive model for stress cracking (SCC) in structural materials. The central objective is to determine the relationship between the activity and selectivity of the microstructure of structural materials to their dissolution kinetics and experimentally measured SCC kinetics. Zinc was chosen as a prototype metal system. The SCC behavior of two oriented single-crystal disks of zinc in a chromic oxide/sodium sulfate solution (Palmerton solution) were determined. It was found that: (1) the dissolution rate is strongly (hkil)-dependent and proportional to the exposure time in the aggressive environment; and (2) a specific slip system is selectively active to dissolution under applied stress and this slip line controls crack initiation and propagation. As a precursor to potential microgrvity experiments, electrophoretic mobility measurements of zinc particles were obtained in solutions of sodium sulfate (0.0033 M) with concentrations of dissolved oxygen from 2 to 8 ppm. The equilibrium distribution of exposed oriented planes as well as their correlation will determine the particle mobility.

Schwarz, J. A.↗

DOE OSTI2023

Evaluation of enzymatic depolymerization of PET, PTT, and PBT polyesters

Millions of tons of waste polyester plastics, including polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT), end up in the environment as soil and water contaminants. Recent advances in enzymatic polyester degradation have motivated researchers toward biorecycling of plastic wastes. Leaf-branch compost cutinase (LCC) enzymes have been proven to be effective in the biodegradation of PET. This study focuses on enzymatic depolymerization of waste PET, PTT, and PBT materials by using an ICCG variant of LCC (LCC ICCG ) produced from Escherichia coli BL21(DE3). The degradation efficiency of the polyesters was determined by the monomer terephthalic acid (TPA) released from the depolymerization reaction. It was found that the most efficient depolymerization was achieved for PET, followed by PTT and PBT. A kinetic model based on Langmuir adsorption and the Michaelis-Menten equation was developed to describe the enzymatic depolymerization of PET, PTT, and PBT with various enzyme and substrate loadings. The model simulation results revealed that the LCCICCG enzyme loading should be linearly increased as the work capacity of the polyester substrate increases. A specific enzyme loading of 0.91 mg/g PET is suggested to achieve 90% depolymerization of PET within three days. Furthermore, the experimental data and model simulation results can be used to help further engineer the enzyme and process to achieve a complete biodegradation of polyester wastes at large scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1986

Oxidation and embrittlement of Ti-6Al-2Sn-4Zr-2Mo alloy

A thermogravimetric analysis monitoring study has been conducted for Ti-6Al-2Sn-4Zr-2Mo in the 593-760 C range, with a view to its total oxidation kinetics in laboratory air. In addition, tensile elongation was obtained for selected foil specimens after their exposure to simulated Space Shuttle reentry conditions. The total weight gain with time exhibited two parabolic stages separated by a transient region which is the result of a simultaneous increase in the parabolic growth rate constant for the oxide and in oxygen solubility at the oxide-metal interface. A model for the total oxidation kinetics accounting for the two individual components (oxide growth and solid solution formation) is proposed; the activation energy for oxygen diffusion in the alpha-solid solution is shown to approximate the activation energy for the degradation of tensile elongation of the alloy in its foil gage condition.

Shenoy, R. N.↗

DOE OSTI2025

Tailoring the Reaction Heterogeneity for Robust Li‐Rich Cathodes

The practical application of Li-rich Mn-based layered oxides (LLO) cathode is hindered by severe capacity and voltage degradation resulting from severe oxygen release and irreversible phase transition. In this work, the reaction heterogeneity, which describes the spatially resolved electrochemical divergence within individual cathode particles, is engineered through compositional gradient design to couple Li + transport kinetics and the anion redox activity between particle interiors and surfaces. It is revealed that Co/Mn concentration gradient within particles creates heterogeneous phase content distribution and structural ordering, inducing surface-bulk reaction heterogeneity that significantly impacts the overall electrochemical performance. Specifically, Li 2 MnO 3 -poor and Co-enriched surface effectively mitigates the oxygen loss and enhances electrochemical reaction kinetics, benefited from the reduced surface redox reactivity and induced highly ordered intra-layered cationic arrangement. Meanwhile, the Li 2 MnO 3 -enriched core with slight Li/Ni intermixing provides high reversible capacity and strong mechanical stability. Consequently, the greatly enhanced anion redox reversibility, Li + diffusion dynamics, and structure stability endow LLO with exceptional electrochemical properties, showing a capacity retention of 86.0% and a reduced voltage decay of 0.518 mV per cycle after 500 cycles at 1 C. This work provides a valuable strategy to tailor the redox chemistry and achieve robust LLO.

25 ENERGY STORAGE↗

DOE OSTI2026

Diffusion of NiH on Ni(111) and of Ni with Adsorbed H on Ni(111) in the Context of Ni Coarsening in Solid Oxide Cells

In the Ni-based hydrogen electrode of a solid oxide cell (SOC), Ni coarsening is an important degradation mechanism and could be enhanced by NiH diffusing on the Ni particle surfaces. Here, in this work, the average lifetime and diffusion distance of NiH on Ni(111) are computed using density-functional theory and kinetic Monte Carlo methods. It is found that NiH is extremely short-lived and, thus, cannot promote coarsening in the SOC. Also, the diffusion of Ni on Ni(111) is shown to be at most slightly accelerated by H along NiH dissociation paths involving the movement of Ni with a nearby H. Based on this result, coarsening is not likely to be dramatically accelerated by the diffusion of Ni with H on Ni(111). However, support is provided for the experimental procedure of measuring the product of surface coverage and single-species diffusivity of Ni on Ni(111) in a hydrogen-rich atmosphere.

Ni coarsening↗

DOE OSTI2025

Computational Modeling of Molten Salt Infiltration and Oxidation in Nuclear Graphite

Graphite is utilized as a moderator and reflector in advanced nuclear reactor designs due to its high thermal conductivity, neutron moderation properties, and resistance to radiation damage. However, its longterm performance and reliability are challenged by degradation mechanisms such as molten salt infiltration in molten salt reactors (MSRs) and oxidation in gas-cooled reactors (GCRs). These mechanisms can compromise the structural integrity and operational lifetime of graphite components, necessitating a more detailed assessment of their physical behavior. This report focuses on the development of computational models for molten salt infiltration and oxidation of graphite to aid the design and performance analysis of graphite components. For molten salt infiltration, a computational framework is developed that couples incompressible Navier-Stokes and phase-field model to simulate the penetration of molten salt into graphite?s interconnected pore structure. Initial model verification is performed using two-phase flows in two dimensions, demonstrating the models ability to capture fundamental physical behavior and agree with analytical solution. This framework is then applied to a realistic IG110 nuclear graphite , where a computed tomography extracted pore geometry is used to analyse the infiltration behavior of FLiNaK molten salt. This model provides insights into how the microstructure and other relevant parameters influence the transport pathways of molten salt into graphite, potentially offering a means to rapidly evaluate a graphite grade?s resistance to infiltration. For oxidation, the report details pore-scale mass and heat transport models, describing the diffusion of gases, reaction kinetics, and thermal effects. Additionally, this report highlights inconsistencies in the existing volume-averaged macroscopic model, particularly in upscaling of reaction kinetics and flux terms, and surface to volume transformations. These inconsistencies suggest that current formulations may not accurately capture the experimentally observed graphite oxidation process, highlighting the need for improved model development. This work advances the development of physics-based computational models for graphite degradation, contributing to improved predictive models for next-generation nuclear reactor designs. Future efforts will focus on refining the infiltration model to address non-physical behaviors and enhance its robustness. Additionally, for oxidation, further studies will employ the principles of volume averaging to rigorously derive the upscaled equations, potentially in collaboration with subject matter experts.

Computational Modeling of Molten Salt Infiltration↗