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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electrochemical noise studies on localized corrosion of Ni and Ni-20Cr in molten ZnCl 2

The electrochemical noise (ECN) technique was employed to study corrosion of two model systems, i.e. pure Ni and a binary Ni-20 wt%Cr (Ni20Cr) alloy in molten ZnCl 2 at 623 K. Here we measured ECN transients in current and open-circuit potential from two nominally identical Ni-Ni and Ni20Cr-Ni20Cr electrodes and one galvanic Ni-Ni20Cr electrode pair. The behavior of ECN is quite distinct among the three-electrode systems, and it is correlated with the various microscopic observations of micro- and nano-scale morphological features. Based on the ECN study coupled with the microstructural analysis, the origins of ECN in the molten salt environment as well as the mechanisms of localized corrosion in the three systems are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

A space-time adaptive finite element method with exponential time integrator for the phase field model of pitting corrosion

In this paper we propose a space-time adaptive finite element method for the phase field model of pitting corrosion, which is a parabolic partial differential equation system consisting of a phase variable and a concentration variable. A major challenge in solving this phase field model is that the problem is very stiff, which makes the time step size extremely small for standard temporal discretizations. Another difficulty is that a high spatial resolution is required to capture the steep gradients within the diffused interface, which results in very large number of degrees of freedom for uniform meshes. To overcome the stiffness of this model, we combine the Rosenbrock–Euler exponential integrator with Crank–Nicolson scheme for the temporal discretization. Moreover, by exploiting the fact that the speed of the corroding interface decreases with time, we derive an adaptive time stepping formula. For the spatial approximation, we propose a simple and efficient strategy to generate adaptive meshes that reduces the computational cost significantly. Thus, the proposed method utilizes local adaptivity and mesh refinement for efficient simulation of the corrosive dissolution over long times in heterogeneous media with complex microstructures. We also present an extensive set of numerical experiments in both two and three dimensional spaces to demonstrate efficiency and robustness of the proposed method.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Network structure in alteration layer of boroaluminosilicate glass formed by aqueous corrosion

Exogenously-added LiCl has been shown to slightly accelerate the corrosion rate of a boroaluminosilicate glass called International Simple Glass (ISG) in aqueous solutions over forward- and residual-rate regimes, while KCl and CsCl impede. To understand the effect of exogenously added electrolytes on resulting hydrous species and the network structure of alteration layers, infrared spectroscopy was implemented. It was found that the fraction of molecular water relative to the surface-bound hydroxyl species is lower in the KCl and CsCl conditions compared to the LiCl and pure water conditions. An approximation for the spectral features of the thin surface films from an experimentally-obtained specular-reflectance infrared (SR-IR) spectrum was proposed; results indicate no significant difference in the Si-O bonding network of the alteration layers formed in the presence of exogenously added LiCl, KCl and CsCl. Furthermore, the observed change in corrosion rates might be linked to the relative abundance of molecular water species in the porous network, rather than the silicate bonding structure.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

The effects of neutron and ionizing irradiation on the aqueous corrosion of SiC

Chemical vapor deposited (CVD) SiC and nuclear-grade SiC/SiC composite materials were exposed to light water reactor (LWR) conditions at the MIT Nuclear Reactor (MITR) here. Three sets of samples were exposed within flowing PWR-chemistry-coolant under either 1) neutron and ionizing irradiation with resulting radiolysis products, 2) radiolysis products without neutron flux, 3) loop coolant. Post-irradiation examination (PIE) exhibited an increase in corrosion from radiolysis products (particularly H 2 O 2 ), and potentially a further increase from radiation damage. For CVD SiC, regardless of exposure location, the in-situ observed corrosion rate was less than 1 µm per year, potentially within acceptable limits for LWR application.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Hydrothermal corrosion of laser printed SiC fibers under extreme environment

We report SiC/SiC fiber composites are proposed cladding materials to improve the accident tolerance of commercial light water nuclear reactor fuel. To evaluate their viability, understanding the kinetics of corrosion under irradiation and high-temperature, high-pressure aqueous environment is critical. In the present work, the microstructure and mechanical properties of novel SiC fibers manufactured by Laser Chemical Vapor Deposition (LCVD) are introduced. The LCVD technology has control over microstructure and stoichiometry while allowing for high purity manufacturing, all key qualities needed in search of an optimum SiC fiber for nuclear energy applications. The isolated hydrothermal corrosion of commercially available carbon-rich Hi-Nicalon Type-S fibers is compared to the LCVD stoichiometric and LCVD silicon-rich fibers. Autoclave testing was carried out at 310°C and 14 MPa in the absence of irradiation. In a separate study, the effect of gamma irradiation on the fibers in the room-temperature environment was analyzed. It was observed from the experiments that the dissolution of the fibers was highly dependent on the stoichiometric ratio, fiber surface morphology and thermal pre-treatment of fibers. Contrary to previous findings, fiber dissolution was also visible under low-temperature gamma irradiation in aqueous environment with LCVD fibers showing lower dissolution.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Corrosion behavior of a series of combinatorial physical vapor deposition coatings on SiC in a simulated boiling water reactor environment

Here, the simulated boiling water condition corrosion properties of multilayer and combinatorial physical vapor deposition metal coatings (Zr, Cr, and/or Ti) deposited on a SiC f -SiC composite were investigated. Various compositions within the ternary system were corroded to the most suitable composition preventing underlying SiC f -SiC from further attack. Mass measurements and visual observations were conducted to identify which coatings formed protective oxides and which coatings spalled. Transmission electron microscopy was conducted to observe the microstructure of the physical vapor deposition metal layer before and after corrosion as well as identify the oxide which were forming.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Impact of corrosion layer composition and thermal pretreatment on the radiolytic generation of molecular hydrogen from aluminum alloys

To fully evaluate the feasibility of extending the dry storage of aluminum-clad spent nuclear fuel (ASNF) in helium-backfilled cannisters, the amount of radiation-induced molecular hydrogen (H 2 ) generated and the impact of absorbed radiation dose on the ASNF corrosion layer composition must be accurately assessed. Here, in this study, we report a slowing in the rate of radiolytic H 2 generation for pre-corroded AA1100 and AA6061 aluminum alloy coupons irradiated to up to 53 MGy of absorbed cobalt-60 gamma dose. By exploring a variety of thermal pretreatment conditions for AA6061 coupons, we find that the “steady-state” yield of H 2 depends more on the aluminum alloy used than on the treatments applied prior to dry storage. Scanning electron microscopy and positron annihilation lifetime spectroscopy techniques also provided evidence for gamma radiation-induced defects in the corrosion layers of the investigated aluminum alloy coupons for high absorbed doses (~50 MGy), the consequences of which on cladding integrity and H 2 generation should be explored in future works.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
DOE OSTI2021

Air-stable, earth-abundant molten chlorides and corrosion-resistant containment for chemically-robust, high-temperature thermal energy storage for concentrated solar power

A dramatic reduction in man-made CO 2 emissions could be achieved if the cost of electricity generated from concentrated solar power (CSP) plants could become competitive with fossil-fuel-derived electricity. The solar heat-to-electricity conversion efficiency of CSP plants may be significantly increased (and the associated electricity cost decreased) by operating CSP turbines with inlet temperatures ≥750 °C instead of ≤550 °C, and by using thermal energy storage (TES) at ≥750 °C to allow for rapidly dispatchable and/or continuous electricity production. Unfortunately, earth-abundant MgCl 2 -KCl-based liquids currently being considered as low-cost media for large-scale, high-temperature TES are susceptible to oxidation in ambient air, with associated undesired changes in liquid composition and enhanced corrosion of metal alloys in pipes and tanks containing such liquids. In this paper, alternative high-temperature, earth-abundant molten chlorides that are resistant to oxidation in ambient air are identified via thermodynamic calculations. Here, the oxidation resistance, and corrosion-resistant containment, of such molten chlorides at 750 °C are then demonstrated. Such an air-tolerant strategy, involving chemically-robust, low-cost TES media paired with effective containment materials, provides a critical advance towards the higher-temperature operation of, and lower-cost electricity generation from, CSP plants.

14 SOLAR ENERGY↗
DOE OSTI2024

How irradiation promotes intergranular stress corrosion crack initiation

Irradiation assisted stress corrosion cracking (IASCC) is a form of intergranular stress corrosion cracking that occurs in irradiated austenitic alloys. It requires an irradiated microstructure along with high temperature water and stress. The process is ubiquitous in that it occurs in a wide range of austenitic alloys and water chemistries, but only when the alloy is irradiated. Despite evidence of this degradation mode that dates back to the 1960s, the mechanism by which it occurs has remained elusive. Here, using high resolution electron backscattering detection to analyze local stress-strain states, high resolution transmission electron microscopy to identify grain boundary phases at crack tips, and decoupling the roles of stress and grain boundary oxidation, we are able to unfold the complexities of the phenomenon to reveal the mechanism by which IASCC occurs. The significance of the findings impacts the mechanical integrity of core components of both current and advanced nuclear reactor designs worldwide.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Interplay between Catalyst Corrosion and Homogeneous Reactive Oxygen Species in Electrochemical Ozone Production

In this study, electrochemical ozone production (EOP), a six-electron water oxidation reaction, offers promising avenues for creating value-added oxidants and disinfectants. However, progress in this field is slowed by a dearth of understanding of fundamental reaction mechanisms. In this work, we combine experimental electrochemistry, spectroscopic detection of reactive oxygen species (ROS), oxygen-anion chemical ionization mass spectrometry, and computational quantum chemistry calculations to determine a plausible reaction mechanism on nickel- and antimony-doped tin oxide (Ni/Sb–SnO 2 , NATO), one of the most selective EOP catalysts. Antimony doping is shown to increase the conductivity of the catalyst, leading to improved electrochemical performance. Spectroscopic analysis and electrochemical experiments combined with quantum chemistry predictions reveal that hydrogen peroxide (H 2 O 2 ) is a critical reaction intermediate. We propose that leached Ni 4+ cations catalyze hydrogen peroxide into solution phase hydroperoxyl radicals ( • OOH); these radicals are subsequently oxidized to ozone. Isotopic product analysis shows that ozone is generated catalytically from water and corrosively from the catalyst oxide lattice without regeneration of lattice oxygens. Further quantum chemistry calculations and thermodynamic analysis suggest that the electrochemical corrosion of tin oxide itself might generate hydrogen peroxide, which is then catalyzed to ozone. The proposed pathways explain both the roles of dopants in NATO and its lack of stability. Our study interrogates the possibility that instability and electrochemical activity are intrinsically linked through the formation of ROS. In doing so, we provide the first mechanism for EOP that is consistent with computational and experimental results and highlight the central challenge of instability as a target for future research efforts.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Anions in Corrosion: Influence of Polymer Electrolytes on the Interfacial Ion Transfer Kinetics of Cu at Au(111) Surfaces

The corrosion kinetics of metals in the presence of polymer electrolytes—which are often used in devices for the electrochemical production of hydrogen, hydrocarbons, and alcohols—is convoluted by transport and ill-defined reactive interfaces which mask the fundamental reaction kinetics. Underpotential-deposited monolayers of Cu at Au(111) surfaces provide a structurally welldefined active site for interfacial ion transfer, with a fixed number of sites available for adsorption. Here, we investigate the adsorption behavior of Cu at Au(111) surfaces across a series of sulfate and sulfonate electrolytes, to understand how anion structure influences the kinetics of elementary interfacial ion-transfer reactions. The influence of anion structure is most significant at high adsorbate coverage, with similar adsorption isotherms and kinetics observed for all three molecular sulfates and sulfonates. In contrast, a suspended perfluorosulfonic acid ionomer reduced both the equilibrium coverage of Cu as well as the standard exchange rate at Au(111) at low coverages of Cu. These results suggest that electrocatalyst corrosion is inhibited for metal nanoparticles supported at polymer electrolytes due to changes in adsorbate coverage as well as suppressed kinetics for interfacial ion transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Preliminary Modeling of Chloride Deposition on Spent Nuclear Fuel Canisters in Dry Storage Relevant to Stress Corrosion Cracking

This study presents a method that can be used to gain information relevant to determining the corrosion risk for spent nuclear fuel (SNF) canisters during extended dry storage. Currently, it is known that stainless steel canisters are susceptible to chloride-induced stress corrosion cracking (CISCC). However, the rate of CISCC degradation and the likelihood that it could lead to a through-wall crack is unknown. This study uses well-developed computational fluid dynamics and particle-tracking tools and applies them to SNF storage to determine the rate of deposition on canisters. The deposition rate is determined for a vertical canister system and a horizontal canister system, at various decay heat rates with a uniform particle size distribution, ranging from 0.25 to 25 µm, used as an input. In all cases, most of the dust entering the overpack passed through without depositing. Most of what was retained in the overpack was deposited on overpack surfaces (e.g., inlet and outlet vents); only a small fraction was deposited on the canister itself. These results are provided for generalized canister systems with a generalized input; as such, this paper is intended to demonstrate the technique. This study is a part of an ongoing effort funded by the U.S. Department of Energy, Nuclear Energy Office of Spent Fuel Waste Science and Technology, which is tasked with doing research relevant to developing a sound technical basis for ensuring the safe extended storage and subsequent transport of SNF. This work is being presented to demonstrate a potentially useful technique for SNF canister vendors, utilities, regulators, and stakeholders to utilize and further develop for their own designs and site-specific studies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Molecular dynamics of the early stages of high-temperature corrosion

In this work, we performed molecular dynamics simulations of the high-temperature oxidation of metal alloys composed of Al, Cr, and Fe and compared their behavior with that of pure Fe. The metal alloy elements (Al and Cr) segregated to the surface during oxidation, producing a lower stress gradient at the metal/environment interface compared to pure Fe. We have found that the lowered stress gradients produced in the alloy material appear to play a key role in the development of corrosion. Interfaces with lower stress gradients have reduced rates of H 2 O adsorption, especially for the ferritic (bcc) alloys. The diffusivity of oxygen and hydrogen drops more rapidly for the interfaces with reduced stress gradients. The stress gradient is also diminished when the gas pressure is increased, indicating that the Fe-Cr-Al alloy system is more resistant to oxidation than pure Fe at higher pressures. Therefore, we conclude that the lower stress gradients at the alloy/environment interface reduce the stress concentration and can slow down the rate of the initial oxide scale growth. We also compared bcc and fcc alloys with pure Fe based on our three evaluation criteria (peak stress, stress gradient, and summation of stress in the oxide scale). We found that the alloys have lower values under the three criteria compared to pure Fe. The bcc alloy has the best score under a water rich environment and the fcc alloy is proven to be better for peak stress and summation of stress in the oxide scale under an oxygen rich environment. For surface segregation to occur, we find that a minimum content of Al or Cr in the near-surface region must be achieved. We also learned that the role of Al is more important than that of Cr in terms of corrosion resistant behavior at relatively higher temperatures for the Fe-Cr-Al ternary alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Nondestructive Evaluation of Stress Corrosion Cracking in a Welded Steel Plate Using Guided Ultrasonic Waves

Stress corrosion cracking (SCC) had occurred in early-generation high-level nuclear waste tanks constructed by welding carbon steel. This paper describes an ultrasonic inspection system and its fundamental ability to detect and quantify the length of SCC on thick welded steel plates. The finite element method (FEM) was applied to simulate the welding process to estimate the welding residual stress field. Growth of stress corrosion cracks is driven by crack stress intensities exceeding the subcritical cracking threshold intensity. The subject plate was experimentally inspected with ultrasonic nondestructive evaluation (NDE) techniques to characterize the extent of SCC. The NDE system uses a piezoelectric transducer to generate guided waves in the thick steel plate, and a scanning laser Doppler vibrometer (SLDV) to measure multidimensional time–space wavefield data over a user-defined scanning area in the plate surface. The measured wavefield data can show wave interactions in a localized area in the plate due to the presence of the discontinuities of the SCC. To generate an inspection image that can precisely show the crack’s location and/or the dimension, the wavefield data are further processed to generate inspection image that maps the entire sample plate so the crack can be clearly identified in the plate while its length can be readily estimated. In conclusion, the ultrasonic test results for crack length agree well with the visually estimated length and are close to that predicted by the FEM for cracks in the weld residual stress field.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Material Selection and Corrosion Studies of Candidate Bearing Materials for Use in Molten Chloride Salt

Molten chloride salts are being given strong consideration for use in heat transfer and storage in concentrating solar power (CSP) systems as well as in some nuclear reactor applications. Containment of the molten salt, particularly at the highest temperatures, is a major material concern and has received considerable study. Another material issue is the pumps that will be required to move the molten salt along with the bearing materials that will be required to have sufficient corrosion resistance as well as wear resistance in the high temperature salt. A pair of coordinated studies in our laboratory has addressed the corrosion, and the wear issues of candidate bearing materials including the selection of candidate materials as well as their performance in a molten sodium chloride-potassium chloride-magnesium chloride salt environment. This work addresses the selection of candidate materials and their chemical compatibility with the molten salt. The studies have identified material pairs that have suitable properties for use as bearings that would be immersed in molten chloride salt.

14 SOLAR ENERGY↗
DOE OSTI2024

Studying microbially induced corrosion on glass using ToF-SIMS

Microbially induced corrosion (MIC) is an emerging topic that has huge environmental impacts, such as long-term evaluation of microbial interactions with radioactive waste glass, environmental cleanup and disposal of radioactive material, and weathering effects of microbes. Time-of-flight secondary ion mass spectrometry (ToF-SIMS), a powerful mass spectral imaging technique with high surface sensitivity, mass resolution, and mass accuracy, can be used to study biofilm effects on different substrates. Understanding how to prepare biofilms on MIC susceptible substrates is critical for proper analysis via ToF-SIMS. We present here a step-by-step protocol for preparing bacterial biofilms for ToF-SIMS analysis, comparing three biofilm preparation techniques: no desalination, centrifugal spinning (CS), and water submersion (WS). Comparisons of two desalinating methods, CS and WS, show a decrease in the media peaks up to 99% using CS and 55% using WS, respectively. Proper desalination methods also can increase biological signals by over four times for fatty acids using WS, for example. ToF-SIMS spectral results show chemical compositional changes of the glass exposed in a Paenibacillus polymyxa SCE2 biofilm, indicating its capability to probe microbiologically induced corrosion of solid surfaces. This represents the proper desalination technique to use without significantly altering biofilm structure and substrate for ToF-SIMS analysis. ToF-SIMS spectral results showed chemical compositional changes of the glass exposed by a Paenibacillus bacterial biofilm over 3-month inoculation. Finally, possible MIC products include various phosphate phase molecules not observed in any control samples with the highest percent increases when experimental samples were compared with biofilm control samples.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Corrosion of AISI 310 and 316 in Molten Hydroxide Under Steam Electrolysis Conditions

Steam electrolyzers, utilizing molten hydroxide electrolyte, offers potential for improvement in electrochemical efficiency, cost reduction, use of conventional materials of construction and process scale up for large scale hydrogen production. Stainless steels, used for the fabrication of cell components (current collector, gas separator, wet seals, and manifolds) experience accelerated corrosion in the presence of molten hydroxide electrolyte in both oxidizing (anodic) and reducing (cathodic) atmospheres. In this study, the corrosion behavior of AISI 310 and 316 in hydroxide melt has been studied at 600°C for 50 h. Melt immersion tests revealed formation of the porous lithium iron oxide at the melt-oxide interface for both AISI 310 and 316. Inductively coupled plasma optical emission spectrometry (ICP-OES) analysis showed the presence of Cr in the electrolyte melt obtained from samples exposed to oxidizing atmosphere. Thermochemical analysis was performed to validate the experimental results.

corrosion↗
DOE OSTI2020

Impact of Permanganate Oxidation of Glycolate on Corrosion of the Defense Waste Processing Facility (DWPF) Recycle Collection Tank (RCT), Transfer-line and Waste Tank Materials of Construction (MoC)

Savannah River Remediation (SRR) is evaluating the use of glycolic acid to replace formic acid as an alternate reductant for the Defense Waste Processing Facility (DWPF) at Savannah River Site (SRS). The replacement is aimed at reducing facility hazards, improving pH stability and rheological control, and lowering off gas production. Glycolate, which is the product that may remain, can also be carried downstream to High-Level Waste and Low-Level Waste facilities. Complete oxidation of glycolate and other organic species from the Sludge Receipt and Adjustment Tank (SRAT) may be necessary to minimize thermolytic hydrogen generation that can cause flammability issues. The glycolate oxidation may be performed in the Recycle Collection Tank (RCT). The RCT heel would be adjusted with sodium hydroxide to maintain the solution caustic and sodium nitrite as corrosion inhibitor prior to the addition of condensate that can be from the contents of the Slurry Mix Evaporator Condensate Tank (SMECT) or Offgas Condensate Tank (OGCT). The RCT tank collects the waste to be transferred via the Low Point Pump Pit – Recycle Pump Tank (LPPP-RPT) through a jacketed transfer-line to the Tank Farm facility. Scoping studies were performed to evaluate an oxidizing agent and sodium permanganate was selected as the best option for glycolate destruction. Testing was recommended to determine the impact on the Materials of Construction (MoC) due to the addition of sodium permanganate. The targeted concentration of sodium permanganate used equated to a 7:1 molar permanganate to glycolate ratio (nominally 0.002 M permanganate). However, to conservatively maximize the permanganate corrosivity, in some cases no glycolate was added.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗