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At least 55 records · Page 3

Coupling of radiation and grain boundary corrosion in SiC

Abstract Radiation and corrosion can be coupled to each other in non-trivial ways and such coupling is of critical importance for the performance of materials in extreme environments. However, it has been rarely studied in ceramics and therefore it is not well understood to what extent these two phenomena are coupled and by what mechanisms. Here, we discover that radiation-induced chemical changes at grain boundaries of ceramics can have a significant (and positive) impact on the corrosion resistance of these materials. Specifically, we demonstrate using a combination of experimental and simulation studies that segregation of C to grain boundaries of silicon carbide leads to improved corrosion resistance. Our results imply that tunning of stoichiometry at grain boundaries either through the sample preparation process or via radiation-induced segregation can provide an effective method for suppressing surface corrosion.

Materials Science↗

Lessons Learned Using in-situ TEM Liquid Corrosion of Al Alloys

Al and Al alloys are of interest in energy applications due to their strength and low weight [1] in addition to their electrochemical properties for aluminum-air batteries for energy storage [2]. However, Al alloys also are susceptible to corrosion in a variety of environments including liquid electrolytes and in solar panels [3], which has led to a great deal of research to understand and improve corrosion resistance in these materials. Al metal forms a native, passivating oxide layer in the presence of ambient air, which slows corrosion initiation. However, pitting still occurs as this protective layer breaks down in the presence of electrolytes. Thin metal Al films were used in these experiments to observe initiation and growth of pitting, which can be used as an approximation of corrosion initiation behavior in bulk samples.

alluminum alloys↗

A systematic study of lanthanide titanates (A 2 Ti 2 O 7 ) chemical durability: corrosion mechanisms and control parameters

Dense lanthanide titanates ranging from La 2 Ti 2 O 7 to Yb 2 Ti 2 O 7 were synthesized by spark plasma sintering with similar micro-sized microstructure, and their chemical durability and degradation mechanisms were investigated by semi-dynamic leaching tests. Different corrosion mechanisms from incongruent to congruent dissolution were observed with preferential elemental releases of lanthanides in A 2 Ti 2 O 7 (A = La to Gd) and Ti in Er 2 Ti 2 O 7 and Yb 2 Ti 2 O 7 . Initial leaching was controlled by surface dissolution and long-term dissolution shifted to a diffusion-controlled mechanism for titanate pyrochlores from Sm 2 Ti 2 O 7 to Yb 2 Ti 2 O 7 . Both short-term and long-term leaching rates decreased from La 2 Ti 2 O 7 to Yb 2 Ti 2 O 7 , and materials became more corrosion resistant with decreasing ionic radius ratios of the rare-earth elements and titanium. Amorphous passivation films of several nm-thick enriched with Ti formed on the surfaces of the corroded materials, and the formation mechanisms were governed either by surface reorganization with preferential release of lanthanides or dissolution-precipitation from saturated bulk solutions with preferential release of titanium. Finally, these results demonstrate that the ionic size plays a dominant role in determining chemical durability of lanthanide titanates and a strong correlation is established among chemical composition/structural variation, passivation film formation and corrosion mechanisms, and materials chemical durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructural, Corrosion, and Mechanical Characterization of Friction Stir Welded Al 6022-to-ZEK100 Mg Joints

Friction stir welded (FSW) aluminum–magnesium lightweight vehicle joints have gained significant interest due to their high strength-to-weight ratio. In this work, the corrosion resistance of this material is analyzed through electrochemical tests, which include open circuit potential (OCP) inspection and potentiodynamic polarization (PD) scanning. Weight loss measurements tested the corrosion rate of the FSW weld through cyclic corrosion testing (CCT) according to the standard SAEJ 2334. Mechanical properties were also investigated, including lap-shear strength, micro- and nano-hardness mapping, and true stress–strain curves as a function of local processing history. The electrochemical results indicate that the center weld zone’s corrosion property stays between the two base alloys. Indentation-based testing demonstrated that the weld zone behaves differently from base alloys. Lap shear strength surprisingly did not drop much even after eight weeks of cyclic corrosion tests, indicating that the joint did not allow any ingress of the electrolyte.

36 MATERIALS SCIENCE↗

Corrosion resistance of functionally graded TiN/Ti coatings for proton exchange membrane fuel cells

Bipolar Plates (BPP) are important components of proton exchange membrane fuel cell (PEMFC) stacks. In the development of innovative fuel cell designs, it is advantageous to use aluminum for these applications, however, this material lacks the necessary corrosion resistance. Since the performance of PEMFC stacks depends on BPP properties, in particular, corrosion resistance, depositing titanium nitride (TiN) thin films onto aluminum substrates may improve their efficiency and durability. Present work focuses on improving corrosion resistance and hydrophobicity of TiN/Ti by using N graded films deposited onto aluminum substrates (AA-1100) by grid-assisted magnetron sputtering (GAMS). Electrochemical impedance spectroscopy (EIS) with potentiodynamic and potentiostatic polarization are used to investigate the performance of the substrate/film system at room temperature and 70 oC, thus simulating a prototypic PEMFC electrolyte environment. Electrochemical test results showed that graded TiN films improved corrosion resistance when compared with both the homogeneous films and the AA1100 uncoated substrate. Furthermore, contact angle results reveal improved hydrophobicity for both homogeneous and graded TiN coatings when compared with the AA1100 substrate.

25 ENERGY STORAGE↗

One dimensional wormhole corrosion in metals

Corrosion is a ubiquitous failure mode of materials. Often, the progression of localized corrosion is accompanied by the evolution of porosity in materials previously reported to be either three-dimensional or two-dimensional. However, using new tools and analysis techniques, we have realized that a more localized form of corrosion, which we call 1D wormhole corrosion, has previously been miscategorized in some situations. Using electron tomography, we show multiple examples of this 1D and percolating morphology. To understand the origin of this mechanism in a Ni-Cr alloy corroded by molten salt, we combined energy-filtered four-dimensional scanning transmission electron microscopy and ab initio density functional theory calculations to develop a vacancy mapping method with nanometer-resolution, identifying a remarkably high vacancy concentration in the diffusion-induced grain boundary migration zone, up to 100 times the equilibrium value at the melting point. Deciphering the origins of 1D corrosion is an important step towards designing structural materials with enhanced corrosion resistance.

36 MATERIALS SCIENCE↗

Applied Research and Development to Support Open Water Testing at PacWave – Task 5: Development of additively manufactured, functionally graded, corrosion resistant clads for wave energy applications

In this task, we focused on developing corrosion-resistant claddings for wave energy applications. Wave energy systems are exposed to saline conditions, which are corrosive to many metallic structural materials (e.g., carbon steel). Corrosion-resistant (stainless) steels are typically alloyed with >18% chromium (Cr) and >8% nickel (Ni), which dramatically raises material costs and can hinder the development of wave energy systems; thus, coatings are a necessary corrosion protection method for most. Non-metallic coatings (paint, epoxy) have shorter service lives, limited resistance to mechanical stress and wear, plus additional costs of inspection and eventual replacement. Therefore, overlay stainless steel (SS) claddings have a cost-effective use case for protecting components from corrosion, particularly for those that may be subject to mechanical stress / wear and with long service lives.

16 TIDAL AND WAVE POWER↗

Enhanced steam oxidation resistance of uranium nitride nuclear fuel pellets

Here, the steam oxidation resistance of UN and UN-(20 vol%)ZrN fuel pellets is evaluated to enhance understanding of steam corrosion mechanisms in advanced nuclear fuel materials. In situ neutron diffraction shows the modified UN fuel pellets form a (U 0.77 ,Zr 0.23 )N solid-solution and the sole crystalline oxidation product detected in bulk is (U 0.77 ,Zr 0.23 )O 2 . U 2 N 3 is not detected in significant quantities during the steam oxidation of UN or (U 0.77 ,Zr 0.23 )N and stable lattice parameters show that hydriding does not take place. Steam oxidation rates, obtained via sequential Rietveld refinement show how (U 0.77 ,Zr 0.23 )N has a higher activation energy (79 ± 1 kJmol -1 vs. 50 ± 5 kJmol -1 ), higher onset temperature (430 °C vs. 400 °C) and slower reaction rates for steam oxidation up to 616 °C, than pure UN. Throughout, both UN and (U 0.77 ,Zr 0.23 )N exhibit linear (non-protective) oxidation kinetics, signifying that degradation of the fuel pellets is caused by the evolution of gaseous products at the interface followed by oxide scale spallation. This quantitative and mechanistic understanding of material degradation enables better defined operating regimes and points towards (U,Zr)N solid solutions as a promising strategy for the design of advanced nuclear fuel materials with enhanced steam corrosion resistance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electron beam surface remelting enhanced corrosion resistance of additively manufactured Ti-6Al-4V as a potential in-situ re-finishing technique

This study explores the effect of surface re-finishing on the corrosion behavior of electron beam manufactured (EBM) Ti-G5 (Ti-6Al-4V), including the novel application of an electron beam surface remelting (EBSR) technique. Specifically, the relationship between material surface roughness and corrosion resistance was examined. Surface roughness was tested in the as-printed (AP), mechanically polished (MP), and EBSR states and compared to wrought (WR) counterparts. Electrochemical measurements were performed in chloride-containing media. It was observed that surface roughness, rather than differences in the underlying microstructure, played a more significant role in the general corrosion resistance in the environment explored here. While both MP and EBSR methods reduced surface roughness and enhanced corrosion resistance, mechanical polishing has many known limitations. The EBSR process explored herein demonstrated positive preliminary results. The surface roughness (R a ) of the EBM-AP material was considerably reduced by 82%. Additionally, the measured corrosion current density in 0.6 M NaCl for the EBSR sample is 0.05 µA cm –2 , five times less than the value obtained for the EBM-AP specimen (0.26 µA cm –2 ).

42 ENGINEERING↗

Unsupervised Clustering and Supervised Regression Learning to Select High Temperature Oxidation-Resistant Materials

High temperature oxidation and corrosion degradation mechanisms dictate the lifetime of materials critical to energy production. The combination of modeling and experimental approaches such as machine learning (ML) and data analytics, with sufficient experimental data, can accelerate the development of new materials while limiting its cost. In the present work, ML will be applied to two high temperature oxidation data libraries (Oak Ridge National Laboratory and National Air and Space Administration) that comprised of about 5000 mass change sample datasheets for a variety of materials and temperatures in dry air and air + 10 % H2O. A python code was developed to prepare the data for machine learning by collecting and formatting oxidation rate constants, alloy compositions and environment of exposure into a single data frame. Scikit-learn library and Statistics and Machine Learning Toolbox within MathWorks were then used to perform unsupervised clustering and supervised regression learning. The impact of dataset distribution on the performance of the developed ML models was evaluated. Potential strategies to improve the predictions and enhance extrapolative capability of the previously trained model were investigated.

Romedenne, Marie [ORNL] (ORCID:0000000317936561)↗

Performance of Structural Alloys in Bio-oil Production, Upgrading, and Storage Systems

Selection of corrosion-resistant, cost-effective structural materials for the process and containment vessels required for the production, upgrading, and storage of biomass-derived oils has been the subject of study in our laboratory for many years. The wide variety of biomass resources and the many liquefaction techniques and processing conditions result in products with a broad range of properties and compositions. Here, this paper will address the materials issues in three distinct areas. In production, materials are exposed to temperatures that range from 350 to 550 °C depending upon the process. Generally, austenitic stainless steels have performed reasonably well, although thicker oxide scales and intergranular attack have sometimes been observed. For storage and transport of the bio-oil products, temperatures experienced by the containment materials are not expected to exceed 50 °C. Our studies have shown that most raw bio-oils contain significant concentrations of organic acids, and low-molecular-weight organic acids were quite corrosive to carbon and low alloy steels. For some applications, subsequent processing is required, which includes hydrotreating or co-processing with a petroleum-derived liquid. These processes utilize a catalyst that requires periodic retreatment with a sulfidizing gas, and the exposure to this gas at elevated temperatures can cause appreciable corrosion to the more common austenitic stainless steels. The materials considered most cost-effective and sufficiently corrosion-resistant for each of these environments were identified.

36 MATERIALS SCIENCE↗

Atom Probe characterization of neutron irradiated commercial ZIRLO® and AXIOM X2® alloys

As part of the Mechanistic Understanding of ZIrconium Corrosion (MUZIC) program, this team has been instrumental to obtain EPRI and Westinghouse sponsorships to prepare the neutron irradiated ZIRLO® and X2® from Vogtle nuclear power plant and ship them from Studsvik’s (Sweden) hot cells to Idaho National Laboratory (INL) to be part of the NSUF library. The uniqueness of these sets of neutron irradiated alloys is that they are at the same two extremes of the fuel cycles, allowing us to study the microchemistry evolution as a function of irradiation doses, exposure time and solute content. Advanced commercial Zirconium-Niobium (Zr-Nb) alloys, such as ZIRLO® and AXIOM®, have been developed by Westinghouse to enhance the corrosion resistance of fuel cladding material for longer service time. This study specifically aims at investigating the neutron irradiation induced Nb redistribution in AXIOM® X2® to understand the effect of neutron irradiation induced microchemistry changes and the irradiation enhanced corrosion resistance observed in ZrNb alloys. The detailed sample information on chemical composition and irradiation is given in shown in Table 1a and 1b respectively. To study the neutron IIP/nanoclusters and Nb concentration in the solid solution, atom probe tomography (APT) is the primary tool to obtain reliable chemical information. APT specimens were prepared in shielded focused ion beam (FIB) at the Irradiated Materials Characterization Laboratory (IMCL) at INL followed by APT analysis at CAES facility using LEAP 4000XR

36 MATERIALS SCIENCE↗

Corrosion Testing Of Additively Manufactured Stainless Steel 316H In Molten Salt Environments

The development of a new ASTM standard for evaluating the corrosion resistance of additive manufactured (AM) stainless steel (SS) 316H in chloride molten salts is critical for the use of these materials in extreme environments such as molten salt reactors (MSRs). This report pertains to a work package of the Advaned Materials and Manufacturing Technologies (AMMT) developing a systematic methodology to link changes in AM fabrication parameters, namely surface finishing, porosity, microstructure, and chemical heterogeneity, to corrosion performance in NaCl-MgCl2 salt, a proposed secondary coolant for MSRs. During Fiscal Year 2024, Idaho National Laboratory investigators in the AMMT program, utilized SS316H bars, fabricated with laser bed powder fusion at Los Alamos National Laboratory, to establish and optimize the workflow for evaluating these process-to-performance relationships. Standard practices for specimen preparation were established using these specimens, with particular focus on descaling and sectioning methods that align with ASTM guidelines. A comprehensive experimental design for static corrosion testing was developed, with pre- and post-exposure analysis utilizing optical microscopy and scanning electron microscopy. So far standard descaling techniques were optimized, one static corrosion test was conducted on the LANL AM SS316H specimens, and pre- and post-corrosion practices were established. In addition, the work package yielded a review paper on corrosion testing gaps for AM materials in nuclear applications and submitted a proposal for a rapid-turnaround experiment to the Nuclear Science User Facilities Program to investigate the combined effects of proton irradiation and corrosion on AM SS316H. This work package establishes a foundation for evaluating processing-to-performance relationships for AM SS316H in harsh conditions, contributing to the safe and efficient design of components for next-generation nuclear reactors. The creation of a standardized methodology and the generation of relevant publications and future research pathways represent significant strides towards integrating AM materials into critical applications where corrosion resistance is paramount.

36 MATERIALS SCIENCE↗

Development of hydrothermal corrosion model and BWR metal coating for CVD SiC in light water reactors

SiC/SiC fiber composites with CVD SiC overcoats are potential candidates for light water reactor advanced accident tolerant cladding materials. Understanding its corrosion kinetics in Light Water Reactor (LWR) conditions is essential to evaluate the concept's viability. Existing models only account for the temperature and oxygen concentration effect on the hydrothermal corrosion behavior applicable to LWR operating conditions. However, the development of a general corrosion rate for CVD SiC that accounts for the impact of irradiated microstructure, flow rate, electrical resistivity, pH, and surface roughness is critical for the practical realization of SiC/SiC-based cladding concepts. After a rigorous experimental campaign, this work updates the existing hydrothermal corrosion model to predict hydrothermal corrosion in LWRs. Numerical radiation and coolant chemistry analysis for LWRs conducted based on the updated corrosion kinetic models suggests that CVD SiC is likely a viable environmental barrier coating for Pressurized Water Reactors while questionable for Boiling Water Reactors (BWR) when the effect of irradiation damage on SiC corrosion is considered. An effective mitigation strategy for the double-layer metal coating is proposed for BWR applications. The double-layer metal coating comprising a FeCrAl overcoat with an intermediate Cr bond coating was observed to provide a stable protective barrier against SiC dissolution in BWR conditions. Finally, the proposed metal coating was also fully adherent following quench and burst tests.

36 MATERIALS SCIENCE↗

Corrosion evaluation of metal foams in eutectic molten salts for high temperature latent heat energy storage application

High-temperature Thermal Energy Storage (TES) has drawn great attention as a technology that can increase the role and profitability of micro nuclear reactors in the decentralized clean energy market. Various research needs have been proposed by Idaho National Laboratory (INL) in "the Integrated Energy Systems: 2020 Roadmap" with the goal of utilizing the high temperature of 550 degrees or more generated in the 4th generation reactor to industrial purposes from the standpoint of integrated energy systems [1]. With the recent development of the 4th generation nuclear power plant, including micro nuclear reactor, there is a great deal of interest in researching how to efficiently couple a heat source to an industrial process through thermal processing. Texas A&M University (TAMU) and INL are currently collaborating to develop a novel latent heat storage design called HITB (Heat pipe-Integrated Thermal Battery). As part of the small-scale experimental demonstration research for HITB, a study for storage medium selection was conducted at TAMU. Eutectic salts have attracted interest as high-temperature heat storage medium for HITB. Especially, chloride molten salts and fluoride molten salts are considered promising candidates due to their high melting temperature, thermal stability, and high latent heat of fusion. Since eutectic salts have poor thermal conductivity in general, it is critical to distribute materials with high thermal conductivity evenly to facilitate the charging and discharging of heat. In this study, metal foam was considered in the HITB system to overcome the poor heat transfer characteristics of eutectic salts. In order to improve heat transfer, it is necessary to study materials with high thermal conductivity, corrosion resistant to molten salts, such as fins, extended surfaces, particles, microcapsulation, or foam structure. Porous structure of copper or aluminum can increase heat transfer area, form a thermal transfer network, and increase the effective thermal conductivity of thermal storage medium [2]. Since the melting temperature is required to be at least 450? in the current HITB design, various eutectic salts are being considered. FLiNaK and FLiBe, which are famous for fluoride salts, are good candidates, but due to the sharp rise in the price of LiF recently, they are excluded for economic reasons to be applied to large-capacity thermal energy storage. On the other hand, chloride salts are very cheap and easy to obtain, have a high melting temperature, and have a high latent heat of fusion, so they are recently in the spotlight as a phase change material. However, because of the hygroscopic nature of chloride salts, HCl gas due to impurity is easy to be released and is particularly vulnerable to corrosion. Chloride eutectic salts have been tested and suggested for metal alloys that are particularly resistant to corrosion, such as SS304, SS316, Hastelloy, Inconel 625, Incoloy 800H, which has low thermal conductivity, and is very expensive [3-6]. Porous materials with high thermal conductivity such as copper and aluminum have been tested for stability in fluids such as paraffin or water as metal foam or metal fin structures, but high temperature corrosion tests were not performed on various eutectic salts yet. Therefore, this study investigated the high temperature corrosion characteristics of metal alloys, such as C10100 foam, C10100 plate, 6101 alloy foam, and SS316 plate, while immersed in the candidate eutectic salts. A total of 20 tests for SS316 coupons and 10 tests for C10100 coupons were performed to ensure the repeatability of the present measurements. Since it is difficult to completely remove the salt inside metal foam due to the complex inner structure of the metal foam, only the surface condition was observed with a microscopy and scanning electron microscopy (SEM) image, except for measuring the corrosion rate and average mass loss.

25 ENERGY STORAGE↗

Screening aqueous organic redox couples for spontaneous hydrogen generation on catalysts

Two low-cost redox couples with near neutral or alkaline pH - 7,8-dihydroxyphenazine-2-sulfonic acid (DHPS) and chrome chelated ethylenediaminetetraacetic acid (Cr-EDTA) with ammonia – are identified to generate hydrogen evolution spontaneously on Pt/C catalysts. Cr-EDTA redox couple has two times higher hydrogen evolution rate than that of DHPS, and the charged Cr-EDTA molecules are fully utilized to generate hydrogen gas, while ~ 50% of DHPS molecules are utilized to produce hydrogen spontaneously on Pt/C catalysts. The Cr-EDTA electrolyte enables cost reduction by allowing cheap raw material of Cr and corrosion resistant alloy instead of costly superalloy for catalytic reactor systems. Furthermore, the Cr-EDTA with ammonia as a negolyte for flow batteries was validated to suppress hydrogen evolution side reaction, reach 99% of coulombic efficiency in flow cell operation paired with Fe(CN)6 redox couple near neutral pH.

08 HYDROGEN↗