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At least 37 records · Page 2

Final report on assessment of molten salt corrosion testing of unirradiated and ion irradiated advanced manufactured high entropy alloys

Generation IV reactors and future fusion reactor designs have led to more demanding materials performance requirements due to their increased operating temperatures, corrosive coolants, and increased radiation doses compared to the current light-water reactor fleet. Among the innovative nuclear technologies under development, molten salt reactors stand out for their potential to offer superior fuel utilization, intrinsic safety characteristics, and economic viability. Of the proposed Generation IV designs, the gas fast reactor operates at 450 to 850°C and the molten salt reactor operates at 565 to 850°C, with the molten salt reactor design needing molten salt corrosion resistant materials [1, 2]. These increased temperatures and more extreme corrosion environments necessitate higher material performance, such as creep strength, radiation-tolerant microstructures, corrosion resistance, and high-temperature tensile properties. Hastelloy-N, a nickel-based alloy with additions of molybdenum and chromium, has been successfully employed to contain molten fluoride salt at temperatures up to 705°C. However, Hastelloy-N becomes embrittled upon neutron irradiation, primarily due to the accumulation of helium produced by (n,a) transmutation reactions. Furthermore, the corrosive nature of molten fluoride and chloride salts presents a formidable challenge, as these salts can react with and dissolve alloying elements such as Cr, Mo, and Fe, leading to selective leaching, loss of protective oxide layers, and accelerated degradation. High entropy alloys (HEAs) and refractory high entropy alloys (RHEAs) have emerged as a prominent area of interest, due to their ability to achieve tailored chemical compositions for specific applications. Unlike conventional alloys, HEAs are characterized by having multiple principal elements in equimolar or near equimolar ratios, leading to an unconventional alloying strategy [3]. This alloying strategy is believed to promote unique properties, such as single-phase stabilization of chemically compatible elements, lattice distortion effects due to atomic radius differences, and proposed sluggish diffusion effects. For extreme-environment applications, RHEAs have garnered much research interest because of the possibility of creating relatively ductile materials that can operate in extremely high-temperature environments, beyond the operating temperatures where other Ni-based superalloys begin to lose strength [4-6]. Idaho National Laboratory (INL) initiated a joint international effort with the Czech Republic to explore the feasibility of manufacturing HEAs for high-temperature nuclear applications using advanced manufacturing. This effort was funded at INL by the United States Department of Energy's Office of Nuclear Energy under the Advanced Reactor Technologies and Advanced Materials and Manufacturing Technologies (AMMT) Program. The HEAs were specifically designed for the corrosive and irradiation environments experienced in gas-cooled fast reactors, molten salt reactors, and fusion power. These alloys have been manufactured by multiple processes to determine the impact of manufacturing processes on the performance of the alloys in corrosive and irradiation environments. Preliminary molten salt corrosion testing showed that equimolar MoNbTiV and MoNbTi alloys exhibit exceptional performance, with arc-melted variants demonstrating only minimal degradation after 1000 hours of exposure to molten chloride salt at 700°C. Conversely, Nb2TiVZr2 showed significant molten salt corrosion susceptibility and microstructural instability during high-temperature molten salt exposures, and was, therefore deemed unfit for molten salt reactor applications. The MoNbTiV, MoNbTi, and Nb2TiVZr2 alloys were further evaluated through ion irradiation experiments conducted at the Michigan Ion Beam Laboratory at the University of Michigan. The microstructural stability and the evolution of irradiation-induced defects were characterized to assess the irradiation resistance of each of these alloys.

36 - MATERIALS SCIENCE↗

Iron surface corrosion in supercritical CO2 at atomic scale investigated by molecular dynamics simulations

Understanding the corrosion behavior of steels in supercritical carbon dioxide (S-CO2) is essential for ensuring the safe application of S-CO2 as a heat-transfer fluid in high-temperature energy systems, including advanced nuclear reactors. In this work, molecular dynamics (MD) simulations using ReaxFF potential are performed to explore the atomic-scale corrosion mechanisms of body-centered cubic iron (BCC-Fe) in S-CO2. The results show that CO2 molecules in S-CO2 decompose at the Fe surface, generating free C and O atoms that form Fe-C and Fe-O bonds and subsequently produce oxides and carbides. Concurrently, Fe atoms dissolve from the surface and diffuse into the S-CO2 region, resulting in interdiffusion of Fe, C and O atoms at the interface. The corrosion-layer thickness calculations show that high pressure and temperature induced by S-CO2 have stronger effects than surface orientation on the corrosion process. In addition, surface Fe atoms undergo substantial displacement under S-CO2 exposure, further accelerating corrosion. When a radiation-induced void is introduced near the Fe surface, the corrosion is enhanced. The void-matrix interface expands the reaction surface area and simultaneously induces corrosion reactions inside the bulk, resulting in a deeper penetration of C and O and thicker corrosion layers. All these results indicate that high-temperature, high-pressure and radiation-induced voids can seriously affect the corrosion of Fe in S-CO2, and must be considered to better use S-CO2 in nuclear facilities.

Li, Wenhua↗

Corrosion Behavior of Hydrophobic Coatings in Aqueous CO2 Environments

Internal corrosion is caused by gas impurities such as CO2, moisture, and H2S, leading to material degradation. To combat this, the National Energy Technology Laboratory (NETL) developed a novel hydrophobic coating to reduce surface hydrophobicity and enhance the corrosion resistance of steel. NETL’s approach uses multi-layer hydrophobic coatings, a novel and promising coating that could potentially revolutionize the industry's approach to internal corrosion mitigation. This work aims to investigate the corrosion performance of the hydrophobic coating and determine the water uptake. Electrochemical corrosion experiments were carried out on bare X65 carbon steel without and with coating in 3.5 wt.% NaCl saturated with CO2 at 20 °C to follow the water uptake as a function of exposure time. Linear polarization resistance (LPR) was used to determine the corrosion rate for carbon steel immersed in a NaCl electrolyte saturated with CO2. Electrochemical impedance spectroscopy (EIS) of uncoated and coated bare carbon steel was investigated. The analyses of impedance models and water uptake behaviors of hydrophobic coatings were studied for 200 hours during the corrosion process. The water uptake was estimated using the Brasher and Kingsbury relation. The results showed that the superhydrophobic coating that was developed used innovative nano-based materials to act as protection layers on the surface of metallic parts against mechanical aggressors, corrosion, and fouling agents.

corrosion behavior↗

Dynamic and static corrosion of chromium-alumina refractory in simulated nuclear waste glass

Monofrax® K-3, a chromium–alumina refractory, is widely used in nuclear waste glass melters due to its high durability. However, aggressive vitrification conditions still lead to corrosion that limits melter lifespan. Here, this study investigates two key corrosion modes, subsurface and melt-line corrosion, under static and dynamic conditions, using a custom setup enabling precise control of melt velocity and temperature. Experimental results, interpreted using diffusion-limited dissolution models, show that (i) subsurface corrosion increases by approximately 10% per mm/s increase in melt velocity, while melt-line corrosion remains virtually unaffected, (ii) corrosion rate dependence on temperature is inversely proportional to melt viscosity, and (iii) glass composition affects both corrosion modes similarly, based on Cr 2 O 3 , Al 2 O 3 , and alkali contents. The experimental data also allowed the determination of diffusion coefficients of major dissolving species, which were found to be consistent between the melt-line and subsurface corrosion models, indicating their suitability for future CFD studies.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗

Hot corrosion behavior of 304 & P91 graded composite transition joint under molten sulfate salts

A novel graded composite transition joint (GCTJ) between AISI 304 stainless steel and ASTM A335 P91 steel, has been demonstrated remarkablely superior creep performance compared to the conventional dissimilar metal weldment (DMW) under equivalent conditions. However, this advance is challenged by hot corrosion under salt deposition at elevated temperatures. Here, this study investigates the hot corrosion behavior of 304&P91 GCTJ exposed to sulfate salts at 700°C. Compared to the 304 steel, corrosion attacks initiate in the P91 triangle, where the dual-phase microstructure of ferrite and tempered martensite significantly influences pitting initiation. Anodic dissolution mainly occurs within the tempered martensite due to more vulnerable sites within the tempered martensite. With prolonged exposure, corrosion propagates across both phases, and the corrosion depth within the P91 triangle is related to the exposed surface area ratio between 304 and P91. Electrochemical analysis reveals the occurrence of galvanic corrosion between the 304 and P91, with a positive linear relationship between anodic dissolution current density (I a ) and the exposed surface area ratio between 304 and P91 in molten salts, further emphasizing the critical impact of this ratio on the corrosion severity in the P91 triangle. These findings underscore the importance of transition zone design optimization in mitigating localized corrosion.

Galvanic corrosion↗

Synergistic Effects of Molten Salt Corrosion and Proton Irradiation on Grain Boundary Strength in Ni-20Cr

Nickel-based alloys are leading contenders for use as structural materials in molten salt reactors. While there have been extensive studies on the impact of fluoride/chloride-based molten salt corrosion on the microstructural evolution of various nickel-based alloys, the effects of simultaneous molten salt corrosion and radiation on the mechanical integrity of grain boundaries (GBs) remain underexplored. In this study, we use a Ni-20Cr model alloy to investigate this issue, subjecting it to simultaneous molten fluoride salt corrosion and proton irradiation. We performed cross-sectional and chemically-sensitive electron microscopy characterization of the microstructures of these materials, identifying the characteristic corrosion-induced microstructure and local chemical heterogeneity near GBs. After developing a sample preparation method for reliable characterization of GB strength, we assess the mechanical degradation of GBs using in situ push-to-pull micro tensile tests. Our findings reveal that voids induced by corrosion are the primary influence on the failure mode of GBs, regardless of whether proton irradiation is present. For materials that exhibit ductile fracture, those subjected to simultaneous corrosion and radiation exhibit lower yield strengths than those exposed to corrosion alone, which may be linked to the previously observed phenomenon of proton irradiation-decelerated intergranular corrosion in molten salt.

36 - MATERIALS SCIENCE↗

The Effect of Flow on CO2 Corrosion of Self-Healing Metallic Coatings

Internal corrosion is an issue that affects natural gas pipelines, a significant part of the United States’ energy infrastructure. Over time, this corrosion has worn away longstanding pipelines due to the original construction materials used for the lines and impurities in the gas and liquid streams flowing through them. The main impurities in natural gas are H2O, CO2, H2S, and O2. One of the leading causes of corrosion is the CO2 dissolved in water, giving rise to carbonic acid formation, which can further dissolve the steel pipe. The National Energy Technology Laboratory (NETL) has been studying different solutions to this problem. One potential answer is a self-healing sacrificial metallic coating applied by a novel cold spray technique. This study explored the impact of flow on corrosion with this coating and carbon steel when exposed to a saturated CO2 environment by simulating the pipeline flow profile in a small-scale lab setting. The samples were evaluated using multiple electrochemical techniques that found corrosion rates and were backed up with surface analysis to conclude the behavior of the corrosion mechanisms. The cold spray coating exhibited steel corrosion protection under flow conditions. This study has significantly advanced our understanding of CO2 corrosion, particularly in the context of natural gas pipelines and coating design.

carbon steel↗

The Effect of Flow on CO2 Corrosion of Self-Healing Metallic Coatings

Internal corrosion is an issue that affects natural gas pipelines, a significant part of the United States energy infrastructure. Over time, this corrosion has worn away longstanding pipelines due to the original construction materials used for the lines and impurities in the gas and liquid streams flowing through them. The main impurities in natural gas are H2O, CO2, H2S, and O2. One of the leading causes of corrosion is the CO2 dissolved in water, giving rise to carbonic acid formation, which can further dissolve the steel pipe. The National Energy Technology Laboratory (NETL) has been studying different solutions to this problem. One potential answer is a self-healing sacrificial metallic coating applied by a novel cold spray technique. Previous studies at NETL have shown that the zinc-rich self-healing coating can withstand corrosion through passivation and create a barrier to the diffusion of corrosive species. This study explored the impact of flow on corrosion with this coating and carbon steel when exposed to a saturated CO2 environment by simulating the pipeline flow profile in a small-scale lab setting. The samples were evaluated using multiple electrochemical techniques that found corrosion rates and were backed up with surface analysis to conclude the behavior of the corrosion mechanisms.

CO2 corrosion↗

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↗

Mitigate Stress Corrosion Cracking (SCC) in High-strength Al Castings (CRADA 508)

Development of high strength, corrosion resistant, aluminum alloys is important to a number of industries, including automotive, aerospace, power, etc. Understanding how processing methods such as casting, chemistry, additives and recycle content affect an alloy’s microstructure and performance in real world environments is crucial to their implementation. One major concern is how the repeated exposure to saline solutions can be detrimental to the structural integrity of aluminum alloy components. This study was undertaken as a collaboration between Eck Industries and PNNL to investigate the stress corrosion cracking (SCC) and corrosion behavior of aluminum alloys. This work examines the SCC response of three different materials set. First is cast A206 Al alloy produced by three different casting techniques (i.e., permanent mold, and sand casting with and without chill) and with or without nano forming additives as potential grain refiners. The second materials set comprises Al alloy tubes extruded by PNNL’s ShAPE process and produced using raw material with three different ratios of twitch and pre-consumer Al 6061 scrap. Finally, the third materials set comprises two Al-Si-Mg-Fe alloys with controlled Si% and Fe% to mimic recycle grade Al alloys. The corrosion behavior of these materials was characterized using SCC testing and scanning electrochemical cell microscopy (SECCM) technique; mechanical behavior was characterized using tensile testing, and microstructure was characterized using optical and electron microscopy techniques. Of the A206 Al alloys, the samples with nano forming additives performed poorly compared to those without. The best SCC performance (i.e. least degradation in mechanical properties) was demonstrated by A206 alloy sand cast with chill while the permanent mold sample showed the worst SCC performance. The SECCM was performed on A206 alloy sand cast with chill to understand the effect of microstructure and determine the location-dependent corrosion properties on grain boundaries (GB) and inside grains (IG) on the sample. The corrosion potential and current measured on GB and IG at various points on the sample established that the GB locations are more cathodic and corrosive than the IG locations. Further work needs to be conducted to investigate the mechanisms behind the observed dependence of SCC on casting technique and nano forming additives. Among the ShAPE extruded tubes, SECCM data suggests the decreasing order of tendency to corrode as follows: 100% twitch > 75% twitch > 50% twitch. Finally, both variants of the Al-Si-Mg-Fe alloys showed a large volume fraction of Fe- and Si-containing intermetallics and additional work is needed to discern differences in their respective corrosion responses. In summary, correlating local electrochemical behavior (e.g. via SECCM) with micro/nanostructure, in conjunction with bulk mechanical behavior, can help identify the right fabrication method and alloy chemistry to minimize SCC issues in Al alloys.

36 MATERIALS SCIENCE↗

Atomistic Mechanisms of Stress-Dependent Molten Salt Corrosion in NiCr Alloys

Ni-based structural alloys in molten salt environments often experience simultaneous mechanical loading and corrosive attack, yet the mechanisms governing stress-corrosion interactions remain unclear. Prior studies largely emphasize tensile stress, while the role of compressive stress has received limited attention. Here, reactive molecular dynamics simulations are used to investigate the coupled effects of applied strain and corrosion in Ni 0.75 Cr 0.25 exposed to molten FLiNaK at 800 °C. A Σ5(210) grain boundary model is subjected to tensile (+4%) to compressive (−4%) uniaxial strains, and corrosion behavior is evaluated through fluorine adsorption, charge redistribution, and grain boundary evolution. Tensile strain accelerates intergranular corrosion susceptibility by reducing local atomic packing through elastic dilation and increasing excess free volume at the grain boundary, which enhances atomic mobility and salt infiltration. In contrast, compressive strain can suppress corrosion by promoting the formation of a ridge-like surface layer along the grain boundary, limiting salt access to the underlying alloy. These results provide atomistic insight into how stress states influence grain boundary corrosion in molten salts.

36 - MATERIALS SCIENCE↗

Enhancing corrosion resistance of lightweight metal alloys through laser shock peening

In this study, we investigated the effects of laser shock peening (LSP) on the corrosion resistance of lightweight metal alloys, specifically AA6061 and AZ31. LSP was performed underwater, using a nanosecond pulse laser and without using a protective coating or layer on the workpiece. The corrosion behaviors of these alloys were analyzed through electrochemical tests, including open circuit potential, electrochemical impedance spectroscopy, and potentiodynamic polarization measurements. The results demonstrated that LSP significantly improved the polarization resistance, and higher laser power intensities led to increased corrosion resistance and reduced corrosion rates. This enhancement in anti-corrosion performance is attributed to the formation of a protective oxide layer on the surface, acting as a barrier against corrosion. In conclusion, the findings underscore the potential of laser surface treatment as a viable technique for enhancing the corrosion resistance of lightweight metal alloys.

36 MATERIALS SCIENCE↗

Composite coatings from polycarbosilane derived SiC and Al/SiC cermet active fillers as protective barriers against steel corrosion

Stainless steel is used throughout the world as a structural material. However, it undergoes corrosion damage when exposed to extremely corrosive media, such as the marine environment. An alternative to solve this problem lies in the development of coatings that can withstand extreme conditions but also be easily deposited with inherently corrosion-resistant materials such as silicon carbide (SiC). The present study shows a simple method to produce Al/SiC cermet powders by attrition milling. The resulting cermet powders with a metallic matrix and hemispherical morphology, were employed as fillers in polycarbosilane (PCS) solutions that were sprayed on A304 stainless steel substrates. Al/SiC composite coatings were produced after heating the sprayed suspensions at 700 °C for 1 h in Ar atmosphere. The resulting composite coatings exhibited low surface energies (< 35 mN/m), water contact angles of 53°, and adhesion strength of up to 30 MPa. Finally, corrosion tests were performed in a cyclic corrosion test chamber, showing that these coatings effectively reduced the corrosion rate of stainless steel by 87%, reaching corrosion rate values of 0.007 g/cm 2 year.

36 MATERIALS SCIENCE↗

Validating corrosion models: Influence of physical properties

In chloride containing environments, two metals in physical contact can undergo galvanic corrosion limiting the lifetime of components. Being able to accurately predict galvanic corrosion damage distributions over time has not been widely presented in literature. Therefore, Finite Element Method (FEM) corrosion models were experimentally validated for two galvanic couples as a function of governing equations, environment, anode material, anode:cathode ratio, and time. Carbon steel/stainless steel (CS/SS) and zinc/stainless steel (Zn/SS) galvanic couples were exposed to NaCl solutions at room temperatures for up to 14 days. For the galvanic couples and environments, the Laplace equation with variable conductivity and reactions was sufficient to model the experimental corrosion damage. Increasing the chloride concentration for the CS/SS galvanic couple, regardless of the anode:cathode ratio, decreased the observed and modeled corrosion damage. Decreasing the anode:cathode ratio (i.e., increasing the cathode length), increased the experimentally observed and modeled corrosion damage. For small anode:cathode ratios, the governing equations deviate over long time periods with the Nernst-Plank equation being conservative. For the Zn/SS galvanic couple, the cathode length controls the dominant cathodic reduction reaction. For small cathode lengths, the hydrogen evolution reaction is dominant. For larger cathode lengths, the oxygen reduction reaction is dominant. The results are discussed with regard to the influence of solution chemistry, ohmic drop, and governing reactions. Overall, validated FEM models were presented, and the resultant models, physics, and mechanisms can be applied to other corrosion scenarios with confidence.

Carbon steel↗

Electrochemical Corrosion and Catalysis Dynamics of Tin Oxide during Water Oxidation

Metal oxide corrosion severely limits anodic electrocatalysis, particularly at high potentials in acidic environments, where degradation pathways remain poorly defined. This study establishes explicit connections between corrosion and electrocatalysis on tin oxide during water oxidation by examining the roles of lattice defects, reactive oxygen species, interfacial pH variations, and speciation of corroded tin in acid. We first demonstrate the presence of structural defects such as oxygen vacancies and substoichiometric Sn(II) species by integrating electron paramagnetic resonance spectroscopy, ultraviolet photoelectron spectroscopy, and Mott–Schottky analysis. Kohn–Sham density functional theory calculations reveal that explicit water structures thermodynamically stabilize reaction intermediates and lower reaction overpotentials. Moreover, we propose that water dissociation leads to hydrogen-bonding networks formed by H* and OH* intermediates, which may span the entire catalyst surface and decrease the interfacial pH to drive corrosion. In contrast, the electrochemical generation of reactive oxygen species is shown to play a minor role in catalyst corrosion during water oxidation using inductively coupled plasma mass spectrometry coupled with selective chemical scavengers. Square-wave voltammetry combined with rotating ring-disk electrodes is used to reveal that under open-circuit conditions, only Sn(IV) cations chemically dissolve from tin oxide, while both Sn(IV) and Sn(II) species electrochemically corrode during water oxidation. Our results unveil a dynamic and complicated interplay between corrosive and catalytic pathways on metal oxide electrocatalysts: a decrease in interfacial pH due to water oxidation exacerbates Sn(II)/Sn(IV) corrosion. Subsequently, the electrochemical corrosion of Sn(II)/Sn(IV) facilitates product formation from lattice oxygen, while the redeposition of corroded Sn(II) as Sn(IV) can enable oxygen exchange with water. By elucidating the roles of defects and interfacial chemistry, this work provides a roadmap for engineering improved electrocatalysts that balance activity and stability, a critical step toward scalable and durable energy technologies.

36 MATERIALS SCIENCE↗

Impact of Irradiation on Corrosion Performance of Hybrid Organic/Inorganic Coatings on Austenitic Stainless Steel

The effects of gamma radiation on the performance of two corrosion-resistant coatings applied to stainless-steel 304L (SS304L) surfaces are presented. Specifically, the ability of the coatings to mitigate corrosion of SS304L surfaces as a function of the dose received (0–1300 Mrad) and dose rate (176 compared to 1054 rad/s) is evaluated using electrochemical methods, spectroscopy, and microscopy. Coating A, an organic/inorganic hybrid coating consisting of a two-part silica ceramic component and a polymer linker was evaluated in comparison to Coating B, which utilized Coating A as a topcoat for a commercial, off-the-shelf, Zn-rich primer. Post irradiation, Coating A demonstrated some corrosion protection following exposure to low levels of gamma radiation, but coating degradation occurred with an increased exposure dose and resulted in isolated regions of corrosion initiation. For Coating B, greater corrosion resistance was observed compared to Coating A due to the sacrificial nature of the Zn at elevated doses of gamma radiation. No effect of the dose rate (for the single dose examined) was observed for either coating. It is proposed for Coating B that as the polymer coating thermally degrades above 250 °C (bond scission of the polymer occurs), the remaining Zinc layer adhered to the SS304L post-irradiation enables enhanced corrosion resistance as compared to Coating A, which displays solely polymer degradation. The results presented herein establish an understanding of coating behavior with radiation exposure, specifically the relationship between corrosion coating performance and radiation dose, and can inform ageing and lifetime management for various applications.

degradation↗

Amine Structure Governs Corrosion Rates of Copper Catalysts in Electrochemical Reactive Capture of CO 2

Reactive capture of CO 2 (RCC) offers an integrated approach that combines CO 2 capture with its direct electrochemical conversion, eliminating the need for CO 2 release from the capture agent. By avoiding the pH, pressure, and temperature swings required for the release step, RCC has the potential to reduce both energy consumption and capital costs compared to the conventional sequential process of CO 2 capture, release, concentration, and conversion. Amines, widely used in industrial CO 2 capture, face challenges in RCC systems due to their incompatibility with transition metal catalysts as well as their tendency to promote electrode corrosion and parasitic hydrogen evolution. Identifying suitable combinations of amines and catalysts is therefore critical to enabling integrated CO 2 capture and conversion. Here, this work systematically investigates the performance of four primary and four secondary amines for RCC on polycrystalline Cu catalysts. Among the eight tested amines, only dimethylamine showed no measurable Cu corrosion near the open circuit potential. In contrast, ammonia, methylamine, ethylamine, monoethanolamine, diethylamine, diethanolamine, and piperazine all induced Cu corrosion. Corrosion rates correlate with the pK a and steric hindrance of the amines, highlighting key parameters for catalyst–amine codesign. Grand canonical DFT calculations indicate a correlation between the adsorption strength of protonated amines, their pK a , and the extent of Cu corrosion, suggesting that both the surface binding of protonated amines and the lability of their protons play critical roles in corrosion acceleration near open circuit potentials. These finding suggest that amines with high pK a values and weak binding of their protonated forms to Cu surfaces are preferred, as they offer better corrosion resistance.

Choi, Jounghwan [Univ. of California, Los Angeles,↗

Property Measurements of LiF-NaF-KF Molten Salts Doped with Corrosion Products and Oxygen

Measurements of thermophysical properties of molten salts are needed for modeling and simulation activities that support the development of molten salt reactor (MSR) technologies. Properties of interest including transition temperatures, phase behavior, heat capacity, density, volumetric thermal expansion, surface tension, viscosity, thermal diffusivity, thermal conductivity, and vapor pressure are being performed at Argonne. Results of these property measurements are suitable for use in evaluating reactor performance during startup and the early operating life of the reactor. Ingressions of oxygen and moisture into the fuel salt are expected to occur at different times during the operating life of the reactor due to system leaks, maintenance, and refueling activities. The presence of these environmental contaminants induces corrosion of structural materials. The introduction of corrosion-derived species, oxygen and moisture is expected to affect the physical and chemical properties of the salt and operation of the reactor. Previous work performed at Argonne evaluated the effects of fission product dopants on the thermal properties of eutectic LiF-NaF-KF (FLiNaK). Properties of FLiNaK are commonly used to represent those of fluoride-bearing fuel salts. Metallic corrosion products such as chromium and nickel ions together with dissolved oxygen are expected to affect system redox differently than the accumulation of fission products. Work summarized in this report was performed to measure the effects of corrosion products and dissolved oxygen on the phase transitions, and specific heat capacity of FLiNaK. Thermophysical property measurements were made using four salts that were prepared by doping aliquots of a eutectic mixture of FLiNaK with surrogate corrosion products. Controlled additions of CrF 3 and NiF 2 were used as surrogates for corrosion product contamination anticipated during extended reactor operations in which fuel salt is in contact with steel reactor components. Controlled additions of UF 4 from two sources containing known amounts of UO 2 at different concentrations were used to represent oxygen contamination. The phase transitions and specific heat capacities of the four salts were measured by using differential scanning calorimetry. Measurements were made at temperatures spanning the range of 500−900 °C, which is the expected operating range of MSRs. Measured property values were compared to values measured previously with eutectic FLiNaK without dopants. Differences between property values measured for the doped and non-doped salts were compared with the uncertainties of the measurements to determine the significance of the effect of corrosion products and oxygen on salt properties.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗