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At least 199 records · Page 11

High-performance corrosion-resistant high-entropy alloys

This disclosure provides alloy compositions comprising the main constituent elements iron, nickel, cobalt, molybdenum, and chromium. In one embodiment, the alloy comprises 10.0 to 30.0 wt % iron; 30.0 to 60.0 wt % nickel; 10.0 to 25.0 wt % cobalt; 1.0 to 15.0 wt % molybdenum; 15.0 to 25.0 wt % chromium by weight; where the sum of iron and nickel is at least 50 wt %; and, where the balance comprises minor elements, the total amount of minor elements being about 5% or less by weight. The alloy compositions have use as coatings to protect metals and alloys from corrosion in extreme environments where corrosion is a major concern such as with exposure to sea water or sea water with CO 2 .

Hawk, Jeffrey A.↗

High operating temperature heat transfer fluids for solar thermal power generation. Final report

This is the final technical report for the DOE MURI project on developing high-operating temperature heat transfer fluids for solar thermal power generation. This project aimed to evaluate liquid metals as a heat-transport fluid and potential energy storage medium for concentrated solar powered (CSP) systems. The project consisted of five phases, starting with fluid selection and screen and ending with potential CSP integration. The initial fluid selection arrived at heavy liquid metals as candidate fluids such as lead bismuth eutectic (LBE) as the prime liquid-alloy candidate to be studied, given the conditions above. Fifty-seven liquid compositions were initially identified with liquidus temperatures lower than 200°C, composed of elements that provide no driving force to the reduction of Cr 2 O 3 or Al 2 O 3 passivation layers in pipe material which is required for corrosion prevention. LBE was identified as the primary candidate fluid after these compositions were compared against computational thermodynamic modeling to screen all of the selected systems that would be compatible with our design objectives. Twenty-eight of these compositions were also investigated with the rapid characterization methods; the accuracies of the liquidus temperature and the specific heats predicted by the computations were better than 3 percent and 9 percent, respectively. We conducted numerus corrosion tests of various Fe-Cr-Al based steels in LBE and its variants at temperate as high as 800°C. It was found that minor additions to the liquid did not provide sufficient corrosion protection to warrant their use in real applications. Furthermore, we investigated the detailed mechanism of corrosion between heavy liquid metal and the pipe material at these very high temperatures. A liquid metal loop was constructed to operate at these high temperatures. The loop construction and operation lead to valuable lessons learned that will be needed for industrial scale loops. Furthermore, we learned that electromagnetic pumps at these extreme temperatures will have to be reengineered and redesigned to be used for CSP applications.

14 SOLAR ENERGY↗

Plutonium Oxidation State Distribution in the Presence of WIPP-Relevant Organics and Iron Corrosion Products

The oxidation state and solubility of plutonium (Pu) in high ionic strength synthetic WIPP (Waste Isolation Pilot Plant) brines as a function of pC H+ in the presence and absence of WIPP-relevant organic ligands (EDTA [Ethylenediaminetetraacetic acid], oxalate, citrate, acetate) and iron corrosion products (magnetite and metallic iron) at 𝑇 = 23 ± 2 ∘C was thoroughly studied by long-term batch solubility experiments (between approximately 800-1,100 days) from an undersaturation approach. The oxidation state of Pu in the WIPP environment has been a topic of interest since the initial Compliance Certification Application (CCA). This study aims to investigate the solubility of Pu under the expected WIPP conditions and to determine the oxidation state of the solid phase that will control the solubility. One of the most important results of this study is that the Pu oxidation state was analyzed both from the surface area of the corrosion products and in the precipitated solid. The analysis of the Pu oxidation state on the surface of the iron mineral from the ongoing undersaturated experiments is more relevant to the performance assessment of nuclear waste disposal than short term batch (plutonium-iron phase) experiments. The X-ray Absorption Near-Edge Spectroscopy (XANES) analysis showed that Pu oxidation state is different on the metal surface and in the precipitated solid. Pu(III) is the dominant oxidation state in the metallic iron (Fe 0 ) system in the presence and absence of organics. Pu(IV) is the dominant oxidation state in the magnetite system in the presence and absence of organics. Also, organics stabilize Pu(IV) in the magnetite system. Analysis of Pu in the precipitated solid by Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that Pu formed an inner-sphere complex with iron with minor amounts of PuO 2 present. X-ray diffraction (XRD) results indicate that metallic iron and magnetite did not oxidize in three years in the alkaline and high ionic strength system. Under these conditions (8 < pC H+ < 10 at T = (22 ± 2) °C under nitrogen atmosphere, the solubility of Pu changes by up to three orders of magnitude (10 -5 and 10 -8 M). The spread in solubility is highest at pC H+ = 9. Pu(III) and Pu(IV) showed different solubility behavior in the synthetic WIPP brine. A summary of the data collected in this report will be submitted to Sandia National Laboratories as part of a parameter update report which will outline the changes to the OXSTAT parameter for the 2026 Compliance Recertification Application (CRA-2026). The experiments performed were done according to the U.S. Department of Energy (DOE) approved Test Plan entitled “Effects of Radiolysis, Organic Complexation, and Redox Conditions on the Speciation and Oxidation State Distribution of Pu(III/IV)” (LCO-ACP-25). All data reported were obtained under the Los Alamos National Laboratory-Carlsbad Office (LANL-CO) Quality Assurance Program, which is compliant with the DOE Carlsbad Field Office, Quality Assurance Program Document (CBFO/QAPD).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Peening Techniques for Surface Modification: Processes, Properties, and Applications

Surface modification methods have been applied to metals and alloys to change the surface integrity, obtain superior mechanical properties, and improve service life irrespective of the field of application. In this review paper, current state-of-the-art of peening techniques are demonstrated. More specifically, classical and advanced shot peening (SP), ultrasonic impact peening (UIP), and laser shock peening (LSP) have been discussed. The effect of these techniques on mechanical properties, such as hardness, wear resistance, fatigue life, surface roughness, and corrosion resistance of various metals and alloys, are discussed. This study also reports the comparisons, advantages, challenges, and potential applications of these processes.

microstructure↗

First Principles Determination of the Potential-of-Zero-Charge in an Alumina-Coated Aluminum/Water Interface Model for Corrosion Applications

The surfaces of most metals immersed in aqueous electrolytes have a several-nanometer-thick oxide/hydroxide surface layer. This gives rise to the existence of both metal|oxide and oxide|liquid electrotlyte interfaces, and makes it challenging to correlate atomic length-scale structures with electrochemical properties such the potential-of-zero-charge (PZC). The PZC has been shown to be correlated the onset potential for pitting corrosion. Here, we conduct large-scale Density Functional Theory and ab initio molecular dynamics to calculate the PZC of a Al(111)| γ -Al 2 O 3 (110)| water double-interface model within the context of aluminum corrosion. By partitioning the multiple interfaces involved into binary components with additive contributions to the overall work function and voltage, we predict the PZC to be -1.53 V vs SHE for this model. Furthermore, we calculate the orbital energy levels of defects like oxygen vacancies in the oxide, which are critical parameters in theories associated with pitting corrosion. We predict that the Fermi level at the PZC lies above the impurity defect levels of the oxygen vacancies, which are therefore uncharged at the PZC. From the PZC estimate, we predict the voltage needed to create oxygen vacancies with net positive charges within a flatband approximation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Suppressing Universal Cathode Crossover in High‐Energy Lithium Metal Batteries via a Versatile Interlayer Design**

Abstract The universal cathode crossover such as chemical and oxygen has been significantly overlooked in lithium metal batteries using high‐energy cathodes which leads to severe capacity degradation and raises serious safety concerns. Herein, a versatile and thin (≈25 μm) interlayer composed of multifunctional active sites was developed to simultaneously regulate the Li deposition process and suppress the cathode crossover. The as‐induced dual‐gradient solid‐electrolyte interphase combined with abundant lithiophilic sites enable stable Li stripping/plating process even under high current density of 10 mA cm −2 . Moreover, X‐ray photoelectron spectroscopy and synchrotron X‐ray experiments revealed that N‐rich framework and CoZn dual active sites can effectively mitigate the undesired cathode crossover, hence significantly minimizing Li corrosion. Therefore, assembled lithium metal cells using various high‐energy cathode materials including LiNi 0.7 Mn 0.2 Co 0.1 O 2 , Li 1.2 Co 0.1 Mn 0.55 Ni 0.15 O 2 , and sulfur demonstrate significantly improved cycling stability with high cathode loading.

Xie, Chuyi↗

Suppressing Universal Cathode Crossover in High‐Energy Lithium Metal Batteries via a Versatile Interlayer Design**

Abstract The universal cathode crossover such as chemical and oxygen has been significantly overlooked in lithium metal batteries using high‐energy cathodes which leads to severe capacity degradation and raises serious safety concerns. Herein, a versatile and thin (≈25 μm) interlayer composed of multifunctional active sites was developed to simultaneously regulate the Li deposition process and suppress the cathode crossover. The as‐induced dual‐gradient solid‐electrolyte interphase combined with abundant lithiophilic sites enable stable Li stripping/plating process even under high current density of 10 mA cm −2 . Moreover, X‐ray photoelectron spectroscopy and synchrotron X‐ray experiments revealed that N‐rich framework and CoZn dual active sites can effectively mitigate the undesired cathode crossover, hence significantly minimizing Li corrosion. Therefore, assembled lithium metal cells using various high‐energy cathode materials including LiNi 0.7 Mn 0.2 Co 0.1 O 2 , Li 1.2 Co 0.1 Mn 0.55 Ni 0.15 O 2 , and sulfur demonstrate significantly improved cycling stability with high cathode loading.

25 ENERGY STORAGE↗

TCF - Sustainable Well Cement for Geothermal, Thermal Recovery, and Carbon Storage wells

Primary cementing is the most important operation performed on a subterranean well. Cement, placed in the annulus between the casing and the formations, serves as a hydraulic seal preventing fluids and gas migrations, protecting steel casing from corrosion, and supporting the well structure. Poor cementing jobs can be directly responsible for wells not reaching their full capacity, casing corrosion, compromised well integrity and, in the worst-case scenarios, well collapse. Geothermal, thermal recovery, and carbon storage wells offer environments that are especially difficult for cements to survive while the required lifespan of these wells can be years. In these wells currently used cements cannot provide durable well integrity, and new solutions are necessary. The necessity of stabilizing the electric grid, increasing its flexibility, and providing energy on demand will further expand the market of durable cement solutions for applications in high-temperature underground reservoir thermal energy storage wells (HT RTES). The design challenges of special cement systems for such wells originate from chemistry limitations of currently used well cements, aggressive environments, temperature and repeated shock conditions associated with them, and very weak formations that are not uncommon in these wells. During the last 70 years the most common systems for thermal-well construction have been Ordinary Portland Cement (OPC) (absolute majority of the wells), silica-lime system, and high aluminum cement-containing formulations. The major issues of calcium-silicate hydrates, that form during the hydration of OPC resulting in hardened material, are their poor chemical resistance to acids due to the calcium interactions with acid anions followed by its eventual dissolution, even in mild acids, such as carbonic acid from CO 2 dissolution, and inadequate bonding to the steel causing serious casing corrosion problems (Sugama & Pyatina, 2019). Performance of OPC-based cement may be significantly improved with organic additives; however, those are limited by their temperature stability. An alternative to calcium-silicate cement was developed by BNL and commercialized by Halliburton as ThermaLock TM cement. Calcium-aluminate-phosphate-based chemistry of the material allowed overcoming acid-resistance problems of OPC, especially in CO 2 -rich geothermal environments. In 2012-2015, building upon this experience, BNL developed Thermal Shock Resistant Cement (TSRC) with the support of Geothermal Technology Office (GTO) of DOE. TSRC has high-temperature stable chemistry, superior properties of cement-metal casing bond and corrosion protection (4-times better than currently used OPC-based formulation), significantly outperforms common well-cements in thermal-shock tests, has self-healing properties, and like ThermaLock TM is CO 2 resistant incorporating carbonate ions into stable hydrates (Gill et al., 2012).

15 GEOTHERMAL ENERGY↗

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↗

Predicting and Controlling Corrosion (Abbreviated Final Report)

Corrosion accumulates significant replacement costs in the transportation, utility, manufacturing, and infrastructure sectors. It also underpins several of LLNL’s core missions in stockpile stewardship, defense, and energy security. Whereas most corrosion and aging models are empirically parameterized to describe well-defined conditions late in the reaction, the factors that determine the early stages of corrosion—during which mitigation could be most impactful— are poorly understood. This project addressed the critical need for new approaches to predict the kinetics of corrosion initiation based on firm physical and chemical understanding. The activities encompassed degradation of relevant metals in both hydrogen-rich and environmental corrosion scenarios. The team integrated state-of-the-art multiscale simulation, in situ characterization, and data science within three technical thrusts: hydriding of Ti alloys; aqueous corrosion of Al and Ni-Cr alloys; and degradation of additively manufactured 316L stainless steel. In each case, novel capabilities were developed to identify and track the impacts of key atomistic, compositional, and microstructural features on the metal systems. For hydriding, protocols were developed to tightly integrate multiscale models, advanced multimodal characterization, and machine learning to determine how hydrogen interacts with native passivating surface oxides and nucleates new undesired phases, shedding new light on the critical role of grain boundaries, interfaces, and atomically disordered regions. For aqueous corrosion, the project demonstrated methods to predict dissolution rates of metal surfaces in corrosive solutions, to measure and understand microstructural and grain orientation effects on corrosion susceptibility, and to investigate competing growth and dissolution kinetics of surface oxides. For additively manufactured metals, analysis using state-of-the-art microscopy techniques revealed the role of specific heterogeneities invoked during laser processing, including cellular structure, dislocations, and precipitates, on corrosion susceptibility. In addition to new capabilities and understanding, the project provided an avenue for workforce development, as well as key partnerships with stakeholders in corrosion science.

08 HYDROGEN↗

Integrated Molten Salt Reactor Modeling Capabilities in NEAMS Thermal Hydraulics Tools

The DOE neams program supports a full range of computational thermal fluids analysis capabilities and code developments for a broad range of advanced reactor concepts. The research and development approach under the thermal fluids technical area synergistically combines three length and time scales in a hierarchical multi-scale approach. To enable multi-scale thermal fluids capability using these codes, a key joint effort has been underway to develop an integrated system- and engineering-scale thermal fluids analysis capability, through integration of SAM and Pronghorn codes, both based on the MOOSE framework. This report summarizes recent advances in developing an integrated system- and engineering-scale modeling capability for the msr concept, which has gained significant interest in recent years. A consistent framework was established by coupling Pronghorn and SAM through the Saline interface, with thermophysical properties provided by the Molten Salt Thermal Property Database (MSTDB-TP). Further improvements were made to the coupling schemes and domain-overlapping strategies, enhancing the stability and robustness of multi-code simulations. Verification and validation efforts demonstrate the accuracy of this integration across a range of benchmark problems, including one-dimensional heated pipe flows, three-dimensional natural convection loops with evolving isotopic compositions, and \gls{msre} demonstration cases. Within Pronghorn, new capabilities were introduced to model corrosion and noble-metal plating phenomena, supported by an extended thermal-hydraulics framework and refined turbulence treatments. To capture two-phase flow behavior, a multiphase Euler–Euler model was implemented in Pronghorn, including advanced closure relations, high-resolution advection techniques, and capillary force reconstruction. Preliminary verification cases confirm the fidelity of the approach, while planned validation efforts target canonical multiphase benchmarks and application to msr components such as the msre pump bowl. Finally, updates to SAM’s msr mass transfer modeling were extended to consider noble gas migration into porous structures like graphite. The point kinetics model was updated to include reactivity feedback contributions from any defined species, such as xenon. The gas transport model was expanded for applicability to gas mixtures, bubble efflux phenomena, and species transport between liquid and gas phases. A selection of multi-scale Sherwood number correlations from MOSCATO/NekRS and multi-phase correlations from literature have been added for improved accuracy in calculating mass transfer coefficients. A companion effort on developing system-level redox corrosion has also been incorporated into SAM. Collectively, these enhancements strengthen the predictive capability of SAM and Pronghorn for simulating MSR thermal-hydraulics, corrosion, multiphase behavior, and fission-product transport, providing a more complete toolset for design, safety analysis, and licensing support of next-generation \gls{msr}s.

42 - ENGINEERING↗

Average hydrodynamic radius analysis reveals critical solvation thresholds in high-concentration lithium electrolytes

Understanding the solvation structures of lithium salts in carbonate- and ether-based electrolytes is central to explaining the exceptional stability of high-concentration electrolytes (HCEs) and localized high-concentration electrolytes (LHCEs). Conventional techniques such as vibrational spectroscopy and one-dimensional NMR provide only limited information, typically restricted to coordination ratios and ion-pair distributions, without revealing the actual size and mass of solution complexes. Here, in this study, we introduce an average hydrodynamic radius (AHR) analysis based on internally referenced DOSY NMR, which enables direct estimation of the average volume and molecular weight of lithium–solvent complexes in solution. Using LiFSI–EMC and LiFSI–EMC–TTE electrolytes, we demonstrate that the onset of effective lithium metal stabilization and aluminum corrosion suppression coincides with the formation of very large complexes, whose average volume exceeds 300 times that of free EMC molecules. This finding supports a new “blocking mechanism,” wherein bulky solvated complexes impede direct solvent access to reactive surfaces. The AHR analysis thus not only clarifies the fundamental origin of HCE and LHCE effectiveness, but also provides a broadly applicable experimental framework for probing complex solvation structures and guiding rational electrolyte design.

Concentrated electrolytes↗

Design new epoxy nanocomposite coatings based on metal vanadium oxy-phosphate M 0.5 VOPO 4 for anti-corrosion applications

Epoxy nanocomposite coatings are an essential way to protect petroleum storage tanks from corrosion. For this purpose, the new nanocomposite epoxy coatings (P-M/epoxy composites) have been successfully designed. The P-M/epoxy composites are based on the metal vanadium oxy-phosphate M 0.5 VOPO 4 (where M = Mg, Ni, and Zn). The function of P-M/epoxy composites as anti-corrosion coatings was explored using electrochemical and mechanical tests. Using electrochemical impedance spectroscopy (EIS), it has been noticed that the pore resistance and polarization resistance of the P-M/epoxy composites remain higher as compared to the neat epoxy. The P-M/epoxy composites have the greatest impact on the cathodic dis-bonded area and water absorption. Besides, P-M/epoxy composites exhibit a very high order of mechanical properties. Further, Mg 0.5 VOPO 4 has the greatest effect on the anti-corrosion properties of epoxy coating followed by Zn 0.5 VOPO 4 and Ni 0.5 VOPO 4 . All these properties lead to developing effective anti-corrosion coatings. Thus, the net result from this research work is highly promising and provides a potential for future works on the anti-corrosion coating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermoluminescence and optically stimulated luminescence response of Al 2 O 3 coatings deposited by mist-chemical vapor deposition

Aluminum oxide (Al 2 O 3 ) is a widely used ceramic material which can be applied as a protective coating on metallic structures to improve corrosion resistance and mechanical properties. Al 2 O 3 also has great potential as a functional thin film device in optoelectronics. When it is doped with carbon (Al 2 O 3 :C), this material system can serve as a reliable radiation dosimeter. The combination of optoelectronic, dosimetric, and protective properties demonstrated by Al 2 O 3 uniquely positions it for dual use applications in nuclear forensics, nonproliferation and safeguards, emergency response, retrospective dosimetry, and nondestructive inspection. Here, in this study, an innovative ultrasonic mist-chemical vapor deposition (Mist-CVD) system was used to deposit thin (nm level) Al 2 O 3 coatings on 304 stainless steel substrates. The single aliquot regeneration (SAR) and additive dose reconstruction techniques were then used to investigate the thermoluminescence (TL) and optically stimulated luminescence (OSL) response of the coated substrates to increasing doses of β irradiation. This study demonstrates that nm-thick Al 2 O 3 coatings hold promise as novel nano-dosimeters which could be leveraged for a series of applications such as nonproliferation and safeguards, retrospective dosimetry, and nondestructive inspection.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Economic Analysis of Condition-Monitoring-Based Predictive Maintenance in Power Plants under Market Elasticity

Condition-monitoring-based predictive maintenance can increase the power plant availability by preventing forced outages. However, the actual on-stream time depends on market elasticity and dynamics, which are affected by cost and penetration of other power generation technologies. This paper develops a systematic approach for the economic analysis of investment in condition monitoring technologies with due consideration of market elasticity. Focus is on corrosion monitoring in coal-fired power plants (CFFPs) since corrosion in high-temperature coal-fired boilers is a leading cause of equipment failure. Investment in sensor networks for measuring corrosion and operating conditions like metal temperature and concentrations of O 2 and SO 2 is investigated. The unscented Kalman filter is used to estimate corrosion in the waterwall section of the boiler under multiple sensor networks. Electricity produced by CFPPs in the future in the U.S. due to changes in availability under market elasticity is studied. Sensitivity of the incremental net present value to factors like the number, type, and cost of sensors is analyzed.

Electrochemistry↗

SAVY-4000 Corrosion Evaluation Plan

Nuclear material packages, with few exceptions, outside of an approved engineered contamination barrier must meet packaging, surveillance, and testing requirements designed to protect workers from airborne contamination per Department of Energy (DOE) Manual 441.1-1, Nuclear Material Packaging. The SAVY-4000 containers were developed at Los Alamos National Laboratory (LANL) in conjunction with Nuclear Filter Technology Inc. (NFT Inc.) as a general purpose vented manually-compliant container system for staging and storage of plutonium for LANL and the DOE complex. The SAVY-4000 containers have a 316L stainless steel containment barrier, which was selected based on its corrosion resistant properties. These containers were approved for use in 2014 with a five-year design life; LANL requested and DOE has approved lifetime extension from 5 to 15 years. The 10-year lifetime extension was proposed as a conservative recommendation based on the corrosion observations for the metal components in surveillance and results from laboratory studies. Extensive accelerated aging studies have been done on the SAVY-4000 O-ring with very little evidence of significant degradation when subjected to aggressive elevated temperature and radiation conditions. Therefore, our current conservative lifetime estimate for the O-ring and the filter is 40 years at 80°C. Additional work is ongoing in a phased approach to further extend the design life of the Manual compliant SAVY-4000 storage container; the limiting component for further life extension is still the 316L containment barrier.

36 MATERIALS SCIENCE↗

Electron Linear Accelerator Additive Manufacturing

Superconducting electron linear accelerators open up new opportunities for advanced materials processing. High energy electrons penetrate deeper within materials, increase the processing depth and rate and enables production of far-from-equilibrium materials and selective processing within a material surface and subsurface. With support from the Office of Naval Research, NASA, and DoE, Mainstream Engineering commissioned a superconducting linear electron accelerator to investigate advanced materials processing and additive manufacturing. The goal of Mainstream's Electron Beam Enabled Advanced Manufacturing (EBEAM) center is to develop unique, far-from-equilibrium materials and alleviate significant technological deficiencies. We will present results of irradiating various metals and their unique material properties. Monte Carlo simulations electron beam and sample interaction were used to optimize the processing parameters and study far-from-equilibrium processing conditions. Applications include stainless steel additive manufacturing for small modular nuclear reactors and dissimilar metal bonding of corrosion-resistant cladding for next-generation molten salt reactors.

36 MATERIALS SCIENCE↗