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At least 217 records · Page 12

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↗

3D printable polymeric lightning strike protection system for fiber reinforced composites

The current embodiments include all-polymeric protective material for mitigating lightning strike damage. The protective material includes a hybrid matrix comprising PANI and MXene dispersed within a thermosetting epoxy resin. This hybrid matrix can be painted, printed, or applied as a conductive polymeric layer to a FRCP structure, for example an aircraft fuselage, wing, empennage, control surface (aileron, flap, slats, rudder, elevator) or a wind turbine blade. The protective material not only withstands lightning strikes, but also functions as shielding against electromagnetic interference and is corrosion-resistant and lightweight.

Kumar, Vipin↗

In-Situ Pipeline Coatings for Methane Emissions Mitigation and Quantification from Natural Gas Pipelines

Addressing the current health of the nation’s existing 3 million miles of pipeline infrastructure is key to preventing further climate change. In 2020, natural gas production exceeded 34 trillion cubic feet (Tcf). Roughly 75% of natural gas consists of methane (CH 4 ), which is up to 25 times more powerful than carbon dioxide (CO 2 ) at trapping heat within the atmosphere over a 100-year period, and studies from the Environmental Defense Fund (EDF) estimate approximately 2% of all the natural gas produced will be lost during normal operations due to unaddressed leaks. This does not even consider the risks of major disaster due to pipeline failure, or the losses and extra fuel costs incurred due to corrosion and scale deposits in under-maintained pipelines. The objective of the proposed research is to demonstrate the protection capabilities and economic benefits of Oceanit’s internal pipe surface treatment, known as DragX™. DragX™ is a chemically resistant, water-and-oil repellent nanocomposite system that can be readily applied in-situ on natural gas transmission and distribution pipelines with a minimum of surface preparation. This makes it an ideal candidate for in-place retrofitting and refurbishment of existing pipelines without the need for expensive extraction and replacement. DragX™ is also able to significantly reduce the surface roughness, and subsequently, the frictional drag forces within a pipeline, improving throughput, decreasing energy costs of pressurization and pumping, and allowing for longer pipeline operation without interruption, reducing the methane emitted during pipe isolation and venting. As part of this project, Oceanit has utilized the Department of Energy’s support to fully develop, de-risk and prove the DragX™ core technology is both economically viable and commercially desirable to pipeline operators and energy companies alike. DragX™ material properties were optimized in this effort both for ease of applicability, to provide value in certain key parameters, and was demonstrated on pilot applications exceeding 2 miles in length. Beyond the already field demonstrated applications, this innovative nanocomposite surface treatment has the potential to be the backbone for CO 2 and Hydrogen transporting pipeline infrastructure. The learnings from this project could accelerate the deployment of surface treatment technologies related to the energy transition infrastructure, thus benefitting the clean energy initiatives in the United States and all around the world.

03 NATURAL GAS↗

High-Temperature Corrosion of Chromia-Forming Ni-Based Alloys in CO 2 Containing Impurities

Future technologies require structural materials resistant to environmental degradation in high-temperature CO 2 -rich environments. In this work, we exposed several commercially available Ni-based alloys (230, 263, 282, 617, 625, and 740H) to atmospheric pressure gases intended to simulate the compositions expected in future direct-fired supercritical CO 2 power cycles. The alloys were exposed to 95% CO 2 + 4% H 2 O + 1% O 2 and the same gas containing 0.1% SO 2 at temperatures of 600, 650, 700, 750, and 800 °C for 2500 h. With minor exceptions, chromia scales formed on all alloys at all temperatures in the SO 2 -free gas, yielding parabolic growth rates that followed an Arrhenius temperature dependence. Behavior in the SO 2 -containing gas was more complex. Generally, the alloys performed well at temperatures of 650, 750, and 800 °C. While some alloys further performed relatively well across the whole temperature range, several of the alloys experienced chromia failure resulting in non-protective duplex oxide scales and high oxidation rates, at temperatures of 600 and 700 °C. Deviation from protective behavior was associated with internal sulfide formation and, additionally for the case of 600 °C, external sulfate formation. Extensive carburization accompanied growth of the non-protective duplex oxide scales, which made it more difficult for the alloy to recover after initiation of the sulfur-induced accelerated corrosion process. The thermodynamic and kinetic factors influencing the accelerated corrosion in the presence of sulfur are discussed. The results suggest that caution is required when assessing compatibility of Ni-based alloys for CO 2 -based systems when sulfur-based impurities are expected.

36 MATERIALS SCIENCE↗

Microstructural examination of interactions between chromia-based refractory and nuclear glass in a melter

This study shows the effects of nuclear waste glass production on Monofrax K-3 refractory corrosion. A continuously fed research-scale melter containing an Fe- and Ni-rich simulated nuclear waste feed with borosilicate glass-forming chemicals was cyclically melted at 1150°C and idled at 1050°C for a total of 11 weeks. Chemical maps using scanning electron microscopy show the interactions between the quenched melt and the refractory. Nanoscale X-ray-computed tomography was used for a three-dimensional visualization of certain parts of the interface. Unreacted K-3 consists of primarily corundum (Al,Cr) 2 O 3 and spinel (Fe 2+ ,Mg)(Al,Cr) 2 O 4 interlocking crystalline phases. Some of the Cr from the refractory interacts with the Ni and Fe from the melt to form a reaction layer comprising (Ni,Fe 2+ )(Cr,Fe 3+ ) 2 O 4 spinel crystals. Simultaneously, melt components (Na,Si) infiltrate into the refractory. This interaction proceeds at the expense of the integrity of the refractory structure. Intact refractory grains (e.g., (Al,Cr) 2 O 3 ) as well as the reaction layer itself can lose mechanical integrity and spall off into the melt, especially near the top of the melter. As the reaction layer can be a protective boundary for the refractory against further melt infiltration, a reduction in the reaction layer thickness allows an increase in refractory corrosion.

36 MATERIALS SCIENCE↗

Geometric Optimization of an Electrochemical Purification Cell to Prevent Corrosion in CSP Plants During Operation

When exposed to moisture or oxygen, molten chloride salts produce corrosive impurities which degrade containment alloys. As a result, this can significantly decrease the lifetime and increase costs of molten-salt-based systems. To overcome this barrier, we designed and modeled an electrochemical purification cell to remove the corrosive impurity MgOH+. Various reactor architectures, including constant stirred tank reactors (CSTRs) and plug flow reactors (PFRs) were investigated. Steady-state thermoelectric properties were evaluated, allowing assessment of the effects of structure and design parameters such as flow rate, cell length, and cross-sectional area of molten salt. The results suggest that our design could most effectively increase reliability and decrease costs of molten-chloride-salt-based systems by protecting them during continuous operation using an annular plug flow reactor.

chloride salts↗

Mechanical, corrosion, and wear properties of biomedical Ti–Zr–Nb–Ta–Mo high entropy alloys

The microstructures, mechanical, corrosion, and wear behaviors of the Ti x ZrNbTaMo (x = 0.5, 1, 1.5, and 2, molar ratio) high entropy alloys (HEAs) were studied in this work. It was found that the Ti–Zr–Nb–Ta–Mo HEAs showed a dendrite structure with two body-centered-cubic (BCC) solid solution phases. The Ti 0.5 ZrNbTaMo HEA exhibited a high hardness of about 500 HV, high compressive strength approaching 2,600 MPa, and large plastic strain of over 30%. Furthermore, the highly-protective oxide films formed on the surface of Ti–Zr–Nb–Ta–Mo HEAs in the phosphate buffer saline (PBS) solution, which resulted in the high corrosion resistance of the HEAs. The Ti–Zr–Nb–Ta–Mo HEAs exhibited the greater dry- and wet-wear resistance than that of the traditional biomedical Ti6Al4V alloy. The results also indicated that with the decrease in the Ti content, the wear resistance of the Ti–Zr–Nb–Ta–Mo HEAs in the PBS solution improved. Finally, the Ti 0.5 ZrNbTaMo alloy presented the highest corrosive wear resistance among the four HEAs owing to its combination of good mechanical properties and high chemical stability.

36 MATERIALS SCIENCE↗

Technical Performance of Refractory Liners for Molten Chloride Salt Thermal Energy Storage Systems

A chloride-based molten-salt system that uses a ternary blend of MgCl2/KCl/NaCl is investigated to provide higher temperature thermal energy storage capability. Despite higher thermal stability, molten chlorides present several unique challenges, including the design of internal refractory-ceramic liners to prevent the corrosion and thermal stress of alloy tank shells. This work discusses issues and potential solutions related to containment of molten chloride salt, specifically the optimization of the refractory material at the molten salt interface (hot face). The down-selected hot face candidate limits permeation of salt through the material and forms a highly stable secondary surface phase in equilibrium with the molten salt. A mortar is created using the corrosion resistant hot face brick. Brick and mortar composite are subjected to mechanical stress/strain analysis, in order to calculate composite material properties and better inform thermomechanical models. The U.S. Department of Energy Generation 3 (DOE Gen3) program seeks to develop higher efficiency CSP plants that can provide cost-competitive, flexible power in the U.S. electric grid. The proposed Gen3 Liquid Pathway CSP plant closely resembles the configuration of current nitrate salt power towers with two-tank storage (Gen2). The differences between Gen2 and Gen3 include the types of compatible materials used in salt storage tank construction. Stainless steel loses strength at Gen3 temperatures, and although nickel superalloys would be capable of withstanding sustained high temperatures, these materials are prohibitively expensive at scale. Uninsulated tank shells also pose a significant risk as common steels are highly susceptible to chemical attack from molten chloride salt. To address these concerns, refractory-ceramic based containment materials are proposed to line the inside of the hot and cold storage tanks. In doing so, stainless or carbon steel shells may be used in construction depending on the level of insulation provided. The composition of the internal liner requires careful consideration to maximize the efficacy of multiple parameters including corrosion resistance, strength at operating temperature, durability, and cost. This is particularly true for the material at the interface with the salt, known as the "hot face", which is responsible for protecting the insulating layers between the tank shell and the hot face brick layer. The molten salt in this system is superheated over 300 °C above its freeze temperature. Therefore, unlike other industrial processes which use refractory-lined vessels, it is not expected that a freeze plane will develop in the hot face. Therefore, the hot face must be designed to withstand chemical corrosion and inhibit permeation of molten salt into the insulating layers. A down selection was performed to identify a hot face candidate best equipped to maintain thermal, mechanical, and chemical integrity when exposed to molten salt over extended periods of time. Long-duration chemical capability experiments were conducted with the down selected hot face refractory fully immersed in molten chloride salt for up to 3000 hours. The average salt penetration does not exceed 100 microns. When extrapolated to 20 and 30 years of continuous exposure, the expected salt penetration depth is approximately 2.0 mm and 2.9 mm, respectively. A magnesium-rich secondary phases develops at the salt/refractory interface. X-ray diffraction identifies the material as forsterite (Mg2SiO4), which is reported to form synthetically in molten chloride salt solutions. These results suggest the selected hot face will adequately inhibit salt permeation. While there is optimism that the hot face brick will inhibit salt permeation, mortar joints are typically the weakest point of a refractory brick liner. From a thermochemical perspective, differing thermal expansion coefficients may result in the mortar and brick to grow independent of each other, creating gaps through which molten salt can penetrate. To address this issue, NREL has developed an in-house mortar composed of the down selected hot face brick that has been shown to be compatible with the salt. Compressive stress/strain analyses have been performed on the brick/ mortar composites to generate stress/strain curves. Modulus of elasticity and Poisson's ratio of the composite may be calculated from the stress/strain curves, in order to provide more representative data to finite element mechanical models for accurate approximation of stress on the tank shell and the amount of thermal expansion expected within the tank liner.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Effect of Applied Stress on the Selective Oxidation of Alloy 600 Exposed to PWR Primary Water and Rhines Pack Environments

A mechanistic understanding of corrosion and oxidation processes is crucial to ensure long-term resistance to stress corrosion cracking of Ni-base structural alloys in pressurized water reactor (PWR) primary and secondary systems. Aqueous corrosion of Ni-base alloys under PWR primary water conditions was previously compared to gaseous oxidation with comparable oxygen potentials. However, those studies considered only stress-free conditions, which removes a critical parameter for understanding stress corrosion behaviors. A significant knowledge gap exists for the role of applied stresses on selective internal oxidation in gaseous environments. A micro-4-point-bend jig was designed to facilitate stress in a Rhines Pack set-up. Selective oxidation at different stress and strain conditions was investigated in a series of Rhines Pack experiments for Alloy 600. Focused ion beam milling enabled the extraction of site-specific specimens containing selected high-energy grain boundaries from tensile and compressive stress regions. Analytical transmission electron microscopy was employed to analyze the microstructure and chemical composition of the resulting oxides. Protective surface oxide films and selective intergranular oxides were observed at different conditions. The implications of these fundamental differences are discussed relative to intergranular attack and stress corrosion cracking mechanisms in PWR primary water.

stress, 4-point-bend, selective oxidation, Alloy 6↗

Solar mirrors and methods of making solar mirrors having improved properties

An article for reflecting solar energy includes a coating stack having solar reflecting films and metal oxide films, the coating stack applied on a major surface of a glass substrate, and a protective overcoat comprising a first and a second surface, wherein the first surface of the protective overcoat is disposed toward the solar reflective films and metal oxide films; and a polymer encapsulant over outer wall surfaces of the coating stack, the second surface of the protective overcoat and over peripheral edges of the coated article, the encapsulant having a base layer, a top layer and metallic corrosion-inhibitive material in the base layer.

14 SOLAR ENERGY↗

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↗

A Novel Optical Instrument for On-Line Measurement of Particle Size Distribution—Application to Clean Coal Technologies

A flow cell is a critical measurement interface for many optical instruments. However, the flows are often sampled under harsh conditions, such as under high pressure and/or high temperature, in the presence of particles, moisture, vapors with high dew points or corrosive gases. Therefore, obtaining a high-optical-quality flow cell that does not perturb the measurement is a significant challenge. To address this challenge, we proposed a new flow cell that employs a unique laminar coaxial flow field (for the purge and sample flows). A test system was built to conduct particle size distribution (PSD) measurements with no sampling bias using a state-of-the-art analyzer (Malvern Panalytical Insitec). The results revealed that the measurement zone is well defined solely by the sample flow, and the optical windows are well protected by the purge flow, with minimal risk of any depositions from the sample flow. Using this flow cell, the Insitec can successfully measure PSD under high pressure and temperature under moist, corrosive conditions without generating any sampling bias. Importantly, we successfully applied this flow cell for on-line PSD measurement for the flue gas of a 100 kWth pressurized oxy-coal combustor operating at 15 bara.

Cheng, Mao (ORCID:0000000213273900)↗

Current and candidate additives for environmentally acceptable lubricants—A review

The world consumes approximately 40 million tons of lubricants annually, and nearly half of them end up in the environment because of leaks, discharges, and evaporation, causing significant environmental and economic impacts. The need for moving toward environmentally acceptable lubricants (EALs) is increasingly being recognized. Synthetic ester, polyalkylene glycol, vegetable oil, and water are among the base fluids approved by the U.S. Environmental Protection Agency for EALs. However, neat base fluids cannot fully meet the lubrication requirements without incorporating functional additives such as anti-wear, antioxidant, corrosion inhibitor, and viscosity modifiers. Both the performance and environmental compatibility of lubricant additives are critical. In this article, current and candidate EAL additives, both in liquid and solid forms, are reviewed, with a focus on their functionalities in friction and wear reduction, toxicity, and biodegradability. Finally, a perspective for future research on EAL additives is discussed.

42 ENGINEERING↗

Computational design of high entropy alloy coating for hydrogen turbine applications

This project aims to develop novel high entropy alloy (HEA)-based coatings to protect critical components in hydrogen-fueled turbine power system. The HEA-coatings will demonstrate superior performance in hydrogen combustion environment to commercial NiCoCrAlY coating in current natural gas turbine system. The HEA coating facilitates the formation of a protective scale of alpha-alumina to slow down the inward diffusion of oxidizing species and the outward diffusion of metal elements, and possesses ultrahigh corrosion and spallation resistance to prolong the service lifetime of critical components in hydrogen turbine power system. Aimed to accelerate the discovery of novel HEA coating compositions, high throughput computational modeling including CALPHAD and density functional theory and machine learning are performed to predict phase stability, oxygen permeability, oxidation rate constant, coefficient of thermal expansion, and mechanical properties. Based on the modeling and machine learning prediction, experimental validation is performed. Preliminary results will be presented and approaches to minimize oxidation will be discussed.

alloy design↗

Ab Initio Design of High-Entropy Thermal/ Environmental Barrier Coatings

Next generation thermal/environmental barrier coatings (TEBC) require carefully balancing various properties including phase stability, thermal conductivity, coefficient of thermal expansion (CTE), mechanical properties, and resistance against hot corrosion and water vapor recession. This work mainly focuses on rapid design of cost-effective high entropy rare-earth disilicates and aluminum garnets to protect SiC-based ceramic matrix composites and nickel-based superalloys in the hot section of gas turbine engines using density functional theory methods. Our calculations identify several low-cost high entropy TEBC exhibiting ultralow thermal conductivity at 1500 K and desirable CTE while maintaining good mechanical properties, including Er1/2Y3/4Yb3/4Si2O7, Gd1/4Er1/4Y3/4Yb3/4Si2O7, Eu1/4Er1/4Y3/4Yb3/4Si2O7, and (Y1/4Gd1/4Er1/4Yb1/4)3Al5O12. This work also aims to gain fundamental understanding of oxygen diffusion in model disilicates. Minimizing oxidizer (such as water vapor and oxygen) permeability through the EBC layer can significantly decrease the growth rate of thermally grown oxide and extend the service life of the coating system. Oxygen diffusion mechanisms including formation energy of defects under varying oxygen conditions and defect migration energy barriers will be presented.

coefficient of thermal expansion↗

Hydrothermal Corrosion of First-Generation Dual-Purpose Coatings on Silicon Carbide for Accident-Tolerant Fuel Cladding

In this study, four different commercial coatings, TiN, Cr, CrN, and Cr/CrN (multilayer) were deposited by physical vapor deposition (PVD) on high resistivity chemical vapor deposited (CVD) SiC for the dual purpose of corrosion mitigation and fission gas hermeticity. The coatings were exposed for up to 2600 hours in flowing high temperature (288-350°C), high purity, liquid water with dissolved hydrogen (0.15-3ppm) or dissolved oxygen (1-2ppm). The Cr/CrN coatings did not adhere well and spalled quickly during exposure. In oxygenated conditions, none of the coatings were protective . CrN coatings spalled preferentially at defect sites, but reacted slowly enough in the absence of defects to potentially be chemically protective. TiN coatings fully oxidized within a few hundred hours and spalled. In hydrogen, all the coatings were chemically stable. Coating failures were identified and attributed to localized spallation, potentially related to coating defects. Coating improvements are recommended to reduce spallation and improve coating protection for future generations of dual-purpose coatings.

36 MATERIALS SCIENCE↗

Initiation of dusting corrosion in high-temperature alloys under CO exposure

Carbon monoxide is commonly encountered in energy systems, yet its reactivity with structural alloys—critical heat-resistant components in these systems—has been largely overlooked compared to the well-documented effects of oxidizing gases. In contrast, we demonstrate the high-temperature reaction of CO with NiAl using in-situ low-energy electron microscopy and X-ray photoemission electron microscopy. Our results show that CO dissociates into atomic oxygen and carbon, resulting in two concurrent reactions: selective oxidation of aluminum to form Al 2 O 3 and the initiation of dusting corrosion through carbon dissolution into the alloy and subsequent carbon deposition on the surface. These reactions produce spatially distinct surface products, preventing the formation of a continuous protective Al oxide layer. These results reveal a preference for the dissociative pathway of CO over the classic Boudouard disproportionation reaction that forms CO 2 . These insights not only advance our understanding of CO-induced alloy degradation but also highlight the practical implications for managing alloy stability and optimizing catalysis in carbon-rich environments, such as those in petrochemical processing and hydrocarbon combustion.

36 MATERIALS SCIENCE↗