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At least 19 records

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

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

14 SOLAR ENERGY↗

Predicting and understanding corrosion in molten chloride salts

Abstract Molten chloride salts are stable at higher temperatures than many other salts, including nitrate salts, and are thus promising for heat transfer and/or thermal energy storage in concentrating solar power, nuclear power, and other thermal energy storage applications. However, corrosion in molten chloride salts remains a significant problem. While many studies have been devoted to evaluation of corrosion, we find that a comprehensive method for predicting corrosion in molten chloride salts is lacking. Here, we present an evaluation of corrosion in molten chloride salts using Ellingham diagrams and chloride-oxide stability diagrams, which enable prediction of alloy performance in molten chloride salts and allow corrosion results to be interpreted at a fundamental level. Graphical abstract

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

First-principles-derived transport properties of Molten chloride salts

Molten salts have many applications ranging from a heat transfer medium in both generation IV nuclear reactor designs and the solar industry to thermal storage systems. While molten salts show promising properties for these applications, there still exists a knowledge gap for the transport properties of molten salts at elevated temperatures. This work uses ab initio Molecular Dynamics to investigate the transport properties of KCl, LiCl, KCl-LiCl eutectic, NaCl, MgCl 2 , and NaCl-MgCl 2 eutectic molten salt systems. Further, the properties presented here are the diffusion coefficient, viscosity, and isochoric heat capacity. These properties are compared to experimental data where available and other computational work in cases where no experimental data is available. This is the first work to explore timescales over 100 ps via AIMD for the determination of transport properties in molten salts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Transmission Electron Microscopy of High-Temperature Inconel-625 Corrosion by Molten Chloride Salts

This paper describes an approach to monitor high temperature molten chloride (MgCl 2 -NaCl-KCl) salt corrosion of Inconel-625 alloy in real time at high spatial resolution. The approach is based on a micro-environmental-cell assembly integrated into a transmission-electron-microscope goniometer to examine in situ the salt-alloy interface during corrosion, employing real time electron diffraction and imaging. It establishes procedures to minimize incorporation of H 2 O or O 2 from atmosphere in the chloride salts during sample fabrication and corrosion, which is critical to understanding the fundamental corrosion mechanisms. A clustering algorithm and a 2D Gaussian fit function are used to determine diffraction spot intensities in in situ diffraction patterns, to quantify alloy corrosion. This facilitates quantitative observation of the evolution of individual grains, in contrast to conventional macroscopic corrosion rate quantification. The isothermal corrosion rate of Inconel-625 in an anhydrous, unoxidized salt-stack is 220 ± 30 μm year -1 at 700 °C and 350 ± 20 μm year -1 at 800 °C. However, the corrosion rate at 700 °C increases five-fold to 1000 ± 170 μm year -1 when the salt stack is air-exposed, indicating the dominant effects of hydrated or oxidized impurities on corrosion acceleration. Furthermore, real time imaging of the microstructure evolution suggests that corrosion is initiated at grain boundaries.

14 SOLAR ENERGY↗

Evaluation of external tubular configurations for a high-temperature chloride molten salt solar receiver operating above 700°C

Next-generation concentrating solar power (CSP) tower technologies target operating temperatures exceeding 700°C to increase the thermal-to-electric conversion efficiency. Molten chloride salts are one possible alternative to current commercial molten nitrate salts to enable the higher operating temperature. This paper analyzes the predicted optical, thermal-fluids, and structural performance of traditional external tubular solar receiver configurations applied with a chloride salt heat transfer fluid (HTF) and inlet/outlet temperatures of 500°C/735°C, and considers sensitivity analysis and optimization relative to receiver sizing, tube sizing, number of panels, flow circuit configurations, and solar flux concentration under constraints on internal velocity, pressure drop, wall thickness, and required creep-fatigue lifetime. The high temperature conditions increase the significance of inelastic deformation mechanisms such as creep relative to that expected in commercial 565°C nitrate salt designs. High-temperature creep and creep-fatigue damage in the metal alloy tubes are the key factors that limit allowable solar flux concentration and achievable receiver thermal efficiency at the near-800°C wall temperature conditions. For a traditional external cylindrical receiver configuration, the design parameters and conditions capable of satisfying all constraints produced, at best, a design point receiver efficiency of 78.2%, or 80.5% when excluding receiver intercept efficiency. Variation in the optimal receiver performance relative to uncertainty in the binding maximum velocity, minimum wall thickness, and minimum lifetime constraints is presented.

14 SOLAR ENERGY↗

Quantitative Voltammetry Measurements of High-Concentration Actinides in Molten Chloride Fuel Salts

Molten chloride mixtures containing high concentrations of UCl 3 (i.e., >70 wt%) are candidates for next-generation molten salt reactor (MSR) fuel salts that enable new plant optimization and fuel cycle strategies. MSR licensing, however, is contingent on the development of effective material control and accounting (MC&A) practices for these salts. To close this gap, we have developed an electroanalytical approach that enables accurate in situ measurements of uranium concentrations in these highly loaded fuel salts. This methodology uses a multielectrode array voltammetry sensor combined with digital simulations that account for non-idealities such as uncompensated resistance effects. The theory-based numerical simulations of voltammetry responses yielded correction factors that are agnostic of electrochemical cell geometry and produced consistent voltammetry peak current results when correcting for varying amounts of ohmic resistance. In doing so, we have demonstrated accurate concentration measurements for UCl 3 in LiCl-KCl-UCl 3 across a range of mass fractions between 55 and 72.3 wt% at 550 °C.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Effects of Particle Size and Concentration of Magnesium Oxide on the Lubricating Performance of a Chloride Molten Salt for Concentrating Solar Power

One engineering challenge for the next-generation concentrating solar power (CSP) is to identify appropriate heat transfer and thermal energy storage media. A chloride salt mixture (20 wt % NaCl + 40 wt % MgCl 2 + 40 wt % KCl) in a molten phase is proposed as a potential fluid for carrying the heat as well as lubricating the CSP pump bearings. Due to the hygroscopic nature of MgCl 2 , the presence of magnesium oxide (MgO) particles is inevitable. In order to understand the impact of MgO particles, this study investigated the tribological behavior of the molten chloride salt mixture containing MgO of various particle sizes and concentrations. Tests were conducted at 750 °C in a dry Ar environment using a zirconia ball sliding against a Haynes 244 alloy disc lubricated by the molten salt. There was a clear trend of the increased friction coefficient and wear loss for a larger particle size and/or a higher concentration of MgO. Distinct wear mechanisms were identified for the ceramic ball and alloy disc. Results provide fundamental insights for this new research avenue of molten salt lubrication for CSP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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)↗

Electrodeposited nickel coatings for exceptional corrosion mitigation in industrial grade molten chloride salts for concentrating solar power

Molten chloride salt eutectics are attractive candidates for use as thermal energy storage media and heat transfer fluids in generation-three concentrating solar thermal power (Gen3 CSP) plants. However, corrosion of alloys in molten chloride salts, especially at high temperatures, is an extremely challenging problem that studies focus on lower temperatures, shorter durations, or analytical grade, and high-purity, salts. To date, there has been no study on corrosion or corrosion mitigation in an industrial-grade salt at a high temperature such as 750 °C. To alleviate this knowledge gap, the study presents new multiscale fractal-textured Ni coatings on various alloy surfaces for effective corrosion mitigation at 750 °C in molten chloride salts. Using the electrodeposition method, durable double-layer textured coatings were formed on stainless steel alloys (SS316, SS310, and SS347) and In800H. The corrosion performance of the coatings is investigated in both analytical-grade purity and, for the first time, practically relevant industrial-grade chloride salts. Ni-coated ferrous alloys showed an exceptionally reduced corrosion rate in the range of 350–480 μm/y in analytical-grade salts, and between 450 and 490 μm/y in purified industrial-grade salts at 750 °C. Ni coatings on ferrous alloys reduced corrosion rates by as much as 70% compared to uncoated surfaces and were comparable to the expensive Ha230 alloy with a high Ni content. As a result, by the use of innovative fractal corrosion mitigation coatings, for the first time, low-cost structural alloys are rendered viable for use with industrial-grade chloride salts, which is profoundly beneficial in practical systems.

14 SOLAR ENERGY↗

Modeling the Impact of Grain Size on Corrosion Behavior of Ni-Based Alloys in Molten Chloride Salt via Cellular Automata

Molten chloride salts hold significant promise as both thermal transfer and storage media for next-generation concentrated solar power (CSP) systems. However, molten chlorides pose a considerable corrosion risk to structural materials, particularly Ni-based alloys. One approach to enhancing corrosion resistance is through the optimization of grain structure; however, it remains uncertain whether increasing or decreasing grain size enhances corrosion resistance. A cellular automata (CA) program was developed to evaluate the interplay between grain size and corrosion in Ni-based alloy. Our CA program tracks alloy composition, surface roughness, and thickness loss via a graphical user interface, displaying corrosion and diffusion status, and multiple user input cards for tuning the simulation. CA simulations of Inconel 625 indicate enhanced corrosion resistance with increased grain size, with passivating oxides offering limited protection. Additionally, the temporal evolution of alloy surface roughness demonstrates notable fluctuations, with abrupt increases attributed to corrosion along vertical grain boundaries and sudden decreases to grain detachment from the protective film.

Materials Science↗

Design of a Continuous Electrochemical Purification Reactor for Corrosion Mitigation in Molten Chloride Salt Systems

The utility of molten chloride salts in concentrating solar power (CSP) is dependent on the ability to maintain low corrosive impurities. Without proper purification, the corrosion rates of containment alloys exceed the industry standard of corrosion—under 20 μm/year. An extensive body of literature focuses on the initial purification stage of molten chloride salts. However, occurrences such as maintenance, leaks, and so forth expose the salt to the atmosphere and reintroduce impurities. Therefore, it is critical to develop a purification strategy that can control impurity levels during CSP plant operation. Here we present the design and fabrication of a purification vessel to continuously remove impurities out of flowing molten salt.

Witteman, Liam↗

Direct Measurement of Cl − Activity in Metal Chloride Molten Salts using a Cl 2 /Cl − Electrode

Molten metal chloride salts are promising candidates for advanced heat transfer fluids in generation IV nuclear reactors and beyond. The activity of the chloride ion in the salt has a large influence on the redox characteristics of the corresponding molten salt. There exists a knowledge gap for the direct measurement of chlorobasicity (Lewis basicity) in molten-salt mixtures. Here, the focus of this work was to develop a Cl 2 /Cl − electrode for the direct measurement of chloride activity in molten metal-chloride salt mixtures. The LiCl–KCl eutectic system was utilized as the reference melt to determine the change in chloride ion activity as increasing concentrations of MgCl 2 are added to the LiCl–KCl eutectic working electrode. The results of the measurements indicated a reduction in chloride ion activity as the concentration of magnesium chloride increased, consistent with the complexation of free chlorides by Lewis acidic magnesium cationic species. The Temkin model was used to estimate the thermodynamic properties of MgCl 4 2− complex.

Chloride↗

Elucidating the corrosion mechanism of commercial Ni-based superalloys in UCl3 containing-chloride molten salt systems

Elucidating the role of UCl3 in the corrosion mechanism of Ni-based superalloys exposed to chloride molten salts Trishelle Copeland-Johnson1, Michael Woods1, Ruchi Gakhar1, Daniel J. Murray1, Guoping Cao1, Lingfeng He1 1Idaho National Laboratory, Idaho Falls, ID, United States The United States Department of Energy (DOE) aims to diversify the domestic energy portfolio towards more sustainable options, including implementation of molten salt reactor (MSR) technology. Chloride molten salts have been investigated as an appropriate MSR coolant and fuel because their relatively inexpensive, abundant, and exhibit favorable thermophysical properties. However, the corrosivity of chloride molten salts have not been extensively studied, especially with the inclusion of actinide products, such as UCl3. Accordingly, the development of nuclear structural materials with excellent corrosion performance is critical to the successful implementation of MSRs, particularly from a mechanistic perspective. In this investigation, we attempt to elucidate the interfacial corrosion mechanism between Ni-based structural materials, such as Inconel 617, and UCl3-containing salt systems through a multi-modal advanced characterization approach, including electron microscopy techniques. The findings from this investigation will expand the knowledgebase of chloride molten salt corrosion of MSR structural materials for strategic property-to-performance design.

36 - MATERIALS SCIENCE↗

High Temperature Ternary Chloride Molten Salt Pump

A ternary chloride (MgCl2-NaCl-KCl) molten salt pump has been developed to operate up to 720°C. The design is the result of a thermal, structural and material study of critical components. The vertical overhung pump incorporates first of a kind salt-wetted hydrodynamic bearings. Several bearing material pairings were tested which include: colmonoy grades, stellite grades, and a novel NiWC-based alloy (i.e. HybrimetTM NiWC3b) used as a High Velocity Oxygen Fuel (HVOF) coating. The coating withstands the corrosion effects of the molten salt, and is also used to protect a 316L stainless steel pump reservoir. The pump bowl assembly components are made of Inconel 625. A Nitrogen flushed carbon ring seal is used to keep salt vapors from interacting with external ambient air. Preliminary testing shows a promising pump design for use in the Concentrating Solar Power Gen 3 systems and sets the ground for further development of the HybrimetTM NiWC3b as a competitive alternative to available superalloys.

Handy-Cardenas, Lewis (ORCID:0009000744006972)↗

Elucidating the corrosion mechanism of Ni-based superalloys in the presence of uranium-containing chloride molten salt

The United States Department of Energy (DOE) is committed to the advancement of nuclear reactor technology through initiatives such as the Advanced Reactor Development Program (ARDP), in an effort to diversify the United States energy portfolio towards more sustainable energy options. The ARDP includes demonstration by industry partners of molten chloride fast reactors (MCFRs). Construction of MCFRs requires qualified nuclear structural materials. Unfortunately, there are no current materials that are fully qualified by the Nuclear Regulatory Commission for the construction of molten salt reactors, including MCFRs. Adapting current structural material qualifications requires expansion of our current knowledgebase on the property-performance relationships regarding corrosion performance. In this investigation, we assess microstructural changes in a Ni-based superalloy after exposure to a UCl3¬-containing chloride salt eutectic mixture through a correlated multi-modal approach combining several advanced characterization techniques, including scanning electron microscopy/focused ion beam (SEM/FIB) and transmission electron microscopy (TEM). SEM/FIB analysis will illustrate changes in elemental composition, microstructure, and isotopic information acquired from energy x-ray dispersive spectroscopy (EDS), electron backscatter diffraction (EBSD), and secondary ion mass spectroscopy (SIMS), respectively. This information will then aid in identifying localized regions to elucidate the corrosion mechanism with TEM through a combination of electron diffraction, electron energy loss spectroscopy (EELS), and additional EDS. The findings from this investigation will further expand our assessment of the corrosion performance of structural materials in molten salt chloride systems, aiding to developing fully qualified materials for construction of MCFRs.

36 MATERIALS SCIENCE↗

Assessing the interfacial corrosion mechanism of Inconel 617 in chloride molten salt corrosion using multi-modal advanced characterization techniques

The United States Department of Energy (DOE) has committed to expanding the domestic clean energy portfolio in response to the rising challenges of energy security in the wake of climate change. Accordingly, the construction of a series of Generation IV reactor technologies are being demonstrated, including sodium-cooled, small modular, and molten chloride fast reactors (MCFRs). To date, there are no fully qualified structural materials for constructing MCFRs. A number of commercial structural alloys have been considered for the construction of MCFRs, including alloys from the Inconel and Hastelloy series. Informed qualification of structural materials for the construction of MCFRs in the future can only be ensured by expanding the current fundamental knowledgebase of information pertaining to material performance under environmental stressors relevant to operation of the reactor, including corrosion susceptibility. The purpose of this investigation is to illustrate how a correlative multi-modal electron microscopy characterization approach, including the novel application of focused-ion beam 3D reconstruction capabilities, can elucidate the corrosion mechanism of a candidate structural material Inconel 617 for MCFR in NaCl-MgCl 2 eutectic salt at 700°C for 1,000 h. Evidence of intergranular corrosion, Ni and Fe dealloying, and Cr-O enrichment along the grain boundary, which most likely corresponds to Cr 2 O 3 , is a phenomenon that has been documented in other Ni-based superalloys exposed to chloride molten salt systems. Additional corrosion products, including the formation of insoluble MgAl 2 O 4 , within the porous network produced by the salt attack is a novel observation. In addition, Mo 3 Si 5 and τ 2 precipitates are detected in the alloy bulk and are dissolved by the salt. Furthermore, the lack of detection of design γ' precipitates in Inconel 617 after 1,000 h could indicate that the molten salt corrosion mechanism has indirectly induced a phase transformation of Al 2 TiNi (τ 2 ) and Ni 3 (Al,Ti) (γ’) phase. This investigation provides a comprehensive understanding of molten salt corrosion mechanisms in a complex material system such as a commercial structural alloy for applications in MCFRs.

36 MATERIALS SCIENCE↗