Fractal textured surfaces for high temperature corrosion mitigation in molten salts
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Optimizing the Operational Parameters of an Electrochemical Purification Cell for Corrosion Mitigation in CSP Plants During Operation: Preprint
To make concentrating solar power (CSP) cost-competitive, the next generation of CSP plants will increase efficiency by operating at a higher temperature, which will require a new thermal energy storage material. One option for the thermal energy storage material is a ternary chloride salt that is stable at the temperatures required, but reacts easily with the atmosphere to form MgOHCl, a corrosive impurity. If left unchecked, this impurity will corrode the containment alloys, potentially leading to dangerous spills. We are working to design an electrochemical purification cell to remove MgOHCl from the molten chloride salt during CSP plant operation. In this paper, we use predictive modeling to assess the rate at which purification must occur. Additionally, we analyze possible process flow pathways for the molten chloride salts. Ultimately, we determine that implementation of a single reactor through which all chloride salts flow is the most efficient design to reduce impurity concentration below 0.1 mol % impurity.
concentrating solar power↗
Mitigating Corrosion in Mg Sheet in Conjunction with a Sheet-Joining Method that Satisfies Structural Requirements within Sub-assemblies
This work was undertaken as a LightMAT project funded by the DOE-Vehicles Technology Office. The goal of this work was to develop corrosion protection strategies that simultaneously mitigate corrosion and achieve Class-A surface finish for Mg components in automotive applications. While automotive metals such as steel and aluminum are protected against corrosion through a variety of coating schemes/packages, the efficacy of these existing coating schemes for Mg and Mg- joints is not clear and needs to be determined. Therefore, five commercially available coating schemes and two joining techniques (riveting and Arplas resistance spot welding) were evaluated. The corresponding individual Mg sheet coupons or Mg/Mg joint test coupons were provided by Magna that were then corrosion tested at PNNL using ASTM B117 procedure. The microstructures and mechanical properties of the coupons were analyzed to determine the effectiveness of the joining and corrosion mitigation strategies. Of the coating schemes evaluated, Henkel Bonderite MgC 2.0 pre-treatment + E-coat showed the best corrosion protection and surface finish for individual Mg coupons and Arplas resistance spot welded coupons. However, the strength of Mg/Mg welded joint was reduced after corrosion testing due to some corrosion at the weld nugget. Mg/Mg rivet joints in conjunction with Chemetall oxisilan pre-treatment + polyurethane coating showed good corrosion resistance and some discoloration on the surface finish. Coating schemes comprising pre-treatment with Alodine 5200 + E-coat or Bonderite 1455 + polyurethane coating, in conjunction with Al rivet joints, showed significant corrosion and extensive discoloration of the surface. We anticipate that the results from this work will provide useful guidance to the automotive industry in selecting the appropriate combinations of corrosion protection coatings and joining techniques to fabricate light-weight Mg-based automotive components.
36 MATERIALS SCIENCE↗
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↗
Novel textured surfaces for superior corrosion mitigation in molten carbonate salts for concentrating solar power
Corrosion of metals in contact with molten salts used for thermal energy storage and heat transport at high temperatures is a serious impediment to the development of next-generation concentrating solar thermal systems. Toward addressing this limitation, novel multiscale fractal-textured Ni coatings on a variety of substrate alloys are presented in this study for exceptional corrosion mitigation in molten carbonate salts at a high temperature. Strongly adherent, durable, single-layer, and double-layer multiscale fractal coatings were fabricated using the electrodeposition method. Corrosion performance of the coatings on SS310, SS316, SS347, and In800H was studied in molten carbonate salt (32% Li 2 CO 3 +33% Na 2 CO 3 +35% K 2 CO 3 ) at 750 °C. Single-layer coatings are stable up to 300 h immersion, whereas double-layer coatings are stable beyond 750 h. The corrosion rate of double-layer Ni coatings on ferrous alloys was reduced by as much as 60% from that of uncoated surfaces and was about 18% below that of higher cost, high Ni content Ha230. The study represents the first-ever report of corrosion characteristics of alloys in carbonate salts at 750 °C and the first demonstration of a means of dramatically reducing corrosion in carbonate salts at a high temperature. The article is significant in that it provides a viable approach for low-cost structural alloys to be corrosion-resistant to molten carbonate heat transfer fluids and storage media in high-temperature concentrating solar thermal applications. Furthermore, the corrosion-resistant coatings provide opportunities for the use of low-cost, ferritic alloys instead of the expensive nickel-based alloys in practice.
14 SOLAR ENERGY↗
Progress and opportunities in corrosion mitigation in heat transfer fluids for next-generation concentrating solar power
Concentrating solar power (CSP) systems have gained considerable eminence in converting solar thermal energy into electrical power in recent years. According to the U.S. Department of Energy's Gen3 roadmap, the CSP system should operate > 700 °C, as its efficiency depends directly on the operating temperature of the heat transfer fluids (HTFs). A significant challenge, however, is the corrosion of containment materials by the HTFs that is exacerbated at the higher temperatures. A comprehensive review of the high temperature stable HTFs, their properties, corrosion mechanisms on different alloys, and corrosion mitigation measures is of much importance for directing a concerted research and development in the field, which forms the motivation for this compendium. First, molten salt HTFs and their thermophysical properties, along with liquid metals, are introduced. Corrosion of structural materials in different HTFs including molten salts, liquid metals, and supercritical carbon-di-oxide at various temperatures and the corrosion mechanisms are comprehensively reviewed. In addition, several corrosion mitigation methods are discussed. Finally, future directions for HTFs and corrosion mitigation methods in molten salts are proposed. As a result, the holistic review presented here will serve as the foundation for further research addressing relevant challenges and enabling the promise of achieving cost-competitive CSP.
14 SOLAR ENERGY↗
Microencapsulation Technology for Corrosion Mitigation by Smart Coatings
A multifunctional, smart coating for the autonomous control of corrosion is being developed based on micro-encapsulation technology. Corrosion indicators as well as corrosion inhibitors have been incorporated into microcapsules, blended into several paint systems, and tested for corrosion detection and protection effectiveness. This paper summarizes the development, optimization, and testing of microcapsules specifically designed to be incorporated into a smart coating that will deliver corrosion inhibitors to mitigate corrosion autonomously. Key words: smart coating, corrosion inhibition, microencapsulation, microcapsule, pH sensitive microcapsule, corrosion inhibitor, corrosion protection pain
Buhrow, Jerry↗
Effect of Drying on Corrosion Mitigation of Hanford Transfer Lines
Radioactive waste is stored in underground, carbon-steel double-shell tanks at the Department of Energy Hanford site. The waste is transferred between the tanks and other assets using the transfer lines spanning throughout the various tank farms at Hanford. The transfer lines consist of a pipe-in-pipe design, small diameter pipes, and are not piggable. Recent inspection data of the transfer lines have shown areas with corrosion on both interior of the encasements and exterior of the primary pipes, with nearly 50 percent wall loss on the primary pipes and nearly 25% wall loss on the encasement pipes due to pitting corrosion. The visual inspections of the transfer lines have shown presence of corrosion products near the pipeline risers and beyond. It has been hypothesized that the corrosion is predominantly due to the high humidity conditions and in some cases is driven by the presence of residual hydrotest water in the encasement and the associated contact with the safety significant primary pipe. Therefore, drying of the transfer lines could lead to corrosion mitigation. Experimental studies are being conducted to understand the effect of environmental conditions, especially, relative humidity and temperature, on transfer line grade carbon steel corrosion and on mitigating corrosion. The experimental conditions are selected based on the seasonal temperature changes, and relative humidity conditions ranging from 30 to 100 percent. The experimental data will be used as guidance for maintaining a dry environment that will help mitigate the transfer-line corrosion caused by the high humidity conditions.
Shukla, Pavan K.↗
Fractal coatings of Ni and NiYSZ for high-temperature corrosion mitigation in solar salt
This paper introduces a novel approach to corrosion mitigation using electrodeposited, fractal Ni and NiYSZ coatings. Highly adherent, durable multiscale coatings with fractal dimensions above 1.80 were fabricated. Corrosion characteristics of coated plain and etched surfaces of In800H, SS310, SS316 and SS347, in comparison to Ha230, were studied in molten 60% NaNO 3 + 40% KNO 3 at 600 °C. The corrosion rate of coated Fe-based alloys reduced by up to 68% compared to uncoated alloys and was on par with or lower than the corrosion rate of Ha230. Furthermore, the corrosion-resistant coatings provide for use of low-cost alloys in high temperature corrosive environments.
36 MATERIALS SCIENCE↗
Method for identification of redox control parameters for corrosion mitigation in molten fluoride salts
Structural material corrosion is a significant concern for the development of molten salt-cooled reactors (MSR) and redox control was proposed to mitigate the corrosion. This study presents an efficient approach to identify the partial pressure of F 2 gas for fluorine driven corrosion, the concentration ratios of UF 4 /UF 3 and ZrF 4 /ZrF 2 , and the partial pressure ratio of HF/H 2 needed to limit metal corrosion and its subsequent dissolution in molten fluoride salts. The identification procedure is made by simply using auxiliary axes in Ellingham diagrams. This approach greatly simplifies the optimization of redox control methods in studying the material corrosion in molten salts.
36 MATERIALS SCIENCE↗
Controlled thermal pre-treatment of ZMG232G10® for corrosion mitigation under simulated SOFC interconnect exposure conditions
The IT-SOFC candidate interconnect material ZMG232G10® was thermally pre-treated in air and in H 2 – 3% H 2 O to mitigate dual atmosphere corrosion. Bare and pre-treated steel samples were exposed to a dual atmosphere exposure condition (dry air/metal/4% H 2 – N 2 (bal.) + 3% H 2 O) for 500h at 600°C. Corrosion products and oxide morphology developed on the air-exposed surfaces were analyzed. Pre-treatments of the metal in oxidizing (air) and reducing (H 2 – 3% H 2 O) gas atmospheres provide improved passivation against dual atmosphere corrosion compared to bare steel. Further, the uniform and iron-free oxide scale developed during the pre-treatment of alloy in the low pO 2 H 2 – 3% H 2 O gas atmosphere provides an effective diffusion barrier against the outward transport of cations and oxidation of iron observed under dual atmosphere conditions.
36 MATERIALS SCIENCE↗
Field Testing of High Current Electrokinetic Nanoparticle Treatment for Corrosion Mitigation in Reinforced Concrete
Electrokinetic Nanoparticle (EN) treatment was used as a rapid repair measure to mitigate chloride induced corrosion of reinforced concrete in the field. EN treatment uses an electric field to transport positively charged nanoparticles to the reinforcement through the concrete capillary pores. Cylindrical reinforced concrete specimens were batched with 4.5 wt % salt content (based on cement mass). Three distinct electrokinetic treatments were conducted using high current density (up to 5 A/m2) to form a chloride penetration barrier that was established in 5 days, as opposed to the traditional 6-8 weeks, generally required for electrochemical chloride extraction (ECE). These treatments included basic EN treatment, EN with additional calcium treatment, and basic ECE treatment. Field exposures were conducted at the NASA Beachside Corrosion Test Site, Kennedy Space Center, Florida, USA. The specimens were subjected to sea water immersion at the test site as a posttreatment exposure. Following a 30-day post-treatment exposure period, the specimens were subjected to indirect tensile testing to evaluate treatment impact. The EN treated specimens exhibited 60% and 30% increases in tensile strength as compared to the untreated controls and ECE treated specimens respectively. The surfaces of the reinforcement bars of the control specimens were 67% covered by corrosion products. In contrast, the EN treated specimens exhibited corrosion coverage of only 4%. Scanning electron microscopy (SEM) revealed a dense concrete microstructure adjacent to the bars of the treated specimens as compared to the control and ECE specimens. Energy dispersive spectroscopic (EDS) analysis of the polished EN treated specimens showed a reduction in chloride content by a factor of 20 adjacent to the bars. This study demonstrated that EN treatment was successful in forming a chloride penetration barrier rapidly. This work also showed that the chloride barrier was effective when samples were exposed to field conditions at one of the most severely corrosive environments in North America.
Cardenas, Henry↗
Determining the Efficiency of Nitrogen Blanketing to Mitigate Corrosion in Hanford’s Transfer Line System
The Hanford site stores large quantities of radioactive waste in underground, carbon-steel, double-shell tanks. The waste is transferred between the tanks using piping that consists of carbon-steel pipes and carbon-steel encasements. The transfer lines have shown extensive corrosion on both the interior of the casing and exterior of the carrier pipes. Nitrogen blanketing, used to displace the oxygen in the transfer lines, was hypothesized to reduce the corrosion of the transfer lines. Experimental studies were conducted to investigate the effect of oxygen concentration on the corrosion rate and the initiation of pitting on carbon steel. The results indicated that controlling the oxygen concentration to 0% effectively mitigates corrosion. However, at 5 vol% oxygen, a significant increase in the general corrosion rate and pitting corrosion is observed.
Atmospheric Corrosion↗
Reduction of Methane Leaks through Corrosion Mitigation Pre-treatments for Pipelines with Field Applied Coatings
Corrosion of buried, coated steel pipelines transporting natural gas is a significant source of methane emissions, from pipeline venting required for maintenance and repairs and from pipeline leaks and incidents. Corrosion of steel under field applied coatings is an important safety concern for the pipeline industry. This project investigates the application of a field applied alloy over girth welds to mitigate external corrosion of buried coated steel pipelines. Various metallic coating options were considered, which were required to meet several criteria: (1) it must resist corrosion under open-circuit or mild cathodic protection conditions, (2) it must protect the substrate steel, and (3) it must not negatively affect the adhesion of the field coating. Finite element models and lab testing were performed of alloy coating compositions to identify promising alloy types underneath disbonded coatings. Polarization curves of coating alloys were generated to provide the boundary conditions for the COMSOL model to compute potential and current distributions around coated areas. Sacrificial and corrosion-resistant metal alloy coatings were evaluated and optimized using corrosion modeling and laboratory electrochemical testing, where aluminum alloy 5356 (5% Mg) and steel alloy B9 (9% Cr) were selected. Corrosion test coupons were designed and fabricated using thermal spray aluminum 5356 and welded B9 steel overlays on API 5L grade X42 line pipe steel. The corrosion test coupons, with simulated pipe coating damage, were tested in a laboratory soil box and a field pipeline site in Texas for 3-months. Corrosion test coupons were then tested for 6-months at field pipeline sites in Texas and Tennessee to quantify corrosion rates and performance of the aluminum and steel alloys under polyethylene tape and 2-part epoxy coatings, various coating holidays, and with and without cathodic protection.
03 NATURAL GAS↗
Field Testing of High Current Electrokinetic Nanoparticle Treatment for Corrosion Mitigation in Reinforced Concrete
This work examines field performance of nanoscale pozzolan treatments delivered el ctrokinetically to suppress chloride induced corrosion of concrete reinforcement. The particles are 20 nm silica spheres coated with 2 nm alumina particles that carry a net positive charge. Earlier work demonstrated that the alumina particles were stripped from the silica carriers and formed a dense phase with an interparticle spacing that is small enough to inhibit the transport of solvated chlorides. A D.C. field was used to inject the particles into the pores of concrete specimens, directly toward the mild steel bars that were embedded within each 3 inch diameter by 6 inch length concrete specimen. The voltage was held constant at 25 v per inch of concrete cover for a period of 7 days. These voltages permitted current densities as high as 3 A/sq m. During the final 3 days, a 1 molar solution of calcium nitrate tetrahydrate was used to provide a source of calcium to facilitate stronger and more densified phase formation within the pores. In a departure from prior work the particle treatments were started concurrent with chloride extraction in order to determine if particle delivery would inhibit chloride transport. Following treatment the specimens were immersed in seawater for 4 weeks. After this posttreatment exposure, the specimens were tested for tensile strength and the steel reinforcement was examined for evidence of corrosion. Scanning electron microscopy was conducted to assess impact on microstructure.
Calle, Luz Marina↗
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↗
Corrosion Mitigation and Increased Discharge Capacity in Aqueous Processed Thick Cathodes using Phosphoric Acid Additives
Aqueous processed cathodes for lithium-ion batteries are favorable for both cost and environmental reasons; however, these electrodes still face significant problems with increasing areal capacities (i.e. thickness). Highly basic slurry conditions (pH in excess of 12) corrode the current collector surface and evolve hydrogen gas. Consequently, bubbling at the electrode interface causes substantial damage to the dried electrode. As the loading of these electrodes is increased, damage becomes severe and results in lack of adhesion and cohesion. Here introduction of phosphoric acid to combat the rise in pH and suppress the corrosion at the current collector surface is investigated. Phosphoric acid was added in increments of 0.5, 1.0, and 1.5 wt% and the subsequent effects on slurry rheology, particle size, adhesion, and electrochemical cycling were investigated. A technique is reported for obtaining thick (6-8 mAh/cm2) cathodes that exhibit reduced surface cracking and improved rate performance as compared to control samples.
Kukay, Alexander↗
Evaluation of the effects of neutron irradiation on first-generation corrosion mitigation coatings on SiC for accident-tolerant fuel cladding
In this work, high purity SiC and SiC/SiC composites coated with commercial TiN, Cr, CrN, or CrN/Cr multilayer coatings were irradiated in Ar or flowing PWR water in the Massachusetts Institute of Technology Nuclear Reactor Laboratory (MITR). Irradiation in Ar was performed in the core. In the water environment, identical samples were placed in one of three different locations: in-core, providing exposure to neutron damage and radiolysis-affected water; above-core, where samples were exposed to radiolysis-affected water but not neutron damage, or outside of the core, where samples were exposed to the coolant water without the effects of radiation. Radiation in Ar revealed significant cracking of all but the TiN coatings, attributed to differential swelling between the coating and substrate. Lattice swelling was not observed in any of the coatings, but 0.2% void swelling was observed in the Cr coating. All of the coatings failed during water exposures in the core. Likewise, CrN/Cr spalled in each condition. Cr was protective, except under radiation damage as a result of cracking, and TiN severely degraded in the core with no coating was found following exposure. A SiC/coating ATF cladding system is anticipated to perform adequately following improvements in coating ductility and purity.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗