DOE OSTI2019
1.0 INTRODUCTION The use of solar energy to produce steam for the generation of electricity is an established technology, with multiple designs for concentrating solar power (CSP) steam generators available commercially and a number of such units currently operating. As part of the effort to improve the overall efficiency of this technology, designers have developed thermal energy storage (TES) mechanisms that employ molten salt to capture a portion of the solar energy available during the day-time hours and make that energy available for steam generation during periods when the sun’s energy is not available. In current TES systems, nitrate salts are used extensively as the medium of energy exchange. However, due to the chemical instability of these salts at temperatures above 600ºC, they are not being considered for use in the next more efficient generation of CSP plants, in which the energy exchange fluids will be required to operate in the range 600ºC to 800ºC. At these higher temperatures, molten chloride salts, such as KCl-MgCl2, are viewed as promising alternatives to the nitrate salts, but, of course, these chloride-based salts are highly corrosive to the engineering alloys commonly used in the construction of pressure vessels, heat exchangers, pumps and piping at high temperatures. Hence, a solution to the problem of material degradation is essential if the next generation of CSP plants is to be commercially viable (Ref 1). In order to effectively address the problem of molten chloride salt corrosion at high temperatures (≥ 750ºC) and thereby to reduce the cost of molten salt tanks and related apparatus, various options have been considered, with one of the most promising being an innovative coatings system developed and applied onto low alloy ferritic or austenitic stainless material. Development of such a coating system would reduce the capital costs of thermal energy storage (TES) and increase the overall efficiency of the concentrating solar power (CSP) system. Although high strength nickel base alloys are well suited for many high temperature applications, they have significant limitations when exposed to molten chloride salt conditions and they are very expensive. Monolithic materials such as the austenitic stainless steels (e.g., SS310 and SS347) and the more common nickel base alloys (e.g., IN625 and IN800H) have exhibited high corrosion rates in molten chloride salt environments (Ref1). Molten salt corrosion of IN625 in salts containing chlorides showed a catastrophic corrosion rate of 1.111”/year at 800ºC (Ref1). Hence, an innovative coatings solution to mitigate molten chloride salt corrosion is needed. Of the many coating techniques available in the market, no one technique appears to be capable of producing effective protection from molten salt corrosion at a relatively low cost. There are thermal spray coating techniques, in particular the twin wire-arc technology, that are attractive when considering the coating of large molten salt tanks because the coatings application rate is high, the overall application cost is low and repairs to the coating can readily be made either in the shop or in the field. However, the twin wire arc coating materials currently available in the market have certain inherent limitations, including porosity and mechanical bonding to the substrate, which limit their effectiveness in providing protection against molten chloride salt corrosion at high temperatures. What is required is an approach that combines the economy and versatility of thermal spray wire-arc technology with the superior resistance of advanced alloys to effectively combat molten chloride salt corrosion at elevated temperatures. Applied Thermal Coatings, Inc. (ATC) has investigated an innovative coatings technology to produce dual layer cermet/ceramic coatings that will be dense and impervious to any corrosive molten salts/fluids, thereby resisting the effects of molten salt corrosion. Development of coatings using this technology will make it possible to fabricate the molten salt systems using a relatively low-cost base material, which will reduce the overall cost of the power generating system and enhance the commercial viability of solar power. 2.0 PROJECT OVERVIEW Of the coating technologies available for the production of a cost-effective method of protection from the effects of high-temperature chloride attack, there are two that offer specific advantages for the CSP/TES application, particularly when used in a way that effectively complements the strengths of each coating method. The first of these is electroless nickel plating, through which a nickel-rich layer is produced on the surface of a component through chemical reduction. The second coating technology is aluminizing, in which aluminum is diffused into the surface of a component and, depending on the composition of the substrate, aluminides are formed. The objective of this project has been to demonstrate the feasibility of a low- cost coating for the protection of pump impellers used for the inductive transport of molten salts. Initial interest focused on an inter-metallic nickel aluminide coating and subsequently, for economic reasons, consideration also was given to a coating composed of iron aluminides. Applying such coatings to low alloy or austenitic stainless-steel substrates will provide the superior resistance to molten chloride salt corrosion and blade tip erosion that normally can be achieved only through the use of more highly alloyed – and, therefore, more expensive - nickel-base materials and it will do so at a substantially lower cost. The coating systems evaluated were designed to take advantage either of the combined strengths of the electroless nickel plating process and the aluminizing process to produce a nickel-aluminide intermetallic coating or to rely solely on the aluminizing process to produce, in conjunction with iron from the substrate, a protective layer consisting of iron aluminides. With respect to the nickel aluminide protection, this has been achieved by first depositing a layer of nickel-rich alloy onto an austenitic stainless substrate using the electroless nickel plating process and then aluminizing the nickel- coated surface to produce the nickel aluminide coating. With respect to the iron aluminide protection, this has been achieved by aluminizing bare austenitic stainless steel. Testing has supported the conclusion that the developed coatings will resist attack by molten chloride salts at high temperatures (550°C to 750°C) and have sufficient hardness to resist blade tip erosion.The steps taken to develop either a low-cost intermetallic nickel aluminide coating using electroless nickel plating and aluminizing or a low-cost iron aluminide coating using aluminizing only, and to demonstrate the quality of the coatings and their effectiveness against molten chloride salt corrosion and erosion at high temperatures (≤ 750ºC) have been as follows: 1. Design of the optimum electroless nickel plating and aluminizing mixtures using advanced thermodynamic analysis; 2. Development of processing parameters for the electroless nickel plating and aluminizing processes, to be used either together or separately; 3. Production of specimens coated using the designated electroless nickel plating process; 4. Production of samples with intermetallic nickel aluminide coating or iron aluminide coating; 5. Investigation of the performance of the intermetallic nickel aluminide coating and the iron aluminide coating when subjected to molten chloride salts corrosion at high temperatures (≥ 750ºC); and, 6. Metallurgical characterization of the microstructure of the coatings, both prior to and after exposure to molten salt environments at elevated temperatures.