A summary of the high temperature alkali metal corrosion program at Brookhaven National Laboratory
Evaluation of refractory alloys for containing liquid and boiling sodium
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Evaluation of refractory alloys for containing liquid and boiling sodium
Abstract To address the issues of limited ionic conductivity and poor interface stability at room and low temperatures in solid‐state electrolytes, a robust intrinsic ferroelectrolyte or nanoferroelectrolyte strategy for engineering solid‐state flexible ferroelectric composite electrolytes utilizing strongly coupled intrinsic ion conducting 2D/2D sodium‐rich anti‐perovskite (NaRAP)/ferroelectric perovskite heterostructures is introduced. Herein, highly scalable PVDF‐based metaferroelectrolytes with Na 2.99 Ba 0.005 OCl/Ca 2 Na 2 Nb 5 O 16 − (CNNO − ) nanosheets into a ferroelectric poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) matrix, through an in situ cross‐linking and spontaneous bridging method, for compact solid‐state sodium batteries (SSBs), are reported. Benefiting from unique well‐dispersed 3D ferroelectric coupled network and the Na 2.99 Ba 0.005 OCl/CNNO − ‐induced PVDF‐HFP ferroelectric β phase, the Na + flux is regulated, thereby inhibiting Na dendrite growth at the interface. Notably, the optimized PH‐5% NC metaferroelectrolyte exhibits rapid ion transport (1.11 × 10 −4 S cm −1 at 25 °C), a wide electrochemical window (> 4.8V), superior conformal mechanical compatibility, improved flexibility, good elasticity and flame retardancy. The solid‐state Na 3 V 2 (PO 4 ) 3 /PH‐5% NC/Na batteries present a stable cycling performance (remaining 56.4 mAh g −1 after 500 cycles at 1 C) even at 0 °C, potential for cost‐effective, safe, stable and compact SSB energy storage over 600 Wh L −1 , vastly surpassing 365 Wh L −1 of the current commercial sodium‐ion liquid‐electrolyte batteries.
Several fast-spectrum nuclear reactors designed to generate high power (~450 MWe) rely on forced convection of media such as supercritical CO 2 , sodium, or liquid lead to cool the nuclear core, operating at temperatures up to 600 °C. Cost-effective, high-strength Fe-based alumina forming austenitic (AFA) alloys are a promising candidate for the fabrication of critical nuclear components. This study investigated laser powder bed fusion (LPBF) processing of an AFA alloy composition optimized for improved creep resistance. Electron microscopy revealed an elongated grain structure along the build direction with a fine sub-grain cellular structure decorated with (Cr,Fe,Nb) 23 C 6 carbide precipitates at the intercellular boundaries. Finally, at temperatures of 20–900 °C, the LPBF alloy's superior tensile properties compared to its arc-melted counterpart and other advanced steels (e.g., SS316) were attributed to the distribution of nano-sized carbide precipitates, whereas the high ductility was attributed to the LPBF alloy's elongated grain structure.
Solar thermal power tower systems are the primary technology being proposed for solar electricity from thermal energy. Operational limits on these towers are often driven by mechanical properties under significant thermal loads, particularly at the receiver where incoming flux is converted to thermal energy. While the solar receiver’s efficiency is largely driven by its optical properties, thermomechanical stresses on the receiver limits the operational envelope. One pathway to higher efficiency is greater allowable solar fluxes on the receiver but novel materials are required. The present study uses computational fluid dynamics to describe a parametric design space for a microvascular carbon/carbon composite solar receiver as a new material option for high flux solar receivers. Simulations are conducted for different microvascular geometries considering the role of material properties and heat transfer fluids, for the impact on thermal efficiency, and allowable strain. Results show that microscale receiver modules made of the proposed carbon/carbon composite could achieve thermal efficiencies over 90% and full-scale receivers can achieve up to 85% thermal efficiency for the design explored considering realistic strain limits, flux levels, and material properties. These values are highly dependent on the heat transfer fluid pairing, the through plane thermal conductivity of the carbon/carbon composite, the path architecture of the microscale receiver, and the incident solar flux profiles.
The Columbia Basin Consulting Group (CBCG) is developing an advanced reactor cooled by Lead-Bismuth (Pb-Bi). The design is being developed for a high level of passive safety. It has the advantages of the classical liquid metal (sodium) reactor, i.e. small size and passive safety, while having the additional advantage of chemically inert coolant.
Next generation fission and fusion nuclear reactors require materials that can withstand operating temperatures greater than 500 °C, neutron irradiation doses of up to 200 displacements per atom (dpa), and potentially corrosive coolants such as the alkali liquid metals sodium, lithium, and NaK (Na33K eutectic alloy). Refractory alloys, such as Nb1Zr (Nb-1wt%Zr) and Molybdenum alloy TZM (Mo-0.5wt%Ti-0.08wt%Zr) have been traditionally considered viable candidates for advanced fission and fusion reactor concepts. However, it is relatively difficult to generate complex geometries of interest from these alloys using traditional manufacturing methods. In addition, there needs to be a concentrated effort to address refractory metal challenges at elevated temperature operation. In order to generate complex geometries of interest, modern manufacturing techniques are considered to increase the technological readiness level (TRL), cost-effectiveness, and schedule savings. This work focused on the continued development of laser powder bed fusion (L-PBF) additive manufacturing (AM) to improve both design flexibility, evaluate microstructure and properties, and ultimately accelerate the TRL and qualification of these processes and alloys for components to potentially be put into service. Niobium alloy Nb1Zr was identified through a down-selection process outlined in previous reports as a candidate to develop in L-PBF AM. Historically, Nb1Zr had been explored for high temperature fast spectrum fission reactors for both terrestrial and space applications. Molybdenum alloy TZM has also been considered for these reactor concepts due to exceptional high-temperature strength, creep resistance, and stability under irradiation. L-PBF AM of TZM has previously been investigated at LANL under the Microreactor program, NASA, ORNL, and in academia. However, due to the crack prone nature of TZM, L-PBF AM of TZM resulted in significant microcracking and additional development is required to pursue viable maturation. Other AM methods have been found to be more successful in printing TZM, and those alternatives approaches are discussed in this effort. The efforts detailed in this report focused on continued development of Nb1Zr through L-PBF and development of TZM via L-PBF and electron powder bed fusion (E-PBF). The objective of this work was to further the development of these AM techniques for the chosen refractory alloys, elucidating and addressing associated challenges through characterization of several demonstration builds. At LANL, Nb1Zr builds were completed using an EOS M290 and M400 machines, and a refractory alloy-dedicated L-PBF system, the Xact Metal XM200G, was installed. The XM200G primary purpose was to do the Nb1Zr parameter development process; however, due to difficulties associated with the machine installation and qualification process, it was decided to pivot development to the larger M400 and M290 machines. Although the supply of Nb1Zr powder was limited, it was sufficient to generate sub-scale metallographic specimens for the purpose of parameter development. This was first accomplished on the EOS M400 then the M290 due to machine schedule availability. Further development of TZM has been initiated at the University of Texas El Paso (UTEP) under contract with LANL to use both a heated build envelope L-PBF machine and E-PBF machine that have been found in the literature to mitigate microcracking. UTEP was provided with TZM powder and build plates to support parallel TZM parameter development across both machines. As part of the contract, UTEP will also be conducting microstructural characterization once optimized process parameters have been identified. The optimized process parameters for each machine will be used to generate a series of metallographic, mechanical, and surface finish specimens for subsequent characterization and testing. In the next section, we provide a detailed discussion of the methodology used for investigating the feasibility of leveraging these alloys for use in advanced reactor applications.
Laboratory methods to determine quantitative nitrogen, hydrogen, oxygen, and carbon impurities in sodium
Generation of electric power by liquid sodium-jet MHD generator
Assembly pumps liquid sodium-potassium /NaK/ eutectic at 950 K for up to 20,000 hours. Design features include - high operating-temperature capability, zero leakage, process fluid lubricant/coolant, insulation system compatible with ionizing radiation environments, and reliability and long life without maintenance.
Micromachining is a chemical means of etching three-dimensional structures, typically in single-crystalline silicon. These techniques are leading toward what is coming to be referred to as MEMS (micro electro mechanical systems), where in addition to the ordinary two dimensional (planar) microelectronics, it is possible to build three-dimensional micromotors, electrically-actuated microvalves, hydraulic systems, and much more on the same microchip. These techniques become possible because of differential etching rates of various crystallographic planes and materials used for semiconductor microfabrication. The University of Cincinnati group in collaboration with NASA Lewis formed micro heat pipes in silicon by the above techniques. Work is ongoing at a modest level, but several essential bonding and packaging techniques have been recently developed. Currently, we have constructed and filled water/silicon micro heat pipes. Preliminary thermal tests of arrays of 125 micro heat pipes etched in a 1 inch x 1 inch x 250 micron silicon wafer have been completed. These pipes are instrumented with extremely small P-N junctions to measure their effective conductivity and their maximum operating power. A relatively simple one-dimensional model has been developed in order to predict micro heat pipes' operating characteristics. This information can be used to optimize micro heat pipe design with respect to length, hydraulic diameter, and number of pipes. Work is progressing on the fabrication of liquid-metal micro heat pipes. In order to be compatible with liquid metal (sodium or potassium), the inside of the micro heat pipes will be coated with a refractory metal (such as tungsten, molybdenum, or titanium).
NASA is undertaking the design of a new spacecraft to explore the planet Jupiter and its three moons Calisto, Ganymede and Europa. This proposed mission, known as Jupiter Icy Moons Orbiter (JIMO) would use a nuclear reactor and an associated electrical generation system (Reactor Power Plant-RPP) to provide power to the spacecraft. The JIMO spacecraft is envisioned to use this power for science and communications as well as Electric Propulsion (EP). Among other potential power-generating concepts, previous studies have considered Thermoelectric and Brayton Power conversion systems, coupled to a liquid metal reactor for the JIMO mission. This paper will explore trades in system mass and radiator area for a nuclear reactor power conversion system, however this study will focus on Stirling power conversion. The Stirling convertor modeled in this study is based upon the Component Test Power Convertor design that was designed and operated successfully under the Civil Space Technology Initiative for use with the SP-100 nuclear reactor i the 1980's and early 1990's. The study design is such that two of the four convertors would operate at any time to generate the 100 kWe while the others are held in reserve. For this study the Stirling convertors hot-side temperature is 1050 K, would operate at a temperature ratio of 2.4 for a minimum mass system and would have a system efficiency of 29%. The Stirling convertor would generate high voltage (400 volt), 100 Hz single phase AC that is supplied to the Power Management and Distribution system. The waste hear is removed from the Stirling convertors by a flowing liquid sodium-potassium eutectic and then rejected by a shared radiator. The radiator consists of two coplanar wings, which would be deployed after the reactor is in space. System trades were performed to vary cycle state point temperatures and convertor design as well as power output. Other redundancy combinations were considered to understand the affects of convertor size and number of spares to the system mass.
Alkali metal thermal to electric converter (AMTEC) designs for space power are numerous, but the selection of materials for construction of long-lived AMTEC devices has been limited to electrodes, current collectors, and the solid electrolyte. AMTEC devices with lifetimes greater than 5 years require careful selection and life testing of all hot-side components. The likely selection of a remote condensed design for initial flight test and probable use with a radioisotope heat source in AMTEC powered planet probes requires the device to be constructed to tolerate operating T greater than 1150K, as well as exposure to Na (g) , and Na (liq) on the high pressure side. The temperatures involved make the characterization of high strength and chemical resistance to Na containing Na 2 O critical. Selection among materials which can be worked should not be driven by ease of fabricablity, as high temperature stability is the critical issue. These concepts drive the selecton of Mo alloys for Na (liq) containment in AMTEC cells for T to 1150K operation, as they are significantly stronger than comparable Nb or Ta alloys, are less soluble in Na (liq) containing dissolved Na 2 O, are workable compared with W alloys (which might be used for certain components), and are ductile at the T greater than 500K of proposed AMTEC modules in space applications.
Alkali metal heat transfer technology was used in the development of conceptual designs for the transport and storage of sensible and latent heat thermal energy in distributed concentrator, solar Stirling power conversion systems at a power level of 15 kWe per unit. Both liquid metal pumped loop and heat pipe thermal transport were considered; system configurations included: (1) an integrated, focal mounted sodium heat pipe solar receiver (HPSR) with latent heat thermal energy storage; (2) a liquid sodium pumped loop with the latent heat storage, Stirling engine-generator, pump and valves located on the back side of the concentrator; and (3) similar pumped loops serving several concentrators with more centralized power conversion and storage. The focus mounted HPSR was most efficient, lightest and lowest in estimated cost. Design confirmation testing indicated satisfactory performance at all angles of inclination of the primary heat pipes to be used in the solar receiver.
Liquid metals and their properties, as applied to space electric-power systems, are discussed as possible heat-transfer and thermodynamic working fluids. Representative liquid metals—lithium, sodium, potassium, NaK-78, lead, and bismuth — tare discussed and compared. Space power requirements are listed and used as a basis for evaluating the potentialities of the liquid metals.
Nuclear fuels using alloys of uranium, or metallic fuels, have many beneficial properties. The classical metallic fuel design uses a loose fitting cylindrical “slug” of fuel placed inside stainless-steel cladding tubes where the gap is filled with sodium. This sodium bond is liquid at operating temperature and conducts heat from the slug to the cladding, especially in early life before fuel swells into contact with the cladding. Despite the benefits of sodium bonding, there is a desire to develop metallic fuel technologies without it chiefly to reduce chemical reaction hazards in spent fuel storage from sodium fast reactors operating on once-through fuel cycles. Elimination of the sodium bond may also help unlock potential benefits for fuel fabrication, reactor neutronics, and compatibility with other types of reactors. Creating a sodium-free metallic fuel revolves around the problem of manufacturing fuel slug geometries which are in close contact with the cladding at beginning of life to facilitate heat transport while alleviating fuel-cladding chemical interactions (FCCI) at this interface and providing enough free volume to accommodate fuel swelling. Accelerating development and qualification of this fuel system will require careful selection of design and manufacturing options. To this end, a design trade-off study was performed to evaluate candidate options. Several design and manufacturing options were assessed, weighted, scored, and ranked with respect to fabrication, normal reactor operation, off-normal scenarios, and back-end considerations. This effort was performed both for “baseline” needs, which represented a once-through fuel cycle at temperatures and burnups known to be viable for sodium-bonded metallic fuel, and for “enhanced” needs to represent opportunities for closed fuel cycles and/or more aggressive temperatures/burnups. The outcomes of this study prioritized a baseline technology using U-Zr alloy with additives to mitigate FCCI, produced in annular slug geometry by continuous casting, clad in austenitic stainless-steel alloy, and followed by a final step to swage the cladding down to close the gap. This study prioritized an enhanced fuel technology using U-Mo alloy, also produced by continuous casting into an annular geometry, followed by coating/plating with an FCCI barrier on the slug, again with a final step to swage the cladding diameter down using oxide dispersion strengthened steel. It was noted that development of the enhanced fuel technology would entail more risk, thus U-Zr alloy was put forth as a backup to U-Mo if challenges are encountered with FCCI barriers, and advanced ferritic/martensitic steels are put forth as a backup to oxide dispersion strengthened steels if swaging and welding are found unworkable.
Power is a critical consideration in planning exploration of the surfaces of the Moon, Mars, and places beyond. Nuclear power is an important option, especially for locations in the solar system where sunlight is limited or environmental conditions are challenging (e.g., extreme cold, dust storms). NASA and the Department of Energy are maintaining the option for fission surface power for the Moon and Mars by developing and demonstrating technology for a fission surface power system. The Fission Surface Power Systems project has focused on subscale component and subsystem demonstrations to address the feasibility of a low-risk, low-cost approach to space nuclear power for surface missions. Laboratory demonstrations of the liquid metal pump, reactor control drum drive, power conversion, heat rejection, and power management and distribution technologies have validated that the fundamental characteristics and performance of these components and subsystems are consistent with a Fission Surface Power preliminary reference concept. In addition, subscale versions of a non-nuclear reactor simulator, using electric resistance heating in place of the reactor fuel, have been built and operated with liquid metal sodium-potassium and helium/xenon gas heat transfer loops, demonstrating the viability of establishing system-level performance and characteristics of fission surface power technologies without requiring a nuclear reactor. While some component and subsystem testing will continue through 2011 and beyond, the results to date provide sufficient confidence to proceed with system level technology readiness demonstration. To demonstrate the system level readiness of fission surface power in an operationally relevant environment (the primary goal of the Fission Surface Power Systems project), a full scale, 1/4 power Technology Demonstration Unit (TDU) is under development. The TDU will consist of a non-nuclear reactor simulator, a sodium-potassium heat transfer loop, a power conversion unit with electrical controls, and a heat rejection system with a multi-panel radiator assembly. Testing is planned at the Glenn Research Center Vacuum Facility 6 starting in 2012, with vacuum and liquid-nitrogen cold walls to provide simulation of operationally relevant environments. A nominal two-year test campaign is planned including a Phase 1 reactor simulator and power conversion test followed by a Phase 2 integrated system test with radiator panel heat rejection. The testing is expected to demonstrate the readiness and availability of fission surface power as a viable power system option for NASA's exploration needs. In addition to surface power, technology development work within this project is also directly applicable to in-space fission power and propulsion systems.