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At least 19 records

Corrosion property of Alloy 625 in Molten FLiNaK salt according to the Tellurium Concentrations

For this work, the corrosion properties of Alloy 625 have been studied in molten FLiNaK salt for 48 h at 700 °C as a function of tellurium (Te) concentrations using immersion tests and electrochemical methods. Under specific Te concentrations, we found that Te-induced corrosion can be suppressed and help protect the alloy against corrosion. The sample after the immersion test containing 0.1 wt.% Te (0.1 wt.% Te sample) had the lowest corrosion depth and mass loss, coupled with the highest charge transfer resistance, obtained using electrochemical impedance spectroscopy (EIS). On the other hand, the alloy with Te content above 0.1 wt.% exhibited severe corrosion penetration and lower charge transfer resistance in FLiNaK. Based on thermodynamical and electrochemical analyses, a corrosion mechanism of Alloy 625 in the molten salt containing Te was theorized involving the formation of stable corrosion products such as Ni/Fe rich layer depleted in Cr, nickel telluride, and chromium oxide.

Hong, Minsung↗

Multiscale characterization of an additively manufactured property graded Ni-base alloy for molten-salts\supercritical-CO 2 heat exchangers

The sequential optimization of strength and corrosion resistance in conventional alloy design procedures often results in a tradeoff between environmental degradation and optimal mechanical properties. A concurrent optimization of these two material properties is essential to efficiently develop high temperature alloys that can withstand harsh environments increasingly required for carbon–neutral energy technologies. In this work, we demonstrate the feasibility of directed energy deposition (DED) to manufacture a dual-corrosion resistant Ni-based alloy (Hastelloy N and Haynes 282), that meets the high temperature operation requirements of a molten-salts\supercritical-CO 2 (sCO 2 ) heat exchanger. A combination of multiscale characterization techniques and computational thermodynamics was employed to evaluate the cracking susceptibilities during fabrication and predict the microstructural stability of the material. Very good agreement was achieved between the observed and predicted phases and phase fractions of the as-printed material. A careful characterization of the transition zone between the two terminal alloy chemistries revealed potential precipitation strengthening (γ') on the Hastelloy N side while columnar-shaped M 23 C 6 and γ' precipitates that formed at grain boundaries (GBs) of the transition zone likely minimized the local interfacial energies. Both these mechanisms are believed to increase the interfacial stability but their performance at high temperatures requires further investigation.

36 MATERIALS SCIENCE↗

Electrochemical stability and corrosion behavior of Ni-Cr alloy in molten LiCl-KCl salt

This study investigated the electrochemical properties and potential-dependent stability of Cr(II) and Ni(II) in a eutectic LiCl-KCl molten salt at 500 °C under an argon atmosphere using a three-electrode cell configuration with a glassy carbon working electrode, Ag/Ag + reference electrode, and graphite counter electrode. Cyclic voltammetry was employed to characterize the Cr(0)/Cr(II)/Cr(III) and Ni(0)/Ni(II) redox transitions, yielding diffusion coefficients of 0.50 (±0.01) × 10 −5 cm 2 s −1 for Cr(II) and 0.91 (±0.16) × 10 −5 cm 2 s −1 for Ni(II) at 500 °C. The redox stability domains of these species provided insight into the corrosion mechanisms of a Ni-Cr alloy (80–20 wt %) in LiCl-KCl salt. The measured open circuit potential of the alloy corresponded to the range of potentials where the Ni(0) and Cr(II) species are stable, indicating a preferential dissolution of Cr. Immersion testing of the alloy for 336 h confirmed significant Cr depletion (or Ni-enrichment) at the surface layer, corroborating Cr dealloying as the dominant corrosion reaction under open circuit conditions. Additionally, the application of a small anodic overpotential (0.11 V) resulted in selective Cr dissolution while a large anodic overpotential (0.25 V) resulted in co-dissolution of both Cr and Ni. Furthermore, these results demonstrate that the corrosion mechanisms of a Ni-Cr alloy in LiCl-KCl depend upon the applied potential, and thus the redox conditions of the molten salt should be carefully controlled in the design of a redox buffer to mitigate corrosion in molten salt environments.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Fabrication and Testing of Solid-Solution Strengthened Corrosion Resistant Alloys For Service in Molten Fluoride Environments

The demand for higher system thermal efficiencies requires the operation of power generation cycles and heat conversion systems at progressively higher temperatures. As the system operating temperature increases, existing materials may not provide adequate mechanical properties or environmental compatibility or both. There is an increasing commercial interest in the development and deployment of liquid-fueled Molten Salt Reactors (MSRs). Hastelloy®N, the highest performing candidate MSR structural alloy, is not capable of operations at temperatures above 700°C, thus limiting the performance of these systems. Using an Integrated Computational Materials Engineering (ICME)-approach and small laboratory scale heats, ORNL developed a class of patented alloys covered by U.S. Patent 9, 435, 011 B2, “Creep-resistant, Cobalt-free alloys for high temperature, liquid-salt heat exchanger systems,” similar to Hastelloy®N in that they are primarily solid solution strengthened. In contrast to precipitation strengthened alloys, the microstructure of solid solution alloys and hence the high temperature mechanical properties are stable for extended periods of time allowing long reactor operating life. The new alloys have shown to possess good resistance to liquid fluorides at temperatures up to 850°C and have significantly improved creep properties when compared to Hastelloy®N. The purpose of the CRADA project was for ORNL to collaborate with Haynes International- a materials producer, MetalTek International- a foundry, and Kairos Power – an advanced reactor developer – to scale-up selected alloys, evaluate their properties, and identify one solid solution strengthened alloy that can meet the property requirements for the reactor being developed by Kairos Power and other similar liquid fluoride-salt cooled reactors. As part of the project, eight alloys were down-selected and fabricated in larger industrial scale heats by Haynes International. Resistance to molten salt was evaluated in flowing FLiNaK and FLiBe by Kairos Power using their Rotating Cage Loop (RCL) system. Accounting for iron deposition during these tests, the new alloys displayed very low net mass change showing excellent corrosion performance in molten salt. Creep properties evaluated at ORNL were found to be better than that of Hastelloy®N and 316 stainless steel. Long-term stabilities of the alloys evaluated by Haynes International showed that these alloys have excellent thermal stability in the temperature range 704.4-815.6°C, with the change in strength and ductility being less than 10-15% after a 4000-hour exposure at 815.6°C. Autogenously Gas Tungsten Arc Welding (GTAW) welded samples showed less than 10% change in yield strength / ultimate tensile strength / total elongation compared to the basemetal, indicating that the alloys have excellent weldability. Three parts were successfully investment-cast using one alloy with very little voiding showing feasibility of fabricating parts using the casting process. This project enabled extensive interaction between the material producer Haynes International, casting supplier MetalTek, and reactor developer Kairos Power. This facilitated testing of materials and components produced using the newly developed alloys by the end-user. This allowed the generation of critical dataset required for down-selection of a few promising alloys for further development. This data is also currently being shared with other reactor designers for them to evaluate the suitability of this alloy for their reactor design. The availability of this alloy will ultimately enable the design and development and deployment of MSRs with increased temperature of operation and thus, improved efficiencies.

99 GENERAL AND MISCELLANEOUS↗

Fabrication and Testing of Solid-Solution Strengthened Corrosion Resistant Alloys For Service in Molten Fluoride Environments

The demand for higher system thermal efficiencies requires the operation of power generation cycles and heat conversion systems at progressively higher temperatures. As the system operating temperature increases, existing materials may not provide adequate mechanical properties or environmental compatibility or both. There is an increasing commercial interest in the development and deployment of liquid-fueled Molten Salt Reactors (MSRs). Hastelloy®N, the highest performing candidate MSR structural alloy, is not capable of operations at temperatures above 700°C, thus limiting the performance of these systems. Using an Integrated Computational Materials Engineering (ICME)-approach and small laboratory scale heats, ORNL developed a class of patented alloys covered by U.S. Patent 9,435,011 B2, “Creep-resistant, Cobalt-free alloys for high temperature, liquid-salt heat exchanger systems,” similar to Hastelloy®N in that they are primarily solid solution strengthened. In contrast to precipitation strengthened alloys, the microstructure of solid solution alloys and hence the high temperature mechanical properties are stable for extended periods of time allowing long reactor operating life. The new alloys have shown to possess good resistance to liquid fluorides at temperatures up to 850°C and have significantly improved creep properties when compared to Hastelloy®N. The purpose of the CRADA project was for ORNL to collaborate with Haynes International- a materials producer, MetalTek International- a foundry, and Kairos Power – an advanced reactor developer – to scale-up selected alloys, evaluate their properties, and identify one solid solution strengthened alloy that can meet the property requirements for the reactor being developed by Kairos Power and other similar liquid fluoride-salt cooled reactors. As part of the project, eight alloys were down-selected and fabricated in larger industrial scale heats by Haynes International. Resistance to molten salt was evaluated in flowing FLiNaK and FLiBe by Kairos Power using their Rotating Cage Loop (RCL) system. Accounting for iron deposition during these tests, the new alloys displayed very low net mass change showing excellent corrosion performance in molten salt. Creep properties evaluated at ORNL were found to be better than that of Hastelloy®N and 316 stainless steel. Long-term stabilities of the alloys evaluated by Haynes International showed that these alloys have excellent thermal stability in the temperature range 704.4-815.6°C, with the change in strength and ductility being less than 10-15% after a 4000-hour exposure at 815.6°C. Autogenously Gas Tungsten Arc Welding (GTAW) welded samples showed less than 10% change in yield strength / ultimate tensile strength / total elongation compared to the basemetal, indicating that the alloys have excellent weldability. Three parts were successfully investment-cast using one alloy with very little voiding showing feasibility of fabricating parts using the casting process. This project enabled extensive interaction between the material producer Haynes International, casting supplier MetalTek, and reactor developer Kairos Power. This facilitated testing of materials and components produced using the newly developed alloys by the end-user. This allowed the generation of critical dataset required for down-selection of a few promising alloys for further development. This data is also currently being shared with other reactor designers for them to evaluate the suitability of this alloy for their reactor design. The availability of this alloy will ultimately enable the design and development and deployment of MSRs with increased temperature of operation and thus, improved efficiencies.

36 MATERIALS SCIENCE↗

Methodology for Thermodynamic Analysis Coupled with Computational Fluid Dynamics Modeling for Casting a Novel Aluminum–Cerium Alloy

In this paper, we present the results of computational fluid dynamics (CFD) analysis to assess castability, porosity, molten metal fluidity and other technological properties of a new Al-Ce alloy. A thermodynamic analysis of a new Al-Ce alloy is done to obtain the physical properties as a function of temperature across both solid and liquid phases. These properties are then used to build the CFD of model the full casting process from initial pouring through to final solidification of the part, here an example of a heavy duty mor mount is used. While several excellent commercial CFD codes exists this process shows that CFD can be used to assess the capability of the alloy to properly fill the mold, as well as give predictions where scattered porosity or large-scale defects may occur in the casting. Further, unlike the commercially available software (e.g., ProCAST, SOLIDCast , MAGMASOFT®) the complex 3D-analysis of the stress / strain fields in cast parts is not performed at this time. However, the availability of free software for assessing the required thermodynamic / thermo-physical properties of new alloys (OpenCALPHAD) and CFD codes such as OpenFOAM® makes the developed option attractive and economical, especially for the analysis of new Al-Ce alloys, for which the available data does not exist.

36 MATERIALS SCIENCE↗

Capturing the softening in T91 steel annealed with molten LBE through interfacial gradient plasticity

In order to study the effect of annealing with molten lead–bismuth eutectic alloy (mLBE) on the mechanical properties of T91 steel, micropillar compression tests were analyzed through the consideration of mechanical interface energy terms within gradient plasticity. The stress–strain curves of the micropillars showed significant stochastic effects, characterized by a different elastic and plastic behavior response for each pillar. Among the various pillars, some exhibited a similar trilinear behavior. Scanning electron microscopy (SEM) images of these specimens demonstrated localized slip deformation and slip planes after compression, while transmission electron microscopy (TEM) images showed the presence of a severe slip zone along the random grain boundaries (RGBs), indicating that the GBs played a dominant role in the deformation/slip. By employing interfacial gradient plasticity that can explicitly account for the presence of GBs, the trilinear response was captured, allowing for the determination of the mechanical interface parameter. As anticipated the pillars which underwent severe slip at the GBs had a lower value for the mechanical interface parameter. Finally, annealing with mLBE can, therefore, in some cases result in softening in the overall stress–strain, as it lowers the mechanical interface energy of GBs.

36 MATERIALS SCIENCE↗

Measurements of Thermophysical Properties of Molten Silicon and Geranium

The objective of this ground base program is to measure thermophysical properties of molten/ undercooled silicon, germanium, and Si-Ge alloys using a high temperature electrostatic levitator and in clearly assessing the need of the microgravity environment to achieve the objective with higher degrees of accuracy. Silicon and germanium are two of the most important semiconductors for industrial applications: silicon is unsurpassed as a microelectronics material, occupying more than 95% of the electronics market. Si-Ge alloy is attracting keen interest for advanced electronic and optoelectronic applications in view of its variable band gap and lattice parameter depending upon its composition. Accurate thermophysical properties of these materials are very much needed in the semiconductor industry for the growth of large high quality crystals.

Rhim, Won-Kyu↗

Evaluate Compatibility of Alloy 244 in NaCl-MgCl 2

Alloy 244 is a potential material of interest for molten salt reactor (MSR) developers employing molten chloride as fuel and coolant salts because of its improved mechanical properties compared to the austenitic stainless steel 316H and the Ni-base alloy Hastelloy-N. However, data are limited on the corrosion behavior of alloy 244 in molten chloride salts. Experimental data on the corrosion behavior of 244 in chloride salts will provide valuable data to MSR developers while simultaneously aiding in improving mechanistic understanding of the role of salt chemistry, alloying constituents and microstructure of 244. This task evaluated the compatibility of alloy 244 in two different eutectic NaCl–MgCl 2 salt mixtures. Similar corrosion behavior in terms of depths of attack and compositional changes in the alloy subsurface was observed after exposure in both salts for 500 h at 750°C. However, severe corrosion attack was observed after 500 h at 850°C in one of the chloride salt mixture. This was most likely due to the combined effects of the differences in the two salt chemistries, distinct microstructure of 244 at 850°C compared to 750°C, and the temperature dependence of the chemical interactions (thermodynamic and kinetic) between the alloying constituents.

36 MATERIALS SCIENCE↗

Carburization of metals by a chemical mechanism of carbon transport through molten fluoride salts

Carburization of structural alloys used in Fluoride Cooled High Temperature Reactors (FHR) can result from the interaction between the metal and graphite components and cause changes in alloy properties. However, carburization requires transport of carbon from graphite to alloy surfaces through the molten fluoride coolant. This work introduces an alternative to previously proposed carbon transport mechanisms. The new mechanism is based on the generation of carbonate ions (CO 3 2- ) by oxide impurities in the salt reacting with graphite. CO 3 2- is then reduced on metal surfaces to deposit carbon. This work demonstrates the reduction of dissolved CO 3 2- on pure Fe, Ni, Cr, Mo, and W surfaces without an applied potential in molten FLiNaK at 700 °C. Finally, we also demonstrate that the interaction between oxide and graphite in molten FLiNaK media produces CO 3 2- .

36 MATERIALS SCIENCE↗

Environment Conscious Ceramics (Ecoceramics): An Eco-Friendly Route to Advanced Ceramic Materials

Environment conscious ceramics (Ecoceramics) are a new class of materials, which can be produced with renewable natural resources (wood) or wood wastes (wood sawdust). This technology provides an eco-friendly route to advanced ceramic materials. Ecoceramics have tailorable properties and behave like ceramic materials manufactured by conventional approaches. Silicon carbide-based ecoceramics have been fabricated by reactive infiltration of carbonaceous preforms by molten silicon or silicon-refractory metal alloys. The fabrication approach, microstructure, and mechanical properties of SiC-based ecoceramics are presented.

Singh, M.↗

The Radiation-Induced Fate of Fission Product Iodine in Molten Salts

Understand and Predict Radiation-Induced Iodine Speciation, Chemistry, and Transport in High-Temperature Molten Salts Award Number: DE-AC07-05ID1451 Gregory P. Holmbeck (Gregory.Holmbeck@inl.gov), Center for Radiation Chemistry Research, Idaho National Laboratory, 1955 N. Fremont Avenue Idaho Falls, ID, 83415, USA. Project Scope The goal of this Chemical and Materials Sciences to Advance Clean Energy Technologies and Low-Carbon Manufacturing project is to understand and predict the radiation-induced speciation, chemistry, and transport of fission product iodine in the triumvirate extremes of high-temperature, ionizing radiation, and corrosive molten salts. This missing fundamental information is critical for the accelerated development and deployment of safe, clean nuclear energy based on molten salt reactor (MSR) and pyrochemical reprocessing technologies. The central hypothesis driving this research is, the radiation-induced conversion of iodide will yield an extensive suite of transient and steady-state iodine radiolysis products that will alter the bulk chemical and physical properties of the irradiated molten salt system—the speciation, distribution, and chemical transport of which will be dictated by the composition and the availability of multivalent metal cations and metal alloy interfaces. To test this hypothesis, this project initiated three synergistic Research Objectives: (1) determine how the inclusion of iodine/iodide influences the chemical and physical properties of complex molten salt mixtures; (2) elucidate the speciation and fundamental chemical behavior of transient and steady-state iodine/iodide species formed by the irradiation of molten and solid salt mixtures; and (3) understand the influence of interfacial processes on determining the final disposition of iodine in high temperature molten salts, notably the structure and chemical speciation of iodine at metal-salt interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New High-Strength Ni-based Alloys for High Temperature Service in Liquid Fluoride Salt Environments

The ever-increasing demand for higher system thermal efficiency necessitates the operation of power generation cycles and heat conversion systems for chemical processes at progressively higher temperatures. As the system operating temperature increases, fewer and fewer materials are available with the required mechanical properties and environmental compatibility. This dearth of materials is particularly acute in structural applications at temperatures above 700°C in liquid Fluoride Salt Cooled High-Temperature Reactors (FHRs) and Concentrated Solar Power (CSP) systems where liquid fluoride and/or liquid chloride salts are used for their high thermal capacity and low thermal conductivity to store and transport heat. It has been shown that fluorides and chlorides can degrade the properties of the material used for storage and transport due to corrosive effects thus affecting the performance and lifetime characteristics. Thus, materials used for storage and transport for fluoride/chloride-salt must at the minimum have good compatibility with the salt by exhibiting low corrosion rates at the required temperatures. In addition, since many of the components will be subject to stresses in service, they need to have sufficient strength to resist plastic deformation, and the resistance to time dependent creep deformation at these temperatures, and stress levels. Achieving the combination of these properties required for higher temperatures is particularly challenging considering traditionally, the expected lifetime of some of the components used in these systems are from 30 years (CSP) to 80 years (FHRs). Although 316 stainless steel and associated redox corrosion reduction techniques are being considered for use in the first generational systems, use of 316SS is limited to operating temperatures up to ~ 650°C, thereby resulting in lower reactor efficiencies. Hastelloy ® N, developed at ORNL in the 1950s-60s for molten salt service is currently the leading candidate FHR structural alloy but has inadequate creep properties at high temperatures. Using a computationally-guided approach, Oak Ridge National Laboratory had developed new high strength alloys strengthened by γ’ precipitates (about 2X the strength of Hastelloy ® N) in small laboratory-scale heats that show good resistance to corrosion by fluorides and improved creep rupture life at temperatures up to 850°C (U.S. Patent Application No. 13/833,357 entitled “High Strength Alloys for High Temperature Service in Liquid-Salt Cooled Energy Systems”- granted U. S. Patent No. 9,540,714).

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Properties of pure nickel after long term exposures to LiOH and vacuum at 775 K

The solid to liquid phase transformation of LiOH at 744.3 K is considered to be an ideal candidate thermal energy storage (TES) mechanism for a Rankine heat engine based solar dynamic system operating at approximately 682 K. While pure nickel is thought to be a suitable containment material for LiOH, long term containment is of concern because molten hydroxides are usually corrosive. Two commercially pure nickel alloys, Ni-200 and Ni-201, were exposed to molten LiOH, its vapor, and vacuum at 775 K for periods ranging from 50 to 5000 h, and simple mechanical property measurements (77 to 900 K tensile and 750 K creep rupture) of exposed alloys were undertaken. The mechanical property test procedures are described and tabular lists of the test data are presented.

Whittenberger, J. D.↗

Additive friction stir deposition induced stress ripples in aluminum alloy

In additive manufacturing, modification of the viscosity of softened or molten metal plays a significant role in the development of mechanical properties distribution. Similar to soft polymers, molten or softened metal usually exhibits vastly different viscoelastic properties. During scratching tests, viscoelastic polymers undergo spatiotemporal stress development and relaxation, causing stress ripples to form on their surfaces. Here, it is observed that friction stir-based solid-state manufacturing can yield similar stress ripples on softened aluminum alloys due to the linear motion of the deposition tool. Softened aluminum alloys exhibit viscoelastic and viscoplastic responses similar to polymeric material during the solid-state deposition process. In the final product, residual stress ripples appear on the surface of the metal alloy due to periodic residual stress relaxation, leading to oscillatory behavior from the bulk mechanical properties of the material. The orientation of the in-built stress pattern formed in the bulk of the additively manufactured metal alloy underneath the visually evident onion ring-like surface pattern formation is diametrically in the opposite direction. The experimentally observed results are consistent with analytical calculation and numerical simulations in terms of behaviors.

36 MATERIALS SCIENCE↗

Structural Fluctuations and Thermophysical Properties of Molten II-VI Compounds

Recently, in support of the microgravity experiment entitled "Crystal Growth of Selected 11-VI Semiconducting Alloys by Directional Solidification," the viscosity of HgZnTe pseudobinary melt was measured using an oscillating-cup viscometer at NASA/Marshall Space Flight Center (MSFC). An unexpected time drift of the measured viscosity, which shows a slow relaxation phenomena at temperatures near the liquidus point, was reproducibly observed. Two sets of data were obtained by cooling the Hg(0.84)Zn(0.16)Te melt from 850 C and stabilizing at temperatures of 790 C, which is just above the liquidus temperature, and stabilizing at temperature of 810 C. While it took one day to reach equilibration at 810 C, five days were required at 790 C A similar relaxation phenomenon was also observed in the measured density of the same liquid. Furthermore, in the density measurements of the HgCdTe melts, which is the pseudobinary system studied in another flight experiment entitled "Growth of Solid Solution Single Crystals," a negative thermal expansion was reported. The liquid density increases from the liquidus point to a maximum value at a temperature approximately 700 C above the liquidus, where normal thermal expansion progressively resumes.

Su, Ching-Hua↗

Mechanical properties of Haynes Alloy 188 after exposure to LiF-22CaF2, air, and vacuum at 1093 K for periods up to 10,000 hours

As part of a program to provide reassurance that the cobalt-base superalloy Haynes Alloy 188 can adequately contain a LiF-CaF2 eutectic thermal energy storage salt, 4900- and 10,000-hr exposures of Haynes Alloy 188 to LiF-22CaF2, its vapor, vacuum, and air at 1093 K have been undertaken. Following such exposures, the microstructure has been characterized and the 77 to 1200 K tensile properties measured. In addition, 1050 K vacuum creep-rupture testing of as-received and molten salt- and vacuum-exposed samples has been undertaken. Although slight degradation of the mechanical properties of Haynes Alloy 188 due to prior exposure was observed, basically none of the losses could be ascribed to a particular environment. Hence, observed decreases in properties are due to thermal aging effects, not corrosive attack. In view of these findings, Haynes Alloy 188 is still deemed to be suitable for containment of the eutectic LiF-CaF2 thermal energy storage media.

Whittenberger, J. D.↗