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At least 289 records · Page 16

Depletion-driven thermochemistry of molten salt reactors: review, method, and analysis

Molten salt reactors (MSRs) are innovative advanced nuclear reactors that utilize nuclear fuel by dissolving it in a high-temperature liquid salt. This unique feature differentiates MSRs from other types of reactors and allows for enhanced safety and economic performance. The liquid fuel also entails several multiphysics effects that can complicate reactor design and operation. One primary effect termed here as depletion-driven thermochemistry is a driving force in altering the multiphysics behavior of the reactor. Essentially, depletion-driven thermochemistry is the effect that fuel depletion has on changing the chemical redox potential of the fuel salt over time. As the fuel is consumed, the redox potential shifts toward a more oxidizing state. Without active control, the changing chemistry due to depletion increases corrosion thereby limiting reactor component lifetimes. Additionally, the changing redox potential of the fuel salt alters the vapor pressures of chemical species dissolved in the fuel salt. Changing vapor pressures of species in the fuel salt is an important parameter to understand when off-gassing volatile species during normal reactor operation, and for source term characterization during accident scenario transients. The present work represents a fundamental step toward modeling and coupling the driving physics (i.e., neutronics and chemistry) involved in altering the redox potential in an MSR. Here, the neutronic code Griffin models the depletion of the fuel-salt system, while the chemical equilibrium code Thermochimica calculates the thermochemical state of the isotopic inventory, using the Molten Salt Thermodynamic Database - Thermochemical (MSTDB-TC). These two codes are tightly coupled to predict the impact of fuel depletion in altering the chemistry in MSR systems. Redox potential control methods are discussed and can be modeled using this multiphysics approach. The vapor pressures of chemical species that could be extracted to an off-gas system, as determined by the reactor’s thermochemical state, are examined. The neutronics-chemistry coupling developed in this work is expected to have potential application for analyzing corrosion, source term evolution, and material safeguards in MSR systems. Lastly, suggestions for areas of further improvements of the models to expand these capabilities by incorporating other coupled physics effects is provided.

Walker, Samuel A.↗

Dynamic and static corrosion of chromium-alumina refractory in simulated nuclear waste glass

Monofrax® K-3, a chromium–alumina refractory, is widely used in nuclear waste glass melters due to its high durability. However, aggressive vitrification conditions still lead to corrosion that limits melter lifespan. Here, this study investigates two key corrosion modes, subsurface and melt-line corrosion, under static and dynamic conditions, using a custom setup enabling precise control of melt velocity and temperature. Experimental results, interpreted using diffusion-limited dissolution models, show that (i) subsurface corrosion increases by approximately 10% per mm/s increase in melt velocity, while melt-line corrosion remains virtually unaffected, (ii) corrosion rate dependence on temperature is inversely proportional to melt viscosity, and (iii) glass composition affects both corrosion modes similarly, based on Cr 2 O 3 , Al 2 O 3 , and alkali contents. The experimental data also allowed the determination of diffusion coefficients of major dissolving species, which were found to be consistent between the melt-line and subsurface corrosion models, indicating their suitability for future CFD studies.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗

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↗

Smart Coating for Corrosion Indication and Prevention: Recent Progress

The authors are developing a smart coating system based on pH-triggered release microcapsules. These microcapsules can be incorporated into various coating systems for corrosion detection, protection and self-repair of mechanical coating damage. This paper will present the results from progress made to date in the controlled release properties of these microcapsules as well as in their corrosion indication and corrosion inhibition function.

Li, Wenyan↗

Hot-salt stress-corrosion of titanium alloys as related to turbine operation

In an effort to simulate typical compressor operating conditions of current turbine engines, special test facilities were designed. Air velocity, air pressure, air dewpoint, salt deposition temperature, salt concentration, and specimen surface condition were systematically controlled and their influence on hot-salt stress-corrosion evaluated. The influence of both continuous and cyclic stress-temperature exposures was determined. The relative susceptibility of a variety of titanium alloys in commonly used heat-treated conditions was determined. The effects of both environmental and material variables were used to interpret the behavior of titanium alloys under hot-salt stress-corrosion conditions found in jet engines and to appraise their future potential under such conditions.

Gray, H. R.↗

Stress-corrosion cracking in metals

Criteria and recommended practices for preventing stress-corrosion cracking from impairing the structural integrity and flightworthiness of space vehicles are presented. The important variables affecting stress-corrosion cracking are considered to be the environment, including time and temperature; metal composition, and structure; and sustained tensile stress. For designing spacecraft structures that are free of stress-corrosion cracking for the service life of the vehicle the following rules apply: (1) identification and control of the environments to which the structure will be exposed during construction, storage, transportation, and use; (2) selection of alloy compositions and tempers which are resistant to stress-corrosion cracking in the identified environment; (3) control of fabrication and other processes which may introduce residual tensile stresses or damage the material; (4) limitation of the combined residual and applied tensile stresses to below the threshold stress level for the onset of cracking throughout the service life of the vehicle; and (5) establishment of a thorough inspection program.

Source record↗

Morphology selection in dealloying: A phase field study of the coupling among kinetic mechanisms

A phase field model is used to investigate how the corrosion rate and morphology of a dealloying metal is controlled by the kinetic rates of bulk solid diffusion, interfacial diffusivity, and interface dissolution. A specific focus is investigating the manner by which variations in these kinetic parameters synergistically influence the onset of a morphological instability at the solid-liquid interface, which is known to precede rapid dealloying corrosion towards highly topologically complex structures such as bicontinuous porous solids. This work demonstrates that this instability can be suppressed by either an increase of interdiffusion in the solid alloy, or by a decreasing rate of dissolution at the solid-liquid interface. When the instability is suppressed, the result is a relatively planar, passivated dealloying front. Importantly, however, coupled changes in kinetic parameters can also promote the morphological instability and sustain fine-scale ligament and pore formation. Finally, the relevance of the solid-liquid interfacial diffusion for determining the rate of dealloying and ligament formation is highlighted. By elucidating the mechanistic influence of bulk and interfacial kinetic factors on the dealloyed morphology, this work helps to rationalize the contrasting morphologies observed in various dealloying systems.

Diffusion↗

Damage-mitigating control of aerospace systems for high performance and extended life

The concept of damage-mitigating control is to minimize fatigue (as well as creep and corrosion) damage of critical components of mechanical structures while simultaneously maximizing the system dynamic performance. Given a dynamic model of the plant and the specifications for performance and stability robustness, the task is to synthesize a control law that would meet the system requirements and, at the same time, satisfy the constraints that are imposed by the material and structural properties of the critical components. The authors present the concept of damage-mitigating control systems design with the following objectives: (1) to achieve high performance with a prolonged life span; and (2) to systematically update the controller as the new technology of advanced materials evolves. The major challenge is to extract the information from the material properties and then utilize this information in a mathematical form so that it can be directly applied to robust control synthesis for mechanical systems. The basic concept of damage-mitigating control is illustrated using a relatively simplified model of a space shuttle main engine.

Ray, Asok↗

Efficient BiVO 4 /CoFeO x H y photoanodes using controlled annealing and conformal linear-sweep electrocatalyst photodeposition

Although monoclinic bismuth vanadate (BiVO 4 ) is a promising photoanode for solar water splitting, its practical use is hindered by imperfect photocurrent generation/collection, low photovoltage compared to the bandgap, and corrosion side reactions that limit durability. Here, we introduce a controlled-annealing sol–gel process for BiVO 4 thin-film photoanodes along with an optimized linear-sweep-voltammetry photodeposition of CoFeO x H y cocatalysts. The resulting BiVO 4 films annealed at 550 °C exhibited a photocurrent density of 4.1 mA/cm 2 at 1.23 V RHE under 1 sun AM 1.5G solar simulation and a low onset potential of 0.26 V RHE due to high majority carrier conductivity, a crystalline bulk with reduced defects as evidenced by x-ray photoelectron spectroscopy and photoluminescence lifetime analysis, and thus enhanced photocarrier collection. However, significant degradation in performance was found due to interfacial photocorrosion. To protect the surface and speed the oxygen-evolution reaction CoFeO x H y cocatalyst layers were deposited. By varying the number of consecutive sweeps and adjusting the applied bias range, an ultra-thin (~15 nm) CoFeO x H y cocatalyst layer was uniformly grown deposited over 30 cycles on the BiVO 4 surface. The resulting BiVO 4 /CoFeO x H y yielded 4.03 mA/cm 2 at 1.23 V RHE and onset potential of 0.24 V RHE , with stable operation (~15 % loss in photocurrent at 1.23 V RHE relative to ~60 % loss in the uncatalyzed control sample). These conformal CoFeO x H y catalytic layers function simultaneously to selectively collect photoexcited holes from the BiVO 4 , catalyze the water-oxidation reaction, and protect the BiVO 4 from photodegradation.

42 ENGINEERING↗

Iodine Satellite

This project is a collaborative effort to mature an iodine propulsion system while reducing risk and increasing fidelity of a technology demonstration mission concept. 1 The FY 2014 tasks include investments leveraged throughout NASA, from multiple mission directorates, as a partnership with NASA Glenn Research Center (GRC), a NASA Marshall Space Flight Center (MSFC) Technology Investment Project, and an Air Force partnership. Propulsion technology is often a critical enabling technology for space missions. NASA is investing in technologies to enable high value missions with very small and low-cost spacecraft, even CubeSats. However, these small spacecraft currently lack any appreciable propulsion capability. CubeSats are typically deployed and drift without any ability to transfer to higher value orbits, perform orbit maintenance, or deorbit. However, the iodine Hall system can allow the spacecraft to transfer into a higher value science orbit. The iodine satellite (iSAT) will be able to achieve a (Delta)V of >500 m/s with <1 kg of solid iodine propellant, which can be stored in an unpressurized benign state prior to launch. The iSAT propulsion system consists of the 200 W Hall thruster, solid iodine propellant tank, a power processing unit, and the necessary valves and tubing to route the iodine vapor. The propulsion system is led by GRC, with critical hardware provided by the Busek Co. The propellant tank begins with solid iodine unpressurized on the ground and in-flight before operations, which is then heated via tank heaters to a temperature at which solid iodine sublimates to iodine vapor. The vapor is then routed through tubing and custom valves to control mass flow to the thruster and cathode assembly. 2 The thruster then ionizes the vapor and accelerates it via magnetic and electrostatic fields, resulting in thrust with a specific impulse >1,300 s. The iSAT spacecraft, illustrated in figure 1, is currently a 12U CubeSat. The spacecraft chassis will be constructed from aluminum with a finish to prevent iodine-driven corrosion. The iSAT spacecraft includes full three-axis control using wheels, magnetic torque rods, inertial management unit, and a suite of sensors and optics. The spacecraft will leverage heat generated by spacecraft components and radiators for a passive thermal control system.

Dankanich, John↗

Unique material requirements in the Space Shuttle Main Engines

Components operating in staged-combustion cycle liquid fuel rocket engines such as the Space Shuttle Main Engines (SSMEs) are subjected to severe temperature changes during start/stop transients, together with extremely high pressures, corrosive gases, high fluid velocities, demanding weight-control criteria, etc. Attention is given to the selection and application of metallic and nonmetallic materials for high temperature resistance, cryogenic properties, and hydrogen and oxygen compatibility. The materials in question include polyimides, Kel-F, Armalon, and Teflon among plastics, and gold and copper platings, weld-overlays and heat treatment modifications among metals and metallic processing techniques. The polymeric materials are oxygen-resistant, and the metallic ones hydrogen-resistant.

Fulton, D. L.↗

Reliability and engineering sciences area. Materials research: Single junction thin film

A test bench was designed and fabricated for the purpose of improving control of hot-spot test accuracy. Electrochemical corrosion research focused on corrosion mechanisms to which both crystalline and a-Si modules may be subjected in central station applications. A variety of cells and several designs were subjected to accelerated stress tests. Humiditiy degradation rates were determined and key electrochemical failure mechanisms were identified. Software was developed for the prediction of power loss resulting from open circuits in an array field of a-Si modules. Failure analysis was continued on the four ARCO Solar Genesis modules. The interactions of water on the silicon module was examined. An autocatalytic photooxidation model was proposed. The reliability and durability of bonding materials and electrical insulation were also studied.

Source record↗

Mach 0.3 Burner Rig Facility at the NASA Glenn Materials Research Laboratory

This Technical Memorandum presents the current capabilities of the state-of-the-art Mach 0.3 Burner Rig Facility. It is used for materials research including oxidation, corrosion, erosion and impact. Consisting of seven computer controlled jet-fueled combustors in individual test cells, these relatively small rigs burn just 2 to 3 gal of jet fuel per hour. The rigs are used as an efficient means of subjecting potential aircraft engine/airframe advanced materials to the high temperatures, high velocities and thermal cycling closely approximating actual operating environments. Materials of various geometries and compositions can be evaluated at temperatures from 700 to 2400 F. Tests are conducted not only on bare superalloys and ceramics, but also to study the behavior and durability of protective coatings applied to those materials.

Fox, Dennis S.↗

Analysis of Eddy Current Capabilities for the Detection of Outer Diameter Stress Corrosion Cracking in Small Bore Metallic Structures

The use of eddy current techniques for the detection of outer diameter damage in tubing and many complex aerospace structures often requires the use of an inner diameter probe due to a lack of access to the outside of the part. In small bore structures the probe size and orientation are constrained by the inner diameter of the part, complicating the optimization of the inspection technique. Detection of flaws through a significant remaining wall thickness becomes limited not only by the standard depth of penetration, but also geometrical aspects of the probe. Recently, an orthogonal eddy current probe was developed for detection of such flaws in Space Shuttle Primary Reaction Control System (PRCS) Thrusters. In this case, the detection of deeply buried stress corrosion cracking by an inner diameter eddy current probe was sought. Probe optimization was performed based upon the limiting spatial dimensions, flaw orientation, and required detection sensitivity. Analysis of the probe/flaw interaction was performed through the use of finite and boundary element modeling techniques. Experimental data for the flaw detection capabilities, including a probability of detection study, will be presented along with the simulation data. The results of this work have led to the successful deployment of an inspection system for the detection of stress corrosion cracking in Space Shuttle Primary Reaction Control System (PRCS) Thrusters.

Wincheski, Buzz↗

In-Situ TEM Molten Salt Corrosion

Molten salt reactors (MSRs) offer a compelling pathway for next-generation nuclear energy, with advantages in thermal efficiency, inherent safety, and flexible fuel management. Yet, halide-based molten salts introduce significant materials challenges, particularly alloy corrosion. Alloy performance in these environments ultimately depends on understanding how corrosion initiates and progresses at the nanoscale, however most existing models rely on post-exposure characterization, leaving degradation mechanisms largely inferred rather than directly observed. NiCr alloys have garnered interest in MSRs applications as the Ni-based matrix provides strength and creep resistance, while Cr content offers oxidation resistance in air. However, NiCr corrosion resistance in chloride salts has proven poor due to preferential chromium dissolution, the formation of Cr-depleted pathways, and grain-boundary attack. This work aims to directly visualize corrosion of Ni-20Cr exposed to LiCl-KCl using in-situ Transmission Electron Microscopy (TEM) to capture real-time microstructural evolution during corrosion. Experiments will be performed at ~800 °C under controlled pressure conditions while utilizing Energy-Dispersive X-ray Spectroscopy (EDS) to analyze elemental redistribution. Observation of chromium depletion fronts, associated surface restructuring, and localized chloride enrichment are expected. Ultimately, this study is expected to provide a link between microscale processes and the macroscopic degradation behaviors relevant to MSR operation in advanced reactor environments. Simultaneously, this approach enables future in-situ investigations regarding alloy composition, salt chemistry, and their influence on corrosion pathways and long-term stability.?

36 - MATERIALS SCIENCE↗

Fundamental Science for Enhancing the Durability of Photoelectrodes for Solar Fuels Production

During the award period, we performed a series of investigations to address a key bottleneck in solar-driven fuel production, which is materials stability. Regardless of the activity of electrocatalysts or selectivity of products, or efficiency of the light absorbers, if the systems are not stable then there is no ultimate technological relevance for solar fuels production. Degradation of semiconductor photoelectrodes is a well-known, long-recognized impediment to implementation of practical stable solar fuels systems. Thus, we aimed to define the thermodynamics and kinetics of the (electro)chemical processes that underpin corrosion of semiconductor photoelectrodes. We also sought to develop protective coatings and kinetic control strategies to extend durability of semiconductor photoelectrodes.

14 SOLAR ENERGY↗