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NASA NTRS1998

The Evolution of Interfacial Sliding Stresses During Cyclic Push-in Testing of C- and BN-Coated Hi-Nicalon Fiber-Reinforced CMCs

Interfacial debond cracks and fiber/matrix sliding stresses in ceramic matrix composites (CMCs) can evolve under cyclic fatigue conditions as well as with changes in the environment, strongly affecting the crack growth behavior, and therefore, the useful service lifetime of the composite. In this study, room temperature cyclic fiber push-in testing was applied to monitor the evolution of frictional sliding stresses and fiber sliding distances with continued cycling in both C- and BN-coated Hi-Nicalon SiC fiber-reinforced CMCs. A SiC matrix composite reinforced with C-coated Hi-Nical on fibers as well as barium strontium aluminosilicate (BSAS) matrix composites reinforced with BN-coated (four different deposition processes compared) Hi-Nicalon fibers were examined. For failure at a C interface, test results indicated progressive increases in fiber sliding distances during cycling in room air but not in nitrogen. These results suggest the presence of moisture will promote crack growth when interfacial failure occurs at a C interface. While short-term testing environmental effects were not apparent for failure at the BN interfaces, long-term exposure of partially debonded BN-coated fibers to humid air resulted in large increases in fiber sliding distances and decreases in interfacial sliding stresses for all the BN coatings, presumably due to moisture attack. A wide variation was observed in debond and frictional sliding stresses among the different BN coatings.

Eldridge, J. I.↗

NASA NTRS1961

Heat-Transfer Measurements at a Mach Number of 4.95 on Two 60 deg Swept Delta Wings with Blunt Leading Edges and Dihedral Angles of 0 deg and 45 deg

An experimental investigation was conducted to evaluate the heat-transfer characteristics of two 60 deg swept delta wings with cylindrical leading edges of 0.25-inch radii and dihedral angles of 0 deg and 45 deg. The tests were conducted at a Mach number of 4.95 and a stagnation temperature of 400 F. The The test-section unit Reynolds number was varied from 1.95 x 10(exp 6) to 12.24 x 10(exp 6) per foot. The results of the investigation indicated that, in a plane normal to the leading edge, the laminar-flow heat-transfer distribution was in good agreement with two-dimensional blunt-body theory. The stagnation-line heat-transfer level could be predicted from two-dimensional blunt-body theory provided the stagnation-line heat-transfer coefficient was assumed to vary as the cosine of the effective sweep. A comparison of the heating rates to the 0 deg dihedral wing (planform sweep of 60 deg) and the 45 deg dihedral wing (planform sweep of 69.3 deg) with equal panel sweep and panel area indicated that the stagnation-line heat-transfer coefficient for the 45 deg dihedral wing could be as much as 40 percent less than the stagnation-line heat-transfer coefficient for the 0 deg dihedral wing at both equal angles of attack and equal lifts. The laminar-flow heat-transfer rate to both wings outside the vicinity of the stagnation line was essentially equal.

Stainback, P. Calvin↗

NASA NTRS2017

Microstructure Based Material-Sand Particulate Interactions and Assessment of Coatings for High Temperature Turbine Blades

Gas turbine engines for military/commercial fixed-wing and rotary wing aircraft use thermal barrier coatings in the high-temperature sections of the engine for improved efficiency and power. The desire to further make improvements in gas turbine engine efficiency and high power-density is driving the research and development of thermal barrier coatings and the effort of improving their tolerance to fine foreign particulates that may be contained in the intake air. Both commercial and military aircraft engines often are required to operate over sandy regions such as in the Middle-East nations, as well as over volcanic zones. For rotorcraft gas turbine engines, the sand ingestion is adverse during take-off, hovering near ground, and landing conditions. Although, most of the rotorcraft gas turbine engines are fitted with inlet particle separators, they are not 100 percent efficient in filtering fine sand particles of size 75 microns or below. The presence of these fine solid particles in the working fluid medium has an adverse effect on the durability of turbine blade thermal barrier coatings and overall performance of the engine. Typical turbine blade damages include blade coating wear, sand glazing, Calcia-Magnesia-Alumina-Silicate (CMAS) attack, oxidation, plugged cooling holes, all of which can cause rapid performance deterioration including loss of aircraft. The objective of this research is to understand the fine particle interactions with typical ceramic coatings of turbine blades at the microstructure level. A finite-element based microstructure modeling and analysis has been performed to investigate particle-surface interactions, and restitution characteristics. Experimentally, a set of tailored thermal barrier coatings and surface treatments were down-selected through hot burner rig tests and then applied to first stage nozzle vanes of the Gas Generator Turbine of a typical rotorcraft gas turbine engine. Laser Doppler velocity measurements were performed during hot burner rig testing to determine sand particle incoming velocities and their rebound characteristics upon impact on coated material targets. Further, engine sand ingestion tests were carried out to test the CMAS tolerance of the coated nozzle vanes. The findings from this on-going collaborative research to develop the next-gen sand tolerant coatings for turbine blades are presented in this paper.

Engine Tests↗

NASA NTRS1993

Chromium and reactive element modified aluminide diffusion coatings on superalloys - Environmental testing

The high temperature performance of reactive element (RE)-doped and Cr/RE-modified aluminide diffusion coatings on commercial Ni-base alloy substrates was determined. In isothermal oxidation at 1100 C in air, RE-doped aluminide coatings on IN 713LC substrates formed a continuous slow-growing n-Al2O3 scale after 44 hrs of exposure. The coatings were protected by either an outer ridge Al2O3 scale with an inner compact Al2O3 scale rich in RE or by a continuous compact scale without any noticeable cracks or flaws. The cyclic oxidation behavior of Cr/RE-modified aluminide coatings on Rene 80 and IN 713LC alloys and of RE-doped aluminide coatings on IN 713LC alloys at 1100 C in static air was determined. Pack powder entrapment from the powder contacting (PC) process detracted significantly from the overall cyclic oxidation performance. Type I hot corrosion behavior of Cr/RE-modified aluminide coatings on Rene 80 and Mar-M247 alloy substrates at 900 C in a catalyzed 0.1 percent SO3/O3 gas mixture was determined. The modified coatings produced from the PC arrangement provided significantly better resistance to hot corrosion attack than commercial low-activity aluminide coatings produced by the above pack arrangement.

Bianco, Robert↗

NASA NTRS2002

Knowledge of Pest Resistance in SiC/BN/SiC Composites Improved

Ceramic-matrix composites (CMC's) consisting of a silicon carbide matrix reinforced with boron-nitride- (BN-) coated silicon carbide (SiC) fibers are strong contenders for commercial and aerospace applications (in particular, the hot sections of high-performance turbine engines in advanced aircraft and generators). They have very good mechanical properties below approximately 600 C and above approximately 1000 C. Between those temperatures, however, the BN coating oxidizes easily, and the oxidation of the SiC matrix is too sluggish to seal off the composite with a protective layer of silica. In that temperature interval, the preferential oxidation of the BN weakens and embrittles the composite. That phenomenon, referred to as "pest" degradation, is the focus of this work, which aims to identify the causes of and remedies for pesting. Previous work established that pesting in Hi-Nicalon (Nippon Carbon Co., Ltd., Japan)/SiC composites was caused by a layer of free carbon that undermined the oxidation resistance of the BN. New work suggests that composites containing a source of carbon are prone to severe pesting and that those that are free of elemental carbon are resistant pesting. Pest resistance was assessed by exposing machined samples for 100 to 150 hr in an atmospheric burner rig at 600 to 1100 C, followed by a tensile fracture test to measure residual mechanical properties and by characterization of the interphase microstructure. Whether the elemental carbon came from intrinsic or extrinsic sources, its presence induced the tensile strength to drop by over 50 percent in the burner rig, with an even more severe loss of fracture strain. A likely mechanism by which burnoff of the carbon layer exposes the BN to accelerated flank attack by ambient oxidants is shown. The BN is replaced with borosilicates that attack the fiber, and ultimately with silica that embrittles the composites by rigidly bonding components. Thus, the study has shown that pesting can be prevented in SiC/BN/SiC, or at least reduced, by simply excluding free carbon. These studies continue, and plans for future work include investigating the role that carbon may play elsewhere in the interphase region.

Thomas-Ogbuji, Linus U.↗

NASA NTRS2006

Test Capability Enhancements to the NASA Langley 8-Foot High Temperature Tunnel

The NASA Langley 8-Foot High Temperature Tunnel produces true enthalpy environments simulating flight from Mach 4 to Mach 7, primarily for airbreathing propulsion and aerothermal/thermo-structural testing. Flow conditions are achieved through a methane-air heater and nozzles producing aerodynamic Mach numbers of 4, 5 or 7 and have exit diameters of 8 feet or 4.5 feet. The 12-ft long free-jet test section, housed inside a 26-ft vacuum sphere, accommodates large test articles. Recently, the facility underwent significant upgrades to support hydrocarbon fueled scramjet engine testing and to expand flight simulation capability. The upgrades were required to meet engine system development and flight clearance verification requirements originally defined by the joint NASA-Air Force X-43C Hypersonic Flight Demonstrator Project and now the Air Force X-51A Program. Enhancements to the 8-Ft. HTT were made in four areas: 1) hydrocarbon fuel delivery; 2) flight simulation capability; 3) controls and communication; and 4) data acquisition/processing. The upgrades include the addition of systems to supply ethylene and liquid JP-7 to test articles; a Mach 5 nozzle with dynamic pressure simulation capability up to 3200 psf, the addition of a real-time model angle-of-attack system; a new programmable logic controller sub-system to improve process controls and communication with model controls; the addition of MIL-STD-1553B and high speed data acquisition systems and a classified data processing environment. These additions represent a significant increase to the already unique test capability and flexibility of the facility, and complement the existing array of test support hardware such as a model injection system, radiant heaters, six-component force measurement system, and optical flow field visualization hardware. The new systems support complex test programs that require sophisticated test sequences and precise management of process fluids. Furthermore, the new systems, such as the real-time angle of attack system and the new programmable logic controller enhance the test efficiency of the facility. The motivation for the upgrades and the expanded capabilities is described here.

Harvin, S. F.↗

DOE OSTI2019

Innovative Approach to SCC Inspection and Evaluation of Canister in Dry Storage

This final report is summarized four years of work of awarded project number DE-NE0008442\IRP-15-9318, title as: “Innovative Approach to SCC Inspection and Evaluation of Canister in Dry” supported by Nuclear Energy University Program\Integrated Research Program, NEUP\IRP, where last year is an extension of no cost project. This research work is focused on the possible degradation of dry storage canister holding used nuclear fuel (UNF), due to exposure of marine atmospheric environment. The canister usually designed from a welded austenitic stainless-steel of types 304 or 316, encased in a concrete shell known as an overpack. This canister designed and licensed for 20 years with an extension period need to be determined, in addition 20 years or more. These casks are located throughout the country in Independent Spent Fuel Storage Installations (IFSFIs) often on the site close to nuclear power plants, that are often located in coastal or lake-side regions where a marine atmospheric salt air environment exist. As a result of several recent decisions, such as not pursuing Yucca Mountain as a long-term geologic repository storage facility for UNF and the cancellation of the construction of a reprocessing facility in the 1980s due to proliferation risks, interim dry storage facilities for long-term storage are vital option for the immediate future of nuclear energy technology. One of the primary concerns with respect to the long-term performance of the storage casks is the potential for corrosion initiation due to deliquescence of salts deposited on the canister surface as aerosols; in regions of high residual weld stresses, this may lead to localized stress corrosion cracking (SCC). Dust and aerosols in the air being drawn though ventilation openings in the overpacks of passively ventilated dry canister storage systems may be deposited on the stainless-steel canister outer surfaces. Under these conditions, localized corrosion attack can occur. Chlorides ions deliquescence on the canister surface, a process by which the salts essentially pull moisture out of the air, creating a concentrated salt brine on the canister surface. Chloride-induced stress corrosion cracking (CISCC) of welded zones is of special concern, as it a well-documented mode of attack for austenitic stainless steels marine environments, and many independent spent fuel storage installations (ISFSIs) are located in coastal areas. Recent canister inspections have shown that chloride salts are present on the surface of in-service canisters at near-marine settings. However, canister surface inspections of satisfactory resolution to detect SCC have never been carried out in details, because access to the canister surfaces through vents in the overpacks is extremely limited, and high radiation fields make removal of the canisters from the overpacks undesirable. Although no significant corrosion damage has not been detected up to date, there is concern that this may lead to pitting corrosion, which could in turn develop into stress corrosion cracking, causing canister structural failure. The initiation and propagation of pitting corrosion has been widely studied in full immersion conditions, but limited studies have been done on marine atmospheric conditions, which is a focus of this work, these includes laboratory and field experimentally and propagation rate modeling of pitting and transition to crack, and crack propagation rate. It is known, however, that the rate of atmospheric corrosion can be affected by variations in relative humidity (RH), salt density, salt type, droplet area, temperature and stainless-steel microstructure and residual stress particularly in welded zones of canisters. The integrated research program has identified potential deterioration mechanisms for the stainless-steel canisters containing the UNF in dry storage that require detailed research and investigation and will have an impact on the performance of long-term interim storage under the normal and extreme environmental conditions experienced during the duration of this storage. The prediction and monitoring of canister corrosion processes while in storage can provide important data for the assessment of interim storage performance and the safety to the public. This report comprises of mainly the published results in different journals and covering a wide range spectrum from susceptible stainless-steel types 304\316 microstructural analysis through the implant test at atmospheric environment, residual stress analysis of mockup canister and simulation, inspection methodology includes nonlinear ultrasound and vibro-thermography and stochastic modeling and simulation of pits propagation rates and transition to cracks. Description of field specimens installed at ISFSI of Main Yankee is given in the following chapters and will be analyzed in the coming future and serves as an important data for a stochastic analysis as it was drawn from the publications and reports described in this report. The purpose of this report is to bring together the project efforts that includes improving in our understanding of structural aging performance at current dry storage casks fleet at ISFSIs in the context of remedial maintenance and inspection applications technologies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Mechanism and kinetics of light alkane dehydrogenation and cracking over isolated Ga species in Ga/H-MFI

The objective of this study is to examine the mechanisms and kinetics of C2H6 dehydrogenation and n-C4H10 dehydrogenation and cracking over isolated Ga species in Ga/HMFI and to compare these results to those reported previously for C3H8 dehydrogenation and cracking. C2H6 dehydrogenation is found to be catalyzed by both [GaH]2+ and [GaH2]+ cations at similar turnover frequencies. Rate measurements over Ga/H-MFI containing predominantly [GaH2]+ cations reveal that C2H6 dehydrogenation rates exhibit a Langmuir.Hinshelwood dependence on C2H6 partial pressure at elevated temperatures (>730 K), consistent with the involvement of chemisorbed [C2H5.GaH]+ species. The reaction kinetics suggest that C2H6 dehydrogenation proceeds via heterolytic C-H cleavage of adsorbed C2H6 by [GaH2]+ cations to form H2 and [C2H5-GaH]+ species, which further decompose via β-hydride elimination to form C2H4. By contrast, C4H10 dehydrogenation and both terminal and central cracking are catalyzed exclusively by [GaH]2+ cations. All three reactions exhibit a Langmuir-Hinshelwood dependence on C4H10 partial pressure and are inhibited by H2. Ratios of dehydrogenation to cracking (total) and terminal to central cracking are approximately independent of C4H10 partial pressure consistent with the involvement of a common C4H10-derived surface intermediate. The observed reaction kinetics are consistent with an alkyl-mediated mechanism occurring over [GaH]2+, analogous to that reported previously for C3H8 dehydrogenation/cracking over Ga/H-MFI (Phadke, N. M.; et al. J. Am. Chem. Soc. 2019, 141, 1614-1627). The mechanism proceeds via facile, heterolytic dissociation of adsorbed C4H10 to form [C4H9-GaH]+-H+ cation pairs via methyl C-H-activated pathways. Dehydrogenation then proceeds via β-hydride elimination, respectively, forming butene, while terminal and central cracking proceed via C-H-activated H+ attack. Methylene activation was also considered but found to occur at a significantly lower rate. Theoretical analysis of the proposed reaction pathways leads to apparent activation enthalpies in good agreement with values extracted from the measured kinetics, thereby supporting the proposed pathways and the roles of [GaH]2+ and [GaH2]+ cations in the dehydrogenation and cracking of light alkanes on Ga/H-MFI.

Phadke, NM↗

DOE OSTI2023

Tellurium Corrosion of Type 304/304L Stainless Steel, Iron, Chromium, and Nickel in High-Temperature Liquid Sodium

Investigating tellurium (Te) corrosion on structural materials is crucial for sodium-cooled fast reactors (SFRs) due to radionuclide presence and knowledge gaps. In this study, Type 304/304L stainless steel (SS304), chromium (Cr), iron (Fe), and nickel (Ni) samples were immersed in low-oxygen environments with Te in liquid sodium at 773 K for 30 days. At 10 ppm oxygen, SS304 showed multiple oxide layers, including a compact NaCrO 2 interlayer and porous Na-Fe-Ni-O outer layers. Tellurium penetrated through the porous layers but was hindered by the NaCrO 2 interlayer. At 0.01 ppm oxygen, Cr had no oxide layer, while Fe and Ni had unstable ones. Tellurium-induced pitting was deeper in Fe and Ni compared to Cr. Oxygen levels and Cr composition are critical factors affecting stable oxide compound layer formation and mitigating Te-induced pitting.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Molecular Iodine Interactions with Fe, Ni, Cr, and Stainless Steel Alloys

The adsorption behavior of molecular iodine is important for understanding the spread of radioiodine in a nuclear accident. Prior experiments indicate that, in addition to the interaction with Fe, molecular iodine [i.e., I 2(g) ] also interacts with the next most abundant components of austenitic stainless steel (i.e., Ni, and Cr) at room temperature. Here, we investigate iodine adsorption on Fe, Ni, and Cr while focusing on understanding the variables affecting adsorption as well as the iodine compounds that are formed during adsorption. Scanning electron microscopy and energy-dispersive X-ray spectroscopy were used to characterize the surfaces of exposed metal particles and aid in the understanding of the morphology and chemistry of iodine interactions with the substrates. Inductively coupled plasma optical emission spectroscopy was used to detect low levels of metal iodides and X-ray photoelectron spectroscopy was used to confirm the formation of the metal iodides. The role of environmental factors (e.g., humidity and oxygen content) for iodine adsorption on metal substrates is addressed. The individual metals demonstrated formation of metal iodides for Fe and Ni particles from interaction with I 2(g) . The formation of metal iodides may indicate the affinity of iodine for the respective metal. In this study, the iodine affinities ranked Fe > Ni > Cr as determined by the quantity of chemisorbed iodine. This trend is also supported by the distributions and proportions of metals in the corrosion product of the stainless steels. The exposures without oxygen and humidity indicate the potential of a multistep iodine adsorption process where iodine first attacks the oxide layer and then chemisorbs to the exposed metal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2001

Environmental Barrier Coatings for Silicon-Based Ceramics

Silicon-based ceramics, such as SiC fiber-reinforced SiC (SiC/SiC ceramic matrix composites (CMC) and monolithic silicon nitride (Si3N4), are prime candidates for hot section structural components of next generation gas turbine engines. Silicon-based ceramics, however, suffer from rapid surface recession in combustion environments due to volatilization of the silica scale via reaction with water vapor, a major product of combustion. Therefore, application of silicon-based ceramic components in the hot section of advanced gas turbine engines requires development of a reliable method to protect the ceramic from environmental attack. An external environmental barrier coating (EBC) is considered a logical approach to achieve protection and CP long-term stability. The first generation EBC consisted of two layers, mullite (3Al2O3-2SiO2) bond coat and yttria-stabilized zirconia (YSZ, ZrO2-8 Wt.% Y2O3) top coat. Second generation EBCs, with substantially improved performance compared with the first generation EBC, were developed in the NASA High Speed Research-Enabling Propulsion Materials (HSR-EPM) Program. The first generation EBC consisted of two layers, mullite (3Al2O3-2SiO2) bond coat and yttria-stabilized zirconia (YSZ, ZrO2-8 wt.% Y2O3) top coat. Second generation EBCs, with substantially improved performance compared with the first generation EBC, were developed in the NASA High Speed Research-Enabling Propulsion Materials (HSR-EPM) Program (5). They consist of three layers, a silicon first bond coat, a mullite or a mullite + BSAS (BaO(1-x)-SrO(x)-Al2O3-2SiO2) second bond coat, and a BSAS top coat. The EPM EBCs were applied on SiC/SiC CMC combustor liners in three Solar Turbines (San Diego, CA) Centaur 50s gas turbine engines. The combined operation of the three engines has accumulated over 24,000 hours without failure (approximately 1,250 C maximum combustor liner temperature), with the engine in Texaco, Bakersfield, CA, accumulating about 14,000 hours. As the commercialization of Si-based ceramic components in gas turbines is on the horizon, a major emphasis is placed on EBCs for two reasons. First, they are absolute necessity for the protection of Si-based ceramics from water vapor. Second, they can enable a major enhancement in the performance of gas turbines by creating temperature gradients with the incorporation of a low thermal conductivity layer. Thorough understanding of current state-of-the-art EBCs will provide the foundation upon which development of future EBCs will be based. Phase stability and thermal conductivity of EPM EBCs are published elsewhere. This paper will discuss the chemical/environmental durability and silica volatility of EPM EBCs and their impact on the coating's upper temperature limit.

Lee, Kang N.↗

DOE OSTI2016

Magnetite Dissolution using Hydrazine-Acid Solution for Chemical Decontamination

Chemical decontamination is committed to giving safe decommissioning of nuclear facilities as well as maintenance during the normal operation under sufficiently reduced radiation field. The removal of radioisotopes from the primary coolant system of nuclear power plant takes place with the dissolution of metal oxide layer. Dissolution of metal oxides in aqueous acidic solutions is primarily controlled by the protonation of metal-oxygen bonding to release the metal ions from the oxide lattices but in the presence of reducing or chelating agents dissolution is often facilitated by the enhanced mass transfer of metal ions together with chelating reagents as well as metal reduction to soluble state such as insoluble ferric ions to soluble ferrous ions of hematite. The mechanisms and kinetics related to the metal oxides dissolution in varied acidic reagents have been reported for many decades even though a general picture of dissolution is not available due to the peculiarity of each oxide in structure, stability of metal ions, solubility, and reactivity. In a number of experimental results and practical reports, organic acids such as oxalic acid, citric acid, ascorbic acid, malonic acid, thioglycolic acid, etc. were used as solvent reagents and many other literatures reported the effectiveness of the chelating agents in dissolution rate such as iminodiacetic acid (IDA), diethylene triamine pentaacetic acid (DTPA), nitrilo triacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA) by the sorption of dissolved metal ions forming stable metal chelates. Also reductive dissolution by the addition of reducing reagents such as hydrazine, vanadium as well as organic acids was reported with effective experimental results. However, organic acids and chelating ligands are often problematic on the safety of radioactive wastes. Organic compounds in a repository potentially form a complex with radionuclides, which increases the mobility of radionuclides and consequently increases the probability of the radioactive contamination of groundwater. Furthermore oxalic acid can cause a severe intergranular attack (IGA) to the type 304 stainless steel. Therefore, the use of organic acids or chelating reagents even though those effects to the dissolution performance is much greater than other chemical components must be minimized or carefully determined with appropriate treatment processes. Alternatively dissolution accommodated by inorganic reducing reagents or catalysts in inorganic acid solutions have been extensively studied for the feasible dissolution outcomes. The mixture of sulfuric acid and sulfurous acids as a dissolution media was reported to increase dissolution rate due to the effect of protonation by H{sub 2}SO{sub 4} and reducing effect of H{sub 2}SO{sub 3}. The increased dissolution of magnetite was also found in sulfur dioxide solution containing copper ions because SO{sub 2} plays as a reducing catalyst to form FeHSO{sub 3}{sup +} with Fe(III) from iron oxides and accordingly the concentration of Fe(III) ions decreases to accelerate the iron oxide dissolution. The present study is concerned with the feasibility of not using the organic compounds for the dissolution of oxide layers. We propose an acidic solution containing sulfuric acid, hydrazine, and copper ions for the effective dissolution of magnetite powders. The effects of both hydrazine and copper ions as a reducing agent and a catalyst respectively to promote the reducing power, as well as temperature will be investigated on the dissolution of magnetite powder. (authors)

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2016

Interactions of SO 2 -Containing Acid Gases with ZIF-8: Structural Changes and Mechanistic Investigations

Zeolitic imidazolate frameworks (ZIFs) are a set of nanoporous metal–organic frameworks (MOFs) with tunable porosity and functionality. Among MOFs, they also show relatively good stability with respect to temperature and humidity. These characteristics lead to their possible applications in separation processes. In many practical separation processes, adsorbents are exposed to a variety of molecular species including acid gases. However, there is little knowledge of the effects of such acid gas exposure on the adsorption and separation properties of ZIFs. Here, the stability of a model ZIF material (ZIF-8) under SO 2 exposure in dry, humid, and aqueous environments has been investigated in detail. Combined characterization by several techniques (PXRD, N 2 physisorption, EDX, XPS, and FTIR) allowed us to track the structural and compositional properties of ZIF-8 before and after SO 2 exposure. We found ZIF-8 is stable after prolonged exposure in dry SO 2 and in humid air without SO 2 . However, exposure to 10–20 ppm concentrations of SO 2 in the presence of high relative humidity led to its irreversible structural degradation over time as evidenced by substantial losses in crystallinity and textural properties. Exposure to similar concentrations of aqueous SO 2 did not lead to bulk degradation. Humid SO 2 exposed ZIF-8 showed a significant presence of sulfur (S) even after reactivation, with vibrational characteristics corresponding to (bi)sulfite and (bi)sulfate groups. A mechanism of ZIF-8 degradation combining the synergistic effects of SO 2 and humidity is proposed. Attack by sulfuric and sulfurous acid species (generated in humid SO 2 ) leads to protonation of nitrogen in the imidazole ring, resulting in cleavage of metal–linker (Zn–N) bonds. Our detailed experimental findings serve as a starting point for developing a generalized mechanism of acid gas interactions with ZIF materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2004

Experimental Aerothermodynamics In Support Of The Columbia Accident Investigation

The technical foundation for the most probable damage scenario reported in the Columbia Accident Investigation Board's final report was largely derived from synergistic aerodynamic/aerothermodynamic wind tunnel measurements and inviscid predictions made at NASA Langley Research Center and later corroborated with engineering analysis, high fidelity numerical viscous simulations, and foam impact testing near the close of the investigation. This report provides an overview of the hypersonic aerothermodynamic wind tunnel program conducted at NASA Langley and illustrates how the ground-based heating measurements provided early insight that guided the direction and utilization of agency resources in support of the investigation. Global surface heat transfer mappings, surface streamline patterns, and shock shapes were measured on 0.0075 scale models of the Orbiter configuration with and without postulated damage to the thermal protection system. Test parametrics include angle of attack from 38 to 42 degs, sideslip angles of 38 to 42 degs, sideslip angles of plus or minus 1 deg, Reynolds numbers based upon model length from 0.05 x 10(exp 6) to 6.5 x 10(exp 6), and normal shock density ratios of 5 (Mach 6 Air) and 12 (Mach 6 CF4). The primary objective of the testing was to provide surface heating characteristics on scaled Orbiter models with outer mold line perturbations to simulate various forms of localized surface damage to the thermal protection system. Initial experimental testing conducted within two weeks of the accident simulated a broad spectrum of thermal protection system damage to the Orbiter windward surface and was used to refute several hypothesized forms of thermal protection system damage, which included gouges in the windward thermal protection system tiles, breaches through the wing new the main landing gear door, and protuberances along the wing leading edge that produced asymmetric boundary layer transition. As the forensic phase of the investigation developed and the condition of recovered debris was examined, increasing emphasis was placed on identifying wing leading edge damage (partially and fully missing reinforced carbon-carbon panels, and eventually holes in the wing leading edge with venting to the wing upper surface) that produced off-nominal heating trends consistent with extracted Orbiter flight recorder temperature data.

Horvath, Thomas J.↗

DOE OSTI2017

Microanalysis of Irradiated Metallic Hydride Nuclear Fuel (U{sub 0.17}ZrH{sub 1.6})

Metallic hydride nuclear fuels (U{sub 0.17} ZrH{sub 1.6}) have been under consideration for use in Light Water Reactors (LWRs). The fuel matrix consists of isolated particles of uranium metal within a zirconium hydride matrix. Erbium was also added as a neutron poison enabling higher reactor performance. These fuels were encased in a Zircaloy-2 cladding with a Bi/Pb eutectic liquid metal filled-gap to improve thermal conductivity. The inner and outer cladding surfaces were oxidized to nominal 1 μm thickness to eliminate hydrogen attack. The fuels were termed UCB to note the location of fabrication as the University of California-Berkeley. Irradiations were performed in the MITR research reactor. The details are described elsewhere. We originally reported on post-irradiation analysis of the fuel elements of two of the rodlets using Scanning Electron Microscopy (SEM) and x-ray energy dispersive spectroscopy (EDS). In this further study, funded as a rapid turnaround experiment (RTE) through the Nuclear Science User Facilities (NSUF) program, we performed high-resolution Scanning Transmission Electron Microscopy (STEM) of thin lift-out specimens prepared from specific regions in the fuel matrix using an SEM-Focused Ion Beam (FIB) instrument, and again compared these results to the unirradiated material. Earlier investigations using SEM-EDS showed that ∼8% of the Zircaloy cladding had dissolved in the Pb-Bi eutectic during irradiation over 1000 hrs. However, the SEM-EDS failed to show any detectable evidence of damage of the fuel matrix. There was no obvious swelling or migration of elements; hence, we focused on these specific regions in greater detail. Much of the data on hydride fuels come from the Space Nuclear Auxiliary Power (SNAP) program from the 1960's. The principle difference between oxide and hydride fuel is the high thermal conductivity of the latter. This feature greatly decreases the temperature drop over the fuel during operation, thereby reducing the release of fission gases to the fraction due only to recoil. However, very unusual early swelling due to void formation around the uranium metal particles has been reported in hydride fuels over 700 deg. C. In this investigation, the fuel did not reach these extreme temperatures. Phases formed in this system have been previously experimentally investigated using thermal analysis techniques, and wavelength and energy dispersive spectroscopy (EDS/WDS) in scanning electron microscopes (SEM). Major changes were observed in the liquid metal and cladding components but at the scale of the SEM observations, it was not readily apparent that any major changes had occurred to the fuel matrix (i.e. U metal particles in the zirconium hydride matrix with interdispersed erbium metal). Rapid oxidation of the SEM mechanically polished cross-sections, may have obscured our ability to see major changes. By using the SEM-FIB slices, it was possible to remove oxide coatings and the smoother surfaces were found to be less susceptible to oxidation once removed from the vacuum chamber. The high spatial resolution of STEM allowed characterization of individual matrix phases.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2016

The Impact of Furnace-Testing on the Microstructure of an Irradiated U-Mo Fuel Plate

The Material Management and Minimization Program (formerly known as the Reduced Enrichment for Research and Test Reactor Program) is responsible for converting research reactors that use highly enriched uranium (HEU) fuels to ones that use low-enriched uranium (LEU) fuels. As part of the development of LEU fuels, a variety of irradiation experiments are being conducted using the Advanced Test Reactor. In addition to the reactor tests, there is interest in generating information about the transient behavior of irradiated fuel plates. For example, it is of interest to determine the temperature at which a blister will form on the surface of a fuel plate, due to fission gas release from the fuel meat, for a particular fuel plate design. Since in-pile testing to determine the 'blister threshold' (the temperature where a blister forms on the surface of a fuel plate) in plate-type fuel is very difficult and expensive and has historically been deemed impractical for fuel qualification testing, an out-of-pile 'blister test' has been developed and employed. This post-irradiation blister anneal test was developed as a conservative simulation of in-pile behavior and has been routinely used for many research reactor fuel designs currently in use. In this test, the irradiated fuel plate is inserted into a furnace at a given temperature, soaked for a period of time, and removed for inspection. If no visible blisters appear, the furnace temperature is increased, and the plate is soaked and inspected again. This process continues until blisters are observed. Recently, a section from an irradiated U-7Mo dispersion fuel plate with Al-4043 matrix, which has a nominal composition of 4.81Si-0.20Fe-0.14Ti-0.16Cu-0.01Cr 0.01Mn-bal Al, was tested in a furnace located in the Hot Fuel Examination Facility, located at the Idaho National Laboratory, up to 500 deg. C, at which point blisters were observed on the surface of the fuel plate section. A sample near the blistered region of the fuel plate section was then characterized using scanning electron (SEM) and transmission electron microscopy (TEM). This paper discusses the results of this characterization and how they compare to those generated for a similar sample characterized after fabrication but before irradiation and for a sample characterized after irradiation but before furnace testing. One goal of this work is to identify the changes in the microstructure during blister testing that contribute to the eventual release of fission gas that results in the development of blisters. SEM analysis of the furnace-tested sample showed that in some locations of the U-7Mo particles, Al-4043 matrix constituents (primarily Si) had penetrated the microstructure along grain boundaries. This provided potential pathways for increased fission gas migration in the fuel meat microstructure during the furnace heating process. Some attack of these boundaries was also observed in the as-fabricated U-7Mo/Al-4043 sample, but there appeared to be additional attack during the furnace annealing. Besides the changes observed in grain boundary features, the TEM analysis showed that the fission gas bubbles that are typically present in the intra-granular regions of the as-irradiated U-7Mo microstructure as a fission gas bubble superlattice had changed in size, morphology, and distribution. The result of this may be an increase in the mobility of the fission gas in intra-granular regions of the fuel. The complete implications of the changes in fission gas morphology and distribution in the fuel meat microstructure and their impact on blistering continues to be investigated. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Impact of lanthanide ion complexation and temperature on the chemical reactivity of N , N , N ', N '-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation

The impact of trivalent lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the n-dodecane radical cation (RH˙+) has been measured by electron pulse radiolysis and evaluated by quantum mechanical calculations. Additionally, Arrhenius parameters were determined for the reaction of the non-complexed TODGA ligand with the RH˙ + from 10–40 °C, giving the activation energy (E a = 17.43 ± 1.64 kJ mol –1 ) and pre-exponential factor (A = (2.36 ± 0.05) × 10 13 M –1 s –1 ). The complexation of Nd(III), Gd(III), and Yb(III) ions by TODGA yielded [LnIII(TODGA)3(NO3)3] complexes that exhibited significantly increased reactivity (up to 9.3× faster) with the RH˙ + , relative to the non-complexed ligand: k([Ln III (TODGA) 3 (NO 3 ) 3 ] + RH˙ + ) = (8.99 ± 0.93) × 10 10 , (2.88 ± 0.40) × 10 10 , and (1.53 ± 0.34) × 10 10 M –1 s –1 , for Nd(III), Gd(III), and Yb(III) ions, respectively. The rate coefficient enhancement measured for these complexes exhibited a dependence on atomic number, decreasing as the lanthanide series was traversed. Preliminary reaction free energy calculations—based on a model [Ln III (TOGDA)] 3+ complex system—indicate that both electron/hole and proton transfer reactions are energetically unfavorable for complexed TODGA. Furthermore, complementary average local ionization energy calculations showed that the most reactive region of model N,N,N',N'-tetraethyl diglycolamide (TEDGA) complexes, [Ln III (TEGDA) 3 (NO 3 ) 3 ], toward electrophilic attack is for the coordinated nitrate (NO 3 – ) counter anions. Furthermore, it is possible that radical reactions with the complexed NO 3 – counter anions dominate the differences in rates seen for the [Ln III (TODGA) 3 (NO 3 ) 3 ] complexes, and are likely responsible for the reported radioprotection in the presence of TODGA complexes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2023

Methodology and Tool for the Physical Security Analysis of Micro and Advanced Reactors

This work proposes a dynamic evaluation methodology to relax the conservatism in physical security evaluation, by leveraging an ongoing work in the Light Water Reactor Sustainability pathway. This methodology is implemented in a dynamic risk assessment tool named Event Modeling Risk Assessment using Linked Diagrams (EMRALD). The work extends EMRALD’s capability to support a sandbox feature where analysts can easily create attack scenarios and modify advanced/small modular reactor (A/SMR) security and safety features using templates. This approach saves time and cost since the analysis does not require creating detailed computer-aided design models, as is commonly required in commercial force-on-force software tools. EMRALD is completely free to use at https://emraldapp.inl.gov. We have developed basic templates including physical barriers, intrusion sensors, physical areas, and safety actions, that can be downloaded from EMRALD’s GitHub site: https://github.com/idaholab/EMRALD. These templates use generic data commonly used for training purposes, which do not reflect any actual operating nuclear reactor. Users may adjust the data in the templates with their own dataset and/or create new templates in EMRALD. The proposed methodology combines security and safety by assessing sabotage effects up to the radiological consequence to the public instead of merely the core damage state. This practice follows the industry standard for advanced non-light-water reactors currently proposed for endorsement by the Nuclear Regulatory Commission. The combination of security and safety is expressed in an achievability-consequence chart. EMRALD can be used to generate data for this chart. A hypothetical case study using a representative sodium-cooled fast reactor (SFR) facility is presented in this report to demonstrate this methodology. This case study does not contain any actual nuclear plant information. This work will benefit A/SMR vendors and utilities to implement security by design during the reactor design iteration phase, such that they do not have to perform upgrades and retrofits to the reactor after it is installed to improve its physical protection system. The tool may also be used to analyze domestic or foreign reactor designs to support the International Nuclear Security Techniques for Advanced Reactors (INSTAR) bilateral missions. Future works are planned to implement the methodology on a reference SFR reactor and a reference high-temperature gas-cooled reactor to obtain insights and lessons-learned for the A/SMR community.

97 MATHEMATICS AND COMPUTING↗