Role of disorder in the synthesis of metastable zinc zirconium nitrides
Not Available
36 MATERIALS SCIENCE↗
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Effect of alloying with Sc, Nb and Zr on reduction-diffusion synthesis of magnetically hard Sm(Fe,Co,Ti) 12 -based monocrystalline powders
Powders of Sm(Fe,Co) 11.2 Ti 0.8 alloys modified with Sc, Nb and Zr, as well as with additional Ti were prepared by reducing mechanically activated raw oxides with Ca metal in the furnace preheated to 990–1250 °C. Expansion of the crystal lattice upon introduction of Nb or additional Ti implies that atoms of these elements replace the smaller Fe atoms in the tetragonal ThMn 12 -type structure. On the other hand, contraction of the lattice upon introduction of Sc or Zr was smaller than what was expected for replacement of the Sm atoms, which suggests that the Sc and Zr atoms replace both the Sm and Fe atoms. Washing away the reduction byproducts expands the crystal lattice of the 1:12 particles and increases their coercivity. The lattice expansion associated with the washing is believed to be caused by interstitial H atoms; more research, however, is needed to establish the mechanism(s) of the washing effect on the coercivity. The earlier reported development of a high coercivity in zirconium-modified monocrystalline particles achieved by increasing the reduction annealing temperature to ≈1200 °C was similarly characteristic of the particles modified with Sc (the coercivity reaches 11.5 kOe) and Nb (8.1 kOe), but not for the particles prepared with additional Ti where the maximum coercivity of 8.3 kOe develops for a lower annealing temperature. Furthermore, it is concluded that Sc, Nb and Zr modify the high-temperature phase equilibria of the Sm(Fe,Co) 11.2 Ti 0.8 alloys allowing for an effective high-temperature processing, whereas the alloy coercivity increases with the synthesis temperature through a different, still unknown mechanism which may involve suppression of the defects specific to the 1:12 crystals.
36 MATERIALS SCIENCE↗
Designing an impedance-based technique for studying corrosion on cladding materials
In nuclear cladding materials, changes in structure and chemistry over the lifetime of claddings can have a significant impact on fuel and reactor performance. Currently, chemical evolution over the lifetime of the fuel and cladding materials can only be inferred using post-irradiation examination. As an alternative to post-irradiation measurements, electrochemical impedance spectroscopy (EIS) can provide an in-pile measurement of changes in chemistry in oxides and hydrides. The objective of this study is to develop an impedance based sensing technology for measuring spatial- and time-resolved in-pile changes in cladding chemistry in order to understand the mechanisms of hydride formation, hydride dealloying and associated cladding corrosion so that a mitigation strategy and technology can be developed for reactor safe operation. Two prototype impedance-based sensors were designed and assembled using Zr-4 as working electrode and Pt as counter and reference electrode. One sensor is tubular type and the other one is plate-type. These sensors will be tested in static autoclave to investigate the effects of various environmental conditions (including temperature, pressure, and water chemistry) on cladding material corrosion mechanisms. These in-situ EIS sensors would provide corrosion-layer parameters in high-temperature water, such as (1) total layer thickness, (2) the evolution of oxide structures as uniform layer dielectric or sublayer(s), and (3) the possible electrochemistry of the volume corrosion process and the solid/liquid interface, such as the cyclic nature of corrosion of Zr alloys in high-temperature water. This work was focused on electrochemical sensor development, targeting cladding oxides/hydrides under thermodynamic equilibria; characterization of samples using Kelvin probe force microscopy (SKPFM), Raman spectroscopy, and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS) to provide high-resolution co-localized characterization of zirconium oxide and metal/oxide interface.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Role of zirconium in neodymium-dopants interactions within uranium-based metallic fuels
Not Available
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
The effect of 0.1 atomic percent zirconium on the cyclic oxidation behavior of beta-NiAl for 300 hours at 1200 C
The long time effect of 0.1 at percent Zr (0.2 wt percent Zr) on the cyclic oxidation behavior of hipped beta-NiAl was studied. Oxidation testing was performed in static air at 1200 C for up to 3000 one-hour exposure cycles. Specific weight change versus time data was modeled with the COSP computer program to analyze cyclic oxidation behavior. The Zr-free stoichiometric alloy oxidized and spalled randomly to bare metal between cycles at a rate high enough to deplete Al to a low enough level that oxidation breakaway took place as nonprotective NiO replaced the alpha-Al2O3/NiAl2O4 scale as the controlling oxide. The Zr minimized this severe type of spalling maintaining the protective alpha-Al2O3 scale even out to 3000 hours for the stoichiometric alloy with no significant Al depletion. A third beta-NiAl alloy containing 0.1 at percent Zr but with 10 percent less Al than the stoichiometric alloy was also tested and showed some depletion of Al, but the protective Al2O3/NiAl2O4 was still maintained to close to 2700 hours.
Barrett, C. A.↗
The effect of 0.1 atomic percent zirconium on the cyclic oxidation behavior of beta-NiAl for 3000 hours at 1200 C
The long time effect of 0.1 at percent Zr (0.2 wt percent Zr) on the cyclic oxidation behavior of hipped beta-NiAl was studied. Oxidation testing was performed in static air at 1200 C for up to 3000 one-hour exposure cycles. Specific weight change versus time data was modeled with the COSP computer program to analyze cyclic oxidation behavior. The Zr-free stoichiometric alloy oxidized and spalled randomly to bare metal between cycles at a rate high enough to deplete Al to a low enough level that oxidation breakaway took place as nonprotective NiO replaced the alpha-Al203/NiAl204 scale as the controlling oxide. The Zr minimized this severe type of spalling maintaining the protective alpha-Al203 scale even out to 3000 hours for the stoichiometric alloy with no significant Al depletion. A third beta-NiAl alloy containing 0.1 at percent Zr but with 10 percent less Al than the stoichiometric alloy was also tested and showed some depletion of Al, but the protective Al203/NiAl204 was still maintained to close to 2700 hours.
Barrett, C. A.↗
Radiation Effects on the Performance of Advanced Sulfur Monochloride Chlorination Processes
Advanced sulfur chloride-based chlorination technologies are being developed to enable efficient recycling of aluminum and zirconium-based materials used in the nuclear industry. However, the impacts of ionizing radiation on the performance of these sulfur chloride compounds are not well established, despite this being critical knowledge for assessing their feasibility and longevity under envisioned process conditions. Here, in the present article, we report on the effects of cobalt-60 gamma irradiation (≤ 5 MGy) on the aluminum alloy 6061 (AA6061-T6) chlorination yield in sulfur monochloride (S 2 Cl 2 ). Our findings indicate that, compared to nonirradiated solvent, radiation-induced changes in the chemical composition of S 2 Cl 2 —identified using Raman spectroscopy—afford an additional, dose-dependent exothermic process prior to the chlorination reaction’s typical thermodynamic behavior. We attribute this new process to reactions involving aluminum species (metal, oxide, or [oxy]hydroxides) and sulfur dichloride (SCl 2 ), an S 2 Cl 2 radiolysis product that accumulates with absorbed gamma dose, but is absent following an AA6061-T6 chlorination study. Despite the exothermicity of this new process, the overall yield of chlorination decreased with increasing preirradiation dose. Consequently, the chemical reactivity, specificity (aluminum metal vs aluminum passivation and corrosion layer constituents), and byproducts of SCl 2 must be more thoroughly evaluated to support the continued development of advanced S 2 Cl 2 chlorination technologies.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Measurements of Total Hemispherical Emissivity of Several Stably Oxidized Metals and Some Refractory Oxide Coatings
A description of the apparatus and methods used for obtaining total hemispherical emissivity is presented, and data for several stably oxidized metals are included. The metals which were tested included type 347 stainless steel, tungsten, and Haynes alloys B, C, X, and 25. No values of emissivity were obtained for tungsten or Haynes alloy B because of the nature of the oxides produced. The refractory oxide coatings tested were flame-sprayed alumina and zirconia. The results of the investigation indicate that strongly adherent, oxidized surfaces of a high stable emissivity can be produced on type 347 stainless steel for which the total hemispherical emissivity varied from 0.87 to 0.91 for temperatures from 600 F to 2,000 F. For this same temperature range, the Haynes alloys tested showed values of total hemispherical emissivity from 0.90 to 0.96 for alloy C, from 0.85 to 0.88 for alloy X, and from 0.85 to 0.89 for alloy 25. Haynes alloy B and tungsten formed nonadherent oxides at elevated temperatures and, therefore, stable emissivities were not obtained. The results obtained for the flame-sprayed ceramics (alumina and zirconia) showed considerably higher values of total emissivity than those measured for coatings applied by other methods. Emissivity values ranging from 0.69 to 0.44 for aluminum oxide and from 0.62 to 0.44 for zirconium oxide were measured for temperatures from 800 F to 2,000 F.
Wade, William R.↗
Nonprotective Alumina Growth in Sulfur-Doped NiAl(Zr)
The 1200 C oxidation behavior of NiAl was examined at various levels of sulfur and zirconium dopants to test the possibility of a critical S/Zr ratio required for adhesion. Cyclic furnace testing for 200 1 -hr cycles and interrupted testing for 500 hr were used as screening tests. Pure NiAl and NiAl(Zr) with 0. 14 at.% Zr were chosen as model base compositions; they exhibited normal, slow-growing scales (3 Mg/sq cm) with excellent adhesion for the Zr-doped alloys. NiAl with about 120 ppma S exhibited a substantial weight loss (-20 Mg/sq cm) in cyclic tests and a very large weight gain (+60 Mg/sq cm) in interrupted tests. The major surface phase remained as alpha -Al2O3. Sulfur doping the NiAl(Zr) alloy caused massive weight gains of 80 - 100 Mg/sq cm, swelling, cracking, and nearly complete conversion into NiAl2O4, and alpha- Al2O3. The initial objective of determining critical S/Zr ratios for adhesion was therefore unattainable. Initiation of the catastrophic attack was examined after a 10 hr exposure, revealing a few sites of broad, raised, and cracked ridges. In cross-section, the ridges appeared as modular intrusions, with a complex, fractal, oxide-metal interface. They were primarily alumina (with occasional entrapped islands of NiAl2O4 or pure Ni metal). They possessed a unique microstructure consisting of 0.3 microns lamellae, separated by 0.1 microns open channels. This allowed for rapid growth controlled by gaseous diffusion. The microstructure is discussed in terms of SO2 evolution and a sulfur-driven de-passivation process.
Smialek, James L.↗
Exploring laser-material interactions of zirconium carbide under additive manufacturing conditions
Zirconium carbide (ZrC) is an ultra-high temperature ceramic with a melting temperature above 3000°C and a broad range of high temperature applications. Given the high melting and sintering temperatures of pure ZrC, producing near-net shape and fully dense parts remains challenging with conventional techniques. In this study, we investigate the fundamental laser-material interactions of ZrC under laser powder bed fusion (LPBF) additive manufacturing (AM) conditions. Normalized enthalpy, a scaling law term that is used in welding and AM literature for detailing laser-material interactions in metallic alloys, was calculated to determine the predictive capabilities of melt pool features in ZrC. Further, the melt pool quality of laser irradiated ZrC was used to compare LPBF relevant laser parameter combinations of laser power, scan speed, and beam diameter. Laser build parameters that resulted in desirable melt pool morphologies were applied to the fabrication of ZrC coupons using LPBF AM. A custom LPBF system was used to determine hatch spacing and layer height parameters that resulted in a fabricated sample with a density of 85% as measured by Archimedes and a Vicker's microhardness of 20.9 ± 1.9 GPa. This investigation reveals the laser-material interactions of ZrC under AM relevant conditions and is the first step towards LPBF fabrication of ZrC parts.
36 MATERIALS SCIENCE↗
Effect of solutes in binary columbium /Nb/ alloys on creep strength
The effect of seven different solutes in binary columbium (Nb) alloys on creep strength was determined from 1400 to 3400 F for solute concentrations to 20 at.%, using a new method of creep-strength measurement. The technique permits rapid determination of approximate creep strength over a large temperature span. All of the elements were found to increase the creep strength of columbium except tantalum. This element did not strengthen columbium until the concentration exceeded 10 at.%. Hafnium, zirconium, and vanadium strengthed columbium most at low temperatures and concentrations, whereas tungsten, molybdenum, and rhenium contributed more to creep strength at high temperatures and concentrations.
Klein, M. J.↗
On the efficacy of post-build thermomechanical treatments to improve properties of Zirconium fabricated using ultrasonic additive manufacturing
Here, hot-isostatic pressing has been applied to Zirconium plate fabricated using the ultrasonic additive manufacturing (UAM) technique to enhance interfacial bond quality. Specimens heated to 800 C for 1 h at 100 MPa pressure showed grain growth across many prior foil-to-foil interfaces, thereby increasing foil adhesion. In addition to the material softening induced by a loss of Hall-Petch strengthening, premature failure of specimens loaded parallel to the build direction was observed. Premature specimen failure was attributed to the local delamination at prior foil-to-foil boundaries where grain growth was pinned by Ti impurities introduced during the UAM process via the interaction between a Ti-alloy buffer foil and the welded Zr-foils underneath. In addition, the presence of Ti along select foil interfaces resulted in the nucleation and growth of secondary (Zr,Ti)(Fe,Cr) laves phases during higher-temperature thermomechanical processing. Using a combination of micro-scale X-ray computed tomography, fractography, and in-situ digital image correlation, the effect of defects along prior foil-to-foil boundaries was revealed as delamination-assisted plasticity accelerated specimen failure in preferred tensile orientations. These findings underscore the importance of impurity control when optimizing weld quality of higher-strength material systems using ultrasonic welding.
36 MATERIALS SCIENCE↗
Benchmarking Surface Tension Measurement Method using two Oscillation Modes in Levitated Liquid Metals
The Faraday forcing method in levitated liquid droplets has recently been introduced as a method for measuring surface tension using resonance. By subjecting an electrostatically-levitated liquid metal droplet to a continuous, oscillatory, electric field, at a frequency nearing that of the droplet’s first principal mode of oscillation (known as mode 2), the method was previously shown to determine surface tension of materials that would be particularly difficult to process by other means, e.g. liquid metals and alloys. It also offers distinct advantages in future work involving high viscosity samples because of the continuous forcing approach. This work presents 1) a benchmarking experimental method to measure surface tension by excitation of the second principal mode of oscillation (known as mode 3) in a levitated liquid droplet and 2) a more rigorous quantification of droplet excitation using a projection method. Surface tension measurements compare favorably to literature values for Zirconium, Inconel 625, and Rhodium, using both modes 2 and 3. Thus, this new method serves as a credible, self-consistent benchmarking technique for the measurement of surface tension
Levitation↗
Optical properties and emissivities of liquid metals and alloys
This paper presents the results from our on-going program to investigate the optical properties of liquid metals and alloys at elevated temperatures. Ellipsometric and polarimetric techniques have been used to investigate the optical properties of materials in the 1000 - 3000 K temperature range and in the 0.3 - 0.1 mu m wavelength range. The ellipsometric and polarimetric techniques are described and the characteristics of the instruments are presented. The measurements are conducted by reflecting a polarized laser beam from an electromagnetically levitated liquid metal or alloy specimen. A Rotating Analyzer Ellipsometer (RAE) or a four-detector Division-of-Amplitude Photopolarimeter (DOAP) is used to determine the polarimetric properties of the light reflected at an angle of incidence of approximately 68 deg. Optical properties of the specimen which are calculated from these measurements include the index of refraction, extinction coefficient, normal spectral emissivity, and spectral hemispherical emissivity. These properties have been determined at various wavelengths and temperatures for liquid Ag, Al, Au, Cu, Nb, Ni, Pd, Pt, Si, Ti, Ti-Al alloys, U, and Zr. We also describe new experiments using pulsed-dye laser spectroscopic ellipsometry for studies of the wavelength dependence of the emissivities and optical properties of materials at high temperature. Preliminary results are given for liquid Al. The application of four-detector polarimetry for rapid determination of surface emissivity and true temperature is also described. Characteristics of these devices are presented. An example of the accuracy of this instrument in measurements of the melting point of zirconium is illustrated.
Krishnan, Shankar↗
Benchmark Gap Assessment for the Manufacturing of High-Assay Low-Enriched Uranium Fuels
This document develops basic critical conditions for spheres—moderated and unmoderated, as well as reflected and unreflected—in consideration of nuclear criticality safety of a potential fuel production facility producing high-assay low-enriched uranium (HALEU) fuel of several different types like tristructural-isotropic (TRISO), uranium metal and alloys, oxide and non-metallic forms. In addition to spherical arrangements, TRISO particle manufacturing process–specific equipment is modeled as it would be for the criticality safety analysis. The objective is to develop representative systems that can then be used for comparison with existing benchmarks. SCALE/TSUNAMI is used to assess the similarity index between these systems to assess validation gaps for possible fuel production applications of proposed advanced reactors. Several different fuel types were evaluated, including TRISO, uranium metal, uranium molybdenum, uranium zirconium, uranium dioxide, uranium nitride, uranium hydride, U-ZrH, and uranium chloride. This selection of fuel types covers a breadth of proposed reactor types, as well as intermediate steps in the production and fabrication of the fuel
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Copper-Multiwall Carbon Nanotubes and Copper-Diamond Composites for Advanced Rocket Engines
This paper reports on the research effort to improve the thermal conductivity of the copper-based alloy NARloy-Z (Cu-3 wt.%Ag-0.5 wt.% Zr), the state-of-the-art alloy used to make combustion chamber liners in regeneratively-cooled liquid rocket engines, using nanotechnology. The approach was to embed high thermal conductivity multiwall carbon nanotubes (MWCNTs) and diamond (D) particles in the NARloy-Z matrix using powder metallurgy techniques. The thermal conductivity of MWCNTs and D have been reported to be 5 to 10 times that of NARloy-Z. Hence, 10 to 20 vol. % MWCNT finely dispersed in NARloy-Z matrix could nearly double the thermal conductivity, provided there is a good thermal bond between MWCNTs and copper matrix. Quantum mechanics-based modeling showed that zirconium (Zr) in NARloy-Z should form ZrC at the MWCNT-Cu interface and provide a good thermal bond. In this study, NARloy-Z powder was blended with MWCNTs in a ball mill, and the resulting mixture was consolidated under high pressure and temperature using Field Assisted Sintering Technology (FAST). Microstructural analysis showed that the MWCNTs, which were provided as tangles of MWCNTs by the manufacturer, did not detangle well during blending and formed clumps at the prior particle boundaries. The composites made form these powders showed lower thermal conductivity than the base NARloy-Z. To eliminate the observed physical agglomeration, tangled multiwall MWCNTs were separated by acid treatment and electroless plated with a thin layer of chromium to keep them separated during further processing. Separately, the thermal conductivities of MWCNTs used in this work were measured, and the results showed very low values, a major factor in the low thermal conductivity of the composite. On the other hand, D particles embedded in NARloy-Z matrix showed much improved thermal conductivity. Elemental analysis showed migration of Zr to the NARloy-Z-D interface to form ZrC, which appeared to provide a low contact thermal resistance. These results are consistent with the quantum mechanics-based model predictions. NARloy-Z-D composites have relatively high thermal conductivities and are promising for further development.
Bhat, Biliyar N.↗
Copper Multiwall Carbon Nanotubes and Copper-Diamond Composites for Advanced Rocket Engines
This paper reports on the research effort to improve the thermal conductivity of the copper-based alloy NARloy-Z (Cu-3 wt.%Ag-0.5 wt.% Zr), the state-of-the-art alloy used to make combustion chamber liners in regeneratively-cooled liquid rocket engines, using nanotechnology. The approach was to embed high thermal conductivity multiwall carbon nanotubes (MWCNTs) and diamond (D) particles in the NARloy-Z matrix using powder metallurgy techniques. The thermal conductivity of MWCNTs and D have been reported to be 5 to 10 times that of NARloy-Z. Hence, 10 to 20 vol. % MWCNT finely dispersed in NARloy-Z matrix could nearly double the thermal conductivity, provided there is a good thermal bond between MWCNTs and copper matrix. Quantum mechanics-based modeling showed that zirconium (Zr) in NARloy-Z should form ZrC at the MWCNT-Cu interface and provide a good thermal bond. In this study, NARloy-Z powder was blended with MWCNTs in a ball mill, and the resulting mixture was consolidated under high pressure and temperature using Field Assisted Sintering Technology (FAST). Microstructural analysis showed that the MWCNTs, which were provided as tangles of MWCNTs by the manufacturer, did not detangle well during blending and formed clumps at the prior particle boundaries. The composites made form these powders showed lower thermal conductivity than the base NARloy-Z. To eliminate the observed physical agglomeration, tangled multiwall MWCNTs were separated by acid treatment and electroless plated with a thin layer of chromium to keep them separated during further processing. Separately, the thermal conductivities of MWCNTs used in this work were measured, and the results showed very low values, a major factor in the low thermal conductivity of the composite. On the other hand, D particles embedded in NARloy-Z matrix showed much improved thermal conductivity. Elemental analysis showed migration of Zr to the NARloy-Z-D interface to form ZrC, which appeared to provide a low contact thermal resistance. These results are consistent with the quantum mechanics-based model predictions. NARloy-Z-D composites have relatively high thermal conductivities and are promising for further development.
Bhat, Biliyar N.↗
Probing the Radial Chemistry of Getter Components in Light Water Reactors via Controlled Electrochemical Dissolution
Getters are among the key functional components in the Tritium Producing Burnable Absorber Rods (TPBARs) of Light Water Reactors, and are used to capture the released tritium gas. They are cylindrical tubes comprised of the alloy zircaloy-4 which is coated with nickel plating both internally and externally. Their exposure to tritium as well as the irradiation environments in the light water reactors changes their structure, chemical composition and chemistry. Understanding the radial tritium distribution is key to gaining insight into the evolution of new chemistry upon irradiation in order to predict getter performance. Consequently, efforts are underway to devise a method that can allow selective probing into the getter core radially to probe the chemistry akin to carefully and selectively peeling of the layers of an onion. We have recently devised an electrochemical dissolution technique for controlled radial dissolution of zirconium based liners; this work describes the first proof-of-concept demonstration of the applicability of this technique on the controlled radial dissolution of nickel plated getters. The technique is complemented with periodic analysis of the electrolyte solution to measure the rates of release of the various elemental components and therefore glean information on their radial distribution across the getter; further complementary microscopy on the exposed surfaces allows us insight into the chemistry at the getter core.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗