Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “zirconium”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Zirconium-diboride silicon-carbide composites: A review

Zirconium diboride (ZrB 2 ) and silicon carbide (SiC) composites have long been of interest since it was observed that ZrB 2 improved the thermal shock resistance of SiC. However, processing of these materials can be difficult due to high and different sintering temperatures and differences in the thermodynamic stability of each material. ZrB 2 –SiC composites have been processed in a variety of ways including hot-pressing, spark-plasma sintering, reactive melt infiltration, pack cementation, chemical vapor deposition, chemical vapor infiltration, stereolithography, direct ink writing, selective laser sintering, electron beam melting, and binder jet additive manufacturing. Each manufacturing method has its own pros and cons. This review serves to summarize more than 60 years of research and provide a coherent resource for the variety of methods and advancements in development of ZrB 2 –SiC composites.

36 MATERIALS SCIENCE↗
DOE OSTI2024

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↗
DOE OSTI2021

Combustion in the ZrF 4 -Mg-Si and ZrF 4 -Al-Si systems for preparation of zirconium silicides

The exothermic reactions in the ZrF 4 –Mg-Si and ZrF 4 -Al-Si systems are investigated by a fast temperature recording (thermocouple) technique, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). A quenching method is used to arrest the combustion process and conduct a layer-by-layer analysis of the products by x-ray diffraction (XRD) and electron microscopy. Two seemingly similar reactive systems exhibited considerably different combustion characteristics, composition, and morphology. Based on these investigations, we propose and discuss phase formation mechanisms at the early stages for each system. Three different pathways involving the reaction of ZrF 4 with other reagents and the Mg 2 Si intermediate are identified to occur in the ZrF 4 –Mg-Si system. Contrary to the complex mechanism in the ZrF 4 –Mg-Si system, the early stage of the combustion process for the ZrF 4 -Al-Si system involves the interaction of ZrF 4 with Al-Si eutectic melt. The exothermic reaction between reduced solid Zr and Si melt is the primary heat-generating step for both systems in spite of substantial differences in the early stages of the reactions. The silicon content in the reactive mixtures governs the phase composition of products. The ZrSi 2 phase, with a high growth rate, forms first on the Zr particle surfaces and then grows by a reactive diffusion mechanism. The ZrSi 2+ Zr reaction produces silicon-lean phases (e.g., ZrSi) when the silicon supply is limited. The combustion temperature also has a considerable influence on the phase compositions of the products. High combustion temperature in the ZrF 4 +2Mg+Si mixture enables the formation of multiphase products (α-ZrSi and β-ZrSi), whereas the relatively lower temperatures in the 3ZrF 4 +4Al+3Si mixture yields a single-phase α-ZrSi. As a result, lower combustion temperatures also make the ZrF 4 -Al-Si system more advantageous for the preparation of zirconium silicides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

First-principles studies of the concentration-dependent tritium diffusion in the zirconium hydrides with and without Sn impurity

We performed first-principles calculations to study the 3 H diffusion in the zirconium hydrides with or without Sn impurity. Our results show that the formation of Zr 3 H x becomes preferable as the 3 H concentration increases. Based on the most stable configurations of Zr 3 H x (x = 0.5, 1.0, 1.5, 2.0), we studied the interstitial 3 H diffusion with or without Sn impurity. The results show that the interstitial 3 H diffusion becomes less probable in the hydrides with a higher 3 H concentration. When introducing a substitutional Sn impurity, the diffusion barriers increase. Therefore, the substitutional Sn in the diffusion pathway hampers the 3 H diffusion in Zr hydrides.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Modeling of High-Temperature Corrosion of Zirconium Alloys Using the eXtended Finite Element Method (X-FEM)

Oxidation modeling in modern nuclear fuel performance codes is currently limited by the lack of coupling with mechanics, thus preventing proper description of how high-temperature oxidation impacts mechanical properties. This is mostly due to the fact that the finite difference formalism adopted in corrosion models is incompatible with the direct coupling with mechanics in the finite element modeling employed in modern nuclear fuel performance codes. In this study, a physically based zirconium alloy corrosion model called the Coupled-Current Charge Compensation (C4) model, which was initially developed for operating temperature conditions, has been updated to include high-temperature corrosion in order to provide additional critical information (e.g., oxygen concentration profile) under loss-of-coolant accident (LOCA) conditions—information lacking in existing empirical models. The C4 model was implemented in the MOOSE finite-element framework developed at Idaho National Laboratory, enabling it to be used in the BISON nuclear fuel performance code based on the MOOSE framework. To precisely track the different interfaces at a relatively low computational cost, the eXtended Finite Element Method (X-FEM) was applied in MOOSE. The model’s results were compared to those of existing empirical models as well as metallographic analysis of high-temperature oxidized Zircaloy-4 coupons. Oxygen diffusivities in the a and ß phases resulting from this comparison closely agree with those found in the literature. The C4 model implemented with X-FEM in MOOSE now has the capability to accurately predict oxide, oxygen-stabilized a, and prior ß phase layer growth kinetics under isothermal exposure at high temperature (1000–1500°C). Furthermore, in contrast with the empirical models, the C4 model accounts for the finite thickness of the fuel cladding. It can predict the oxygen concentration profile evolution through the whole cladding, enabling evaluation of the remaining ductile thickness—a crucial variable for modeling the mechanical behavior of the fuel cladding under LOCA. Furthermore, this implementation allows direct coupling with mechanics, at a low computing cost, using finite-element-based nuclear fuel performance codes such as BISON.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In situ monitoring of microstructure evolution during thermal processing of uranium-zirconium alloys using laser-generated ultrasound

In this study, laser-generated ultrasound was used to monitor microstructure evolution during thermal processing of as-cast, polycrystalline binary uranium-zirconium metallic fuel alloys with compositions of U-20wt.%Zr (U-20Zr), U-50wt.%Zr (U-50Zr) and U-80wt.%Zr (U-80Zr). Ultrasonic waveforms were recorded during heating and cooling the samples from room temperature to >973 K and back. A phase transition temperature for all three compositions was estimated from the temperature at which an abrupt and rapid reduction in ultrasonic velocities was observed. Microstructural features on the length scale of tens of micrometers were inferred from the observation of scattering of ultrasonic waves by elastic heterogeneities above ~823 K in U-20Zr, while a hysteresis in the ultrasonic velocities of U-80Zr upon cooling was attributed to a partial retention of the high temperature phase following thermal annealing. The U-50Zr alloy exhibited a reversible viscoelastic response above 933 K, as evidenced by the observation of high frequency attenuation of the shear component of the waveforms at high temperature. Ultrasonic measurements were supplemented by in situ transmission electron microscopy (TEM). The TEM images revealed that the δ-U-Zr matrix in the three compositions underwent a spinodal decomposition above ~823 K into nanoscale regions. The ultrasonic measurements revealed larger, micron-scale structure evolution in the U-20Zr alloy at the same temperature. This large-scale structure is associated with heterogeneous regions having different Zr content. Our findings show the potential heating rate dependence of microstructural evolution in U-Zr alloys and highlight differences in the thermomechanical response and associated length scales during thermal annealing between single- and dual-phase compositions. These results demonstrate the utility of laser ultrasonics to rapidly and efficiently scan phase boundaries and monitor micrometer-scale structure evolution in metallic fuel alloys.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Irreversible Multielement Diffusion and the Resulting Compositional and Processing Flexibility in the Synthesis and Densification of Lithium Aluminum Lanthanum Zirconium Oxide

Despite the broad interest in Al-doped lithium lanthanum zirconium oxide (LLZO), the wide range of reported ionic conductivities suggests that the effect of processing parameters on the resulting phase purity and bulk conductivity is not well-understood. Here, in this work, we synthesized six separate series of LLZO with variations in Al concentration, Li excess, Li addition order, Li source, densification method, and mother powder to determine the effect on the composition, phase purity, density, and bulk conductivity. We found that a wider range of compositions (6.08–7.61 mol of Li and 0.06–0.23 mol of Al) than previously reported can result in cubic phase stability and that nearly all elements (Li, Al, Zr, and La) are lost to the MgO crucible during calcination and sintering. The manner in which different elements are lost is affected by the processing parameters. We observed that Al-doped LLZO shows great compositional flexibility in stabilizing the cubic phase, offering an explanation for the range of electrochemical performance metrics reported in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The Dependence of Olefin Hydrogenation and Isomerization Rates on Zirconium Metal–Organic Framework Structure

Zirconium metal–organic frameworks (Zr-MOFs) are a structurally diverse and well-defined class of materials studied in heterogeneous catalysis. Previously, we showed that partial dehydration of the Zr 6 O 8 node in NU-1000 results in heterolytic H 2 cleavage over adjacent Lewis acid and base sites, leading to catalytic conversion of 1-butene. In this work, given the ubiquity of the Zr 6 O 8 node as a secondary building unit (SBU) in Zr-MOFs, with many different potential MOF topologies and capping ligands surrounding the cluster, we study the influence of thermal pretreatments and MOF topology (MOF-808, NU-1000, UiO-66, and NU-1000-NDC) on the activity of the Zr 6 O 8 cluster for H 2 activation and 1-butene hydrogenation and isomerization. Diffuse reflectance IR in the presence of H 2 and pyridine shows that both thermal pretreatment and MOF topology affect the Brønsted acidity of protons generated from H 2 activation and their resulting activity for olefin conversion. High isomerization activity of dehydrated NU-1000 is correlated with the formation of μ 3 OH species after H 2 activation. Additionally, catalytic studies show that the geometry of open coordination sites on individual Zr 6 O 8 nodes influences butene hydrogenation. For this reason, MOF-808 gives anomalously low hydrogenation activity, despite its relatively high total number of open coordination sites, as calculated either from its crystal structure or from NH 3 adsorption. Furthermore, these results reiterate the importance of pretreatment in defining MOF catalytic activity and demonstrate that MOF topology, outside of simply affecting node accessibility, influences reactivity at individual nodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Progress and Perspectives: Zirconium Electrodeposition from Different Electrolytes

Zirconium (Zr) possesses outstanding properties, including exceptional chemical resistance and a high melting point, and is therefore desirable for use in a wide variety of challenging environments, such as in nuclear reactors and the chemical processing industry. To minimize the amount of Zr required for any given application, developing methods for generating metallic Zr coatings is highly advantageous. Owing to Zr’s highly negative reduction potential, electrodeposition in traditional solvents at near ambient temperatures remains challenging and thus not well understood. Due to the extreme conditions required to deposit this metal, extensive work has been conducted in molten salt electrolytes, however the broad applicability of this methodology is limited due to its corrosivity. The primary focus of this article is to present an overview of Zr’s electrochemical behavior and to consolidate the efforts of researchers in exploring electrodeposition techniques for Zr involving aqueous, organic, ionic liquid, deep eutectic, and molten salt solvents. With this information, we highlight trends across solvent systems and opportunities for future research.

42 ENGINEERING↗
DOE OSTI2024

In situ potassium and hydrogen ion exchange into a cubic zirconium silicate microporous material

The selective separation of ions from aqueous systems, and even in the human body, is a crucial to overall environmental management and health. Nanoporous materials are widely known for their selective removal of cations from aqueous media, and therefore have been targeted for use as a pharmaceutical to treat hyperkalemia. This study investigated the detailed crystallographic molecular mechanisms that control the potassium ion selectivity in the nanoporous cubic zirconium silicate (CZS) related materials. Using time-resolved in situ Raman spectroscopy and time-resolved in situ X-ray diffraction, the selectivity mechanisms were determined to involve a synchronous cation-cation repulsion process that serves to open a favorable coordination bonding environment for potassium, not unlike the ion selectivity filter process found in potassium ion channels in proteins. Enhancement of ion exchange was observed when the CZS material was in a partial protonated state (≈3:1 Na:H), causing an expansion of the unit-cell volume, enlargement of the 7 member-ring window, and distortion of framework polyhedra, which allowed increased accessibility to the cage structures and resulted in rapid irreversible potassium ion exchange.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Thermal Neutron Scattering Law Evaluations for Zirconium Carbide and Critical Mass Calculations [Slides]

Zirconium Carbide (ZrC) is a refractory material currently being investigated for high temperature reactor applications. ZrC was studied as a base of (U,Zr)C solid solution and UC 2 composite fuels for NERVA-type cores during the Rover program. Testing of the material was performed at Nuclear Furnace 1 (NF-1) located at Los Alamos. Thermal Scattering Law (TSL) evaluations generated with FLASSH are a new contribution to ENDF/B-VIII.1.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

New Cross Section Measurements and Evaluations of Zirconium Isotopes [Slides]

This presentation gives a look to new cross section measurements and evaluations of Zirconium (Zr) isotopes. This lecture includes highlights of accomplishments made in 2022. Additionally, it explains the motivation for investigation, new measurements, and re-evaluation of the Zr isotopes. This presentation concludes with a preliminary evaluation result from RPI 90 Zr evaluation and preliminary results from Eigenvalue sensitivity study on Zr sensitive critical benchmark experiments.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2024

Investigation of Degradation Mechanisms of Cr-coated Zirconium Alloy Cladding in Reactivity-Initiated Accident

Reactivity-initiated accident testing has been performed on two baseline fuel rodlets which were fabricated from Zr-4 cladding and utilized fresh UO 2 fuel pellets. These experiments are part of a larger series of transient irradiations to explore Cr-coated zirconium alloy cladding under Reactivity-initiated accident conditions to evaluate ballooning and burst and sever oxidation characteristic of late-stage failure. The first two irradiations have been completed and post-transient examinations have been performed. In one rod, ballooning and burst occurred, along with oxidation. The second rod leaked and as a result did not balloon as much during the transient. This second rod also experienced increased oxidation compared to the first due to higher temperatures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Comparison of zirconium redistribution in BISON EBR-II models using FIPD and IMIS databases with experimental Post Irradiation Examination

The BISON code framework is utilized to model and analyze zirconium redistribution within UPuZr metallic fuels. The simulation results are compared against past experimental metallography data to validate the BISON code models. Various BISON models are implemented and compared to properly reflect the Zr present in past data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Electrode and Microstructure Dependence of Oxygen Diffusion in Ferroelectric Hafnium Zirconium Oxide Thin Films

Hafnia-based ferroelectrics hold promise to reduce energy demand for computing by enabling compute-in-memory and as non-volatile memories. The ferroelectric phase in this material system is, in part, stabilized by oxygen vacancies. While oxygen vacancies may be a necessity for phase stability, they limit device endurance through diffusion and accumulation into conducting channels. Herein, it is shown that oxygen diffusion is spatially variable within individual grains of ferroelectric hafnium zirconium oxide (HZO). Using 18 O tracers and finite difference modeling, it is shown that grain boundaries and regions near electrode interfaces allow for relatively rapid oxygen diffusion, with values as much as 10 4 larger than the grain cores. Further, the selection of electrode material affects the diffusion coefficients across all microstructural regions. HZO films in contact with TiN electrodes result in more oxygen-deficient HZO films and higher oxygen diffusion coefficients. Tungsten electrodes result in fewer vacancies and lower diffusion coefficients. Diffusion activation energy differences between the HZO with the two electrodes is reconciled by differing populations of charged and uncharged oxygen vacancies. This insight into the local vacancy populations and diffusion pathways provides a platform for designing hafnia-based films, deposition processes, and integration strategies to reduce vacancy gradients and improve performance.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Zirconium‐Based Metal–Organic Frameworks with Free Hydroxy Groups for Enhanced Perfluorooctanoic Acid Uptake in Water

Perfluorooctanoic acid (PFOA) is a highly recalcitrant organic pollutant, and its bioaccumulation severely endangers human health. While various methods are developed for PFOA removal, the targeted design of adsorbents with high efficiency and reusability remains largely unexplored. Here, in this work, the rational design and synthesis of two novel zirconium‐based metal‒organic frameworks (MOFs) bearing free ortho ‐hydroxy sites, namely noninterpenetrated PCN‐1001 and twofold interpenetrated PCN‐1002, are presented. Single crystal analysis of the pure ligand reveals that intramolecular hydrogen bonding plays a pivotal role in directing the formation of MOFs with free hydroxy groups. Furthermore, the transformation from PCN‐1001 to PCN‐1002 is realized. Compared to PCN‐1001, PCN‐1002 displays higher chemical stability due to interpenetration, thereby demonstrating an exceptional PFOA adsorption capacity of up to 632 mg g −1 (1.53 mmol g −1 ), which is comparable to the reported record values. Moreover, PCN‐1002 shows rapid kinetics, high selectivity, and long‐life cycles in PFOA removal tests. Solid‐state nuclear magnetic resonance results and density functional theory calculations reveal that multiple hydrogen bonds between the free ortho ‐hydroxy sites and PFOA, along with Lewis acid‐base interaction, work collaboratively to enhance PFOA adsorption.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Catalytic Degradation of Polyethylene Terephthalate Using a Phase‐Transitional Zirconium‐Based Metal–Organic Framework

Abstract Polyethylene terephthalate (PET) is utilized as one of the most popular consumer plastics worldwide, but difficulties associated with recycling PET have generated a severe environmental crisis with most PET ending its lifecycle in landfills. We report that zirconium‐based metal–organic framework (Zr‐MOF) UiO‐66 deconstructs waste PET into the building blocks terephthalic acid (TA) and mono‐methyl terephthalate (MMT) within 24 hours at 260 °C (total yield of 98 % under 1 atm H 2 and 81 % under 1 atm Ar). Extensive structural characterization studies reveal that during the degradation process, UiO‐66 undergoes an intriguing transformation into MIL‐140A, which is another Zr‐MOF that shows good catalytic activity toward PET degradation under similar reaction conditions. These results illustrate the diversity of applications for Zr‐MOFs and establish MOFs as a new class of polymer degradation catalysts with the potential to address long‐standing challenges associated with plastic waste.

Wu, Yufang↗
DOE OSTI2022

Catalytic Degradation of Polyethylene Terephthalate Using a Phase-Transitional Zirconium-Based Metal–Organic Framework

Polyethylene terephthalate (PET) is utilized as one of the most popular consumer plastics worldwide, but difficulties associated with recycling PET have generated a severe environmental crisis with most PET ending its lifecycle in landfills. We report that zirconium-based metal–organic framework (Zr-MOF) UiO-66 deconstructs waste PET into the building blocks terephthalic acid (TA) and mono-methyl terephthalate (MMT) within 24 hours at 260 °C (total yield of 98 % under 1 atm H 2 and 81 % under 1 atm Ar). Extensive structural characterization studies reveal that during the degradation process, UiO-66 undergoes an intriguing transformation into MIL-140A, which is another Zr-MOF that shows good catalytic activity toward PET degradation under similar reaction conditions. Here these results illustrate the diversity of applications for Zr-MOFs and establish MOFs as a new class of polymer degradation catalysts with the potential to address long-standing challenges associated with plastic waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗