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At least 37 records · Page 2

Synthesis and behavior of bulk iron nitride soft magnets via high-pressure spark plasma sintering

Abstract In this study, dense bulk iron nitrides (Fe x N) were synthesized for the first time ever using spark plasma sintering (SPS) of Fe x N powders. The Fe 4 N phase of iron nitride in particular has significant potential to serve as a new soft magnetic material in both transformer and inductor cores and electrical machines. The density of SPSed Fe x N increased with SPS temperature and pressure. The microstructure of the consolidated bulk Fe x N was characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and superconducting quantum interference device (SQUID) magnetometry. XRD revealed a primary phase of Fe 4 N with secondary phases of Fe 3 N and metallic iron. Finite element analysis (FEA) was also applied to investigate and explain localized heating and temperature distribution during SPS. The effects of processing on interface bonding formation and phase evolution were investigated and discussed in detail to provide insight into fundamental phenomena and microstructural evolution in SPSed Fe x N. Graphic abstract

36 MATERIALS SCIENCE↗

Spark plasma sintering (SPS) densified U 3 Si 2 pellets: Microstructure control and enhanced mechanical and oxidation properties

Dense U 3 Si 2 pellets with controlled grain structure and enhanced thermal-mechanical and oxidation properties are synthesized with spark plasma sintering (SPS). Microstructure and phase composition of the SPS densified pellets are characterized systematically using SEM, EDS, and XRD. Thermal-mechanical properties and oxidation behavior of the sintered silicide fuel pellets are analyzed by laser flash, indentation, and dynamic thermogravimetric analysis. Dense U 3 Si 2 pellets are consolidated by combining high energy ball milling and rapid sintering by SPS, and the microstructure structures are controlled from micron-sized (~5.7 μm grain size) for conventional silicide to a nanocrystalline matrix with an average grain size of ~280 nm. A dominant phase of distorted U 3 Si 2 was identified with lattice expansion due to residual thermal stress upon SPS consolidation and rapid cooling processes. Both micron-sized and nano-sized pellets show exceptional thermal transport properties, consistent with monolithic silicides reported in literature. The SPS-densified pellets possess simultaneously high hardness and fracture toughness. The SPS-densified silicide pellets also demonstrate exceptional oxidation performance with extended onset oxidation temperature above 500 °C and reduced oxidation kinetics, particularly for nano-sized pellets. A strong strain effect was proposed in which compressive stress in nano-sized pellets enhances the oxidation resistance of silicide fuels, as evidenced by the degradation of oxidation performance upon strain relaxation by isothermal annealing. The correlation among the sintering process – microstructure control – physical properties and fuel behavior is established. A new concept of strain engineering is proposed further properties optimization, enabling the development of potential oxidation and corrosion-resistant silicides with extended performance, the key technological challenge of U 3 Si 2 as the leading concept of accident tolerant fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Densification and oxidation behavior of spark plasma sintered Hafnium Diboride-Hafnium Carbide composite

This study reports on the sintering and oxidation behaviors of Hafnium Diboride (HfB 2 ) and Hafnium Carbide (HfC) based ultra-high temperature ceramic (UHTC) composites. Pure Hafnium Diboride, Hafnium Carbide, and HfB 2 -50 vol% HfC composite were consolidated using spark plasma sintering (SPS) without the use of sintering aids. HfB 2 -HfC composite displayed a high sintered density of 98% as compared to 87% density of pure HfB 2 . The increased density of the HfB 2 -HfC composite is attributed to the bimodal powder distribution, which allowed for the smaller HfC particle to occupy the voids between the larger HfB 2 particles resulting in improved packing efficiency. Moreover, the higher planar surface energy, for the (111) and the (200) planes for HfC, contributed to the smaller HfC particle being a significant driving force in the sintering process. Oxidation studies of each material were carried out by exposing them to a high-speed plasma jet in a temperature exceeding 2700 °C. The results of these studies show an improved oxidation resistance of HfB 2 -HfC composite by 54% and 70% over pure HfC and HfB 2 , respectively. The enhanced oxidation behavior is attributed to B 2 O 3 filling in the porosity between the HfO 2 scale and protecting the underlying material. This study provides a new alternative to improve the sinterability of UHTC diborides by introducing another UHTC (i.e., HfC) to form a fully dense composite without sintering aid and superior oxidation resistance.

36 MATERIALS SCIENCE↗

Spark plasma sintering of fuel meats for U 3 O 8 based dispersion fuels

Research and test reactors often use dispersion-type fuel due to its increased thermal conductivity and burn-up capabilities compared to conventional fuel. Al-U 3 O 8 (aluminumtriuranium octaoxide) dispersion fuels have several advantages over their competitors, such as higher service temperature and better stability of oxygen stoichiometry. However, the two-step fabrication of dispersion fuel causes undesirable porosity in cold-pressed fuel meats that is preserved in co-extruded fuel plates. To combat this, spark plasma sintering (SPS) was used for the fabrication of Al-15, 20, and 30 vol% U 3 O 8 and 8 and 12 vol% Mo-U 3 O 8 fuel meats for the Al-U 3 O 8 time. The in situ SPS data was used to construct and validate Master Sintering Curves (MSCs) with accuracies in Al fuels at 0.02 g/cm 3 , and Mo fuels at 0.07 and 0.17 g/cm 3 . The as-sintered fuel meats were characterised using x-ray diffraction (XRD) and scanning electron microscopy (SEM) to understand chemical and physical changes following the SPS process. The pellets exhibited very high relative densities, the U 3 O 8 was observed to undergo reduction to UO 2 .

Aluminium↗

Graded microstructure and mechanical properties of spark plasma sintered Fe-Cr alloys

Developing graded microstructure and mechanical properties is critical for accelerating the design and optimization of structural materials for a wide range of applications. Here, in this study, Fe-Cr alloys were fabricated by spark plasma sintering (SPS) technique. The microstructure, microhardness, and tensile properties of the as-fabricated and thermally annealed variants were investigated. Graded grain structures were created in the as-fabricated cylinders along both axial and radial directions. Grain size was gradually reduced from the sample periphery to the center. Microhardness measurements reveal a gradual decrease of hardness towards the periphery of the samples. The as-fabricated Fe-Cr alloys show a desired combination of tensile strength and elongation, primarily due to the formation of a high density of oxides, voids, dislocations, and grain boundaries. After in-situ thermal annealing at 600 °C under 60 MPa for 2 h using SPS, the Fe-Cr alloys underwent minimal grain growth, and the graded grain structures were retained. The hardness was more uniformly distributed in the annealed variants, and the tensile strength was reduced with an increase in the total elongation, which is attributed to the dissolution of nano-sized oxide particles and the relief of the residual stress. This study demonstrates that SPS coupled with subsequent heat treatment can tailor the graded microstructure and control the mechanical properties of Fe-Cr alloys, showing potential applications in other alloy systems.

36 MATERIALS SCIENCE↗

Coupling of Spark Plasma Sintering with Advanced Modeling to Enable Process Scale-Up: Presentation to DOE-NE [Slides]

The research goal of this project is to develop at Idaho National Laboratory (INL) a first-of-its-kind Multiphysics Object-Oriented Simulation Environment (MOOSE)-based, multiscale, multiphysics spark plasma sintering (SPS) modeling and simulation code application, termed “Freya.” Freya will simulate the thermo-mechanical-electrical aspects of the SPS fabrication process and will be paired with lower length scale sub-models, such as phase-field, to predict the resulting microstructure. SPS is an advanced manufacturing process that can be used to solve a variety of material manufacturing challenges; however, this process is an extremely challenging problem for modeling and simulation. The SPS process is inherently multiphysics and multi-scale, with the macroscale electro-thermo-mechanical behavior linked intricately to the microstructure evolution of the part being sintered. Accurate modeling and simulation tools, specifically geared towards the SPS process, are needed to predict the influence of the multiple variables involved in the manufacturing process. Modeling and simulation accuracy is achieved and demonstrated through comparison to multiple validation experiments. The validation efforts for Freya include both separate effects and complete multiphysics SPS process experiments. One of the key benefits this Laboratory Directed Research & Development (LDRD) project offers stems from the emphasis placed on experimental validation of the Freya models, both on the individual length scales and of the final coupled multiscale multiphysics simulations. Experimental validation of Freya’s multiscale coupling capability provides the technical credibility necessary for potential future industry and research partners to accept the simulation predictions.

36 MATERIALS SCIENCE↗

High-temperature compressive creep tests of U 3 Si 2 with spark plasma sintering: Experiments and finite element modeling

This paper reports a systematic high-temperature creep behavior of dense U 3 Si 2 pellets using a spark plasma sintering (SPS) apparatus at elevated temperatures and pressures under vacuum conditions. The stress exponent was subsequently derived to be 3.21 at 1173 K and 2.17 at 1223 K, respectively, indicating a grain boundary sliding creep mechanism. The creep activation energy was determined to be 203.6 ± 19.0 kJ/mol, which agrees well with the literature. Finite element modeling was performed using the creep parameters fitted from the strain-time plot. Additionally, the results suggest an excellent match with the experimental data, confirming the validity of the experiments. Microstructure characterizations indicate that the main phase of the specimens after creep tests remains to be U 3 Si 2 , with a 4 μm thick layer of nano-sized particles induced from the diffusion between U 3 Si 2 and alumina disc used to avoid electric current passing through the sample. The successful conduct of creep experiments demonstrates the great potential of SPS to perform high-temperature mechanical testing of nuclear fuels under vacuum conditions. The subsequent finite element modeling exhibits excellent capabilities for accurately predicting material performance in the creep tests and provides a practical tool in evaluating nuclear fuels’ performance for a much-extended time scale.

36 MATERIALS SCIENCE↗

Manufacturing Bulk Nanocrystalline Al-3Mg Components Using Cryomilling and Spark Plasma Sintering

In the current study, pure aluminum (Al) powders were cryomilled with and without 3 wt.% pure magnesium (Mg) dopant for varying durations followed by spark plasma sintering (SPS) of powders to prepare bulk components with superior mechanical properties. The crystallite sizes were determined for powders and the bulk components by analyzing the X-ray diffraction (XRD) spectrum. The calculations indicated a reduction in crystallite size with the increase in the cryomilling duration. The results also showed a more significant decrease in the crystallite sizes for Al-3Mg samples than that of pure Al. The changes in the surface morphology of powders were characterized using scanning electron microscopy (SEM). The elemental mapping analysis at nanoscale was carried out using Energy-dispersive X-ray spectroscopy (EDX) in Scanning transmission electron microscopy (STEM). The mechanical properties of the bulk components were assessed using a Vickers Microhardness tester. The test results demonstrated an improvement in the hardness of Mg-doped components. Higher hardness values were also reported with an increase in the cryomilling duration. This article discusses the mechanisms for the reduction in crystallite size for pure Al and Al-3Mg and its subsequent impact on improving mechanical properties.

36 MATERIALS SCIENCE↗

Densification of non-radioactive porous siliceous particles loaded with cesium potassium copper hexacyanoferrate by spark plasma sintering

In the development of a conditioning process for cesium-bearing sorbents from the decontamination of aqueous waste streams, the treatment of a granular material composed of (Cs,K) 2 CuFe(CN) 6 loaded onto mesoporous silica particles has been investigated in an additive-free two-step conditioning process involving (i) calcination at 1000 °C to remove volatile species and (ii) densification by spark plasma sintering. A 92.0 % dense pellet was obtained after 10 min sintering at 850 °C under 100 MPa. Density and microstructural measurements indicate that densification is first driven by the viscous flow of a vitreous phase containing Cs, formed during calcination. Additionally, the density of the sample then increases further during sintering by grain boundary diffusion. However, a limited but non negligible part of cesium is lost during densification.

36 MATERIALS SCIENCE↗

Manufacturing Li 2 TiO 3 -based tritium breeder materials by volume-controlled spark plasma sintering with an optimized microstructure

Multifunctional ceramic breeder materials are highly desirable for the deuterium-tritium fusion to achieve high efficiency in breeding tritium through neutron irradiation of lithium-containing blankets. Li 2 TiO 3 displays unique attributes as a potential ceramic breeder material. An optimized microstructure with three-dimensional interconnected pore structure is required for rapid transport of the tritium for effective fuel cycle, which however enviably results in the degradation of the thermal-mechanical properties of the breeding materials. In this work, nanocrystalline porous Li 2 TiO 3 ceramic pellets with controlled porosities of 14% and 20% are manufactured by volume-controlled spark plasma sintering. An optimized 3D interconnected pore structure is achieved consisting of both micro-sized pores and nano-sized pores embedded in nanocrystalline matrix, which could be beneficial to facilitate easy removal of bred T and He. Further, the 3D interconnected porous structure is well maintained upon isothermal annealing of the SPS-fabricated pellets at relevant operation temperature of the solid breeding materials. Single-phasic porous pellets also display enhanced thermal-mechanical properties, superior to current state-of-the-art materials which establish their potential as a promising tritium breeder material for nuclear fusion applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Effect of V Content on Corrosion Behavior of Al-V Alloys Produced by Mechanical Alloying and Subsequent Spark Plasma Sintering

Al-V alloys produced via high-energy ball milling have been reported to show simultaneous improvement of corrosion resistance and mechanical properties compared to traditional Al alloys. In these alloys, V content plays a crucial role in increasing or decreasing the corrosion resistance. Therefore, the effect of V and microstructure on corrosion of high-energy ball milled and subsequently spark plasma sintered Al-xV alloys (x = 2, 5, 10 at%) has been studied. Cyclic potentiodynamic polarization tests and electrochemical impedance spectroscopic analysis revealed the increment of V content up to 5 at% enhanced the corrosion resistance of the alloy. However, highly heterogeneous microstructure in Al-10 at%V resulted in significant localized corrosion over the immersion time. The electrochemical impedance spectroscopy studies over 14 days of immersion revealed underlying corrosion mechanisms.

36 MATERIALS SCIENCE↗

Spark plasma sintered, MoNbTi-based multi-principal element alloys with Cr, V, and Zr

MoNbTi, MoNbTiZr, CrMoNbTiZr, and MoNbTiVZr multi-principal element alloys (MPEAs) were fabricated via spark plasma sintering (SPS) and investigated for use in high-strength applications. The fabrication method by SPS and powder metallurgy differs from those presented in the prior literature, where most MPEAs are fabricated using arc melting (AM) methods. Here cryogenic milling was used to maximize potential defect sinks (grain boundaries) for radiation resistance and to increase ultimate tensile strength through the Hall-Petch effect. SPS was chosen for consolidation in order to maintain a fine-grained structure during densification. Each alloy was characterized using x-ray diffraction and scanning electron microscopy for phase identification and compositional homogeneity. The base ternary alloy MoNbTi presented a predominantly single BCC system with minor cubic phases. The introduction of additional alloying elements—Zr, V, and Cr—heightened the phase complexity and increased the fractions of a secondary BCC phase and an HCP phase from Zr. The addition of Cr induced a larger fraction of the Laves phase to form. The addition of V caused the precipitation of small Mo inclusions. Thermodynamic analysis was performed to understand the separation of phases in each alloy. Discrepancies among the phase predictions generated by thermodynamic models, phases previously presented in the literature, and the characterization results suggest that MPEA fabrication methods, especially solid-state methods, require significant investigation to ensure that alloys can remain stable throughout their anticipated service lifetimes.

36 MATERIALS SCIENCE↗

Pelletization with Spark Plasma Sintering and Characterization of Metal Iodides: An Assessment of Long-Term Radioiodine Immobilization Options

Four promising iodine “getter” materials (Ag, Cu, Bi, and Sn) for radioiodine capture were assessed in their pure metal-iodide (MI x ) pelletized forms to compare relative chemical durabilities. To study chemical durability, commercial MI x compounds of AgI, BiI 3 , BiOI, CuI, and SnI 4 were converted to dense monolithic pellets using spark plasma sintering. Semidynamic leach testing in the form of modified ASTM C1308 tests was then performed on the pellets in two different forms including unmounted (as-pressed) specimens (i.e., “U”) and epoxy-mounted specimens (i.e., “M”) with polished surfaces. The chemical durability results and sample characterizations showed that three of the five MI x compounds tested (i.e., AgI, CuI, and BiOI) displayed moderate to high leach resistances. Further, the remaining two MI x compounds (i.e., BiI 3 and SnI 4 ), which are both desirable iodine waste forms due to their high iodine loading capacities, readily decomposed during leach testing, indicated by crystallographic changes in the specimens as well as large amounts of iodine detected in the leachate solutions. The instabilities of BiI 3 and SnI 4 raise uncertainties for using the base metals/cations (i.e., Bi 0 /Bi 3+ and Sn 0 /Sn 4+ , respectively) as viable getters for radioiodine capture due to likely poor waste form chemical durabilities after capture and consolidation into waste forms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uranium nitride (UN) pellets with controllable microstructure and phase – fabrication by spark plasma sintering and their thermal-mechanical and oxidation properties

Dense uranium mononitride (UN) pellets with controlled microstructures and tailored grain size from large-grained to a few microns are synthesized by spark plasma sintering (SPS) combined with high energy ball milling. The impacts of the sintering conditions on fuel microstructure, grain size, physical density, and phase behavior are systematically investigated, and the thermal-mechanical properties and oxidation behavior of the SPS densified UN pellets are characterized. Higher sintering temperatures and longer ball milling durations and thus finer starting UN powders promote sintering and densification, and dense UN pellets above 95% theoretical density can be achieved by SPS at 1873 K for 10 min. UN phase purity is maintained in the SPS-densified pellets sintered at a lower temperature and short duration. A phase heterogeneity with secondary UO 2 or uranium sesquinitride (U 2 N 3 ) occurs for the UN pellets sintered at higher temperatures using finer UN powders. The hardness and fracture toughness of the SPS-densified UN pellets increase with smaller grain sizes and higher densities to 7.9 GPa and 3.5 MPa m 1/2 , respectively. Furthermore, both small (1–2 μm) and large grain-sized (30–50 µm) UN pellets exhibit good thermal conductivity. Dynamic oxidation testing by a thermogravimetric analyzer in air shows that the onset temperature for oxidation varies with microstructure and phase heterogeneity of the SPS densified UN pellets. Particularly, the smaller-grained (micron-sized) UN pellets containing uranium oxides and U 2 N 3 display lower weight gain and significantly-reduced oxidation kinetics, and full oxidation completes at a temperature above 1173 K when tested with a ramp rate of 10 K/min.

36 MATERIALS SCIENCE↗

Impact of electrode porosity architecture on electrochemical performances of 1 mm-thick LiFePO4 binder-free Li-ion electrodes fabricated by Spark Plasma Sintering

Thick electrodes with high active material loadings have been intensively studied over the last couple of decades in pursuit of achieving high energy density systems. To optimize and enhance the electrochemical performance of such electrodes, one has to control the pore morphology by, for example, varying the pore size and shape, and the level of porosity. In the present work, the fabrication of thick binder-free LiFePO4 (LFP) electrodes with two different pore sizes (12 and 20 mu m) and porosities (21 vol% and 44 vol%) using Spark Plasma Sintering (SPS) and templating approach is reported. The well-controlled porous architecture inside the thick electrodes is realized by fine-tuning experimental parameters. The impact of porosity architecture on electrochemical performance is quantified and correlated with the 3D tortuosity values determined from both micro-computed tomography and electrochemical impedance-based experimental methods. Based on the micro-computed tomography data analysis, estimated tortuosity values along X, Y, and Z axes reveal an anisotropic effect perpendicularly to the SPS compression axis (Z-direction). This is particularly profoundly observed in the samples with larger pores (20 mu m). The correlation between morphological properties and the rate capability performance is established indicating that the capacity loss happens mainly due to the Li-ion diffusion limitations.

Cathode material↗

Formation and Consolidation of UN Nanostructures in U-Mo Fuel via Mechanical Alloying and Spark Plasma Sintering

Uranium-molybdenum (U-Mo) alloys show promise as a nuclear fuel system due to their high thermal conductivity and high fuel loading capability. However, U-Mo systems suffer from irradiation induced swelling ultimately affecting the cladding via mechanical and chemical interaction. To address these shortcomings, this thesis investigated the formation of uranium mononitride (UN) nanoparticles within a U-10Mo matrix. To promote the formation of UN, U-10Mo powders were mechanically alloyed under a high purity nitrogen cover gas (99.9995%) atmosphere. Variations were made in stainless steel milling media size, duration of milling, and number of times the milling jar was re-aerated with nitrogen gas. UN nanoparticulates were successfully formed within the U-Mo matrix and was characterized utilizing light element analysis, X-ray diffractometry, scanning and transmission-electron microscopy, electron energy loss spectroscopy, and atom probe tomography. Presence of the UN nanoparticles was found as early as 1-hour into the mechanical alloying process, and significant iron contamination found after 10-hours of milling. The U-Mo/UN powders were compacted using spark plasma sintering techniques in order to stabilize the nanostructure. U-Mo/UN compacts containing small amounts of neodymium and helium were analyzed to observe the defect migration tendencies of fission products within the fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Phase stability and magnetic and electronic properties of a spark plasma sintered CoFe – P soft magnetic alloy

More efficient power conversion devices are able to transmit greater electrical power across larger distances to satisfy growing global electrical needs. A critical requirement to achieve more efficient power conversion are the soft magnetic materials used as core materials in transformers, inductors, and motors. To that effect it is well known that the use of non-equilibrium microstructures, which are, for example, nanocrystalline or consist of single phase solid solutions, can yield high saturation magnetic polarization and high electrical resistivity necessary for more efficient soft magnetic materials. In this work, we synthesized CoFe – P soft magnetic alloys containing nanocrystalline, single phase solid solution microstructures and studied the effect of a secondary intermetallic phase on the saturation magnetic polarization and electrical resistivity of the consolidated alloy. Single phase solid solution CoFe – P alloys were prepared through mechanically alloying metal powders and phase decomposition was observed after subsequent consolidation via spark plasma sintering (SPS) at various temperatures. The secondary intermetallic phase was identified as the orthorhombic (Co x Fe 1-x ) 2 P phase and the magnetic properties of the (Co x Fe 1-x ) 2 P intermetallic phase were found to be detrimental to the soft magnetic properties of the targeted CoFe – P alloy.

36 MATERIALS SCIENCE↗

Synthesis of Hf 6 Ta 2 O 17 superstructure via spark plasma sintering for improved oxidation resistance of multi-component ultra-high temperature ceramics

Ultra-high temperature ceramics (UHTCs) have shown aspiration to overcome challenges in the thermal protection system (TPS) by designing new materials referred to as multi-component UHTCs (MC-UHTCs) in the compositional space. MC-UHTCs have shown remarkable improvement in oxidation resistance due to the formation of the Hf6Ta2O17 superstructure during plasma exposure. Herein, the Hf 6 Ta 2 O 17 superstructure is synthesized via a solid-state reaction between HfO 2 and Ta 2 O 5 powder mixtures during spark plasma sintering (SPS). The compositions chosen are 50 vol% of HfO 2 -50 vol% of Ta 2 O 5 (50HO-50TO) and 70 vol% of HfO 2 -30 vol% of Ta 2 O 5 (70HO-30TO). The phase quantification via Rietveld analysis showed Hf 6 Ta 2 O 17 as a principal phase with some residual Ta 2 O 5 phase in both the samples. The high-temperature thermal stability of the samples was evaluated using high-velocity plasma jet exposure for up to 3 min. 50HO-50TO was able to withstand the intense plasma condition, which is attributed to the higher content of the Hf 6 Ta 2 O 17 phase (~84%) and lower strain in the Ta 2 O 5 phase. The augmentation in the Hf 6 Ta 2 O 17 phase to 94.7% (in 50HO-50TO) post plasma exposure has been attributed to the invariant transformation from a liquid state to Hf 6 Ta 2 O 17 at temperatures >2500 °C during testing. The mechanical integrity is elucidated from the insignificant change in the hardness ~13.3 GPa before and 11.2 GPa after plasma exposure of the 50HO-50TO sample. As a result, the Hf 6 Ta 2 O 17 superstructure's thermo-mechanical stability suggests developing novel oxidation-resistant MC-UHTCs in compositional space for reusable space vehicle applications.

36 MATERIALS SCIENCE↗