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At least 235 records · Page 13

Elucidating texture and grain morphology contributions to the micromechanical response of additively manufactured Inconel 625

Microstructural variation of additively manufactured (AM) metal components in comparison to wrought counterparts makes certification for critical applications a challenge. Microscale simulations leveraging modern computational tools may be used to supplement testing of AM microstructures, thus accelerating certification by reducing the number of experiments needed. However, as micromechanical response is closely tied to critical properties like fatigue-life and fracture, utilization of these simulations with macroscale experimental data alone is insufficient. One means to attain microscale experimental data is in situ diffraction data collected from synchrotron X-ray sources. In this work, such data were collected during in situ compression of AM Inconel 625 superalloy. Interpretation of experimental results was assisted by massive (8M element) complementary micromechanical simulations performed on sets of virtual microstructures generated using cellular automata. Together, micromechanical data from diffraction experiments and simulations were used to probe the effects of textured “track” microstructures generated during laser powder bed fusion and directional strength-to-stiffness on micromechanical response. Though fiber-averaged directional strength-to-stiffness ratios were expected to dominate given the high elastic anisotropy of the material, the combination of small variations in texture and specific grain configurations unique to AM microstructures lead to significant variability in micromechanical response after yield. The findings emphasize the importance of high-fidelity microstructural representation that captures key texture components and AM-specific morphology for property prediction of AM metals.

36 MATERIALS SCIENCE↗

Investigate the height dependency of the micro-/defect-structure and mechanical properties of additively manufactured AlF357 aluminum alloy

When the laser powder bed fusion (L-PBF) additive manufacturing method is employed to build parts with increased heights, there is a possibility that defects are increased in part. This study investigates the effect of build height on the micro-/defect-structure and, consequently, the mechanical properties of L-PBF AlF357, an Al-Si-Mg alloy family. Tall vertical cylinders of 316 mm with 15 mm diameter were fabricated and cut into specimens at different heights. Although not much difference is observed in the microstructure (grain size and morphology), the defects' size and population slightly vary with height. Nonetheless, the tensile properties of the L-PBF AlF357 are found to be independent of height. This is ascribed to the approximately identical microstructure and marginal difference in the defect's size and distribution along the heights.

Laser powder bed fusion (L-PBF)↗

Effect of growth dynamics on the structural, photophysical and pseudocapacitance properties of famatinite copper antimony sulphide colloidal nanostructures (including nanosheets)

Facile phase selective synthesis of copper antimony sulphide (CAS) nanostructures is important because of their tunable photoconductive and electrochemical properties. In this study, off-stoichiometric famatinite phase CAS (fCAS) quasi-spherical and quasi-hexagonal colloidal nanostructures (including nanosheets) of sizes, 2.4–18.0 nm were grown under variable conditions of temperature (60–200 °C), time and oleylamine capping ligand concentration using copper(II) acetylacetonate and antimony(III) diethyldithiocarbamate precursors. Data from powder X-ray diffraction, Raman spectroscopy and high-resolution scanning/transmission electron microscopy confirm the tetragonal structure of the famatinite phase. X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy data suggest a correlation of particle size, morphology and composition of the off-stoichiometric fCAS nanostructures with growth temperature and time, and oleylamine concentration. The off-stoichiometric Cu 3-a Sb 1+b S 4±c (a, b, c – mole fractions) nanostructures being severely copper-deficient and antimony-rich, exhibit shallow-lying acceptor copper vacancy states, deep-lying donor states of antimony interstitials, sulphur vacancies and antimony-copper antisites and shallow-lying acceptor surface trapping states. Further, these electronic states are likely implicated in tunable UV-visible absorption and bandgaps between 2.3 and 2.8 eV, and broad visible-NIR photoluminescence with fast recombination of radiative lifetimes between 0.2 and 6.2 ns, confirmed from absorption, steady-state and time-resolved photoluminescence spectroscopies. Additionally, cyclic voltammetry and electrochemical impedance spectroscopy confirm that electrodes of the fCAS nanostructures display slightly variable pseudocapacitance of charge-storage primarily via possible sodium ion intercalation with a high specific capacitance of ~84 F g -1 obtained at a scan rate of 5 mV s -1 . Overall, these results show the influence of composition, in particular point defects, phase quality and morphology on the optical and pseudocapacitance properties of fCAS nanostructures, suitable as solar absorbers or electrodes for energy storage devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of oscillatory speed and mutual overlap on the tribological behavior of PTFE and selected PTFE-based self-lubricating composites

The wear reducing actions of bronze, graphic powder and discontinuous glass fiber within a PTFE matrix have been demonstrated in oscillatory contact with stainless steel, at two different amplitudes, over a range of speeds. The secondary effects on the friction of the PTFE have also been investigated. The effects of oscillation amplitude on frictional surface morphology have been observed for these composites. The friction and wear of the unfilled PTFE matrix were both found to increase as speed increased, with wear going through a transition from a low- to high-rate regime. The speed at which this transition occurs increases with decreasing oscillatory amplitude.

Blanchet, Thierry A.↗

Probing the thermal decomposition of plutonium (III) oxalate with IR and Raman spectroscopy, X-ray diffraction, and electron microscopy

The thermal decomposition of Pu(III) oxalate was analyzed by Raman microspectroscopy, infrared spectroscopy, scanning electron microscopy, and powder X-ray diffraction. These data show that crystalline Pu 2 (C 2 O 4 ) 3 •9H 2 O progressively loses water and oxalate ligands as it is heated, which leads to a decrease in long-range lattice ordering, though minimal changes are observed in gross crystalline morphology. The onset of PuO 2 formation was observed between 200 - 250 °C. Thermal decomposition of oxalate ligands leads to the formation of CO 2 and plutonium oxalate-carbonate moieties, which had not been observed in previously published thermogravimetric measurements of Pu(III) oxalate. Formation of plutonium oxalate-carbonate moieties is believed to be associated with a change in the plutonium oxidation state from 3+ to 4+, which occurs prior to PuO 2 formation. The data provided herein demonstrate the rich spectroscopic nature of a rather underexplored, and technologically relevant, plutonium system. Ideally these results will further future investigations into the Pu(III) oxalate system both experimentally and computationally.

36 MATERIALS SCIENCE↗

Particle size of several plutonium-238 oxide fuel samples from oxalate precipitation processes

Particle size of 238 PuO 2 powders is an important factor in determining the structural integrity of fuel pellets hot-pressed from the oxide powder. Understanding the evolution of particle size during aqueous processing is a first step in assuring control of particle size throughout the pellet formation process. Measured particle sizes are reported here, and discussed in terms of measured particle size changes occurring during calcining, observed aggregation of particulate, and particle morphology. Morphology and aggregation are related to surface energy, which governs granule formation and hot pressing behavior. Results are discussed in terms of reported dependence of oxide morphology on process temperatures and reagent concentrations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Melt Pool characteristics on surface roughness and printability of 316L stainless steel in laser powder bed fusion

Purpose Surface quality and porosity significantly influence the structural and functional properties of the final product. This study aims to establish and explain the underlying relationships among processing parameters, top surface roughness and porosity level in additively manufactured 316L stainless steel. Design/methodology/approach A systematic variation of printing process parameters was conducted to print cubic samples based on laser power, speed and their combinations of energy density. Melt pool morphologies and dimensions, surface roughness quantified by arithmetic mean height (Sa) and porosity levels were characterized via optical confocal microscopy. Findings The study reveals that the laser power required to achieve optimal top surface quality increases with the volumetric energy density (VED) levels. A smooth top surface (Sa < 15 µm) or a rough surface with humps at high VEDs (VED > 133.3 J/mm 3 ) can serve as indicators for fully dense bulk samples, while rough top surfaces resulting from melt pool discontinuity correlate with high porosity levels. Under insufficient VED, melt pool discontinuity dominates the top surface. At high VEDs, surface quality improves with increased power as mitigation of melt pool discontinuity, followed by the deterioration with hump formation. Originality/value This study reveals and summarizes the formation mechanism of dominant features on top surface features and offers a potential method to predict the porosity by observing the top surface features with consideration of processing conditions.

Engineering↗

Development of HPC based phase field simulations tool for modification of alloy morphology to enhance material properties during additive manufacturing (AM) process

Currently, additive manufacturing (AM) technology is extensively used to manufacture aerospace components because of the unique advantages of the technique in producing custom designs, complex geometries in a near-net fashion that significantly reduces the manufacturing cost, and improved energy efficiency. However, the thermodynamic properties of existing aerospace alloys and the thermal conditions that prevail in most of the powder-bed based additive manufacturing processes lead to undesirable columnar / columnar-dendritic microstructures that promote solidification cracking during the process, and the development of anisotropy in the mechanical properties of the as-built components. Time consuming, energy-intensive post AM treatments are required to recover the mechanical properties of the wrought components for which the existing alloy compositions were designed for. However, novel alloy compositions, that exploit the AM thermal conditions to produce fine, equiaxed grain structures in the as-built condition, with mechanical properties equal to or exceeding those of the wrought work-horse alloy, Ti-6Al-4V has recently been demonstrated in Ti-Cu alloys. Significant energy savings up to 66% can be obtained for a typical aerospace component through digitally designing the AM process, process parameters, and alloy composition. The current project focused on developing a fundamental understanding of the evolution of the columnar to equiaxed transition (CET) occurring during solidification under AM thermal conditions in Ti-Cu and Ti-Cu-X alloys using high-fidelity phase field (PF) simulations using the leadership class computing facilities that exist in the national laboratories. The simulations were able to capture the effect of alloy and process conditions on CET, and clearly showed the beneficial effect of a ternary solute addition to Ti-Cu binary alloys on CET. The simulations indicated that bulk nucleation in the liquid ahead of the solidifying epitaxial front was promoted by a large, transient, thermal undercooling promoted by the mismatch between the growth rate of the dendrite tips in the epitaxial front and the imposed solidification rate. AM experiments performed at Raytheon Technologies Research Center using the same thermal conditions used in the PF simulations indicated the formation of equiaxed grains, although the grain size was bigger than the ones reported in the literature. On the other hand, the equiaxed grain size predicted by PF simulations were smaller than the grain size of Ti-Cu alloys reported in the literature. The industry will follow up the existing work in a future program that would involve further optimization of the process for the Ti-Cu-X alloys to demonstrate the application of the process and the alloy to a specific aerospace component.

36 MATERIALS SCIENCE↗

In Situ X-ray Radiography and Computational Modeling to Predict Grain Morphology in $\beta$-Titanium during Simulated Additive Manufacturing

The continued development of metal additive manufacturing (AM) has expanded the engineering metallic alloys for which these processes may be applied, including beta-titanium alloys with desirable strength-to-density ratios. To understand the response of beta-titanium alloys to AM processing, solidification and microstructure evolution needs to be investigated. In particular, thermal gradients (Gs) and solidification velocities (Vs) experienced during AM are needed to link processing to microstructure development, including the columnar-to-equiaxed transition (CET). In this work, in situ synchrotron X-ray radiography of the beta-titanium alloy Ti-10V-2Fe-3Al (wt.%) (Ti-1023) during simulated laser-powder bed fusion (L-PBF) was performed at the Advanced Photon Source at Argonne National Laboratory, allowing for direct determination of Vs. Two different computational modeling tools, SYSWELD and FLOW-3D, were utilized to investigate the solidification conditions of spot and raster melt scenarios. The predicted Vs obtained from both pieces of computational software exhibited good agreement with those obtained from in situ synchrotron X-ray radiography measurements. The model that accounted for fluid flow also showed the ability to predict trends unobservable in the in situ synchrotron X-ray radiography, but are known to occur during rapid solidification. A CET model for Ti-1023 was also developed using the Kurz–Giovanola–Trivedi model, which allowed modeled Gs and Vs to be compared in the context of predicted grain morphologies. Both pieces of software were in agreement for morphology predictions of spot-melts, but drastically differed for raster predictions. The discrepancy is attributable to the difference in accounting for fluid flow, resulting in magnitude-different values of Gs for similar Vs.

36 MATERIALS SCIENCE↗

Microstructure–Property Correlation in a Laser Powder Bed Fusion Processed High-Strength AF-9628 Steel

Laser powder bed fusion additive manufacturing (LPBF-AM) of a low-alloy, high-performance AF-9628 steel results in exceptionally high strength and good ductility. The reasons for such mechanical properties are investigated through detailed microscopy performed at several length scales. Thus, the characterization of melt pool, porosity, grain morphology, phases, and dislocations is performed in the as-printed material. The as-printed material consists of only 0.004 vol% of uniformly distributed porosity, single-phase martensitic laths with an average lath size of ≈2.5 μm, the absence of carbides indicating interstitial trapping of C atom, and high dislocation density in the martensitic laths. Experimental data through microscopy are then fed in analytical models for calculating strengthening contributions from various strengthening mechanisms. Calculated yield strength agrees well with experimentally determined value, and therefore, activation of various strengthening mechanisms is established in as-printed AF-9628.

36 MATERIALS SCIENCE↗

Implementing an aerosol dynamic shape factor for cerium oxide powder

The shape factor (X B ) of bulk powder CeO 2 (cerium oxide) particles is estimated to be X B = 1.34 (dimensionless). This is defined in relation to the measured aerated bulk density (0.91 g cm -3 , Hosokawa Micron, Summit NJ, 2018) of the CeO 2 powder. This information is used to determine the RRF (respirable release factor), and other parameters during drop test experiments of nuclear material storage containers at Los Alamos National Laboratory. The calculation is based on an experimental shape factor (X P = 2.66 dimensionless) for CeO 2 particles of the same (chain aggregate) morphology studied by other researchers. In that work, the shape factor was defined in terms of the maximum possible (compacted) density of CeO 2 material (7.13 g cm -3 ).

61 RADIATION PROTECTION AND DOSIMETRY↗

(Oxy)hydroxides Formed on Aluminum Fuel Materials After Irradiation and Long-Term Wet Storage - 20354

The aluminum cladding of research-reactor fuel experiences general corrosion when in contact with water during in-reactor service and post-discharge wet storage, resulting in the formation of adherent aluminum (oxy)hydroxide films. These (oxy)hydroxides contain chemically-bound water that poses challenges for extended dry storage due to the risk of thermal or radiolytic decomposition releasing free water and/or hydrogen and oxygen gases. This study describes characterization of the (oxy)hydroxides present on several aluminum materials used in reactor operation and subsequently stored wet in the L-Basin storage facility at the Savannah River Site (SRS) for an extended period. Characterization data providing insight into the loading, composition, and morphology of (oxy)hydroxides to be expected on service-exposed aluminum cladding provides valuable benchmarks for designing adequate drying and dry-storage approaches. This work is part of a broader investigation to address knowledge gaps and technical data needs for dry storage of aluminum-clad spent nuclear fuel (ASNF), which included in-lab growth of (oxy)hydroxide films on aluminum alloy substrates to investigate formation behavior, investigation of drying methods to remove existing (oxy)hydroxides from ASNF cladding, and measurement of radiolytic yield of hydrogen from (oxy)hydroxide powders and films. In this study, (oxy)hydroxide films were characterized for three aluminum-alloy materials used in reactors and subsequently stored wet for up to approximately 40 years in L-Basin at SRS: one cropping from a Missouri University Research Reactor (MURR) fuel element (Al-6061 alloy), one cropping from a Universal Sleeve Housing (USH) (Al-6063 alloy), and one Mark-16B fuel assembly (either Al-6061 or Al- 6063). The USH and Mark-16B were used in SRS production reactors. Characterization of the as-received (oxy)hydroxides included scanning electron microscopy (SEM) in both plan-view and cross-section to characterize the (oxy)hydroxide layer's morphology, thickness, and structure. X-ray diffraction (XRD) was used to identify the chemical composition and distinguish between the various aluminum (oxy)hydroxides known to form under reactor and storage conditions. XRD analysis revealed both bayerite (Al(OH)3) and boehmite (AlOOH) on the surface of the MURR and USH samples, as well as bayerite, boehmite, and gibbsite (another Al(OH)3 polymorph) on the surface of the Mark-16B sample. The aluminum trihydroxides, bayerite and gibbsite, are typically associated with corrosion in low-temperature (<80 deg. C) water, while boehmite is expected to form at higher water temperature (>80 deg. C). The presence of bayerite on the USH, which is believed to have operated close to 90 deg. C, suggests that boehmite formed during in-reactor exposure was not protective against further hydroxide growth in low-temperature wet storage. Cross-section scanning electron microscopy (SEM) showed total (oxy)hydroxide layer thicknesses of ∼5- 10 μm for the MURR and ∼5-15 μm for the Mark-16B. The thickness of the USH's (oxy)hydroxide layer was indiscernible by the current mounting and imaging method, despite plan-view SEM and XRD confirming the presence of an (oxy)hydroxide layer. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

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↗

Engineering Supramolecular Hybrid Architectures with Directional Organofluorine Bonds

Understanding how chemical modifications alter the atomic‐scale organization of materials is of fundamental importance in materials engineering and the target of considerable efforts in computational prediction. Incorporating covalent and noncovalent interactions in designing crystals while “piggybacking” on the driving force of molecular self‐assembly has augmented efforts to understand the emergence of complex structures using directed synthesis. In this work, microcrystalline powders of the silver 2‐, 3‐, and 4‐fluorobenzenethiolates are prepared and their structures are resolved by small‐molecule serial femtosecond X‐ray crystallography. These three compounds enable the emergence and role of supramolecular synthons in the crystal structures of 3D metal‐organic chalcogenolates to be examined. The unique divergence in their optoelectronic, morphological, and structural behaviors is assessed. The extent of CHF interactions and their influence on the structure and the observed trends in the thermal stability of the crystals are quantified through theoretical calculations and thermogravimetric analysis.

Kotei, Patience A.↗

Microstructural evolution and intermetallic formation in Zn-3Mg (wt%) powder mixture processed by high-pressure torsion

Severe plastic deformation (SPD) techniques have been used extensively over the past 40 years for producing strong metals and alloys. High-pressure torsion (HPT) is one of the most promising SPD techniques for achieving high strength through nanoscale grain refinement and phase transformation. In this research, a mixture of pure zinc (Zn) and magnesium (Mg) powders, Zn-3Mg (wt%), was HPT-processed under a pressure of 6 GPa for 1, 5, 10, 20, and 30 turns at room temperature to achieve a high strength biodegradable material. In order to understand the effects of pre-consolidation on the resulting microstructure and hardness, HPT processing was performed on loose powders placed in the die and also on a pre-compacted powder mixture and the resulting HPT disks were characterized by X-ray diffraction, scanning electron microscopy, atom probe tomography, and Vickers microhardness. In both cases, the HPT disk microstructures contained nanoscale grains, and stable and metastable strain-induced intermetallics, but an unusual softening appeared at large shear strains. Grain size, grain morphology, and the formation of different intermetallics were analyzed to explain the unusual hardness distribution, and it was found that an inverse Hall-Petch relationship between hardness and grain size exists. It is suggested that thermally-activated phenomena such as grain boundary sliding contributed to the strain-induced softening of this nano-structured biomaterial due to its low melting point. Finally, the current results are compared with those for HPT-processed cast alloys and hybrids of the same composition.

36 MATERIALS SCIENCE↗

Syntheses of gold supported on metal oxides and their application in organic transformations

Herein, we report a general and straightforward synthesis method for gold supported on mesoporous and microporous metal oxides. Supported materials, in general, show higher crystallinity compare to unsupported systems as verified through powder X-ray diffraction (XRD). Also, through XRD, most of the metal is observed to be in its oxide form, whereas the gold support was found to be in its metallic state, which has been further confirmed from TEM. In terms of surface area, the catalyst was not found to follow any trend. Morphology wise, there are no changes observed after doping except in few cases. Combined results from XRD, X-ray fluorescence spectroscopy, Auger, and X-ray photoelectron spectroscopy suggest that gold is mainly in the bulk and very little (0.04% in case of gold doped calcium oxide) or non (in case of gold doped mixed manganese-cerium oxide) on the surface. The presence of Au (0) 4f peaks in XPS further confirms the metallic state of the gold. Oxides of indium, magnesium and calcium have been studied for the organic transformation reactions. An enhancement in activity and product selectivity was observed in the case of the gold supported catalysts. Indium serves as a great catalyst for C–C coupling and electrophilic aromatic substitution reactions and gives >99% conversion. Interestingly, 88% selectivity for C–C coupling and >99% selectivity for aromatic substitution have been achieved at 100 °C and room temperature respectively. Magnesium and calcium give Knoevenagel condensation products. At room temperature with very low catalyst loading, >99% conversion and selectivity were observed for the Knoevenagel reaction with as high as 35.30 TOF. Finally, a mechanism for the C–C coupling reaction has been proposed based on these results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Testing of spark plasma sintered porous tungsten under neon glow discharge cleaning conditions in LTX-β

This paper demonstrates that tungsten (W) based powder reconstituted Plasma Facing Components (PFCs) can be treated in situ in a fusion reactor to remove W oxide and carbon (C) contamination. Doing so should ease the challenge of using these materials in a Capillary Porous System (CPS) with lithium (Li) by enabling better wetting and less contamination of the Li by the underlying CPS. Most powder reconstituted materials including 3D printed and sintered PFCs suffer from a high surface contamination from oxides and surface C, which complicates their use with liquid Li, a primary PFC candidate. Spark plasma sintered porous W samples were fabricated to be used as a CPS with liquid Li. The samples were characterized in terms of morphology and surface chemistry. Analysis confirms a high C and oxygen (O) contamination. We present the results of exposing this type of CPS to Glow Discharge Cleaning (GDC) cycles in the Lithium Tokamak Experiment-β (LTX-β). The sample was exposed to neon (Ne) GDC in the midplane of the low-field side of LTX-β and analyzed in vacuo with Temperature Programmed Desorption (TPD) and Secondary Ion Mass Spectrometry (SIMS) to investigate the effects the Ne GDC had on the chemical composition of the sample. The combination of Ne GDC with rapid heating as done in TPD was successful in reducing the W oxides and removing the C contamination.

Capillary porous system↗