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At least 145 records · Page 8

Solid Phase Gradient Alloying Method via ShAPE

Alloying has been used to confer desirable properties to various metallic systems since the bronze age. For example, Ni, Mn, and Cr are alloyed into an Fe matrix to make steel, which has improved strength and corrosion resistance (as displayed in Fig. 1). In addition to the type of alloying elements, the amount of alloying elements added into a matrix is also very critical for a material’s mechanical property, physical property, machinability, and cost. Conventionally, new alloys are discovered by combining alloy precursors and elemental constituents into a mixture and melting them together. The solidified product or ingot represents a usually non-homogeneous combination of the chemistry with a microstructure dictated by the physics of solidification. It is time and energy intensive to optimize the alloying amounts via the casting process and hence, economically not conducive to rapid alloy discovery. In addition, the cast microstructure seen in the as-cast ingot is often not the ideal, nor even desired structure for optimized performance. Cast materials often need further processing such as homogenization, annealing, and deformation work put in through rolling, forging, extruding, etc. to have favorable microstructures and properties. A faster method to discover new alloy combinations and evaluate them in their worked or processed form is needed. Recently, Laser Engineered Net Shaping was applied to fabricate gradient compositional material for alloy designing. However, the mechanical properties of this gradient alloy were poor due to the existence of impurities, oxidation and cracks that are inherent in the melt-solidification process. Because of these limitations, we propose to use a solid-phase process (ShAPE) to create bulk materials (extrudates) that vary in composition from one end of the extruded solid to the other. Various manufacturing methods for alloy design including conventional casting method, laser based combinatorial method and current solid phase gradient alloying method are displayed and compared in Fig. 2. ShAPE machine and a schematic of ShAPE process are displayed in Fig. 3. Starting material is processed by a rotating and plunging die to form an extrudate. We are proposing through this methodology to invent a new, bulk-scale combinatorial technique. With this novel technique, alloying element can be dissolved into the matrix with a continued gradient without bulk melting. Formation of inter-metallics and defects originating from melt processing can be avoided. In addition, the ShAPE process creates the mixed alloy chemistry, and meanwhile subjects the material to severe plastic strain, which induces the favorable “worked” microstructure. Products from the ShAPE process can be tested in hardness directly providing a path to rapid evaluation of mechanical properties. The ability to create graded structures using friction stir processing (FSP) has been demonstrated, however using the ShAPE process we believe will lead to much faster and higher fidelity results. When combined with high throughput screening methods of physical, mechanical and microstructural property characterization, efficiency and accuracy of alloy design can be significantly improved.

36 MATERIALS SCIENCE↗

Solvent-Cast Solid Electrolyte Membranes Based on a Charged Rigid-Rod Polymer and Ionic Liquids

Solid-state electrolytes are attractive for use in electrochemical devices because they remove the need for a flammable liquid electrolyte while contributing to the structural integrity of the device. We have recently developed a class of solid electrolytes, termed molecular ionic composites (MICs), composed of ionic liquids (ILs) and a rigid-rod polyelectrolyte, poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT). MIC materials, originally obtained through an ion-exchange process between IL and PBDT aqueous solution, possess an unprecedented combination of high ionic conductivity, high thermal stability, low flammability and widely tunable tensile storage moduli. Here we present a facile solvent casting method for preparing MIC membranes. These membranes are uniform, flexible, and tough, with tunable composition and thickness (≥ 40 μm). Unlike the previous ion-exchange method, which only allowed incorporation of hydrophilic ILs, we can now incorporate hydrophobic ILs to prepare MIC membranes for, e.g. battery electrolytes. A sodium (Na) metal symmetric cell constructed with a PBDT-Pyr 14 TFSI membrane as the solid electrolyte shows long-term stable cycling (> 500 h.) at 60 °C. Furthermore, the ability to prepare MICs using both hydrophilic and hydrophobic ILs initiates a wider range of MIC materials and broadens the array of applications accessible by MIC membranes.

25 ENERGY STORAGE↗

Development of high B s Fe–Ni-based metal amorphous nanocomposite by optimization of glass-forming ability

Thermocalc simulations identified compositions with good glass-forming ability (GFA) by locating minima in liquidus temperature, and solidification range in (Fe 70 Ni 30 ) x (B-Si-Nb) 100-x alloys with x = 82% and x = 85%, increased compared to previously developed x = 80% alloys. 3 compositions in the x = 82% system and 1 in the x = 85% system were successfully cast as amorphous magnetic ribbon. Magnetic properties of as-cast alloys showed improvements in Curie temperature and saturation induction, especially for the 85% alloy. Crystallization behavior in the 85% alloy was determined to occur as a 2-step process. Annealing studies showed (Fe 70 Ni 30 ) 82 Nb 2 Si 0 B 16 and (Fe 70 Ni 30 ) 82 Nb 3 Si 0 B 15 alloys to exhibit low coercivity and high B s with annealing. TEM results show significant crystallization in as-cast ribbon. The (Fe 70 Ni 30 ) 85 Nb 0.5 Si 0 B 14.5 alloy as-cast has small, uniformly distributed grains, allowing a useful nanocrystalline alloy to be produced as cast. Lastly, the parameter ΔT xg , the temperature range in which the material can be thermomechanically processed, was in the range of 12–23 °C.

36 MATERIALS SCIENCE↗

Evaluation of Sb-Nd and Te-Nd phases within the U-Zr fuel matrix and their interactions with HT9 alloy

Antimony (Sb) and tellurium (Te) were investigated as potential additives for U-10Zr (wt.%) metallic fuel to limit the fuel-cladding chemical interaction (FCCI) with HT-9 alloy. Neodymium (Nd) was utilized to simulate the formation of lanthanide-based solid fission products which are known to play a detrimental role in FCCI. Fuel alloys of U-Zr-Sb-Nd and U-Zr-Te-Nd were evaluated in their annealed condition and compared against their as-cast conditions. Isothermal diffusion couple experiments were performed between U-Zr-Nd, U-Zr-Sb-Nd, and U-Zr-Te-Nd against the cladding alloy HT9 to evaluate the effectiveness of the additives to stabilize Nd within the fuel alloys, as well as investigate the interaction regions that form between the different fuel alloys and HT9. Further, SbNd and Sb 3 Nd 4 , and TeNd are found to be the primary neodymium-based phases formed in the U-Zr-Sb-Nd and U-Zr-Te-Nd alloys, respectively. The zirconium-based phase, Zr 2 Sb, is also found to form within the former alloy. All phases were found to remain stable through the diffusion experiments and exhibited no interaction with HT9 constituent elements. Preferential interaction between Nd with additivities Te and Sb compared to constituting elements in HT9 was further verified based on density functional theory (DFT) calculated enthalpy of mixing.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Two-layer cathode architecture for high-energy density and high-power density solid state batteries

Solid state batteries with high-energy density and high-power density require the development of thick and energy dense cathodes. Structured cathode electrodes with a double-layer configuration were enabled using a freeze tape casting technique. A bottom dense layer was utilized to enhance the energy density whereas a top porous layer with vertically aligned walls was utilized to enhance the power density. The porous structure of the power layer was achieved by ice templating this layer on top of the densified energy layer of the cathode. This configuration was found to better utilize the active material of the cathodes and was optimized using numerical simulation and computer modeling. Cells with Li metal anode and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) at approximately 5 and 20 mg/cm 2 were cycled at 70 °C at different C-rates. Poly(ethylene oxide) (PEO) with lithium bis-trifluoromethanesulfonimide (LiTFSI) was used for the catholyte and the solid-state electrolyte. The structured cathodes exhibited more than double capacity values as well as better Coulombic efficiency compared to non-structured (single-layer) thick cathodes. In conclusion, synchrotron X-ray tomography and scanning electron microscopy were used to characterize the microstructure of the cathodes.

25 ENERGY STORAGE↗

Improved Productivity with Multilaser Rotary Powder Bed Fusion Additive Manufacturing

Laser powder bed fusion (LPBF) enables the fabrication of intricate, geometrically complex structures with a sufficiently fine surface finish for many engineering applications with a diversity of available feedstock metals. However, the production rate of LPBF systems is not well suited for mass production in comparison to traditional manufacturing methods. LPBF systems measure their deposition rates in 100's of grams per hour, while other processes measure in kilograms per hour or even in the case of processes such as forming, stamping, and casting, 100's of kilograms per hour. To be widely adopted in industry for mass production, LPBF requires a new scalable architecture that enables many orders of magnitude improvement in deposition rate, while maintaining the geometry freedom of additive manufacturing. This article explores concepts that could achieve as much as four orders of magnitude increase in the production rate through the application of (1) rotary table kinematic arrangements; (2) a dramatic number of simultaneously operating lasers; (3) reductions of laser optic size; (4) improved scanning techniques; and (5) an optimization of toroidal build plate size. To theoretically demonstrate the possibilities of production improvements, a productivity analysis is proposed for synchronous reluctance motors with relevance to the electric vehicle industry, given the recent increase in the diversity of printable soft magnetic alloys. The analysis provides insights into the impact of the architecture and process parameters necessary to optimize rotary powder bed fusion for mass production.

36 MATERIALS SCIENCE↗

Advanced Fabrication Techniques of Metal Hydrides for Science and Technology Applications (Abbreviated Final Report)

Lithium Hydride (LiH) atomic properties make it an excellent candidate for thermal energy storage, hydrogen storage, and nuclear reactor technology. High Energy Density (HED) experiments on LiH at the National Ignition Facility (NIF) can also provide critical Equation of State (EOS) and Hugoniot data. Density requirements for LiH vary per application and therefore physical and structural requirements for LiH are non-uniform. Historical production of LiH relies on casting processesthat are limited by density and grain-size control, which leads to unfavorable machinable characteristics. LiH manufacturing is further hindered due to its chemical reactivity and propensity to readily react with moisture. This work aimed at exploring advanced fabrication techniques for LiH such as 1) uniaxial powder pressing methods and 2) laser powder bed fusion (L-PBF) additive manufacturing. Uniaxial powder compaction offers advantageous tailorable mechanical and physical properties via density control, and L-PBF can produce net-shaped complex parts with unique microstructure. Uniaxial pressing proved successful in readily producing LiH with density control.

36 MATERIALS SCIENCE↗

Advanced Fabrication Techniques of Metal Hydrides for Science and Technology Applications (Full Technical Report)

Lithium Hydride (LiH) atomic properties make it an excellent candidate for thermal energy storage, hydrogen storage, and nuclear reactor technology. High Energy Density (HED) experiments on LiH at the National Ignition Facility (NIF) can also provide critical Equation of State (EOS) and Hugoniot data. Density requirements for LiH vary per application and therefore physical and structural requirements for LiH are non-uniform. Historical production of LiH relies on casting processes that are limited by density and grain-size control, which leads to unfavorable machinable characteristics. LiH manufacturing is further hindered due to its chemical reactivity and propensity to readily react with moisture. This work aimed at exploring advanced fabrication techniques for LiH such as 1) uniaxial powder pressing methods and 2) laser powder bed fusion (L-PBF) additive manufacturing. Uniaxial powder compaction offers advantageous tailorable mechanical and physical properties via density control, and L-PBF can produce net-shaped complex parts with unique microstructure. Uniaxial pressing proved successful in readily producing LiH with density control.

36 MATERIALS SCIENCE↗

Determining the effects of U/Pu ratio on subsolidus phase transitions in U-Pu-Zr metallic fuel alloys

Here, ternary alloys consisting primarily of uranium, plutonium, and zirconium (U-Pu-Zr) are among the leading candidate fuel systems considered for fast spectrum nuclear reactors. Despite historical operation data from the testing of U-Pu-Zr rods in the Experimental Breeder Reactor-II, considerable uncertainty about the evolution of phases and microstructure across the ternary composition space exists. Due to sluggish kinetics and other difficulties in handling metal actinide specimens, quantitative measurements of phase-transitions in U-Pu-Zr alloys remain sparse in scientific literature, with most investigators reporting either phase-transition temperatures or phase identification data, but not both from the same specimens. The purpose of this paper is to critically compare experimental and calculated phase transition data and correlate with the microstructure and phase characterization data of as-cast and annealed U-Pu-Zr alloys. Phase transition peaks were measured using differential scanning calorimetry in the subsolidus regions (723-948 K) of three ternary U-Pu-Zr alloys with the same zirconium concentration but various U/Pu ratios. Overlapping peaks were deconvoluted using a Frazier-Suzuki peak fitting algorithm, and the critical peak temperatures and enthalpies were calculated. In general, increasing concentrations of Pu were associated with enhanced thermal stability of the body-centered cubic γ phase upon both heating and cooling. Experimental phase transition temperatures in this study tended to agree well with the predictions of the established ternary phase diagrams and other reported phase transition temperatures in literature. Additionally, the TAF-ID thermodynamic database was used to calculate a U-Pu-40 at.% Zr pseudobinary diagram as well as ternary diagrams from 773 to 973 K. The equilibrium phase transition temperatures tended to be considerably lower than measured peak temperatures upon both heating and cooling. Recommendations for improving the quality of data in future U-Pu-Zr characterization studies are also discussed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electropolishing of a Full-Sized U-10Mo Plate

Electropolishing is used to remove material from the surface of a metal using electric potential and current. U-10Mo fuel is produced from a low enriched uranium plate alloyed with 10% molybdenum (U-10Mo). Electropolishing is being considered in two steps of the process of fabricating this U-10Mo fuel. First, it could be used as a means initially improving the surface finish of the cast plate while removing smut from the casting process from the surface prior to homogenization. Second, it could be used again after homogenization to remove oxidation and continue to improve the surface finish prior to hot rolling. The purpose of this work is to demonstrate the process on full-size ingots and optimize the process. A depleted uranium U-10Mo plate was electropolished three times: the first two times were prior to homogenization and the third after a homogenization step. The first two polishes decreased the overall roughness, as measured by laser confocal microscopy. After each polish, a smoother and shinier blue-gold surface was left on the plate. Upon homogenization, the surface had a more matte appearance and the surface roughness increased back to the pre-homogenization values obtained prior to the initial polish. After electropolishing the homogenized pieces, the changes in surface roughness increased, as measured by laser confocal microscopy. The final polishing step was not long enough to return the surface roughness to pre-homogenization conditions, implying less polishing is needed before the homogenization versus afterwards. Heat generation during the polish was addressed by circulating the electrolyte solution through an external heat exchanger; however, solubility and anodization challenges require further study.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Gapless surface electronic structure of $1T–$$\mathrm{TiSe_2}$ in the distorted phase

Here, low temperature, high resolution angle resolved photoemission experiments performed on bulk $1T–$$\mathrm{TiSe_2}$ samples display conspicuous band folding as the only prominent signature of the periodic lattice distortion. The presence of a bulk electronic gap supporting a charge density wave phase is not confirmed in light of the new data. These observations cast serious doubts on the common belief of an electronic instability as the likely origin for the observed structural transition in $\mathrm{TiSe_2}$.

36 MATERIALS SCIENCE↗

Microstructural characterization of U-20Pu-10Zr-4Sb and U-20Pu-10Zr-4Sb-4Ln

Antimony is being investigated as a potential additive to metallic fuel to control fuel-cladding chemical interactions (FCCI). The most detrimental elements involved in FCCI are fission product lanthanides, leading to brittle intermetallics and low melting eutectic phases. Previous investigations of Sb as an additive focused on U-10Zr, in wt. %, as the fuel. The current investigation expands that to include Pu in the fuel. Here, two alloys, U-20Pu-10Zr-4Sb and U-20Pu-10Zr-4Sb-4Ln (wt. %, Ln=53Nd-25Ce-16Pr-6La) have been investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to characterize the fuel as-cast microstructure and the microstructure after introduction of lanthanides. Sb reacts with Zr initially, forming Zr 2 Sb and Zr 5 Sb 3 , with as much as 20 at. % interstitial Pu present. In the presence of lanthanides, Sb forms Ln 4 Sb 3 with the lanthanides, containing ~14 at. % Pu. The Pu is substitutional for the lanthanides in the crystal lattice.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Magnetostrictive loss reduction through stress relief annealing in an FeNi-based metal amorphous nanocomposite

FeNi-based metal amorphous nanocomposite alloys are emerging soft magnetic materials with promise for high-speed motor applications. Here we demonstrate a technique to optimize magnetic properties in toroidal cores wound from strain annealed (Fe 70 Ni 30 ) 80 Nb 4 Si 2 B 14 amorphous metal ribbon (AMR). In-line strain annealing (SA) of the AMR yields a strip permeability that monotonically decreases with increasing SA tensions. After winding into toroidal cores, dramatic changes in magnetic properties are observed and determined to be of magnetostrictive origin. A procedure to re-anneal wound toroidal cores to reduce hysteresis and reverse magnetostrictive effects is developed inclusive of casting curvature effects. Here, we investigate re-annealing temperatures between 300 – 470 °C for cores produced from each SA condition. Magnetic core loss, W L , coercivity, H c , squareness ratio, K r , and permeability, µ r , are measured as a function of (stress relief) re-annealing temperature to optimally achieve W 1T,400Hz = 0.51 W/kg, H c = 2.42 A/m, K r = 0.22, and µ r = 35,300.

36 MATERIALS SCIENCE↗

Solution-Processable Polymer Donor-Small Molecule Acceptor Bulk Heterojunction Organocatalysts for Enhancing CO 2 -to-CO Photoconversion

Metal-free organic semiconductors have emerged as a kind of promising star material in photocatalysis. However, their photocatalytic efficacy is impeded by the great recombination rate of the photogenerated charge carriers. Herein, we demonstrate the devising of solution-processable organic semiconductor bulk heterojunction (BHJ) systems with varying ratios by using BP3DT and PC 61 BM as the donor (D) and acceptor (A) candidates, respectively, for enhanced selective CO production from CO 2 photoreduction. The prepared BP3DT/PC 61 BM BHJs are solution-processed on both glass substrates (GS) and molecular sieves (MS) via a drop-casting technique to form an active thin film and porous photocatalysts to catalyze CO production. All BP3DT/PC 61 BM BHJs efficiently produce CO as the primary product in the existence of trace-level TEA/H 2 O (0.5 mL). Our results show that the photocatalytic efficiency depended on the D/A w% ratios and its nanoscale phase separation morphology within the BHJ, contributing to the promotion of exciton dissociation. Additionally, the BHJ undergoes an ostensible morphological transition from large-scale phase-separation to a fine mixed homogeneous nanoscale by varying the BP3DT/PC 61 BM blend ratio from 30/70 w% to 70/30 w%, which increases the interfacial area and shortens the distance of the exciton to the D/A surface, and promotes charge carrier separation, corroborated by photo-optical and photoelectrochemical experimental results. Accordingly, the resulting BP3DT/PC 61 BM BHJ@MS with a D/A ratio of 70/30 w% achieves a CO yield of 819 μmol·g cat -1 h -1 , surpassing those of pure PC 61 BM (126 μmol·g cat -1 h -1 ) and BP3DT (72 μmol·g cat -1 h -1 ) by 6.5- to 11.3-fold and also exceeding that of metal-free linear conjugated polymer-based organocatalysts reported to date. Specifically, this is the first work to develop an organic-semiconductor-based BHJ photocatalyst, which may offer a nascent way to design more efficient organocatalysts for CO 2 reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Why Perovskite Thermal Stress is Unaffected by Thin Contact Layers

Metal halide perovskite photovoltaics have emerged as a high efficiency, low-cost alternative that can potentially rival or enhance conventional silicon technology. Despite exceptional initial power conversion efficiencies, achieving compliance with international standards and widespread adoption requires further enhancements to their operational stability. Notably, addressing mechanical strain and stress in brittle perovskites has emerged as a pivotal approach to mitigate chemical degradation and improve reliability during thermal cycling. Here, in this study, a popularized strain engineering strategy is investigated in which a high coefficient of thermal expansion (CTE) hole transport layer (i.e., PDCBT) is cast onto inorganic perovskite (CsPbI 2 Br) at 100 °C. Contrary to previously published results, the X-ray diffraction (XRD):Sin 2 ψ and substrate curvature measurement techniques show that the hole transport layer has no discernible impact on perovskite strain. The accuracy of the XRD:Sin 2 ψ method for measuring strain is highlighted in contrast to an analysis based on shifts of single XRD peaks which can be influenced by multiple artifacts. The findings in this study are in accordance with mechanics theory: thin layers are unable to induce significant strain changes in perovskite thin films as the force they apply is negligible compared to that applied by a thick and stiff substrate.

14 SOLAR ENERGY↗

Polyacrylonitrile-based electrolytes: How processing and residual solvent affect ion transport and stability

Polyacrylonitrile (PAN) is one of the alternative candidate polymer hosts to form solid polymer electrolytes (SPEs) besides the widely used poly(ethylene oxide). In this study, we systematically investigate the processing of PAN based SPEs containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, using dimethylformamide (DMF) as the solvent. The effects of PAN processing procedure including solution mixing, casting, and drying on the morphology, ion transport, solvation structure, Li and oxidative stability of PAN electrolytes are thoroughly examined. In particular, four drying conditions are investigated and the amount of residual DMF is accurately determined using infrared (IR) spectroscopy. Varying the drying conditions can lead to five orders of magnitude decrease in the ionic conductivity. As DMF content decreases, the SPE's stability again Li metal dramatically improves. The practical oxidative stability is also strongly affected by the residual DMF content, ranging from 2.5 V to 3.5 V, much lower than reported values. Finally, the role of the residual DMF solvent is elucidated. DMF content vitally influences ion solvation structure at different concentration regimes, which ultimately dictates the ion conduction mechanism and oxidative stability of PAN based SPEs. In conclusion, this thorough study lays the groundwork for future development of PAN based electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-throughput additive manufacturing and characterization of refractory high entropy alloys

Refractory High Entropy Alloys (RHEAs) and Refractory Complex Concentrated Alloys (RCCAs) are high-temperature structural alloys ideally suited for use in harsh environments. While these alloys have shown promising structural properties at high temperatures that exceed the practical limits of conventional alloys, such as Ni-based superalloys, exploration of the complex phase-space of these materials remains a significant challenge. We report on a high-throughput alloy processing and characterization methodology, leveraging laser-based metal additive manufacturing (AM) and mechanical testing techniques, to enable rapid exploration of RHEAs/RCCAs. We utilized in situ alloying and compositional grading, unique to AM processing, to rapidly-produce RHEAs/RCCAs using readily available and inexpensive commercial elemental powders. We demonstrate this approach with the MoNbTaW alloy system, as a model material known for having exceptionally high strength at elevated temperature when processed using conventional methods (e.g., casting). Microstructure analysis, chemical composition, and strain rate dependent hardness of AM-processed material are presented and discussed in the context of understanding the structure-properties relationships of RHEAs/RCCAs.

36 MATERIALS SCIENCE↗

Bipolar Membranes With Controlled, Microscale 3D Junctions Enhance the Rates of Water Dissociation and Formation

A soft lithographic method is developed for making bipolar membranes (BPMs) with catalytic junctions formed from arrays of vertically oriented microscale cylinders. The membranes are cast from reusable polydimethylsiloxane (PDMS) molds made from silicon masters, which are fabricated on 2" to 4" wafer scales by nanosphere lithography. High-aspect-ratio junctions are made on a length scale similar to the thickness of optimized catalyst layers for water dissociation, creating a platform for probing the dual effects of catalysis and local electric field at the microscale BPM junction. Optimized polymer materials and nanoscale metal oxide catalysts are used in this study. 3D BPMs are tested under reverse and forward bias conditions, exhibiting superior performance relative to their 2D counterparts. Under forward bias in H 2- O 2 fuel cells, 3D BPMs achieve a current density of 1500 mA cm –2 , ≈7 times higher than 2D membranes made from the same materials.

25 ENERGY STORAGE↗