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At least 577 records · Page 32

Irradiation-induced swelling of pure chromium with 5 MeV Fe ions in the temperature range 450–650 °C

A surface coating using pure chromium has been proposed to increase the accident tolerance of Zircaloy cladding in pressurized water reactors. However, there is not much irradiation experience with Cr alloys and especially pure Cr. In the present study, pure chromium was irradiated with 5 MeV Fe ions to 50 peak dpa (displacements per atom) at temperatures of 450, 500, 550, 600 and 650 °C. Then irradiation at the peak swelling temperature of 550 °C was conducted to 50, 100, 150 peak dpa. Swelling at 50 dpa was observed over the entire temperature range studied, 450–650 °C, but appeared to be decreasing strongly at the temperature boundaries of the experiment. After an initial transient of rapid swelling, chromium was observed to swell at a rate of ~0.03–0.04%/dpa (up to 120 local dpa), which is much lower than pure Fe at 0.2%/dpa. This low swelling rate was found to be relatively insensitive to dpa rate, which varied by a factor of ~2 over the depth of data collection. Here, swelling was observed to begin quickly with an incubation period less than 10 dpa. Self-organization in the form of void ordering was observed to be developing at 50 dpa, becoming better defined with increasing dose. The void alignment direction is determined to be the $\langle$111$\rangle$ axial direction.

36 MATERIALS SCIENCE↗

Li Stripping Behavior of Anode‐Free Solid‐State Batteries Under Intermittent‐Current Discharge Conditions

Anode‐free manufacturing holds promise to enable high energy densities and lower Lithium (Li)‐metal solid‐state batteries (LMSSBs). Nevertheless, in contrast to thick Li foil (>50 µm), the stripping capacity of in situ‐formed Li (10–30 µm) is limited due to diminished creep flow, resulting in reduced accessible capacity. This study explores the correlation between stripping capacity and surface roughness of garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte. The results reveal that stripping capacity can be enhanced through the surface modification of solid electrolytes. Additionally, this study scrutinizes the stripping behavior of in situ Li under intermittent‐current discharge conditions, which are more relevant to the operational conditions of electric vehicles (EVs). It is demonstrated that, when compared to constant‐current stripping, intermittent‐current stripping effectively suppresses void formation and enhances the stripping capacity of in situ Li by 40%. It is considered that the intermittent current inhibits the accumulation of Li vacancies, thereby delaying the void formation. These findings provide valuable insights into the development of high‐performance anode‐free LMSSBs for EVs.

25 ENERGY STORAGE↗

Phase transformation mechanism in irradiation-induced superlattice formation

Atomic kinetic Monte Carlo simulations were used to model void superlattice formation under irradiation in molybdenum, driven by anisotropic diffusion of self-interstitial atoms. A change in the phase transformation mechanism from nucleation and growth to spinodal decomposition occurred with increasing dose rate, with both mechanisms leading to superlattice formation. Analysis of a rate-theory based analytical model showed that an observed change in the kinetics of vacancy accumulation, the appearance of a region of positive second derivative in the plot of average vacancy concentration versus time, was caused by the onset of spinodal instability. Further, the analytical model showed that for molybdenum and several other metals where void superlattice formation is commonly observed, the phase transformation likely occurs by nucleation and growth. However, nickel may offer the possibility of experimental observation of the transition between phase transformation mechanisms.

36 MATERIALS SCIENCE↗

Expanded Intercomparison of Nuclear Data Libraries Using Jupiter and Jupiter High-240 Experiments

There is a limited availability of plutonium experiments with sensitivity to lead in the ICSBEP (International Handbook of Evaluated Criticality Safety Benchmark Experiments) Handbook. The Jupiter and Jupiter High-240 experiments were performed at the National Criticality Experiments Research Center as a collaborative effort between Los Alamos National Laboratory and the Japan Atomic Energy Agency to assess lead void coefficients in a plutonium-lead system containing weapons- and reactor-grade plutonium, respectively. Concurrent with benchmark development, an intercomparison of calculations using different nuclear data libraries has been performed to assess the usability of the experimental data for nuclear data adjustment in a “softer-that-fast” neutron energy spectrum. Eigenvalue calculations using MCNP with the ENDF/B-VIII.0 and TENDL-2021 nuclear data libraries calculate closest to the benchmark values for Jupiter. Calculations using JENDL-5 and ENDF/B-VIII.1 match best with the Jupiter High-240 values. Lead void worth calculations using the various nuclear data libraries are all within 3σ of their respective measured values. Perturbation studies between ENDF/B-VIII.0 and ENDF/B-VIII.1 demonstrate an approximate increase in calculated eigenvalues for the Jupiter series experiments by ~240 pcm for plutonium (mostly 239 Pu) and ~120 pcm for lead accompanied by a decrease contributed by ~113 pcm for copper and ~13 pcm for stainless steel. Nuclear data sensitivities and uncertainties investigated using Whisper show slightly lower sensitivity to scatter than a lead-reflected plutonium sphere but greater sensitivity to neutron capture. The sensitivities between Jupiter and Jupiter High-240 for lead are very similar for both ENDF/B-VIII.0 and ENDF/B-VIII.1 nuclear data. These benchmarks are more sensitive to neutron capture in lead than other plutonium benchmark experiments and would be useful for both lead and 240 Pu validation. In conclusion, with the high degree of compensating effects between copper, lead, and plutonium cross sections, additional isolated Pb-Pu and Cu-Pu benchmarks would be beneficial in improving these nuclear data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Automated Manufacturing of Grid Stiffened Panels with Radically Reduced Tooling

Grid stiffened continuous fiber reinforced composite panels are an attractive option for creating lightweight structures due to the tailorability for various applications and the resulting high specific properties. However, the panel stiffeners and stiffener intersections result in high tooling complexity and correspondingly high cost of implementation. These factors have limited the impact of such structures in the composites industry. Previous research has demonstrated the ability to produce high quality, high aspect ratio beams, representative of individual grid stiffeners, using E-glass/PET comingled tow via direct digital manufacturing. Further, prior preliminary efforts have demonstrated the potential to use the same approach to manufacture grid intersections that have continuous fiber in both directions. To expand on the previous efforts in grid stiffeners produced by direct digital manufacture with radically reduced tooling requirements, this effort compares two methods of providing positioning and consolidation, nozzle vs. roller. Both processes are based on a commingled yarn feedstock. The extrusion through a nozzle has been shown to enable grid intersection control through local variations in applied consolidation and serves as the baseline process. However, this approach requires a continuous placement path to create the complete grid stiffened panel as no mechanism for cutting and restarting has been implemented. Alternatively, a newly developed placement head incorporating cut and refeed, mounted to a 6-axis robot, offers the potential of improved path placement efficiency. The two techniques are used to produce similar grid composite stiffeners to evaluate the effectiveness of producing the grid intersections. Rate of deposition of the two end effectors are compared and the quality of the associated grid stiffeners, and intersections, are determined through measurement of geometry, fiber volume fraction and void fraction.

Engineering↗

Microcomputed X-Ray Tomographic Imaging and Image Processing for Microstructural Characterization of Explosives

Microstructural characterization of composite high explosives (HEs) has become increasingly important over the last several decades in association with the development of high fidelity mesoscale modeling and an improved understanding of ignition and detonation processes. HE microstructure influences not only typical material properties (e.g., thermal, mechanical) but also reactive behavior (e.g., shock sensitivity, detonation wave shape). A detailed nondestructive 3D examination of the microstructure has generally been limited to custom-engineered samples or surrogates due to poor contrast between the composite constituents. Highly loaded (>90 wt%) HE composites such as plastic-bonded explosives (PBX) are especially difficult. Here, we present efforts to improve measurement quality by using single and dual-energy microcomputed X-ray tomography and state-of-the-art image processing techniques to study a broad set of HE materials. Some materials, such as PBX 9502, exhibit suitable contrast and resolution for an automatic segmentation of the HE from the polymer binder and the voids. Other composite HEs had varying levels of success in segmentation. Post-processing techniques that used commercially available algorithms to improve the segmentation quality of PBX 9501 as well as zero-density defects such as cracks and voids could be easily segmented for all samples. Aspects of the materials that lend themselves well to this type of measurement are discussed.

36 MATERIALS SCIENCE↗

Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries

Cation-disordered rocksalt (DRX) materials have emerged as a class of novel high-capacity cathodes for Li-ion batteries. However, commercialization of DRX cathodes will require reducing their capacity decay, which has been associated with oxygen loss during cycling. Recent studies have shown that fluorination of DRX cathodes can effectively reduce the oxygen loss and improve the cycling stability; however, the underlying atomic-scale mechanisms remain elusive. Herein, using a combination of electrochemical measurements, scanning transmission electron microscopy, and electron energy loss spectroscopy, we examine the correlation between the electrochemical properties and structural evolution in Mn-redox-based DRX cathodes, Li1.2Ti0.4-xMn0.4+xO2.0-xFx (x = 0 and 0.2). We find that fluorination strongly suppresses structural amorphization and void formation initiated from the particle surface, therefore greatly enhancing the cyclability of the cathode. We further reveal a novel rocksalt-to-spinel-like structural transformation in the DRX bulk, which surprisingly contributes to a gradual capacity increase during cycling. Our results provide important insight for the design of novel DRX cathodes with high capacity and long cycle life.

Li, Linze↗

Towards the Ultimate Strength of Medium‐Entropy Alloys Through Pulsed Lasers

The tensile strength of metals at extreme strain rates is a key predictor of their performance in ballistic and structural impact applications. An important experimental method to reach these extreme strain rates is the use of high-amplitude, short-duration pulsed lasers. The Jupiter Laser Facility at the Lawrence Livermore National Laboratory enabled probing for the first time the mechanical response of several promising High Entropy Alloys at times on the order of nanoseconds (strain rates of ∼10 7 and ∼10 9 s −1 ). The measured strength is in the range of 6 to 10 GPa, ten times the quasistatic value. The mechanisms of plastic deformation and failure were identified and quantified through analysis and molecular dynamics simulation. The reflected wave amplitudes, obtained by VISAR, were used to determine the tensile (spall) stress. The high tensile strength obtained is due to two factors: the strain-rate dependence of plastic flow and the kinetics of void nucleation, growth, and coalescence. The experimental results are compared with an analytical prediction considering both grain-interior and grain-boundary void initiation. Molecular dynamics simulations, conducted at strain rates of 10 8 and 10 9 s −1 , rationalize the experimental results. In conclusion, they provide valuable information about the process of failure evolution, and reveal that grain boundary separation plays a pivotal role in spalling.

Materials science↗

A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities

In this article, lithium metal (Li 0 ) solid-state batteries encounter implementation challenges due to dendrite formation, side reactions, and movement of the electrode–electrolyte interface in cycling. Notably, voids and cracks formed during battery fabrication/operation are hot spots for failure. Here, a self-healing, flowable yet solid electrolyte composed of mobile ceramic crystals embedded in a reconfigurable polymer network is reported. This electrolyte can auto-repair voids and cracks through a two-step self-healing process that occurs at a fast rate of 5.6 µm h -1 . A dynamical phase diagram is generated, showing the material can switch between liquid and solid forms in response to external strain rates. The flowability of the electrolyte allows it to accommodate the electrode volume change during Li 0 stripping. Simultaneously, the electrolyte maintains a solid form with high tensile strength (0.28 MPa), facilitating the regulation of mossy Li 0 deposition. The chemistries and kinetics are studied by operando synchrotron X-ray and in situ transmission electron microscopy (TEM). Solid-state NMR reveals a dual-phase ion conduction pathway and rapid Li + diffusion through the stable polymer-ceramic interphase. This designed electrolyte exhibits extended cycling life in Li 0 –Li 0 cells, reaching 12 000 h at 0.2 mA cm -2 and 5000 h at 0.5 mA cm -2 . Furthermore, owing to its high critical current density of 9 mA cm -2 , the Li 0 –LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) full cell demonstrates stable cycling at 5 mA cm -2 for 1100 cycles, retaining 88% of its capacity, even under near-zero stack pressure conditions.

25 ENERGY STORAGE↗

Radiation‐Resistant Aluminum Alloy for Space Missions in the Extreme Environment of the Solar System

Future human exploration of the solar system demands advanced materials capable of withstanding extreme environments, particularly exposure to solar energetic particle radiation. Current material selection criteria for space applications prioritize a high strength-to-weight ratio, high corrosion resistance and manufacturability, favoring age-hardenable Al-based alloys. However, conventional precipitation-hardened Al alloys suffer from irradiation-assisted dissolution of strengthening phases at doses as low as 0.2 displacements-per-atom (dpa), undermining their performance. Furthermore, these alloys develop radiation-induced defects, such as dislocation loops and voids, even at low doses. This study presents a novel ultrafine-grained (UFG) Al-based alloy, designed using the crossover alloying concept and strengthened by T-phase precipitates, featuring a chemically-complex structure with 162 atoms in its unit cell composed of Mg 32 (Zn,Al) 49 . It is showed that T-phase precipitates have exceptional radiation tolerance up to 24 dpa. Owing to the nanoscale UFG structure, dislocation loops are suppressed, and voids are only observed beyond 75 dpa. Microtensile tests up to 20 dpa confirm the preservation of mechanical performance under irradiation. The results underline the potential of this alloy as a radiation-resistant, lightweight material for future space applications. Three key strategies enable this performance: (i) stabilization of a UFG microstructure, (ii) T-phase precipitation featuring a highly negative Gibbs free energy and chemically-complex giant unit cell, and (iii) precise process control to prevent grain growth during heat treatment and irradiation.

36 MATERIALS SCIENCE↗

New Directions in Focused Ion Beam Induced Deposition for the Nanoprinting of Functional 3D Heterostructures

The focused ion beam (FIB) microscope is well established as a high-resolution machining instrument capable of site-selectively removing material down to the nanoscale. Beyond subtractive processing, however, the FIB can also add material via a technique known as focused ion beam induced deposition (FIBID). Using FIBID, the FIB can thus be employed for the direct-write of complex nanostructures. This work explores new directions in three-dimensional FIBID nanoprinting, harnessing unique features of helium and neon FIBs. In particular, the superior spatial resolution of these novel FIBs is leveraged to fabricate precise multimaterial architectures, an isotope effect is used to create satellite deposits, and dose-controlled implantation of the gaseous ions is used to engineer internal voids. In the context of voids, the fabrication of hollow nanopillars by helium-FIBID due to concurrent milling (as shown previously by others) is revisited. Insight into the chemical and structural composition of the nanostructures is obtained using advanced electron microscopy, accurately revealing buried interfaces, crystallite distributions, chemical compositions, and material transformations. Next-generation devices and technologies that could be enabled by the novel heterostructures demonstrated here are discussed, setting the stage for the potential evolution of FIBID into a versatile platform for functional nanomaterials design and fabrication.

FIBID↗

Tuned Reactivity at the Lithium Metal–Argyrodite Solid State Electrolyte Interphase

Thin intermetallic Li 2 Te–LiTe 3 bilayer (0.75 µm) derived from 2D tellurene stabilizes the solid electrolyte interphase (SEI) of lithium metal and argyrodite (LPSCl, Li 6 PS 5 Cl) solid-state electrolyte (SSE). Tellurene is loaded onto a standard battery separator and reacted with lithium through single-pass mechanical rolling or transferred directly to SSE surface by pressing. State-of-the-art electrochemical performance is achieved, e.g., symmetric cell stable for 300 cycles (1800 h) at 1 mA cm -2 and 3 mAh cm -2 (25% DOD, 60 µm foil). Cryo-stage focused ion beam (Cryo-FIB) sectioning and Raman mapping demonstrate that the Li 2 Te–LiTe 3 bilayer impedes SSE decomposition. The unmodified Li–LPSCl interphase is electrochemically unstable with a geometrically heterogeneous reduction decomposition reaction front that extends deep into the SSE. Decomposition drives voiding in Li metal due to its high flux to the reaction front, as well as voiding in the SSE due to the associated volume changes. Analysis of cycled SSE found no evidence for pristine (unreacted) lithium metal filaments/dendrites, implying failure driven by decomposition phases with sufficient electrical conductivity that span electrolyte thickness. In conclusion, DFT calculations clarify thermodynamic stability, interfacial adhesion, and electronic transport properties of interphases, while mesoscale modeling examines interrelations between reaction front heterogeneity (SEI heterogeneity), current distribution, and localized chemo-mechanical stresses.

25 ENERGY STORAGE↗

Dual material fused filament fabrication of composite core‐shell structures with improved impact resistance and interfacial adhesion

The mechanical performance of parts produced by fused filament fabrication (FFF) has been limited due to the presence of voids and poor interlayer welding. Recent advancements in FFF have enabled the fabrication of void-free objects with strong interlayer welding through the use of semicrystalline polymer shells such as high-density polyethylene (HDPE) along with a high viscosity core polymer like acrylonitrile-butadiene-styrene (ABS). Furthermore, the zero-shear viscosity (η0) of ABS is three orders of magnitude higher than HDPE making the ABS-HDPE core-shell configuration preferable. ABS holds the shape by preventing bulk flow and part bending while HDPE promotes full surface contact across the layers. Most polymers, however, are immiscible which causes a weak weld line along the core-shell interface. Herein, maleic anhydride (MAH) is grafted to the butadiene segment of the ABS core thereby compatibilizing the interface with HDPE, improving the interfacial adhesion. Attenuated total reflectance-Fourier transform infrared spectroscopy was employed to confirm successful grafting. Using a custom-made die affording the core-shell structure, the ABS-g-MAH is shown to improve the impact resistance by 253% and 16% compared to neat HDPE and ABS specimens, respectively. Additionally, a 10% increase compared to the unmodified ABS-HDPE core-shell configuration is observed.

36 MATERIALS SCIENCE↗

Rational design of a uranyl metal-organic framework for the capture and colorimetric detection of organic dyes

A new uranyl containing metal-organic framework, RPL-1: [(UO2)2(C28H18O8)] · H2O (RPL for Radiochemical Processing Laboratory), was prepared, structurally characterized, and the solid-state photoluminescence properties explored. The single crystal X-ray diffraction data reveal the structure of RPL-1 consists of two crystallographically unique three dimensional, interpenetrating nets with a 4,3-connected tbo topology. Each net contains large pores with an average width of 22.8 Å and is formed from monomeric, hexagonal bipyramidal uranyl nodes that are linked via 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (TCPB) linkers. The thermal and photophysical properties of RPL-1 were investigated using thermogravimetric analysis and absorbance, fluorescence, and lifetime spectroscopies. The material displays excellent thermal stability and temperature dependent uranyl and TCBP luminescence. The framework is stable in aqueous media and due to the large void space (constituting 76% of the unit cell by volume) can sequester organic dyes, the uptake of which induces a visible change to the color of the material.

Surbella, Robert G.↗

Gas Transport in the Insensitive High Explosive PBX 9502

Small-scale laboratory experiments were performed to analyze gas transport mechanics in PBX 9502, an insensitive high explosive (IHE) composition. Two independent investigations are reported here. First, gas permeametry and dynamic pycnometry techniques were used to measure the molecular flow (Knudsen) coefficient and the internally interconnected void fraction of pristine and thermally damaged samples in two uniaxial pressing orientations. The permeability of PBX 9502 was found to be unmeasurably low (of the same order of magnitude as PTFE) with gas transport being diffusion-dominated. Secondly, a pressure vessel experiment was developed to measure quasi-static and dynamic gas generation as the explosive was heated to self-ignition (cookoff). The gas generation results and the permeability/diffusivity findings provide evidence that PBX 9502 remains impermeable until seconds prior to self-ignition. At ignition, internal void-pressure drives macro-scale cracking and the sample becomes uniformly incorporated in the following deconsolidating deflagration. These results are discussed within the context of previous observations of pressure-dependent cookoff behavior of PBX 9502 and provide a more complete description of thermal damage evolution in this explosive composition.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Review of the Effects of Polymer Binder Properties on Microstructure and Irreversible Volume Growth of Plastic Bonded Explosives Formulations

The rational design of effective polymeric binders for the formulation of plastic-bonded explosives (PBX) is challenging due to their inherent compositional complexity. The composites comprise irregularly shaped energetic material (EM) powders coated with low weight fractions of polymer via non-equilibrium processes such as slurry coating. Defects can deleteriously affect PBX stability and performance: nano- to micrometer-scale voids can act as loci for hot spots, lowering deflagration and detonation temperatures in unpredictable ways. Furthermore, some nominally desirable polymer properties are at odds with each other: e. g. good flow characteristics are desirable for coating and adhesion, but mechanical stiffness is needed to prevent deformation and cracking of PBX under mechanical stress. Good binder adhesion is critical, but the best means to predict and measure adhesion in PBX is not obvious. Experimental methods of determining binder adhesion on model surfaces may not capture polymer structural configurations relevant to deposition during coating. Molecular dynamics-based computational models have predicted key observables in PBX formulation, suggesting that they may be powerful tools for binder selection. In this review, primarily recent (~2006 and later) literature on polymeric binders for insensitive HE (IHE) is surveyed. We focus on how binder properties influence observable PBX properties as resistance to irreversible volume growth and void formation in PBX formulations mainly (but not exclusively) featuring 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) as the EM (e. g. PBX 9502, LX-17 and others). Conclusions from these studies yield useful guidelines for choosing HE binder candidates, as well as for the general design of highly-filled polymer composite materials. Finally, studies describing challenges in PBX formulation with the newer and more energetically dense high explosive, LLM-105, will be discussed.

adhesion↗

Crystal and electronic structure of the ternary Zintl bismuthide BaLiBi

Reported is the accurate refinement of the structure of the ternary bismuthide BaLiBi, based on single-crystal X-ray diffraction data. This compound crystallizes with the ZrBeSi structure type with the space group P6 3 /mmc (no. 194), a=4.9917(6) Å, c=9.079(2) Å, V=195.92(7) Å 3 with two formula units per unit cell. In addition to being a colored ternary variant of the AlB 2 type, the crystal structure of BaLiBi can be also viewed as a “stuffed” variant of the NiAs structure, where the Bi atoms form a hexagonal close packing, the Ba atoms occupy the octahedral voids in this packing, and the Li atoms are located between adjacent tetrahedral voids on their common triangular faces. Furthermore, in the absence of direct Bi–Bi interactions, the BaLiBi crystal structure rationalized according to the notation (Ba 2+ )(Li + )(Bi 3− ), suggesting an electron-balanced composition, i. e., a Zintl phase. In line with this notation, scalar-relativistic first-principle calculations with the LMTO code reveal a semiconducting ground state, with a bandgap of about 0.6 eV. Fully relativistic electronic structure calculations predict a semimetallic ground state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Minimum feature size control in level set topology optimization via density fields

A level set topology optimization approach that uses an auxiliary density field to nucleate holes during the optimization process and achieves minimum feature size control in optimized designs is explored. The level set field determines the solid-void interface and the density field describes the distribution of a fictitious porous material using the solid isotropic material with penalization. These fields are governed by two sets of independent optimization variables which are initially coupled using a penalty for hole nucleation. The strength of the density field penalization and projection is gradually increased during the optimization process to promote a 0-1 density distribution. In addition, a second penalty regulates the evolution of the density field in the void phase. The treatment of the density field combined with the second penalty mitigate the appearance of small design features. The minimum feature size of optimized designs is controlled by the radius of the linear filter applied to the density optimization variables. The structural response is predicted by the extended finite element method, the sensitivities by the adjoint method, and the optimization variables are updated by a gradient-based optimization algorithm. Numerical examples investigate the robustness of this approach with respect to algorithmic parameters and mesh refinement. The results show the applicability of the combined density level set topology optimization approach for both optimal hole nucleation and for minimum feature size control in 2D and 3D. This comes, however, at the cost of a more complex problem formulation and additional computational cost due to an increased number of optimization variables.

42 ENGINEERING↗