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At least 19 records

Transformational Molecular Layer Deposition Tailor-Made Size-Sieving Sorbents for Post-Combustion CO 2 Capture

This report summarizes the carbon capture research and development conducted by The State University of New York at Buffalo (UB), University of South Carolina (USC), GTI Energy (GTI), and Rensselaer Polytechnic Institute (RPI) for U.S. Department of Energy (DOE) project DE-FE0031730 titled “Transformational Molecular Layer Deposition Tailor-made Size-Sieving Sorbents for Post-Combustion CO 2 capture.” The objective of this project was to develop a transformational molecular layer deposition (MLD) tailor-made size-sieving sorbent integrated with a pressure swing adsorption (PSA) cycle schedule that can be installed in new or retrofitted into existing pulverized coal (PC) power plants for CO 2 capture with a cost of electricity at least 30% lower than a supercritical PC power with CO 2 capture, or approximately $\$$30 per tonne of CO 2 captured, and with it being ready for demonstration by 2030.

20 FOSSIL-FUELED POWER PLANTS↗

Finely tuning the microporosity in phosphoric acid doped triptycene-containing polybenzimidazole membranes for highly permselective helium and hydrogen recovery

High-performance polymer membranes with well-defined microporosity and size-sieving ability are especially attractive for helium and hydrogen recovery. Here, in this study, we report novel macromolecular engineering of polybenzimidazole (PBI) membranes that integrate hierarchical triptycene units for high permeability and polyprotic acid doping for size sieving via controllable manipulation of microporous architecture. The triptycene moieties disrupt chain packing and introduce additional configurational free volume, leading to significantly boosted He and H 2 permeabilities compared to previously reported PBI membranes. The acid doping resulted in crosslinked PBI membranes via hydrogen bonding and proton transfer with dramatically enhanced gas selectivities. Via adjusting the H 3 PO 4 -doping level, triptycene-based polybenzimidazole (TPBI) composite membranes (TPBI-(H 3 PO 4 ) x ) exhibit the highest gas selectivities for He enrichment (i.e., α(He/CH 4 ) = 7052 ± 156) and H 2 purification (i.e., α(H 2 /CH 4 ) = 5128 ± 110) among existing polymeric gas separation membranes. Additionally, under mixed-gas conditions at 150 °C, the TPBI-(H 3 PO 4 ) 0.98 membrane displays a H 2 permeability of 46.7 Barrer and a H 2 /CO 2 selectivity of 16, far beyond the Robeson's 2008 upper bound for H 2 /CO 2 separation. The facile and diverse tunability and excellent gas separation performance make TPBI-(H 3 PO 4 ) x membranes highly attractive for helium and hydrogen separation.

42 ENGINEERING↗

Investigation of competitive sorption and plasticization of hyperaged CANAL ladder polymers for acid gas purification

Identifying membrane materials that have exceptional separation performance and stability to complex CO 2 -containing mixtures is a pressing topic in separation science. In this work, the membrane separation performance for a recently discovered class of contorted polymers synthesized via catalytic arene-norbornene annulation (CANAL) polymerization is presented. These CANAL polymers achieve high CO 2 /CH 4 selectivity of 68 after physical aging (up to ∼1 year), which significantly augments the size-sieving capabilities of the membranes. Binary CO 2 /CH 4 and ternary H 2 S/CO 2 /CH 4 testing result in a 41 % and 50 % enhancement in selectivities, respectively, for hyperaged (∼1 year) contorted CANAL polymers, highlighting their size-sieving capabilities. The remarkably high CO 2 /CH 4 mixed-gas and combined acid gas (CAG, (CO 2 +H 2 S)/CH 4 ) selectivities of 88 and 95, respectively, for CANAL-Me-S 5 F in particular surpass both the 2018 CO 2 /CH 4 mixed-gas and CAG upper bounds. Performance stability was also investigated for high concentrations of CO 2 , revealing a reduction in CO 2 /CH 4 mixed-gas selectivity without compromising CO 2 permeability, suggesting strong sorption of CO 2 but minimal plasticization effects for short testing periods. In addition, time-dependent plasticization shows negligible effects on CO 2 /CH 4 mixed-gas selectivity despite an increase in CO 2 permeability when exposed to high concentrations of plasticizing CO 2 over an extended period of 170 h. This study provides valuable insights into hyperaged CANAL polymers and their performance in practical industrial processes.

03 NATURAL GAS↗

An experiment-informed discrete element modelling study of knife milling for flexural biomass feedstocks

A discrete element method (DEM) based approach is used to study the relationships between material attributes (MAs), processing parameters (PPs), and quality attributes (QAs) for the knife milling of maize stalks. An approximate DEM shape model was conceptualized based on real maize stalks and calibrated based on experimental bending test data for flexural properties (elastic bending stiffness, elastic bending angle limit, elastoplastic ratio, etc.). DEM simulations of maize stalk comminution in a Jordan Reduction Solutions (“JRS”) knife mill were performed to investigate the relationships between the MAs (maize stalk size and breakage stress limit), PPs (impeller rotational speed), and QAs (mass throughput and output particle size distribution (PSD)). The DEM results suggest that stalk length has little influence on mass throughput and PSD, whilst stalks with larger cross sections tend to generate larger sizes of milled particles given the same breakage stress limit. Both the DEM and experimental results show that faster impeller rotation (or higher power) does not necessarily generate higher throughput or smaller output PSD, especially for maize stalks of higher breakage stress limit. The correlations between these MAs, PPs and QAs are found highly stochastic, though breakage stress limit dictates mass throughput, regardless of stalk size. The DEM-predicted output particle size tended to match the experimental data with coarse PSDs based on sieve size but showed weakened fidelity with finer material, indicating the potential for further model improvement.

09 BIOMASS FUELS↗

Ultradynamic Isoreticularly Expanded Porous Organic Crystals

Porous organic materials showcasing large framework dynamics present new paths for adsorption and separation with enhanced capacity and selectivity beyond the size-sieving limits, which is attributed to their guest-responsive sorption behaviors. Porous hydrogen-bonded crosslinked organic frameworks (H C OFs) are attractive for their remarkable ability to undergo guest-triggered expansion and contraction facilitated by their flexible covalent crosslinkages. However, the voids of H C OFs remain limited, which restrains the extent of the framework dynamics. Here in this work, we synthesized a series of H C OFs characterized by unprecedented size expansion capabilities induced by solvents. These H C OFs were constructed by isoreticularly co-crystallizing two complementary sets of hydrogen bonding building blocks to generate porous molecular crystals, which were crosslinked through thiol–ene/yne single-crystal-to-single-crystal transformations. The generated H C OFs exhibit enhanced chemical durability, high crystallinity, and extraordinary framework dynamics. For instance, H C OF-104 crystals featuring a pore diameter of 13.6 Å expanded in DMF to 300 ± 10% of their original lengths within just 1 min. This expansion allows the HCOFs to adsorb guest molecules that are significantly larger than the pore sizes of their crystalline states. Through methanol-induced contraction, these large guests were encapsulated in the fast-contracted H C OFs. These advancements in porous framework dynamics pave the way for new methods of encapsulating guests for targeted delivery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomically Fine-Tuning Organic–Inorganic Carbon Molecular Sieve Membranes for Hydrogen Production

Polymeric membranes with great processability are attractive for the H 2 /CO 2 separation required for hydrogen production from renewable biomass with carbon capture for utilization and sequestration. However, it remains elusive to engineer polymer architectures to obtain desired sub-3.3 Å ultramicropores to efficiently sieve H 2 from CO 2 . Herein, we demonstrate a scalable way of carbonizing polybenzimidazole (PBI) at low temperatures, followed by vapor phase infiltration (VPI) to atomically narrow ultramicropores throughout the films, forming hybrid organic–inorganic carbon molecular sieves (CMSs). One VPI cycle (100 s) for the PBI carbonized at 500 °C remarkably increases H 2 /CO 2 selectivity from 9.6 to 83 at 100 °C, surpassing Robeson’s upper bound. The CMS demonstrates a stable H 2 /CO 2 separation performance when challenged with simulated syngas streams and can be fabricated into thin-film composite membranes, outperforming state-of-the-art membranes. Finally, the scalable approach can be ubiquitous to molecularly fine-tune ultramicropores of leading polymeric membranes to further improve their size-sieving ability and thus separation efficiency.

36 MATERIALS SCIENCE↗

Smart Preprocessing & Robust Integration Emulator

To achieve the desired particle size of biomass feedstocks during preprocessing for trouble-free handling and conversion to produce biofuels and bioproducts, the raw materials must undergo a crucial milling process. The particle size of biomass plays a critical role in subsequent biofuel manufacturing, where a larger area-to-volume ratio facilitates efficient synthesis while balancing the impact of moisture on biomass storage. To optimize biofuel production efficiency and overcome these challenges, it is imperative to accurately predict the particle size distribution (PSD) of the biomass in the design of efficient preprocessing systems. The population balance model (PBM), upon empirical calibration and validation, can provide rapid prediction of post-milling PSD of granular biomass. However, PSD has limitations related to mass conservation and the absence of moisture considerations. To overcome these drawbacks, a deep learning model called the enhanced deep neural operator (DNO+) is implemented in the code. This model not only retains the capabilities of the PBM in handling complex mapping functions but also incorporates additional factors influencing the system. By considering various experimental conditions such as sieve size and moisture content, the trained DNO+ model can effectively predict the PSD after milling for any given feed PSD. To further reduce the reliance on experimental data, the PBM is integrated into the DNO+ model, resulting in a physics-informed DNO+ (PIDNO+). The PIDNO+ model addresses the non-conservation of quality exhibited by the PBM while inheriting the advantages of the DNO+ model in considering multiple influencing factors. Moreover, the PIDNO+ model significantly reduces the amount of data required for model training. Both deep learning models, i.e., DNO+ and PIDNO+, are excellent in predictive performance, offering swift and accurate machine learning-based predictions. The use of this code that contains these models will assist in guiding the proper milling equipment selection and operational conditions to achieve the desired biomass particle sizes, ensuring the efficiency of subsequent biofuel and bioproduct production processes.

Xia, Yidong [Idaho National Laboratory (INL), Idah↗

Ultra-selective CANAL Polymers for Hydrogen-based Membrane Separations after Long-Term Aging

Hydrogen is a critically important molecule in the chemicals and energy industries, driving the need for efficient purification technologies such as membrane-based separations. However, polymer membranes often suffer from physical aging, leading to decreased gas permeability over time. This study leverages the unique aging behavior of contorted microporous polymers, synthesized via catalytic arene-norbornene annulation (CANAL) polymerization, to enhance molecular sieving for H 2 separations. While prior studies demonstrated a 1000% increase in H 2 /CH 4 selectivity with minimal permeability loss over 150 days, we extend this investigation to hyperaged (∼1 year) CANAL polymers and evaluate their performance under various conditions of industrial relevance. We report a remarkable 6100% increase in H 2 /CH 4 selectivity and a 2400% improvement in H 2 /N 2 selectivity, with only a 55% decline in H 2 permeability. These membranes exhibit excellent long-term stability in binary and ternary gas mixtures and at elevated temperatures. Additionally, extended aging enhances H 2 /CO 2 selectivity beyond the 2008 upper bound due to improved size-sieving. High-temperature permeation experiments and grand canonical Monte Carlo simulations reveal that H 2 permeability increases from 570 to 3500 barrer as the temperature rises from 35 °C to 190 °C, while H 2 /CO 2 selectivity declines from 14 to 3 due to the higher diffusion activation energy of CO 2 . Despite this tradeoff, hyperaged CANAL membranes maintain performance beyond the 200 °C upper bound, having selectivity–permeability performance comparable to many state-of-the-art membranes for H 2 /CO 2 separations. As a result, this study highlights the robustness and industrial viability of ultra-selective CANAL polymers for hydrogen purification, contributing to advancements in clean energy and sustainable separation technologies.

36 MATERIALS SCIENCE↗

Molecular Interlocking Multidimensional Modulations of Cathode‐Electrolyte Interface for Constructing High Energy Density Quasi‐Solid‐State Batteries

Gel polymers are regarded as a promising candidate electrolyte for lithium-metal quasi-solid-state batteries, primarily due to their high ionic conductivity and solid-liquid synergistic properties. However, challenges such as interfacial side reactions, limitations in Li + transport caused by interfacial issues, and leaching of transition metals from the cathode have yet to be effectively solved. Herein, a novel gel electrolyte modulation strategy based on electrostatic filler assembly is proposed to address the issues of ineffective capacity utilization and inadequate cycling stability of high-energy-density cathode materials in solid-state lithium-ion batteries. It constructs a 3D interpenetrating charge-bridge network that effectively tackles the phase-separation challenge between fillers and electrolytes at the molecular level. Meanwhile, the molecular interlocking structure effectively inhibits the electrolyte erosion. More critically, it optimizes and stabilizes the cathode-electrolyte interface film, which facilitates the conduction of Li + -ions through a size-sieving mechanism. Consequently, this strategy enables effective adaptation across diverse high-energy-density cathode materials with satisfactory capacity performance (170.4 mAh g −1 at 4.5 V/1 C for LiNi 0.6 Co 0.2 Mn 0.2 O 2 and 194.0 mAh g −1 at 4.3 V/1 C for LiNi 0.9 Co 0.08 Mn 0.02 O 2 ). In conclusion, this investigation offers a straightforward and effective reference for addressing the critical challenges of ionic transport and interface stabilization in the design of gel electrolytes.

cathode-electrolyte interface↗

Nanofiltration Membranes for Li + /Mg 2+ Separation: Materials and Mechanisms

Nanofiltration (NF) membranes have garnered significant interest for Li + /Mg 2+ separation, a crucial step in lithium extraction from brines. The state-of-the-art commercial LiNE-XD membrane exhibits a Li + /Mg 2+ separation factor (SF Li/Mg ) of 42 at pH 3.3, due to the positive charges on the membrane surface and its strong size-sieving ability. Membranes with higher separation factors at a broad pH range are being pursued to improve separation efficiency. This work aims to provide a timely and comprehensive assessment of advanced NF membranes with superior Li + /Mg 2+ separation properties, as well as their structure and property relationships for designing next-generation membranes. We describe transport mechanisms for ions in NF membranes and discuss governing parameters and models employed to quantify the Li + /Mg 2+ separation. High-performance membrane materials are exhaustively introduced, including commercial and modified polyamides, two-dimensional materials, metal–organic frameworks, crown ethers, and their blends. Finally, we critically compare these membranes in an upper bound plot and highlight the opportunities and challenges of NF membranes for practical Li + /Mg 2+ separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Few-cycle atomic layer deposition to nanoengineer polybenzimidazole for H 2 /CO 2 separation

Atomic layer deposition (ALD) creates uniform sub-nanometer films on a variety of surfaces and nanopore walls and has been used to modify polymers to improve surface affinity towards specific molecules, solvent resistance, and barrier properties to gases and vapors. Here, for the first time, we demonstrate that few-cycle ALD can be used to engineer functional polymers at a sub-nanometer scale to improve both molecular size-sieving ability and counterintuitively, gas permeability. Particularly, 1-cycle ALD treatment of polybenzimidazole (PBI) by sequential exposure to trimethylaluminum (TMA) and water vapor remarkably increases H 2 permeability by 120% - 270% and H 2 /CO 2 selectivity by 30% at 35–200 °C. The ALD not only deposits an AlOx layer on the surface but also enables the TMA to infiltrate and react with the bulk PBI to form an AlO x network, disrupting polymer chain packing and increasing chain rigidity. The membrane exhibits excellent stability when challenged with simulated syngas, overcoming the permeability/selectivity tradeoff for H 2 /CO 2 separation. In conclusion, this study showcases a facile and scalable way of engineering polymeric membranes at a sub-nanometer level to improve molecular separation performance.

36 MATERIALS SCIENCE↗

Hydration size-dependent transport of ions across nanoporous graphene membranes

Nanoporous atomically-thin membranes are promising candidates for metal ion separations due to their chemical stability and high permeance and selectivity, but experimental evidence of the mechanisms responsible for ion-ion selectivity is sparse. Here, in this work, we measured the simultaneous diffusion of a dilute mixture of ten different Group I, Group II, and rare earth cations in a salt background across nanoporous graphene (NPG) membranes with sub-nanometer pores. The membranes exhibited ion-ion selectivity, including between similarly-charged ions. Cation transport was governed primarily by the hydrated ion size that was consistent with continuum models of ion diffusion, with additional influence of the ionic charge. Selectivity enhancement was achieved by modifying ion sizes using an ion-selective complexing agent. Our study provides evidence of the importance of size-sieving and electrostatic mechanisms governing ion transport across NPG, and allows for quantitative prediction of transport rates to guide future development of ion-selective atomically-thin membranes.

36 MATERIALS SCIENCE↗

Polymer-Derived Amorphous Aluminosilicate Nanomembranes for H 2 Purification

Aluminosilicate zeolite membranes with robust microporous crystalline structures are attractive for the molecular separation of H 2 from light gases, but their large-scale fabrication is complicated and costly, hindering their practical applications. Herein, we present polymer-derived amorphous aluminosilicate nanomembranes that combine the exceptional processability of polymers with the superior gas separation properties of aluminosilicates. Specifically, thin-film composite membranes comprising 150 nm polydimethylsiloxane were first treated with oxygen plasma to generate 10 nm polyorganosilica (POSi) on the surface, which were then subjected to few-cycle atomic layer deposition (ALD) using trimethylaluminum as a metal precursor and water vapor as a coreactant. This scalable two-step process yields few-nanometer amorphous aluminosilicates with strong size-sieving ability. For example, three-cycle ALD treatment of POSi increases H 2 /CO 2 selectivity from 39 to 200 and H 2 /CH 4 selectivity from 190 to 500, while decreasing H 2 permeance from 990 to 210 GPU at 150 °C, superior to the state-of-the-art membranes. In conclusion, rapid and scalable manufacturing of amorphous aluminosilicate nanolayers can also be of interest for catalysis and adsorption applications.

36 MATERIALS SCIENCE↗

Bioinspired Macrocyclic Molecule Supported Two‐Dimensional Lamellar Membrane with Robust Interlayer Structure for High‐Efficiency Nanofiltration

Abstract 2D lamellar membranes (2DLMs) are used for efficient desalination and nanofiltration. However, weak interactions between adjacent stacked nanosheets result in susceptibility to swelling that limits practical applicability. Inspired by the super adhesion of multi‐point suction cups on octopus tentacles, a 2DLM is constructed from Ti 3 C 2 T x MXene supported by the macrocyclic “multi‐point” molecule cucurbit[5]uril (CB5) and demonstrated for nanofiltration of methyl blue (MB) and enrichment of uranyl carbonate. Experimental results and density functional theory calculations indicate that CB5 rivets to the surface of the nanoflakes through strong stable interactions between its multiple binding sites and surface hydroxyl functional groups on MXene nanosheets. This novel 2DLM exhibits excellent nanofiltration performance (69 L m −2 h −1 bar −1 permeance with 93.6% rejection for MB) and can be recycled at least 30 times without significant degradation. The 2DLM exhibits excellent swelling resistance at high salinity, with a demonstration of selective enrichment of uranyl carbonate from artificial water and natural seawater. The results provide a new strategy for constructing highly stable 2DLMs with interlayer spacing controllable from sub‐nano to nanometer scales, for size‐selective sieving of molecules and ions, high‐efficiency nanofiltration, and other applications.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Effect of particle size on the capture of uranium oxide colloidal particles from aqueous suspensions via high-gradient magnetic filtration

The effectiveness of High Gradient Magnetic Filtration (HGMF) in capturing uranium oxide particles from suspensions was investigated in this study. Two sets of experiments were performed to evaluate the importance of size on the capture of uranium oxide particles. The first considered two batches sieved into size bins of< 5, 5–10, 10–15, and 15–20 µm, while the second was performed using two suspensions with diameters smaller than 1.0 µm and between 1.0 and 1.5 µm. Iron oxide experiments, with particles between 0.3 and 0.8 µm, were performed for calibration purposes. In all experiments, a surfactant (Triton-X100 or sodium dodecyl sulfate) was used to prevent particle aggregation and limit the influence of non-magnetic capture mechanisms. A magnetic field of approximately 1.1 Tesla was generated using a water cooled electromagnet. HGMF was performed using tubular filters packed with ferromagnetic stainless-steel wool. Of the initial four uranium oxide particle sizes, magnetic capture was only observed for particles with a diameter of less than 5 µm, while larger particles experienced no magnetic and minimal total capture. For particles with diameters smaller than 1.0 µm and between 1.0 and 1.5 µm, capture efficiencies increased by 39 ± 9% and 34 ± 6% respectively, solely due to the magnetic field. Although the magnetic force is proportional to particle diameter, the capture efficiency decreased as diameter increased. So these results suggest that Brownian diffusion, which is influential for micron sized particles and increases with decreasing particle size, is acting in conjunction with the magnetic force to influence the efficacy of HGMF for uranium oxide. This important finding underscores the effectiveness of Brownian diffusion in increasing the rate of collision between particles and collector fibers. A stochastic trajectory model was developed to incorporate the influence of Brownian motion on particle behavior and filter removal efficiency. Modeling results are discussed and compared for uranium and iron oxide particles.

42 ENGINEERING↗

Toward a circular economy: zero-waste manufacturing of carbon fiber-reinforced thermoplastic composites

Fiber-reinforced composites are becoming ubiquitous as a way of lightweighting in the wind, aerospace, and automotive industries, but current recycling technologies fall short of a circular economy. In this work, fiber-reinforced composites made of recycled carbon fiber and polyphenylene sulfide were recycled and remanufactured using common processing technologies such as compression and injection molding. An industrially viable size-exclusive sieving technique was used to retain fiber length and reduce variability in the mechanical properties of the remanufactured composites. Fiber length reduction alone could not explain the strength reductions apparent in the composites, which we propose are due to microstructural inhomogeneity as defined by poor dispersion of the fibers. Future recycling efforts must focus on fiber length retention and good dispersion to make composite remanufacturing a viable path toward a circular economy.

36 MATERIALS SCIENCE↗

Scalable Bottom-Up Synthesis of Nanoporous Hexagonal Boron Nitride ( h -BN) for Large-Area Atomically Thin Ceramic Membranes

Nanopores embedded within monolayer hexagonal boron nitride (h-BN) offer possibilities of creating atomically thin ceramic membranes with unique combinations of high permeance (atomic thinness), high selectivity (via molecular sieving), increased thermal stability, and superior chemical resistance. However, fabricating size-selective nanopores in monolayer h-BN via scalable top-down processes remains nontrivial due to its chemical inertness, and characterizing nanopore size distribution over a large area remains extremely challenging. Here, we demonstrate a facile and scalable approach of exploiting the chemical vapor deposition (CVD) process temperature to enable direct incorporation of subnanometer/nanoscale pores into the monolayer h-BN lattice, in combination with manufacturing compatible polymer casting to fabricate centimeter-scale nanoporous atomically thin ceramic membranes. We leverage diffusive transport of analytes including size-selective Ficoll sieving to characterize subnanometer-scale and nanoscale defects that manifest as pores in centimeter-scale h-BN membranes, overcoming previous limitations in large-area characterization of nanoscale defects in h-BN. Our approach opens a new frontier to advance atomically thin membranes to 2D ceramic materials, such as h-BN via facile and direct formation of nanopores, for size-selective separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reducing waste of the hydride-dehydride process for U-6 wt% Nb spherical powders through lower impact and targeted milling

The breakdown of solid metal into powder during the hydride-dehydride process is commercially important for the formation of titanium and other metal powders. Typically, the milling of the brittle hydride powder occurs in a ball mill, where milling media impacts powder particles to break them down. The milling media can impact particles that are larger than desired, as desired, or smaller than desired, indiscriminately making all particles smaller. In this work, we investigate how to minimize waste powder production during milling using two different milling methods, planetary ball milling and milling in a sieve shaker (sieve-milling). Both processes yielded similar amounts of 20–75 μm diameter powder (the target size range); however, sieve-milling generated a significantly smaller amount of undersized waste powder. The powders were characterized by X-ray diffraction, SEM/STEM, and magnetic susceptibility. Several differences between ball milling and sieve-milling processes are discussed. We then conclude that the decreased yield of undersized powder in sieve-milling was due to a combination of lower impact energy in sieve-milling, unreacted metallic cores in the hydride flakes, and the ability to mill target particle sizes during sieve-milling. While these results are from the milling of brittle hydride powder, similar methods may be applicable to other brittle powders, including ceramics or salts.

Chemistry↗