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At least 235 records · Page 13

Green synthesis of cellulose formate and its efficient conversion into 5-hydroxymethylfurfural

5-hydroxymethylfurfural (HMF) production from cellulose is a hot topic, while the rigidity of cellulose limits its efficient conversion into HMF. Cellulose formate has exhibited the great potential for HMF production but it’s synthesis via direct formylation of cellulose in formic acid is difficult. We reported a green synthetic route of cellulose formate and its efficient conversion into HMF. Ball milled cellulose formate (BCF) was synthesized via ball milling followed by formylation in formic acid at 80 °C for 0.5 h. The structure of BCF was thoroughly characterized and BCF was subsequently converted to HMF catalyzed by AlCl3 and HCl in dimethyl sulfoxide (DMSO)-H 2 O media. Results showed that ball milling of cellulose for 1–1.5 h efficiently deconstructed its crystallinity and degree of polymerization, boosting its further formylation and catalytic conversion. An overall 66.9% HMF yield from cellulose was achieved at 150 °C for 20 min using BCF derived from cellulose ball milled for 1.5 h as the substrate. BCF exhibits high reactivity toward HMF due to its excellent solubility and accessibility in DMSO-H 2 O media, and the release of formic acid in reaction further facilitates HMF production. BCF synthesized with different ball milling times shows different degrees of substitution of formyl groups, which could serve as an indicator and regulate the HMF production. The green synthesis of cellulose formate creates an efficient pathway for HMF production.

5-hydroxymethylfurfural↗

Restoring freshwater habitat mosaics to promote resilience of vulnerable salmon populations

Phenotypic diversity and abundance drive salmon resilience in the face of increasing environmental variability. But what happens when human activities fundamentally alter the habitat complexity that drives this diversity? And how can we restore habitats to recover both diversity and abundance to support salmon persistence in a warming climate? Here, we looked at the impact of a large watershed restoration effort on the abundance and climate resilience of the three remaining core natural spring-run Chinook Salmon populations in the California Central Valley (Butte, Mill, and Deer Creek). Butte Creek fish, which have floodplain access, had higher overall productivity and faster juvenile growth compared with Mill and Deer Creek populations, and the proportion of floodplain inundation was positively correlated with Butte Creek adult abundance two years later. While Butte Creek exhibited significant increases in abundance post-restoration (~2000%), it generally exhibited lower phenotypic diversity and only a marginal increase in population stability after restoration based on the coefficient of variation (CV). In particular, Butte Creek salmon tended to exhibit larger drops in escapement following dry years (e.g., return years 2010, 2017) compared with Mill and Deer Creek populations, presumably due to limited inundation of its downstream floodplain. The late-migrating juvenile strategy (i.e., yearling), which disproportionately supported Mill and Deer Creek populations during droughts, was uncommon among Butte Creek adults (averaging 60% of returns for Mill and Deer Creek vs. 0.3% for Butte Creek). Increased spring-run stock complex stability was found, post-restoration, when combining the three spring-run populations (i.e., lower aggregate CV). However, among-river pairwise correlations also suggested increased synchronization in population abundances post-restoration, potentially due to increasing frequency and severity of extreme climatic events (e.g., droughts and ocean warming). This study underscores the importance of restoring a connected mosaic of aquatic habitats across modified landscapes, such as cold water refugia and floodplains, to preserve multiple (across-population) life history pathways for increasing salmon stock complex stability and abundance. These landscape-scale process-based habitat restoration efforts are likely to be crucial for the successful long-term recovery of vulnerable species in a rapidly changing climate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Novel processing route for design and manufacturing of metal toughened nanoceramics: Al–Al 2 O 3 nanocermets

Monolithic alumina is a highly brittle ceramic with a very low fracture toughness, making it an unreliable material for mechanical and structural applications. Ceramic-metal composites (cermets) are the subject of intensive interest to obtain materials which can address the intrinsic brittleness of ceramics without compromising their high strength and light weight. In the present investigation, aluminium-alumina (Al–Al 2 O 3 ) nanocermets were developed. The nanocermets possessed the toughness of Al phase and the strength of reinforced nano Al 2 O 3 particles. Here, the nanocermets green bodies were prepared such that upon sintering each adjacent Al 2 O 3 grain was conformally coated with a continuous Al film. Mechanical milling via a combination of cryo-milling and ball-milling was used to prepare Al–Al 2 O 3 nano-powder mixture. Spark plasma sintering was used to consolidate the green nanocermets. Results show that specimens prepared from 35 h milled powders exhibited superior mechanical properties as compared to other nanocermets, with an improvement in microhardness, elastic modulus, compressive strength, and flexural strength by 88%, 78%, 69% and 40% with respect to sintered pure Al. The indentation toughness of 35 h milled nanocermet showed an increment of 12.5% with respect to sintered pure Al 2 O 3 . Characterization techniques such as XRD, SEM, HR-TEM, X-ray tomography were employed to investigate the phase evolution and structural morphology, while FEM simulations were performed for understanding the crack propagation mechanisms in nanocermets.

36 MATERIALS SCIENCE↗

Formation of uranium nitride nanoparticles via mechanical alloying of uranium-molybdenum alloy fuels in gaseous nitrogen

Uranium-molybdenum (U-Mo) alloys show promise as a nuclear fuel system due to their high thermal conductivity and fuel loading capability. However, U-Mo systems are susceptible to irradiation induced swelling ultimately affecting the cladding via mechanical and chemical interactions. To address these shortcomings, this research investigated the formation of uranium mononitride (UN) nanoparticles within a 90 wt% U/10 wt% Mo (U-10Mo) matrix to act as a prospective defect sink for fission products at nanometric hetero-interfaces. To promote the formation of UN, U-10Mo powders were mechanically alloyed under a high purity nitrogen atmosphere. Variations of the milling process investigated included media size, duration of milling, and number of times the milling jar was re-aerated with nitrogen gas. Characterization of the fuel microstructure was completed using light element analysis, X-ray diffraction, scanning and transmission-electron microscopy, electron energy loss spectroscopy, and atom probe tomography. UN nanoparticles measuring 1–5 nm in radius were observed in the U-Mo matrix as early as 1 h into the mechanical alloying process. Milling time in excess of 10 h was found to lead to deleterious effects induced by the stainless-steel milling media.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

AGR-5/6/7 Fuel Fabrication Report

The U.S. Department of Energy Office of Nuclear Energy (DOE NE) and the Idaho National Laboratory (INL) Advanced Reactor Technologies (ART) Advanced Gas Reactor (AGR) Fuel Development and Qualification program (referred to as AGR Fuel program hereafter) are pursuing qualification of tristructural isotropic (TRISO) coated particle fuel for use in high temperature gas cooled reactors (HTGRs). The AGR Fuel program was established to provide a fuel qualification data set in support of the licensing and operation of an HTGR. BWX Technologies Nuclear Operations Group (BWXT-NOG) was subcontracted to fabricate the fuel for the AGR program. Several investments and innovations were realized in preparation to fabricate fuel for the AGR-5/6/7 irradiation experiments that brought fuel fabrication fully out of the laboratory and into engineering-scale operations. These included: • Increased the kernel fabrication line capacity and uniformity • Upgraded ancillary support equipment and processes for the tristructural isotropic (TRISO) coating furnace • Demonstrated efficient production of the matrix precursor powder by dry jet milling of co mingled components • Demonstrated an engineering-scale method for quick and efficient overcoating TRISO particles with the matrix precursor • Demonstrated an automated, multi cavity compacting system with a volumetric feed system • Demonstrated a combined-cycle thermal treatment furnace These changes increased production rates of some of these processes by an order of magnitude or more while eliminating the use of flammable solvents, multiple grinding and sorting operations, and the weighing out of individual die charges. Three fuel kernel lots were fabricated for production of the fuel for AGR-5/6/7. The initial lot (J52R-16-39316) was certified to fuel specifications but was not used because the kernels had a high fraction of internal fissures that caused an unacceptable fraction of the kernels to fragment when charged to the coating furnace where the TRISO coating would be deposited. Fragmented kernels increased the dispersed uranium in the particles and produced a worrisome fraction of dimpled particles with an elevated probability of in-pile failure. After some efforts to identify the cause of the fissure formation, two additional lots were produced with much lower fissure fractions, J52R-16-69317 and 69318. The latter kernel lot was a backup to the first and was not needed. Multiple kernel batches were composited to form each of the lots so as to simulate a commercial-scale operation where kernel batches would also be composited. Multiple TRISO coating runs were performed and the product characterized so that several could be composited into a TRISO lot. TRISO lot J52R-16-98005 conformed to all fuel specifications except the mean outer pyrocarbon (OPyC) layer thickness was thinner than specified. Furthermore, it was determined that the TRISO lot had a dispersed uranium fraction (DUF) that might result in the compacts not meeting the DUF specification. A review of the role of the OPyC layer and consequences of the DUF by the Technical Coordination Team and INL concluded that the fuel was acceptable for use in the AGR-5/6/7 irradiation experiment. The TRISO particles were overcoated with the matrix precursor that had been produced in a jet-milling operation. The overcoating was performed in equipment originally designed to coat pharmaceuticals. The overcoating process performed well; producing highly spherical and uniform overcoats requiring little upgrading and no recycle or rework. TRISO particles were overcoated with the matrix precursor to achieve nominal volumetric packing fractions (PFs) of TRISO particles of 25% and 40% for the irradiation experiments. The 40% PF compacts occupy the first and fifth test capsule in the test train while the inner three capsules are loaded with 25% PF compacts. The resinated graphite matrix precursor powder was a derivative of the German A3-27 matrix formulation, which differs from previous AGR irradiation campaigns that used an A3-3 formulation. Jet milling of the matrix powder precursor produced a finer mean graphite particle size than the milling operations used for the A3-3 matrix powder precursor. Changes made in the matrix formula and equipment yielded compacts with significantly higher matrix density than was attained in previous AGR irradiation campaigns. The changes in the matrix formulation and the means of milling the powders also complicated resolution of the three fuel compact defect fractions, DUF, exposed kernel fraction (EKF), and the silicon carbide defect fraction (SDF). Characterization data from BWXT-NOG had some anomalous results, so samples of the fuel compacts and overcoated TRISO particles were also analyzed by Oak Ridge National Laboratory (ORNL) to ensure that the defect fractions were accurately characterized.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Fabrication and characterization of nanoscale magnesium diboride and tetraboride for propulsion and hydrogen storage applications

Abstract: Boron-loaded propellants have the potential to dramatically increase the performance of solid fuel ramjets, ducted rockets, and hybrid rocket engines. However, difficult ignition of boron decreases the combustion efficiency of these propellants. One approach to solving this problem involves the use of magnesium diboride, MgB2, which ignites easier than boron. Magnesium tetraboride, MgB4, potentially offers greater energetic performance as B has a higher energy density than Mg. However, the effect of the higher boron/metal ratio on the ignition and combustion is unclear. Nanoscale MgB2 particles and quasi 2D structures are promising propellant ingredients, but the oxidation and combustion properties of nanoscale MgB4 remain unknown. Nanoscale magnesium borides are also of interest as precursors for the synthesis of magnesium borohydride, Mg(BH4)2, a promising hydrogen storage material, but hydrogenation of MgB4 has not been studied yet. The objectives of the present work included synthesis, purification, and high-energy ball milling of MgB2 and MgB4 powders as well as investigation of their hydrogen uptake, thermal decomposition, oxidation, and combustion. The powders were fabricated by combustion synthesis and by heating in a tube furnace. The latter method was superior in the synthesis of MgB4. Oxide impurities in the synthesized powders were removed by acid leaching. Nanoscale powders were obtained by ball-mill exfoliation. The hydrogen intake of the obtained magnesium borides was examined at 700 bar and 300 ℃ and did not reveal any advantage of MgB4 over MgB2. Their thermal decomposition and oxidation were investigated with thermogravimetric analysis (TGA), while their combustion was studied using laser ignition and high-speed video recording. TGA has confirmed prior observations of multistep decomposition of magnesium borides, where each step involves formation of a boride with a higher B/Mg ratio and evaporation of formed magnesium. The oxidation rates of the borides are much higher than that of boron at temperatures over 1200 °C for MgB2 and over 900 °C for MgB4. The burning rates of non-milled MgB₂ and MgB₄ powders were much higher than for the used submicron boron. Milling the MgB₂ and MgB₄ powders further increased their burning rates. The milled MgB4 burned 7.5 times faster than submicron boron.

Combustion of metals, Solid fuels, Propellants, Hy↗

Solvent-free production of carbon materials with developed pore structure from biomass for high-performance supercapacitors

The study aimed at preparing porous carbon materials, with superhydrophilic characteristics and developed micro/mesoporous structure (CSB-800), from corn stover by a solvent-free method including pre-carbonization, ball milling, and activation. The effect of pre-carbonization, ball milling on the detailed structural composition and properties especially the hydrophilicity and porous structures were studied, and the potential application of CSB-800 as electrode in supercapacitors was also investigated. The results revealed that pre-carbonization increased the accessibility of raw materials as well as the efficiency of the ball milling with KOH, leading to small carbon particles with good dispersion behavior. Ball milling promoted the porosity, surface energy, hydrophilicity, crystallinity, and graphitization of the carbon materials. CSB-800 exhibited a high specific surface area of 2440.6 m 2 /g with developed micro and porous structures. The heteroatom nitrogen formed nitrogen-containing groups of N Q and N X, which provided faradaic pseudocapacitance when CSB-800 was used as an electrode material, and this material presented a specific capacitance of 398 F/g at 0.5 A/g in 1 M H 2 SO 4 electrolyte in a three-electrode system, while the value was 243 F/g in a two-electrode system, and the energy density reached 5.01 Wh/kg at a power density of 100 W/kg.

09 BIOMASS FUELS↗

Oxygen enrichment combustion to reduce fossil energy consumption and emissions in hot rolling steel production

The reheating furnace operation in the hot mill is natural gas- and electricity-intensive. Oxygen enrichment combustion for reheating furnaces has been proposed to curb and replace natural gas use. In this study, heat transfer in steel slabs in the combustion environment of a push-type reheating furnace was simulated using a computational fluid dynamics (CFD) model. Two oxygen enrichment methods that optimized for performance were selected— a medium oxygen enrichment (MOE) case and an oxy-fuel (OF) case. A life cycle analysis (LCA) characterized the energy and emission profiles of an integrated iron and steel manufacturing process using the two oxygen enrichment cases for the hot mill. These conditions were evaluated for energy use and carbon intensity and compared with a baseline case. Results show that with oxygen enrichment, natural gas consumption can decrease by 19.6%–26.8%, total energy consumption (natural gas and electricity) can decrease by 15.1%–20.7% in the hot mill. Emissions of greenhouse gases can decrease by 11.1%–15.2% in the two optimized cases with 14%–27% reductions in regulated criteria pollutants (nitrogen oxides, carbon monoxide, particulate matter, volatile organic compounds, black carbon, organic carbon, and volatile organic carbons). There is a tradeoff between reducing natural gas consumption and increasing electricity demand from a life cycle perspective. Although the OF case resulted in higher energy- and emissions-related benefits, the MOE case showed the more desirable heat flux uniformity, which is key to maintaining product quality. The analysis suggests that oxygen enrichment in the reheating furnace process can have a significant impact on hot mill environmental performance and become a contributing factor in transitioning to low-carbon steel manufacturing.

36 MATERIALS SCIENCE↗

Enhancing the Electrode Gravimetric Capacity of Li 1.2 Mn 0.4 Ti 0.4 O 2 Cathode Using Interfacial Carbon Deposition and Carbon Nanotube-Mediated Electrical Percolation

Mn-based cation disordered rocksalt oxides (Mn-DRX) are emerging as promising cathode materials for next-generation Li-ion batteries due to their high specific capacities and cobalt and nickel free characteristic. However, to reach the theoretical capacity, solid-state method synthesized Mn-DRX materials require activation via post-synthetic ball milling, typically incorporating more than 20 wt.% conductive carbon that adversely reduces the electrode level gravimetric capacity. To solve this issue, we firstly deposit amorphous carbon on the surface of the Li 1.2 Mn 0.4 Ti 0.4 O 2 (LMTO) particles to increase the electrical conductivity by a five order of magnitude. Although the cathode material gravimetric first charge capacity reaches 180 mAh/g, its highly irreversible behavior leads to a 70 mAh/g first discharge capacity. Subsequently, to ensure a good electrical percolation network, the LMTO material is ball milled with multi-wall carbon nanotube (CNT) to obtain a 78.7 wt.% LMTO active material loading in the cathode electrode (LMTO-CNT). As a result, a 210 mAh/g cathode electrode gravimetric first charge and 165 mAh/g first discharge capacity are obtained, compared to the respective capacity values of 222 mAh/g and 155 mAh/g for the LMTO ball milled with 20 wt.% SuperP C65 electrode (LMTO-SP). After 50 cycles, the LMTO-CNT delivers a 121 mAh/g electrode gravimetric discharge capacity, largely outperforming the 44 mAh/g value of the LMTO-SP. In conclusion, our study demonstrates that while ball milling is necessary to achieve the theoretical capacity of LMTO, a careful selection of the additive, such as CNT, effectively reduces the required carbon quantity to achieve a higher electrode gravimetric discharge capacity.

25 ENERGY STORAGE↗

Chemical Free Two-Step Hydrothermal Pretreatment to Improve Sugar Yields from Energy Cane

Energy cane is an attractive lignocellulosic feedstock for processing into biofuels and bioproducts. A low-severity two-step hydrothermal pretreatment was investigated on energy cane for the production of monomeric sugar. Pretreatment temperature and time, in addition to the effect of disk milling, were observed for the glucose and xylose yields during hydrolysis. At residence times above 5 min in case of pretreatment at 200 °C, all of the hemicellulose was observed to be solubilized. The pretreatment condition of 200 °C for 10 min with disk milling was observed to provide the highest glucose concentration of 5.4%, and 200 °C for 5 min with disk milling provided the highest xylose concentration of 2.15%. The effect of disk milling in improving the sugar concentrations during hydrolysis was significant, especially at lower pretreatment temperatures and times. Low xylose yields at higher temperatures were attributed to the formation of degradation products at increased severity.

09 BIOMASS FUELS↗

Briquetting characteristics of woody and herbaceous biomass blends: Impact on physical properties, chemical composition, and calorific value

Abstract Intercropping (or polyculture) is gaining a lot of interest as it increases yields, allows better utilization of resources (water and nutrients), and provides better land management. The objective of this study is to understand the briquetting characteristics of woody and herbaceous biomass blends, which might result from intercropping. Tests were conducted on blends of lodgepole pine, switchgrass, and corn stover biomass using three hammer mill screen sizes (i.e., 4.8, 12.7, and 19.05 mm), three blend moistures (12%, 15%, and 18%, w.b.), and two‐ and three‐blend ratios (i.e., 1:1 and 1:1:1) using a pilot‐scale hydraulic briquette press. The briquette properties, such as unit and bulk density, durability rating after 5 days of storage (as they tend to attain stable density), and the energy consumption of the process were measured. The results indicate that moisture content of 12% and 15% (w.b.) and smaller hammer mill screen size of 4.8 mm increased the unit and bulk densities to >750 and >430 kg/m 3 and moisture content (15% and 18% (w.b.)) and hammer mill screen size of 12.7 and 19.05 mm produced briquettes with durability rating values of >95%. The higher moisture content of 18% (w.b.) and the hammer mill screen size of 12.7 and 19.05 mm had the highest energy consumption. The proximate and ultimate analysis showed that energy content improved by blending lodgepole pine with both corn stover and switchgrass and also showed increased calorific value and reduced ash content. Scanning electron microscopy micrographs showed interlocking of particles and cracks in the briquettes. © 2020 Society of Chemical Industry and John Wiley & Sons, Ltd

Tumuluru, Jaya Shankar↗

Inadvertent Hatchery Rainbow Trout Oncorhynchus mykiss Discovered in Native Westslope Cutthroat Trout Oncorhynchus clarkii lewisi Habitat: A Cautionary Tale

Abstract Fish hatcheries across North America release billions of fish into the wild every year to augment harvest opportunities in sport, commercial, and tribal fisheries, as well as to recover depressed populations. Despite these benefits, wild fish populations may be negatively affected when hatchery fish compete and/or hybridize with native species. Native Westslope Cutthroat Trout Oncorhynchus clarkii lewisi have decreased by 90% across their historic range; however, the Flathead River in Montana is a rangewide stronghold for these imperiled fish. The primary threat to Westslope Cutthroat Trout is hybridization with invasive Rainbow Trout O. mykiss, which leads to hybrid swarm formation and genomic extinction. We collected Rainbow Trout in Mill Creek, a tributary of the Flathead River, downstream from a hatchery that produces the species, and used otolith 87Sr/86Sr to determine whether individual fish were inadvertently introduced from the hatchery. Differences in 87Sr/86Sr among water samples from Mill Creek and the marine-derived hatchery food provided high-classification accuracy to determine the natal origins of Mill Creek Rainbow Trout. We found that 83 of the 106 Rainbow Trout collected (78%) were of hatchery origin. Otolith microstructure analysis indicated these fish had been in Mill Creek for ~1–32 weeks prior to capture. Our results illustrate the utility of otolith 87Sr/86Sr to identify hatchery fish in natural habitats and point to a source of invasive Rainbow Trout that pose conservation risks to native fishes in the drainage.

60 APPLIED LIFE SCIENCES↗

On duality of color and kinematics in (A)dS momentum space

We explore color-kinematic duality for tree-level AdS/CFT correlators in momentum space. We start by studying the bi-adjoint scalar in AdS at tree-level as an illustrative example. We follow this by investigating two forms of color-kinematic duality in Yang-Mills theory, the first for the integrated correlator in AdS 4 and the second for the integrand in general AdS d +1 . For the integrated correlator, we find color-kinematics does not yield additional relations among n -point, color-ordered correlators. To study color-kinematics for the AdS d +1 Yang-Mills integrand, we use a spectral representation of the bulk-to-bulk propagator so that AdS diagrams are similar in structure to their flat space counterparts. Finally, we study color KLT relations for the integrated correlator and double-copy relations for the AdS integrand. We find that double-copy in AdS naturally relates the bi-adjoint theory in AdS d +3 to Yang-Mills in AdS d +1 . We also find a double-copy relation at three-points between Yang-Mills in AdS d +1 and gravity in AdS d– 1 and comment on the higher-point generalization. By analytic continuation, these results on AdS/CFT correlators can be translated into statements about the wave function of the universe in de Sitter.

gauge-gravity correspondence↗

Revealing the landscape of globally color-dual multi-loop integrands

Abstract We report on progress in understanding how to construct color-dual multi-loop amplitudes. First we identify a cubic theory, semi-abelian Yang-Mills, that unifies many of the color-dual theories studied in the literature, and provides a prescriptive approach for constructingD-dimensional color-dual numerators through one-loop directly from Feynman rules. By a simple weight counting argument, this approach does not further generalize to two-loops. As a first step in understanding the two-loop challenge, we use aD-dimensional color-dual bootstrap to successfully construct globally color-duallocaltwo-loop four-point nonlinear sigma model (NLSM) numerators. The double-copy of these NLSM numerators with themselves, pure Yang-Mills, and$$\mathcal{N}$$= 4 super-Yang-Mills correctly reproduce the known unitarity constructed integrands of special Galileons, Born-Infeld theory, and Dirac-Born-Infeld-Volkov-Akulov theory, respectively. Applying our bootstrap to two-loop four-point pure Yang-Mills, we exhaustively search the space of local numerators and find that it fails to satisfy global color-kinematics duality, completing a search previously initiated in the literature. We pinpoint the failure to the bowtie unitarity cut, and discuss a path forward towards non-local construction of color-dual integrands at generic loop order.

Physics↗

Small instantons in weakly-gauged holographic models

Small instantons can play an important role in Yang-Mills theories whose gauge couplings are sizeable at small distances. An interesting class of theories where this could occur is in weakly-gauged holographic models (dual to Yang-Mills theories interacting with strongly-coupled CFTs), since gauge couplings are indeed enhanced towards the UV boundary of the 5D AdS space. However, contrary to expectations, we show that small instantons in these non-asymptotically-free models are highly suppressed and ineffective. This is due to the conservation of topological charge that forbids instantons to be localized near the UV boundary. Despite this fact we find non-trivial UV localized instanton-anti-instanton solutions of the Yang-Mills equations where the topological charges annihilate in the AdS bulk. These analytic solutions arise from a 5D conformal transformation of the uplifted 4D instanton. Our analysis therefore reveals unexpected nonperturbative configurations of Yang-Mills theories when they interact with strongly-coupled CFTs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Effects of mechanically alloying Al 2 O 3 and Y 2 O 3 additives on the liquid phase sintering behavior and properties of SiC

In order to improve the sintering of SiC, mixtures of Al 2 O 3 and Y 2 O 3 powders are commonly included as sintering additives. The aim of this work was to use mechanically alloyed Al 2 O 3 –Y 2 O 3 mixtures as sintering additives to promote liquid phase sintering of SiC using spark plasma sintering. The results showed that milling reduced the particle size of the powders and led to the formation of complex oxide phases (YAP, YAM, and YAG) at low temperatures. As the ball milling time increased, the mass loss of specimens sintered with mechanically alloyed Al 2 O 3 –Y 2 O 3 mixtures decreased, and accordingly the relative density increased. However, the hardness and flexural strength of sintered SiC specimens first increased and then decreased. Because the specimens prepared with oxides milled for a long time contained too much YAG/YAP and accordingly too much liquid at sintering temperature. This negatively affected the mechanical properties of the SiC specimens because of the increased volume of the complex oxide phases, which have inferior mechanical properties to SiC, in the sintered specimens. In conclusion, when the ball milling time was 6h, the hardness (24.02 GPa) and flexural strength (655.61 MPa) of the SiC specimens reached maximum values.

36 MATERIALS SCIENCE↗

Formation of Stable Radicals by Mechanochemistry and Their Application for Magic Angle Spinning Dynamic Nuclear Polarization Solid-State NMR Spectroscopy

High-field magic angle spinning (MAS) dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (SSNMR) is becoming a common technique for improving the sensitivity in NMR by the hyperpolarization of nuclear spins. Recently, we have shown that gamma irradiation is capable of creating long-lived free radicals that are amenable to MAS DNP in quartz and a variety of organic solids. Here, we demonstrate that mechanochemical ball milling is able to generate millimolar concentrations of stable radical species in diverse materials, such as polystyrene, cellulose, borosilicate glass, and fused quartz. High-field electron paramagnetic resonance (EPR) was used to obtain further insight into the nature of the radicals formed in ball milled quartz and borosilicate glass. Finally, we further show that radicals generated in quartz by ball milling can be used for solid-effect DNP. We obtained 29 Si DNP enhancements of approximately 114 and 33 at 110 K and room temperature, respectively, from a sample of ball milled quartz.

36 MATERIALS SCIENCE↗

Importance of multimodal characterization and influence of residual Li 2 S impurity in amorphous Li 3 PS 4 inorganic electrolytes

Amorphous Li 3 PS 4 (LPS) solid-state electrolytes are promising for energy-dense lithium metal batteries. LPS glass, synthesized from a 3:1 mol ratio of Li 2 S and P 2 S 5 , has high ionic conductivity and can be synthesized by ball milling or solution processing. Ball milling has been attractive because it provides the easiest route to access amorphous LPS with a conductivity of 3.5 × 10 –4 S cm –1 (20 °C). However, achieving the complete reaction of precursors via ball milling can be difficult, and most literature reports use X-ray diffraction (XRD) or Raman spectroscopy to confirm sample purity, both of which have limitations. Furthermore, the effect of residual precursors on ionic conductivity and lithium metal cycling is unknown. In this work, we illustrate the importance of multimodal characterization to determine LPS phase and chemical purity. To determine the residual Li 2 S content in LPS, we show that (1) XRD and 31 P solid state nuclear magnetic resonance (ssNMR) are insufficient and (2) Raman loses sensitivity at concentrations below 12 mol% Li 2 S. Most importantly, we show that 7 Li ssNMR is highly sensitive. Using 7 Li ssNMR, we investigate the effect of ball milling parameters and develop a robust and highly reproducible procedure for pure LPS synthesis. We find that as the residual Li 2 S precursor content increases, LPS conductivity decreases and lithium metal batteries exhibit higher overpotentials and poor cycle life. Furthermore, our work reveals the importance of multimodal characterization techniques for amorphous solid-state electrolyte characterization and will enable better synthetic strategies for highly conductive electrolytes for efficient energy-dense solid-state lithium metal batteries.

25 ENERGY STORAGE↗