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At least 667 records · Page 37

Mineral-Ground Micro-Fibrillated Cellulose Reinforcement for Polymer Compounds

Additive Manufacturing (AM) is quickly becoming a mainstream, energy efficient manufacturing technique for complex and custom components. ORNL has taken polymer AM into the next level with Big Area Additive Manufacturing (BAAM). However, we need to develop the strength of AM materials (specifically polymers) to satisfy the mechanical requirements of structural parts. Also, it is crucial that the developed process can easily be scaled up to have a significant impact in the manufacturing industry of US. Furthermore, renewable, bio-derived AM materials are desirable from a sustainability perspective. In the first phase of this project the mechanical properties of polymer AM components were significantly improved developing a micro fibrillated cellulose (MFC)-reinforced composite material system that is derived from biomass and compatible with BAAM. Unfortunately, the improvements were observed only with freeze-dried MFCs, and freeze-drying is a very slow process and is not industrially scalable. Furthermore, MFCs were not available in large quantities at low cost. However, FiberLean has reached 12,000 tons/year capacity (60,000 tons/year including the minerals). FiberLean offers MFCs at a scale and order of magnitude lower price than current market participants. With their recently developed novel (patent pending) drying process FiberLean can achieve over 50% solid content commercially. In the 2nd phase of the project, the original objective was to investigate this new novel drying process along with compounding with different formulations to optimize and adapt to large scale additive manufacturing. However, the compounded materials prepared via this approach were very brittle and demonstrated poor mechanical performance. Therefore, the project was focused more on a scalable chemical surface modification of MFCs to enable their drying via conventional oven process with minimal agglomeration and better dispersion in PLA polymer matrix. Fiberlean and ORNL have worked together in this project to develop mineral-ground microfibrillated cellulose (MFC) - reinforced additive manufacturing feedstock materials with significantly improved mechanical properties. Properly surface modified and dried Fiberlean cellulose microfibrils led to tensile strength increases up to ~40% and elastic modulus increases up to 70% with the addition of 30% MFC into PLA matrix. The work has led to a high impact journal article and a provisional patent. Opportunities for a follow up work to demonstrate the technology in large scale and application of it to AM applications are currently being searched.

36 MATERIALS SCIENCE↗

Progress of simulations for reacting shear layers

An attempt was made to develop a high speed, chemically reactive shear layer test rig. The purpose of the experiment was to study the mixing of oxidizer and fuel streams in reacting shear layers for various density, velocity, and Mach number. The primary goal was to understand the effects of the compressibility upon mixing and combustion in a fundamental way. Therefore, a two-dimensional shear layer is highly desirable for its simplicity to quantify the compressibility effects. The RPLUS 2D code is used to calculate the flow fields of different sections of the test rig. The emphasis was on the supersonic nozzle design, the vitiation process for the hot air stream and the overall thermodynamic conditions of the test matrix. The k-epsilon turbulence model with wall function was successfully implemented in the RPLUS code. The k and epsilon equations are solved simultaneously and the LU scheme is used to make it compatible with the flow solver.

Yu, Sheng-Tao↗

Solvent selection for biphasic extraction of 5-hydroxymethylfurfural via multiscale modeling and experiments

We introduce a comprehensive conceptual framework for selecting solvents for reactive extraction in biphasic organic-water systems and demonstrate it for the separation of HMF (5-hydroxylmethylfurfural), a platform chemical produced in the acid-catalyzed dehydration of hexoses. We first perform in silico screening of ~2500 solvents, from the ADFCRS-2018 database using the ADF COSMO-RS implementation, and classification, based on the solvent partition coefficient. We then determine experimentally the partition coefficients for HMF, fructose, and products of HMF rehydration (levulinic acid (LA), and formic acid (FA)), the mutual water-organic solvent solubilities, and the separation factors in >50 select solvents spanning multiple homologous series at room temperature and a typical reaction temperature with in situ sampling. We find that COSMO-RS is excellent for screening purposes (typical error in most cases within a factor of ~2). Increased temperatures lead to significant reduction in partitioning, and room temperature measurements are clearly inadequate for solvent selection. Upon down selecting classes of solvents based on separation performance, we perform experimental thermal stability and reaction compatibility studies of a small set of solvents at relevant reactive-extraction temperatures. We discover that many substituted phenols exhibit an order-of-magnitude increase in partitioning compared to conventional solvents due chiefly to hydrogen bond interactions and show the necessary stability but retain a significant fraction of water and LA, factors that need to be considered in technoeconomic analysis. In contrast, anilines, aldehydes, and acids are good to excellent regarding separation but incompatible with this specific reaction medium. Furthermore, this multifaceted framework can be extended to other biomass-derived products and processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The nature and suppression strategies of interfacial reactions in all-solid-state batteries

Solid-state Li batteries are promising energy storage devices owing to their high safety and high theoretical energy density. However, the serious interfacial reaction between solid state electrolytes and cathodes deteriorates the battery performance, impeding the realization of long-term cyclability. The buried nature of the interphase layer presents a significant challenge in achieving a comprehensive understanding of the underlying interfacial reaction mechanisms. Herein, we systematically explore the interfacial reaction evolutions and interphase compositions and electronic properties between the popular oxide cathodes and sulfide solid electrolytes (SSEs). This includes analysis of the chemical and electrochemical reactions between cathodes/coatings and SSEs, as well as the electrochemical self-decomposition of SSEs by thermodynamic phase equilibrium analysis. Herein, we disclose that the driving force of the electrochemical reaction at the chemical potential of μ Li is much stronger than that of the chemical reaction, which dominates the interfacial reaction. Preventing the formation of an electronically conductive interphase is crucial in inhibiting the continuous interfacial degradation during long-term cycling, which can be achieved through the optimized combination of cathodes and SSEs, as well as the introduction of functional coatings between them. Based on these findings, the percentage of molar fraction ( f ) of electronically conductive species in the formed interphase is proposed as a key factor for indicating the interfacial stability for the first time. Furthermore, we propose a specific high-throughput screening scheme to filter the functional coating materials by comprehensively evaluating their functionality. The tiered screening identifies 48 coating materials with optimal properties. The work highlights the significant roles of rational coupling of the cathodes and SSEs, and optimizing interfacial coating materials for solid-state batteries. It opens new avenues for engineering an interphase with improved interfacial compatibility to realize long-term cyclability.

25 ENERGY STORAGE↗

Conventional and Bimodal Nuclear Thermal Rocket (NTR) Artificial Gravity Mars Transfer Vehicle Concepts

A variety of countermeasures have been developed to address the debilitating physiological effects of "zero-gravity" (0-g) experienced by cosmonauts and astronauts during their approximately 0.5-1.2 year long stays in LEO (Low Earth Orbit). Longer interplanetary flights, combined with possible prolonged stays in Mars orbit, could subject crewmembers to up to approximately 2.5 years of weightlessness. In view of known and recently diagnosed problems associated with 0-g, an artificial gravity spacecraft offers many advantages and may indeed be an enabling technology for human flights to Mars. A number of important human factors must be taken into account in selecting the rotation radius, rotation rate, and orientation of the habitation module or modules. These factors include the gravity gradient effect, radial and tangential Coriolis forces, along with cross-coupled acceleration effects. Artificial gravity (AG) Mars transfer vehicle (MTV) concepts are presented that utilize both conventional NTR, as well as, enhanced "bimodal" nuclear thermal rocket (BNTR) propulsion. The NTR is a proven technology that generates high thrust and has a specific impulse (I (sub sp)) capability of approximately 900 s - twice that of today's best chemical rockets. The AG/MTV concepts using conventional NTP carry twin cylindrical "ISS-type" habitation modules with their long axes oriented either perpendicular or parallel to the longitudinal spin axis of the MTV and utilize photovoltaic arrays (PVAs) for spacecraft power. The twin habitat modules are connected to a central operations hub located at the front of the MTV via two pressurized tunnels that provide the rotation radius for the habitat modules. For the BNTR AG/MTV option, each engine has its own "closed" secondary helium-xenon gas loop and Brayton rotating unit that can generate tens of kilowatts (kW (sub e)) of spacecraft electrical power during the mission coast phase eliminating the need for large PVAs. A single inflatable "TransHab-type" habitation module is also used with multiple vertical floors oriented radial to the MTV spin axis. The BNTR MTV's geometry - long and linear - is naturally compatible with AG operation. By rotating the vehicle about its center-of-mass and perpendicular to its flight vector at approximately 3.0 - 5.2 rpm, a centrifugal force and AG environment corresponding to approximately 0.38 - 1.0 g can be established to help maintain crew fitness out to Mars and back. Vehicles using NTP/BNTP can more readily accommodate the heavier payload mass and increased RCS propellant loading associated with AG operation, and can travel faster to and from Mars thereby reducing the crew's exposure to galactic cosmic radiation and solar flares. Mission scenario descriptions, key vehicle features and operational characteristics for each propulsion options are presented using the lift capability and payload volumes estimated for the SLS-1A and HLV.

Nuclear Propulsion↗

Rapid Automated Annotation and Analysis of N-Glycan Mass Spectrometry Imaging Data Sets Using NGlycDB in METASPACE

Imaging N-glycan spatial distribution in tissues using mass spectrometry imaging (MSI) is emerging as a promising tool in biological and clinical applications. However, there is currently no high throughput tool for visualization and molecular annotation of N-glycans in MSI data, which significantly slows down data processing and hampers the applicability of this approach. In this work, we present how METASPACE, an open-source cloud engine for molecular annotation of MSI data, can be used to automatically annotate, visualize, analyze, and interpret high-resolution mass spectrometry-based spatial N-glycomics data. METASPACE is an emerging tool in spatial metabolomics, but the lack of compatible glycan databases has limited its application for comprehensive N-glycan annotations from MSI datasets. We created NGlycDB, a public database of N-glycans, by adapting available glycan databases. We demonstrate the applicability of NGlycDB in METASPACE by analyzing MALDI-MSI data from formalin-fixed paraffin-embedded (FFPE) human kidney and mouse lung tissue sections. We added NGlycDB to METASPACE for public use, thus facilitating applications of MSI in glycobiology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effective Model for Fractional Topological Corner Modes in Quasicrystals

High-order topological insulators (HOTIs), as generalized from topological crystalline insulators, are characterized with lower-dimensional metallic boundary states protected by spatial symmetries of a crystal, whose theoretical framework based on band inversion at special k points cannot be readily extended to quasicrystals because quasicrystals contain rotational symmetries that are not compatible with crystals, and momentum is no longer a good quantum number. In this work, we develop a low-energy effective model underlying HOTI states in 2D quasicrystals for all possible rotational symmetries. By implementing a novel Fourier transform developed recently for quasicrystals and approximating the long-wavelength behavior by their large-scale average, we construct an effective k · p Hamiltonian to capture the band inversion at the center of a pseudo-Brillouin zone. We show that an in-plane Zeeman field can induce mass kinks at the intersection of adjacent edges of a 2D quasicrystal topological insulators and generate corner modes (CMs) with fractional charge, protected by rotational symmetries. Our model predictions are confirmed by numerical tight-binding calculations. Furthermore, when the quasicrystal is proximitized by an s-wave superconductor, Majorana CMs can also be created by tuning the field strength and chemical potential. Our work affords a generic approach to studying the low-energy physics of quasicrystals, in association with topological excitations and fractional statistics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Process for High-Rate Fabrication of Alumina Nanotemplates

An anodizing process, at an early stage of development at the time of reporting the information for this article, has shown promise as a means of fabricating alumina nanotemplates integrated with silicon wafers. Alumina nanotemplates are basically layers of alumina, typically several microns thick, in which are formed approximately regular hexagonal arrays of holes having typical diameters of the order of 10 to 100 nm. Interest in alumina nanotemplates has grown in recent years because they have been found to be useful as templates in the fabrication of nanoscale magnetic, electronic, optoelectronic, and other devices. The present anodizing process is attractive for the fabrication of alumina nanotemplates integrated with silicon wafers in two respects: (1) the process involves self-ordering of the holes; that is, the holes as formed by the process are spontaneously arranged in approximately regular hexagonal arrays; and (2) the rates of growth (that is, elongation) of the holes are high enough to make the process compatible with other processes used in the mass production of integrated circuits. In preparation for fabrication of alumina nanotemplates in this process, one first uses electron-beam evaporation to deposit thin films of titanium, followed by thin films of aluminum, on silicon wafers. Then the alumina nanotemplates are formed by anodizing the aluminum layers, as described below. In experiments in which the process was partially developed, the titanium films were 200 A thick and the aluminum films were 5 m thick. The aluminum films were oxidized to alumina, and the arrays of holes were formed by anodizing the aluminum in aqueous solutions of sulfuric and/or oxalic acid at room temperature (see figure). The diameters, spacings, and rates of growth of the holes were found to depend, variously, on the composition of the anodizing solution, the applied current, or the applied potential, as follows: In galvanostatically controlled anodizing, regardless of the chemical composition of the solution, relatively high current densities (50 to 100 mA/cm2) resulted in arrays of holes that were more nearly regular than were those formed at lower current densities. . The rates of elongation of the holes were found to depend linearly on the applied current density: the observed factor of proportionality was 1.2 (m/h)/(mA/cm2). For a given fixed current density and room temperature, the hole diameters were found to depend mainly on the chemical compositions of the anodizing solutions. The holes produced in sulfuric acid solutions were smaller than those produced in oxalic acid solutions. The arrays of holes produced in sulfuric acid were more ordered than were those produced in oxalic acid. . The breakdown voltage was found to decrease logarithmically with increasing concentration of sulfuric acid. The breakdown voltage was also found to decrease with temperature and to be accompanied by a decrease in hole diameter. The hole diameter was found to vary linearly with applied potential, with a slope of 2.1 nm/V. This slope differs from slopes (2.2 and 2.77 nm/V) reported for similar prior measurements on nanotemplates made from bulk aluminum. The differences among these slopes may be attributable to differences among impurities and defects in bulk and electron-beam-evaporated aluminum specimens.

Myung, Nosang↗

GeSn alloys with ∼21% Sn grown by effusion cell molecular beam epitaxy

We report the epitaxial growth of high quality GeSn alloys with Sn compositions up to 21.25 ± 1% by effusion-cell molecular beam epitaxy (MBE). Achieving such a high Sn content with effusion cells is particularly significant, since these sources typically impose stronger radiative heating on the substrate, which is a factor long considered a major obstacle to high-Sn GeSn epitaxy. Contrary to the prevailing assumption that high growth rates are good for suppressing Sn segregation, we demonstrate that carefully controlled low fluxes, combined with stable ultra-low substrate temperatures, enable significant Sn incorporation even under effusion-cell conditions. Structural analyses by high-resolution x-ray diffraction, reciprocal space mapping, atomic force microscopy, and transmission electron microscopy confirm sharp interfaces, high crystallinity, and smooth surfaces at high Sn contents. Furthermore, these findings establish the feasibility of MBE-grown high-Sn GeSn even under diffusion cells, thereby broadening opportunities for Si-compatible photonic and quantum devices.

Alloys↗

Distribution of Fe3+ and H in Minerals During Partial Melting and Metasomatism of Spinel Peridotite

Oxygen fugacity and water content are crucial parameters for many chemical and physical properties of the Earth's mantle, for example bearing on fluid type, melting initiation, and deformation. However, the exact behaviour of Fe3+ and H during melting and metasomatism is still under debate. Here, the Fe3+/ΣFe ratio (Mössbauer and EMP) and water content (FTIR) of peridotite minerals are examined in mantle xenoliths from Kilbourne Hole (KH), NM, and Dish Hill (DH), CA (USA). These spinel peridotites have compositions consistent with partial melting with variable degrees of metasomatism (undetectable to cryptic to modal). Pyroxenites also allow to examine melt-rock reactions. Bulk-rock Fe2O3 content of the KH peridotites correlates with indices of melting (positive with bulk-rock Al2O3 and Cpx Yb contents, and negative with spinel Cr#) confirming that Fe3+ behaves as an incompatible element during melting. Correlations of the Fe3+/ΣFe ratio of minerals with these indices, however, indicates that Fe3+ is incompatible in Cpx but compatible in Opx and spinel during melting. Water contents in olivine, Cpx and Opx from most KH peridotites can be explained by partial melting and correlate negatively with the Fe3+/ΣFe ratio of spinel and Opx but positively with that of Cpx. This indicates partial control of Fe3+ on the incorporation of H in pyroxene, but not related to a redox equilibrium in Cpx. The higher Fe3+/ΣFe ratio of spinel in the metasomatized KH and DH peridotites, and in the pyroxenites confirms that oxidation characterizes modal metasomatism. Metasomatism, however, is not necessarily accompanied by water addition.

Peslier, A. H.↗

Advanced Moderation Module for High-Temperature Micro-Reactor Applications

Development and deployment of micro-reactors that provide competitive efficiency, prevailing compactness, and inherent safety is an immediate focus of the U.S. nuclear industry. For thermal neutron micro-reactors operating at elevated temperature for optimized efficiency, such as micro molten-salt reactors (MSRs), heat-pipe reactors, and very-high temperature reactors (VHTRs), high-performance moderator based on metal hydride can enhance the neutron economy and therefore achieve reduced weight and enhanced portability. As unclad metal hydride inevitably decomposes at elevated temperature, an enclosure is required for hydride moderator to deliver desired performance at elevated temperatures. Conventional moderator enclosure solutions based on high-temperature alloys introduce extraneous neutron penalty into the micro-reactor, affecting the neutronic benefits provided by the hydride moderator. Additionally, the compatibility between the high-temperature alloy enclosure and the micro-reactor matrix is also a potential issue. In this report, we disclose an Advanced Moderator Module (AMM) concept enabled by an innovative enclosure solution combining the advantages of refractory metals, ceramic matrix composites (CMCs), and advanced coating technology to serve as hydrogen permeation barrier up to very-high temperatures. A schematic description of the AMM structure is illustrated in Figure A1. The AMM contains a moderating material core made of metal hydride with high thermal stability, such as YH 2-x . The hydride core is enclosed by an H 2 barrier layer coated on a ductile refractory metal liner to minimize hydrogen loss during high-temperature operation. A ceramic matrix composite (CMC) cladding is adopted to provide further structural strength, especially during power transients. Between the CMC cladding and metal liner, an extra diffusion barrier coating is inserted to suppress the chemical interaction at elevated temperatures. Hence, based on a series of innovative material solutions, the AMM is capable of containing the metal hydride core at elevated temperature (>900oC) inside coated and lined CMC envelop with negligible hydrogen loss throughout the microreactor lifetime. The benefit of the AMM technology was assessed based on a comprehensive multi-stage reactor-physics analysis. Advanced moderation based on hydride metals (such as YH2-x) enables reaching optimum moderation with higher fuel content than traditional VHTR technology, which is required to design compact micro-reactor cores targeting long-life operation. The AMM enclosure technology provides lower thermal neutron absorption rates than traditional solutions (based on stainless steel or Mo-based alloy such as TZM), which reduces the fissile enrichment requirements by 6-8% on a TRISO-fueled design based on the EMPIRE core. Finally, combining the hydride moderator with neutron transparent enclosure solutions provides significant potential to boost neutronics performance of micro-reactors in terms of increased core lifetime or reduced size and weight by 30-50% on a micro-reactor based on the Holos Quad technology. The progress and plans for on-going development and demonstration efforts are also discussed in this report. The current demonstration of AMM is focused on the hydrogen diffusion barrier demonstration under thermal cycling, while radiation tolerance demonstration is planned. The next step of the demonstration plan will be the assembly of miniature AMM for high-temperature testing, which can be used as a prototype for future pilot scale demonstration.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Conventional and Bimodal Nuclear Thermal Rocket (NTR) Artificial Gravity Mars Transfer Vehicle Concepts

A variety of countermeasures have been developed to address the debilitating physiological effects of zero-gravity (0-g) experienced by cosmonauts and astronauts during their approximately 0.5 to 1.2 year long stays in low Earth orbit (LEO). Longer interplanetary flights, combined with possible prolonged stays in Mars orbit, could subject crewmembers to up to approximately 2.5 years of weightlessness. In view of known and recently diagnosed problems associated with 0-g, an artificial gravity (AG) spacecraft offers many advantages and may indeed be an enabling technology for human flights to Mars. A number of important human factors must be taken into account in selecting the rotation radius, rotation rate, and orientation of the habitation module or modules. These factors include the gravity gradient effect, radial and tangential Coriolis forces, along with cross-coupled acceleration effects. Artificial gravity Mars transfer vehicle (MTV) concepts are presented that utilize both conventional NTR, as well as, enhanced bimodal nuclear thermal rocket (BNTR) propulsion. The NTR is a proven technology that generates high thrust and has a specific impulse (Isp) capability of approximately 900 s-twice that of today's best chemical rockets. The AG/MTV concepts using conventional Nuclear Thermal Propulsion (NTP) carry twin cylindrical International Space Station (ISS)- type habitation modules with their long axes oriented either perpendicular or parallel to the longitudinal spin axis of the MTV and utilize photovoltaic arrays (PVAs) for spacecraft power. The twin habitat modules are connected to a central operations hub located at the front of the MTV via two pressurized tunnels that provide the rotation radius for the habitat modules. For the BNTR AG/MTV option, each engine has its own closed secondary helium(He)-xenon (Xe) gas loop and Brayton Rotating Unit (BRU) that can generate 10s of kilowatts (kWe) of spacecraft electrical power during the mission coast phase eliminating the need for large PVAs. A single inflatable TransHab-type habitation module is also used with multiple vertical floors oriented radial to the MTV spin axis. The BNTR MTV's geometry-long and linear-is naturally compatible with AG operation. By rotating the vehicle about its center-of-mass (CM) and perpendicular to its flight vector at approximately 3.0 to 5.2 rpm, a centrifugal force and AG environment corresponding to approximately 0.38 to 1.0 g can be established to help maintain crew fitness out to Mars and back. Vehicles using NTP/ Bimodal Nuclear Thermal Propulsion (BNTP) can more readily accommodate the heavier payload mass and increased RCS propellant loading associated with AG operation, and can travel faster to and from Mars thereby reducing the crew's exposure to galactic cosmic radiation and solar flares. Mission scenario descriptions, key vehicle features and operational characteristics for each propulsion option are presented using the lift capability and payload volumes estimated for the Space Launch System (SLS)-1B and followon Heavy Lift Vehicle (HLV).

Nuclear Propulsion↗

Mixed polyester recycling can enable a circular plastic economy with environmental benefits

The mixed and varied nature of fossil-based and bio-based plastic waste requires complex and costly separations to enable compatibility with recycling technologies. A circular plastic economy based on mixed polyesters through cleaving ester bonds to produce monomers, while re-utilizing bio-based monomers to produce high-quality sustainable plastics, charts an exciting solution. However, the feasibility of such a circular economy solution remains underexplored. Here, in this study, we conducted a techno-economic analysis and life-cycle assessment of three polyester depolymerization recycling processes-methanolysis, glycolysis, and acid hydrolysis-for a mixed feedstock (polyethylene terephthalate [PET], polylactic acid [PLA], and polybutylene adipate terephthalate [PBAT]). Methanolysis outperforms glycolysis and hydrolysis economically and environmentally due to more efficient downstream separations, generating products with a 31% decrease in selling price and 21%-46% reduction in acidification, carcinogenic toxicity, fossil-fuel depletion, global warming potential, particulate formation, and smog formation compared to conventional polyester manufacturing. This study highlights the viability of a circular plastic economy for mixed polyesters via a single chemical recycling process.

09 BIOMASS FUELS↗

Development of a Grid-Independent Geos-Chem Chemical Transport Model (v9-02) as an Atmospheric Chemistry Module for Earth System Models

The GEOS-Chem global chemical transport model (CTM), used by a large atmospheric chemistry research community, has been re-engineered to also serve as an atmospheric chemistry module for Earth system models (ESMs). This was done using an Earth System Modeling Framework (ESMF) interface that operates independently of the GEOSChem scientific code, permitting the exact same GEOSChem code to be used as an ESM module or as a standalone CTM. In this manner, the continual stream of updates contributed by the CTM user community is automatically passed on to the ESM module, which remains state of science and referenced to the latest version of the standard GEOS-Chem CTM. A major step in this re-engineering was to make GEOS-Chem grid independent, i.e., capable of using any geophysical grid specified at run time. GEOS-Chem data sockets were also created for communication between modules and with external ESM code. The grid-independent, ESMF-compatible GEOS-Chem is now the standard version of the GEOS-Chem CTM. It has been implemented as an atmospheric chemistry module into the NASA GEOS- 5 ESM. The coupled GEOS-5-GEOS-Chem system was tested for scalability and performance with a tropospheric oxidant-aerosol simulation (120 coupled species, 66 transported tracers) using 48-240 cores and message-passing interface (MPI) distributed-memory parallelization. Numerical experiments demonstrate that the GEOS-Chem chemistry module scales efficiently for the number of cores tested, with no degradation as the number of cores increases. Although inclusion of atmospheric chemistry in ESMs is computationally expensive, the excellent scalability of the chemistry module means that the relative cost goes down with increasing number of cores in a massively parallel environment.

CTM↗

Durability of YSZ Coated Ti2AlC in 1300 °C Mach 0.3 Burner Rig Tests

A thermal barrier coating system survived burner rig testing at 1300 °C for 500 h. A 160 µm thick yttria stabilized zirconia (YSZ) coating was applied to a Ti2AlC MAX phase bar sample by plasma spray physical vapor deposition (PS-PVD) and tested face-on in an atmospheric Mach 0.3 jet fuel burner, using 5-h thermal cycles. No thermal barrier coating (TBC) spallation or recession was observed, only a 2.4 mg/cm2 mass gain. The modest weight gain precluded severe volatility losses under high velocity burner conditions. The coating surface exhibited colonies of (111)flourite fiber-textured columns separated by craze patterns, with no visible moisture attack. The metastable tetragonal t' YSZ phase was obtained initially, transitioning to equilibrium teq and cubic YSZ, but with little detrimental monoclinic. The thickness of the alumina TGO was ~21 to 23 μm under the heated YSZ face and ~13 to 15 μm on the uncoated, cooler backside. The backside exhibited removal of initial transient TiO2 nodules and partial etching of the underlying Al2O3 scale by volatile hydroxides formed in high temperature, high velocity water vapor. Aerodynamic forces produced some bending of the cantilevered sample via creep. The test indicated exceptional stability of YSZ coatings on Ti2AlC under turbine conditions, with thermal expansion matching playing a key role. The purpose of this study was to demonstrate long term durability of YSZ/MAX phase system in aggressive high temperature burner rig testing. MAX phases have been keenly studied because of their unique crystal structure and intriguing properties (Refs. 1 and 2). Having Mn+1(Al,Si)(C,N)n general composition, they are defined as ceramics, but possess unusual desirable attributes such as high conductivity, thermal shock resistance, easy machinability, and deformation tolerance. The mechanical properties derive from weak M-(Al,Si) bonding in the basal plane that leads to sliding and kinking in preference to catastrophic crack growth. Like most ceramics they are phase stable at high temperatures, generally up to 1500 °C. High temperature oxidation resistance is excellent for alumina-forming Ti3AlC2, Ti2AlC, and Cr2AlC, as reviewed by Tallman, et al. (Ref. 3). Compatibility with α-Al2O3 scales is further enhanced in cyclic exposures by a close matching of thermal expansion coefficients, (Ref. 4) i.e., (~9.3, 10.2, 11.3×10–6/K for Al2O3, Ti2AlC, and YSZ, to be discussed). Turbine environments generally contain 10 percent water vapor in the combustion gases, therefore moisture effects can be a concern for some materials (Ref. 5). Furnace tests of MAX phases in high temperature steam generally showed little effect on Al2O3 scale growth (Ref. 6). However, high velocity and high pressure gas can influence scale losses by the formation of volatile reaction products, such as TiO(OH)2 and Al(OH)3 (Refs. 7 to 10). This phenomenon had been discussed for 1100 to 1300 °C high pressure burner rig tests of Ti2AlC (Ref. 11). A single cubic growth rate parameter kcubic was measurably lower than comparable furnace TGA data, but it could be matched reasonably well if corrected for a slight volatility term. In general, a two-parameter cubic-linear growth-volatility law was believed to apply. Corresponding scale volatility loss rates, directly measured at 1300 °C on a pre-oxidized sample, were moderate (0.012 mg/cm2/h) and largely attributed to removal of the initial TiO2 transient scale. A related CH4 burner study of high purity Cr2AlC MAX phase demonstrated 1200 °C durability after 500 rapid (5 min. heat and 2 min. cool) thermal shock cycling (29 h hot time) (Ref. 12). Heating and cooling rates were ~1000 and 500 °C per minute, with a gas velocity of 5 m/s, producing a 75 °C/mm gradient. A 7 μm Al2O3 surface scale and a 13 μm Cr7C3 depletion zone formed with no signs of failure. No evidence of scale volatility was evident, although weight change was not provided, the velocity was moderate, and the total hot time was not extensive. The same high gradient BRT was used to produce 1400 °C surface temperatures for a YSZ/Cr2AlC/IN738 system in the first study of MAX phases used as bond coats for thermal barrier coatings (TBC) (Ref. 25). Here TBC failure was reported after 745 cycles, with only a 1.5 μm Al2O3 scale entrained within a porous, Cr7C3 bondcoat depletion phase. YSZ thermal barrier coatings have been considered to be a compatible complement to Al-MAX phases because of thermal expansion matching and extremely low volatility in water vapor. Initial studies showed superior oxidative stability up to 1300 °C, for long times (at least 500 h) for Ti2AlC substrates and less (268 h) for Cr2AlC, while withstanding large alumina TGO scale thickness (~35 to 40 μm) (Refs. 13 and 14). By comparison, typical superalloy systems can only survive 1150 °C maximum interface temperatures for extended periods, with a maximum sustained TGO below 10 μm (Ref. 15). High temperature SiC based systems are known to form slow-growing SiO2 scales. But these are subject to rate enhancement and volatile Si(OH)4 products in the presence of water vapor, as described comprehensively by Opila, et al. (Refs. 5, 16 to 19). Net weight losses are generally observed in high velocity, high pressure burner rig studies (e.g., 0.084 mg/cm2/h at 1300 °C) (Ref. 20). Furthermore, the loss rates have been shown from chemical physics to scale with v1/2 and pH2O 2 (Ref. 16). Low activity, moisture-resistant environmental barrier coatings (EBC), such as rare earth silicates, are needed to prevent substrate recession under turbine conditions (Refs. 21 to 23).

Smialek, James L.↗

A Universal Design of Lithium Anode via Dynamic Stability Strategy for Practical All‐Solid‐State Batteries

Abstract All‐solid‐state Li‐metal battery (ASSLB) chemistry with thin solid‐state electrolyte (SSE) membranes features high energy density and intrinsic safety but suffers from severe dendrite formation and poor interface contact during cycling, which hampers the practical application of rechargeable ASSLB. Here, we propose a universal design of thin Li‐metal anode (LMA) via a dynamic stability strategy to address these issues. The ultra‐thin LMA (20 μm) is in situ constructed with uniform highly Li‐ion conductive solid‐electrolyte interphase and composite‐polymer interphase (CPI) via electroplating process. As a result, the passivation layer with poor Li‐ion conduction on Li anode can be dissolved and small surface resistance can be achieved due to the good compatibility of CPI to SSEs. The cycling of Li symmetric cell with Li 6 PS 5 Cl thin film electrolyte (<100 μm) shows a high critical current density of >2.0 mA cm −2 with excellent cycling stability at 1.0 mA cm −2 . The ASSLBs paring with Ni‐rich LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode demonstrated the feasibility of engineered LMA design by presenting good rate capability from 0.1 C to 1.0 C at room temperature, as well as long‐term cycling stability (81 % retention after 100 cycles). This work represents a general pathway to make thin dendrite‐free LMA available for high‐energy‐density ASSLBs.

Deng, Tao [Department of Chemical and Biomolecular↗

A Universal Design of Lithium Anode via Dynamic Stability Strategy for Practical All‐Solid‐State Batteries

Abstract All‐solid‐state Li‐metal battery (ASSLB) chemistry with thin solid‐state electrolyte (SSE) membranes features high energy density and intrinsic safety but suffers from severe dendrite formation and poor interface contact during cycling, which hampers the practical application of rechargeable ASSLB. Here, we propose a universal design of thin Li‐metal anode (LMA) via a dynamic stability strategy to address these issues. The ultra‐thin LMA (20 μm) is in situ constructed with uniform highly Li‐ion conductive solid‐electrolyte interphase and composite‐polymer interphase (CPI) via electroplating process. As a result, the passivation layer with poor Li‐ion conduction on Li anode can be dissolved and small surface resistance can be achieved due to the good compatibility of CPI to SSEs. The cycling of Li symmetric cell with Li 6 PS 5 Cl thin film electrolyte (<100 μm) shows a high critical current density of >2.0 mA cm −2 with excellent cycling stability at 1.0 mA cm −2 . The ASSLBs paring with Ni‐rich LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode demonstrated the feasibility of engineered LMA design by presenting good rate capability from 0.1 C to 1.0 C at room temperature, as well as long‐term cycling stability (81 % retention after 100 cycles). This work represents a general pathway to make thin dendrite‐free LMA available for high‐energy‐density ASSLBs.

Deng, Tao [Department of Chemical and Biomolecular↗

Photocatalytic Semiconductor–Metal Hybrid Nanoparticles: Single-Atom Catalyst Regime Surpasses Metal Tips

Semiconductor–metal hybrid nanoparticles (HNPs) are promising materials for photocatalytic applications, such as water splitting for green hydrogen generation. While most studies have focused on Cd containing HNPs, the realization of actual applications will require environmentally compatible systems. Using heavy-metal free ZnSe-Au HNPs as a model, we investigate the dependence of their functionality and efficiency on the cocatalyst metal domain characteristics ranging from the single-atom catalyst (SAC) regime to metal-tipped systems. The SAC regime was achieved via the deposition of individual atomic cocatalysts on the semiconductor nanocrystals in solution. Utilizing a combination of electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy, we established the presence of single Au atoms on the ZnSe nanorod surface. Upon increased Au concentration, this transitions to metal tip growth. Photocatalytic hydrogen generation measurements reveal a strong dependence on the cocatalyst loading with a sharp response maximum in the SAC regime. Ultrafast dynamics studies show similar electron decay kinetics for the pristine ZnSe nanorods and the ZnSe-Au HNPs in either SAC or tipped systems. This indicates that electron transfer is not the rate-limiting step for the photocatalytic process. Combined with the structural-chemical characterization, we conclude that the enhanced photocatalytic activity is due to the higher reactivity of the single-atom sites. This holistic view establishes the significance of SAC-HNPs, setting the stage for designing efficient and sustainable heavy-metal-free photocatalyst nanoparticles for numerous applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗