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At least 1,135 records · Page 63

What can we learn from N 2 O isotope data? – Analytics, processes and modelling

The isotopic composition of nitrous oxide (N 2 O) provides useful information for evaluating N 2 O sources and budgets. Due to the co–occurrence of multiple N 2 O transformation pathways, it is, however, challenging to use isotopic information to quantify the contribution of distinct processes across variable spatiotemporal scales. Here, we present an overview of recent progress in N 2 O isotopic studies and provide suggestions for future research, mainly focusing on: analytical techniques; production and consumption processes; and interpretation and modelling approaches. Comparing isotope–ratio mass spectrometry (IRMS) with laser absorption spectroscopy (LAS), we conclude that IRMS is a precise technique for laboratory analysis of N 2 O isotopes, while LAS is more suitable for in situ/inline studies and offers advantages for site–specific analyses. When reviewing the link between the N 2 O isotopic composition and underlying mechanisms/processes, we find that, at the molecular scale, the specific enzymes and mechanisms involved determine isotopic fractionation effects. In contrast, at plot–to–global scales, mixing of N 2 O derived from different processes and their isotopic variability must be considered. We also find that dual isotope plots are effective for semi–quantitative attribution of co–occurring N 2 O production and reduction processes. More recently, process–based N 2 O isotopic models have been developed for natural abundance and 15 N–tracing studies, and have been shown to be effective, particularly for data with adequate temporal resolution. Here, despite the significant progress made over the last decade, there is still great need and potential for future work, including development of analytical techniques, reference materials and inter–laboratory comparisons, further exploration of N 2 O formation and destruction mechanisms, more observations across scales, and design and validation of interpretation and modelling approaches. Synthesizing all these efforts, we are confident that the N 2 O isotope community will continue to advance our understanding of N 2 O transformation processes in all spheres of the Earth, and in turn to gain improved constraints on regional and global budgets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High‐Loading Lithium‐Sulfur Batteries with Solvent‐Free Dry‐Electrode Processing

Abstract Lithium‐sulfur (Li‐S) batteries, with their high energy density, nontoxicity, and the natural abundance of sulfur, hold immense potential as the next‐generation energy storage technology. To maximize the actual energy density of the Li‐S batteries for practical applications, it is crucial to escalate the areal capacity of the sulfur cathode by fabricating an electrode with high sulfur loading. Herein, ultra‐high sulfur loading (up to 12 mg cm −2 ) cathodes are fabricated through an industrially viable and sustainable solvent‐free dry‐processing method that utilizes a polytetrafluoroethylene binder fibrillation. Due to its low porosity cathode architecture formed by the binder fibrillation process, the dry‐processed electrodes exhibit a relatively lower initial capacity compared to the slurry‐processed electrode. However, its mechanical stability is well maintained throughout the cycling without the formation of electrode cracking, demonstrating significantly superior cycling stability. Additionally, through the optimization of the dry‐processing, a single‐layer pouch cell with a loading of 9 mg cm −2 and a novel multi‐layer pouch cell that uses an aluminum mesh as its current collector with a total loading of 14 mg cm −2 are introduced. To address the reduced initial capacity of dry‐processed electrodes, strategies such as incorporating electrocatalysts or employing prelithiated active materials are suggested.

Chemistry↗

An experimental investigation of the effectiveness of Ar-CO 2 shielding gas mixture for the wire arc additive process

Wire arc additive manufacturing (AM) is the process by which a large, metallic structure is built layer-by-layer using a welding arc to melt a wire feedstock. A novel opportunity exists to alter the shielding gas composition to fabricate distinct geometrical features without altering the other AM parameters. In this paper, shielding gases with varied concentrations of Argon (Ar) and CO 2 was used to deposit three distinct geometric shapes (walls, infill, and overhang) using a wire-based additive manufacturing system utilizing the gas metal arc welding (GMAW) surface tension transfer (STT) process. Computer-aided design (CAD) models were sliced with a custom-built slicer, and the sliced algorithm was converted into optimal robotic toolpaths. A custom virtual instrument (VI) was built in LabVIEW to compare the temperature profiles on the surface during each deposition process. After each deposition, the geometric features were scanned, and the surface waviness value was evaluated. Tensile and Charpy impact coupons were extracted from the wall geometries in the longitudinal and transverse directions and tested. The results indicated that a higher CO 2 content produced higher melt pool temperatures to an extent, while lower contents of CO 2 resulted in a dimensionally accurate geometry. The data also indicated that the 2%/98% CO 2 /Ar blend produced scatter in tensile strength and the analysis of variance (ANOVA) shows significant difference. However, the intermediate range of CO 2 (5–10%) resulted in uniform tensile properties. Altogether, these results indicate that a 5%/95% CO 2 /Ar blend is the ideal shielding gas for lowering process temperatures and improving mechanical properties in wire arc additive manufacturing using the gas metal arc welding surface tension transfer process. Additionally, varying concentrations of Ar/CO 2 can be used within the same part in order to modify the local properties or process parameters such as strength, toughness, temperature, or dimensional features. This may improve overall manufacturing quality without sacrificing specific properties.

42 ENGINEERING↗

Single-Grain Bulk YBa{sub 2}Cu{sub 3}O{sub y} Superconductors Grown by Infiltration Growth Process Utilizing the YbBa{sub 2}Cu{sub 3}O{sub y} + Liquid Phase as a Liquid Source

The top-seeded infiltration growth (IG) processed YBa{sub 2}Cu{sub 3}O{sub y} (Y-123) has several advantages compared to the same material produced by other melt process techniques. There is usually no shrinkage, a limited number of pores, and an uniform secondary phase particle dispersion in the Y-123 matrix. These characteristics of the IG process are very attractive for several industrial applications. In this paper, we produced a large single-grain Y-123 by IG and top seeded melt-growth process. Utilizing commercial YbBa{sub 2}Cu{sub 3}O{sub y} (Yb-123) and a homemade Y{sub 2}BaCuO{sub 5} (Y-211), we produced bulk YBa{sub 2}Cu{sub 3}O{sub y} samples using Yb-123 + liquid (1:1) as a liquid source. Four facet lines on the top surfaces of the as-grown samples indicated a uniform growth from the seed up to sample edges. Magnetization measurements by SQUID magnetometer showed a sharp superconducting transition with T{sub c},{sub onset} at 92.1 K. The critical current density at 77 K and self-field was 39,000 A/cm{sup 2}. Trapped field results confirmed that single grain Y-123 samples were produced utilizing the above process. Our results prove that Yb-123 + liquid (1:1) as a liquid source is effective in producing single grain Y-123 material by IG process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Scaling Limits and Generic Bounds for Exploration Processes

We consider exploration algorithms of the random sequential adsorption type both for homogeneous random graphs and random geometric graphs based on spatial Poisson processes. At each step, a vertex of the graph becomes active and its neighboring nodes become blocked. Given an initial number of vertices N growing to infinity, we study statistical properties of the proportion of explored (active or blocked) nodes in time using scaling limits. We obtain exact limits for homogeneous graphs and prove an explicit central limit theorem for the final proportion of active nodes, known as the jamming constant, through a diffusion approximation for the exploration process which can be described as a unidimensional process. We then focus on bounding the trajectories of such exploration processes on random geometric graphs, i.e., random sequential adsorption. As opposed to exploration processes on homogeneous random graphs, these do not allow for such a dimensional reduction. Instead we derive a fundamental relationship between the number of explored nodes and the discovered volume in the spatial process, and we obtain generic bounds for the fluid limit and jamming constant: bounds that are independent of the dimension of space and the detailed shape of the volume associated to the discovered node. Lastly, using coupling techinques, we give trajectorial interpretations of the generic bounds.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Discrete Approximations of Determinantal Point Processes on Continuous Spaces: Tree Representations and Tail Triviality

We prove tail triviality of determinantal point processes μ on continuous spaces. Tail triviality has been proved for such processes only on discrete spaces, and hence we have generalized the result to continuous spaces. To do this, we construct tree representations, that is, discrete approximations of determinantal point processes enjoying a determinantal structure. There are many interesting examples of determinantal point processes on continuous spaces such as zero points of the hyperbolic Gaussian analytic function with Bergman kernel, and the thermodynamic limit of eigenvalues of Gaussian random matrices for Sine{sub 2},Airy{sub 2},Bessel{sub 2}, and Ginibre point processes. Our main theorem proves all these point processes are tail trivial.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Numerical Investigation of Novel Oxygen Blast Furnace Ironmaking Processes

Oxygen blast furnace (OBF) ironmaking process has the potential to realize “zero carbon footprint” production, but suffers from the “thermal shortage” problem. This paper presents three novel OBF processes, featured by belly injection of reformed coke oven gas, burden hot-charge operation, and their combination, respectively. These processes were studied by a multifluid process model. The applicability of the model was confirmed by comparing the numerical results against the measured key performance indicators of an experimental OBF operated with or without injection of reformed coke oven gas. Then, these different OBF processes together with a pure OBF were numerically examined in aspects of in-furnace states and global performance, assuming that the burden quality can be maintained during the hot-charge operation. The numerical results show that under the present conditions, belly injection and hot charge, as auxiliary measures, are useful for reducing the fuel rate and increasing the productivity for OBFs but in different manners. Hot charge should be more suitable for OBFs of different sizes because it improves the thermochemical states throughout the dry zone rather than within a narrow region in the case of belly injection. The simultaneous application of belly injection and hot charge leads to the best process performance, at the same time, lowering down hot-charge temperature to achieve the same carbon consumption and hot metal temperature as that achieved when applying the hot charge alone. This feature will be practically beneficial in the application of hot-charge operation. In addition, a systematic study of hot-charge temperature reveals that optimal hot-charge temperatures can be identified according to the utilization efficiency of the sensible heat of hot burden.

36 MATERIALS SCIENCE↗

Effect of Welding Processes on the Microstructure, Mechanical Properties and Residual Stresses of Plain 9Cr-1Mo Steel Weld Joints

9Cr-1Mo steel designated as P9 is widely used in the construction of power plants and high-temperature applications. It is chosen for fabricating hexcan fuel subassembly wrapper components of fast breeder reactors. Arc welding processes are generally used for fabricating 9Cr-1Mo steel weld joints. A-TIG welding process is increasingly being adopted by the industries. In the present study, shielded metal arc (SMA), tungsten inert gas (TIG) and A-TIG welding processes are used for fabricating the 9Cr-1Mo steel weld joints of 10 mm thickness. Effect of the above welding processes on the microstructure evolution, mechanical properties and residual stresses of the weld joints has been studied in detail. All the three weld joints exhibited comparable strength and ductility values. 9Cr-1Mo steel weld joint fabricated by SMAW process exhibited lower impact toughness values caused by coarser grain size and inclusions. 9Cr-1Mo steel weld joint fabricated by TIG welding exhibited higher toughness due to finer grain size, while the weld joint fabricated by A-TIG welding process exhibited adequate toughness values. SMA steel weld joint exhibited compressive residual stresses in the weld metal and HAZ, while TIG and A-TIG weld joint exhibited tensile residual stresses in the weld metal and HAZ.

36 MATERIALS SCIENCE↗

Processing Parameter Effects on Residual Stress and Mechanical Properties of Selective Laser Melted Ti6Al4V

Selective laser melting (SLM) process is characterized by large temperature gradients resulting in high levels of residual stress within the additively manufactured metallic structure. SLM-processed Ti6Al4V yields a martensitic microstructure due to the rapid solidification and results in a ductility generally lower than a hot working equivalent. Post-process heat treatments can be applied to SLM components to remove in-built residual stress and improve ductility. Residual stress buildup and the mechanical properties of SLM parts can be controlled by varying the SLM process parameters. This investigation studies the effect of layer thickness on residual stress and mechanical properties of SLM Ti6Al4V parts. This is the first-of-its kind study on the effect of varying power and exposure in conjunction with keeping the energy density constant on residual stress and mechanical properties of SLM Ti6Al4V components. It was found that decreasing power and increasing exposure for the same energy density lowered the residual stress and improved the % elongation of SLM Ti6Al4V parts. Increasing layer thickness resulted in lowering the residual stress at the detriment of mechanical properties. The study is based on detailed experimental analysis along with finite element simulation of the process using ABAQUS to understand the underlying physics of the process.

36 MATERIALS SCIENCE↗

Techno-Economic Analysis of Magnesium Extraction from Seawater via a Catalyzed Organo-Metathetical Process

Magnesium (Mg) has many useful applications especially in various Mg alloys which can decrease weight while increasing strength. To increase the affordability and minimize environment consequence, a novel catalyzed organo-metathetical (COMET) process was proposed to extract Mg from seawater aiming to achieve significant reduction in total energy and production cost comparing with the melting salt electrolysis method currently adopted by US Mg LLC. A process flowsheet for a reference COMET process was set-up using Aspen Plus which included five key steps, anhydrous MgCl2 production, transmetallation, dibutyl Mg decomposition, n-BuLi regeneration, and LiCL electrolysis. The energy and production cost and CO2 emission were estimated based on the Aspen modeling using Aspen economic analyzer. Our results showed that it is possible to produce Mg from seawater with a production cost of $2.0/kg-Mg while consuming about 35.3 kWh/kg-Mg and releasing 7.0 kg CO2/kg-Mg. A simplified US Mg manufacturing process was also generated using Aspen and the cost and emission results were estimated for comparison purpose. Under our simulation conditions, the reference COMET process maintain a comparable CO2 emission rate and can save about 40% in production cost and save about 15% energy compared to the simplified US Mg process.

Liu, Jian (ORCID:0000000153297408)↗

Mechanical Characteristics of Additively Manufactured ODS 316L and 316H Alloys with and Without Post-build Processing

This research aims to explore an accelerated development path for oxide dispersion-strengthened (ODS) alloys by integrating additive manufacturing (AM) technologies with recent advances in ODS materials and traditional manufacturing methods. Novel AM and post-build processing routes have been developed for ODS austenitic alloys, specifically Fe-Cr-Ni alloys like 316L and 316H. Electron microscopy and mechanical characterizations were conducted to evaluate the effects of process variables on microstructure and properties, aiming for an economically feasible route property optimization. Traditionally, ODS alloy production involves multi-day high-energy mechanical milling of alloy powder with yttria (Y 2 O 3 ) followed by powder consolidation via extrusion or other methods and additional thermomechanical processing (TMP) for property control. Here, to address these challenges associated with this complex and costly approach, we propose exploring alternative, cost-effective processing routes focusing on AM and traditional TMP methods. The new ODS alloy processing routes have achieved up to a 400% increase in yield strength and a 60% increase in ultimate tensile strength compared to wrought stainless steels while still maintaining significant ductility and fracture toughness. This paper details the novel and economical AM-based processing routes for ODS austenitic alloys, combined with post-build TMPs, and discusses the mechanical and microstructural characteristics of the developed materials.

Byun, Thak Sang [Oak Ridge National Laboratory (OR↗

Utilization of Hemp Processing Waste for 3D Printing of Biocomposites

Unlike stem biomass, the residues after the extraction of cannabidiol (CBD) oil from hemp flower are challenging to utilize because of their high extractive content (~ 40%, mainly lipids) and are typically considered waste and landfilled. This study presented a novel approach to effectively valorize this underutilized hemp processing waste via chemical processing for three-dimensional (3D) printing applications. Hemp processing waste was processed with sodium hydroxide (NaOH) to control extractives for solving nozzle clogging and then applied as a biofiller in polylactic acid (PLA) composites to improve the mechanical strength. The novelty of this work lies in demonstrating that controlled extractive removal via NaOH treatment not only improves processability but also enhances mechanical performance in 3D-printed biocomposites. We systematically investigated the effect of the processed biofiller content (2.5–10 wt%) on the mechanical and thermal properties of the biocomposites. The decrease in the content of extractives reduced the non-structural components and improved the surface compatibility of the hemp waste with the PLA matrix, thereby enhancing the polymer-biofiller interactions. The best performance was achieved at 2.5 wt% loading, where Young’s modulus increased from 2.3 GPa to 2.6 GPa and tensile strength from 42.7 MPa to 48.8 MPa. Interestingly, the complete removal of extractives also reduced the mechanical strength of their biocomposites, indicating the interfacial adhesion effects of extractives. Furthermore, this study provides new insights into balancing extractive content for optimal mechanical properties, offering a sustainable solution for waste valorization in additive manufacturing.

Additive manufacturing↗

Parameters, Properties, and Process: Conditional Neural Generation of Realistic SEM Imagery Toward ML-Assisted Advanced Manufacturing

Abstract The research and development cycle of advanced manufacturing processes traditionally requires a large investment of time and resources. Experiments can be expensive and are hence conducted on relatively small scales. This poses problems for typically data-hungry machine learning tools which could otherwise expedite the development cycle. We build upon prior work by applying conditional generative adversarial networks (GANs) to scanning electron microscope (SEM) imagery from an emerging advanced manufacturing process, shear-assisted processing and extrusion (ShAPE). We generate realistic images conditioned on temper and either experimental parameters or material properties. In doing so, we are able to integrate machine learning into the development cycle, by allowing a user to immediately visualize the microstructure that would arise from particular process parameters or properties. This work forms a technical backbone for a fundamentally new approach for understanding manufacturing processes in the absence of first-principle models. By characterizing microstructure from a topological perspective, we are able to evaluate our models’ ability to capture the breadth and diversity of experimental scanning electron microscope (SEM) samples. Our method is successful in capturing the visual and general microstructural features arising from the considered process, with analysis highlighting directions to further improve the topological realism of our synthetic imagery.

36 MATERIALS SCIENCE↗

Image Processing Pipeline for Fluoroelastomer Crystallite Detection in Atomic Force Microscopy Images

Phase transformations in materials systems can be tracked using atomic force microscopy (AFM), enabling the examination of surface properties and macroscale morphologies. In situ measurements investigating phase transformations generate large datasets of time-lapse image sequences. The interpretation of the resulting image sequences, guided by domain-knowledge, requires manual image processing using handcrafted masks. Here this approach is time-consuming and restricts the number of images that can be processed. Her in this study, we developed an automated image processing pipeline which integrates image detection and segmentation methods. We examine five time-series AFM videos of various fluoroelastomer phase transformations. The number of image sequences per video ranges from a hundred to a thousand image sequences. The resulting image processing pipeline aims to automatically classify and analyze images to enable batch processing. Using this pipeline, the growth of each individual fluoroelastomer crystallite can be tracked through time. We incorporated statistical analysis into the pipeline to investigate trends in phase transformations between different fluoroelastomer batches. Understanding these phase transformations is crucial, as it can provide valuable insights into manufacturing processes, improve product quality, and possibly lead to the development of more advanced fluoroelastomer formulations.

36 MATERIALS SCIENCE↗

Life cycle greenhouse gas emissions of hydrogen fuel production from chlor-alkali processes in the United States

By-product hydrogen from chlor-alkali processes can help meet the increasing demand for hydrogen fuel in early fuel cell electric vehicle markets (e.g., California) in the U.S. Hydrogen produced from chlor-alkali plants is typically combusted for process heat on site, vented to the atmosphere (i.e., wasted), or sold to the external merchant hydrogen market. Whether it is combusted, vented, or sold as a commodity, relevant information is lacking as to the life-cycle environmental benefits or trade-offs of using by-product hydrogen from chlor-alkali plants. A life-cycle analysis framework was employed to evaluate well-to-gate greenhouse gas (GHG) emissions associated with by-product hydrogen from chlor-alkali processes in comparison with hydrogen from the conventional centralized natural gas steam methane reforming (central SMR) pathway. U.S.-specific, plant-by-plant, and up-to-date chlor-alkali production characteristics were incorporated into the analysis. In addition to the venting and combustion scenarios, to deal with the multi-functionality of the chlor-alkali processes that simultaneously produce chlorine, sodium hydroxide, and hydrogen, two different co-product allocation strategies were adopted mass allocation and market value allocation. It was estimated that by-product hydrogen production from chlor-alkali processes creates 1.3-9.8 kg CO 2 e/kg H 2 of life-cycle GHG emissions on average, which is 20-90% less than the conventional central SMR pathway. The results vary with co-product treatment scenarios, regional electric grid characteristics, on-site power generation, product prices, and hydrogen yield. Despite the variations in the results, it was concluded that the life-cycle GHG emission reduction benefits of using by-product hydrogen from chlor-alkali processes are robust. In conclusion, with a diverse set of scenario analyses, the study developed a comprehensive and detailed life-cycle GHG emissions inventory of the chlor-alkali by-product hydrogen pathway and quantified sensitivity indices in the context of different assumptions and input parameter values.

08 HYDROGEN↗

Bioalcohol production from acidogenic products via a two-step process: A case study of butyric acid to butanol

This article presents the full study (lab-scale experimental study and large-scale techno-economic analysis) results of a two-step catalytic process for the conversion of organic waste–derived butyric acid to butanol. Butanol from biomass resources like organic waste promise to become an attractive and sustainable fuel and industrial precursor due to an increase in greenhouse gas content in the atmosphere. Therefore, research in this field is important for energy applications and reduction in greenhouse gas emissions. In this regard, a two-step process was applied in this study to produce butanol from butyric acid that can potentially be derived from organic waste. The two-step process consists of the (1) esterification of butyric acid to methyl butyrate and (2) hydrogenolysis of this methyl butyrate to butanol. The first reaction, esterification of butyric acid, was optimized using carbon-based catalysts. The production of butanol from methyl butyrate via hydrogenolysis was investigated using bimetallic Pt–Co catalysts. The hydrogenolysis of methyl butyrate on these catalysts under optimal conditions of 250 °C, 5 MPa H 2 , and a feed/catalyst weight ratio of 11.2 led to 54.1% selectivity toward 1-butanol. Based on the experimental results, an integrated process simulation model was developed to determine the economic potential of the two-step production of butanol from butyric acid. Using this model, the techno-economic feasibility of the two-step process was analyzed. Here, the minimum selling price (MSP) of 1-butanol produced from butyric acid using this process was US dollars 3.388 per gallon of gasoline equivalent (GGE). This MSP is in the range of recent biofuel market prices of US dollars 2.03/GGE to US dollars 3.83/GGE.

09 BIOMASS FUELS↗

Friction stir processing of dual certified 304/304L austenitic stainless steel for improved cavitation erosion resistance

Cavitation phenomenon is known to be prevalent in equipment in hydraulic environments. Understanding cavitation and improving the cavitation resistance of commonly used materials is of interest for both scientific and economic reasons. In this study, friction stir processing was employed to modify commercial dual certified AISI 304/304L austenitic stainless steel plates. The cavitation erosion resistance of the processed plates was evaluated and compared to that of the unprocessed steel. A temperature control algorithm was employed to maintain a target tool temperature during the processing. The cross sections of the processed nuggets were evaluated using optical microscopy, scanning electron microscopy and Vickers hardness testing. Cavitation testing was performed conforming to ASTM G134 on specimens cut out of the nuggets of the commercially unprocessed and the processed 304/304L steel. The tool temperature was found to affect the microstructure and the cavitation performance. Friction stir processed steel showed 3 times better cavitation resistance than the unprocessed 304/304L. Surface cavitation patterns and cavitation rates were characterized and the mechanisms of material removal were discussed.

Jiang, Xiujuan↗

Weighted gene co-expression network analysis reveals potential genes involved in early metamorphosis process in sea cucumber Apostichopus japonicus

Highlights: • Gene expression profiles of sea cucumber were systematically examined. • Gene co-expression modules of sea cucumber were analyzed for the first time. • The module MEdarkmagenta is highly related to the early metamorphosis process. • Genes associated with the early metamorphosis process were identified. Sea cucumbers, one main class of Echinoderms, have a very fast and drastic metamorphosis process during their development. However, the molecular basis under this process remains largely unknown. Here we systematically examined the gene expression profiles of Japanese common sea cucumber (Apostichopus japonicus) for the first time by RNA sequencing across 16 developmental time points from fertilized egg to juvenile stage. Based on the weighted gene co-expression network analysis (WGCNA), we identified 21 modules. Among them, MEdarkmagenta was highly expressed and correlated with the early metamorphosis process from late auricularia to doliolaria larva. Furthermore, gene enrichment and differentially expressed gene analysis identified several genes in the module that may play key roles in the metamorphosis process. Our results not only provide a molecular basis for experimentally studying the development and morphological complexity of sea cucumber, but also lay a foundation for improving its emergence rate.

60 APPLIED LIFE SCIENCES↗