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At least 1,117 records · Page 62

Methane pyrolysis by Joule heating for graphitic carbon and hydrogen production

The global energy transition toward sustainability requires technologies that can decarbonize energy carriers and fuels while producing valuable materials. Methane, a primary component of natural gas, is both a high-energy-density fuel and a significant greenhouse gas. This study reports an approach for methane pyrolysis utilizing Joule heating within the deposition substrate to drive the endothermic reaction. With electric current passing through a resistive porous carbon cloth, heat is generated to break C-H bonds of methane molecules. Here, the decomposition of methane as it flows through the cloth results in hydrogen production and the formation of conformally layered graphite around the carbon fibers. The effects of input power, chamber pressure, feedstock flow rate, and process duration on hydrogen and graphite production are characterized via in situ mass spectrometry and laser absorption spectroscopy, resulting in methane conversion rates up to 88%, with hydrogen and carbon yields of 82% and 72%, respectively. Material characterization verifies uniform high-quality graphite deposition, with a Raman I D /I G ratio of 0.1 and 3.38 Å d-spacing. This Joule heating method for catalyst-free methane pyrolysis offers the potential for advancing hydrogen production technology by simultaneously producing valuable materials such as solid graphite, thus enhancing the economic viability of the fuel decarbonization process.

Energy Resources↗

Demystifying In Situ Pyrolysis Chemistry for High-Performance Polyanionic Cathodes in Sodium-Ion Batteries

In this article, the carbon coating strategy has emerged as an indispensable approach to improve the conductivity of polyanionic cathodes. However, owing to the complex reaction process between precursors of carbon and cathode, establishing a unified screening principle for carbonaceous precursors remains a technical challenge. Herein, we reveal that carbonaceous precursor pyrolysis chemistry undeniably influences the formation process and performance of Na 3 V 2 (PO 4 ) 3 (NVP) cathodes from in situ insights. By investigating three types of carbonaceous precursors, it is found that O/H-containing functional groups can provide more bonding sites for cathode precursors and generate a reducing atmosphere by pyrolysis, which is beneficial to the formation of polyanionic materials and a uniform carbon coating layer. Conversely, excessive pyrolysis of functional groups leads to a significant amount of gas, which is detrimental to the compactness of the carbon layer. Furthermore, the substantial presence of residual heteroatoms diminishes graphitization. In this case, it is demonstrated that carbon dots (CDs) precursors with suitable functional groups can comprehensively enhance the Na+ migration rate, reversibility, and interface stability of the cathode material. As a result, the NVP/CDs cathode displays outstanding capacity retention, maintaining 92% after 10,000 cycles at a high rate of 50 C. Altogether, these findings provide a valuable benchmark for carbon source selection for polyanionic cathodes.

25 ENERGY STORAGE↗

High-throughput, in situ imaging of multi-layer powder-blown directed energy deposition with angled nozzle

Laser metal additive manufacturing (AM) has become an increasingly popular technology due to its flexibility in geometry and materials. As one of the commercialized additive processes, powder-blown directed energy deposition (DED) has been used in multiple industries such as aerospace, automotive, medical device, etc. However, a lack of fundamental understanding remains for this process, and many opportunities for alloy development and implementation can be identified. A high-throughput, in situ DED system capable of multi-layer builds that can address these issues is presented here. In this work, implications of layer heights and energy density are investigated through an extensive process parameter sweep, showcasing the power of a high-throughput setup while also discussing multi-layer interactions.

47 OTHER INSTRUMENTATION↗

Single liquid source plasma-enhanced metalorganic chemical vapor deposition of high-quality YBa2Cu3O(7-x) thin films

High quality YBa2Cu3O(7-x) films were grown in-situ on LaAlO3 (100) by a novel single liquid source plasma-enhanced metalorganic chemical vapor deposition process. The metalorganic complexes M(thd) (sub n), (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate; M = Y, Ba, Cu) were dissolved in an organic solution and injected into a vaporizer immediately upstream of the reactor inlet. The single liquid source technique dramatically simplifies current CVD processing and can significantly improve the process reproducibility. X-ray diffraction measurements indicated that single phase, highly c-axis oriented YBa2Cu3O(7-x) was formed in-situ at substrate temperature 680 C. The as-deposited films exhibited a mirror-like surface, had transition temperature T(sub cO) approximately equal to 89 K, Delta T(sub c) less than 1 K, and Jc (77 K) = 10(exp 6) A/sq cm.

Zhang, Jiming↗

Low-frequency variability of sea level as related to the heat balance of global oceans

The TOPEX/POSEIDON mission will determine global changes of sea level with unprecedented accuracy. Our main objective is the use TOPEX/POSEIDON data, concurrent in situ ocean measurements, and other satellite observations to document and diagnose physical processes by which heat is exchanged with the atmosphere, stored in the ocean, or transported by ocean circulation. During the prelaunch period, our objectives are to advise the project on an improved method of retrieving sea level data and prepare for the application of TOPEX/POSEIDON data by developing a diagnostic model using in situ measurements and altimeter observations from Geosat and the European Remote Sensing satellite.

Liu, W. Timothy↗

In Situ X-ray Radiography and Computational Modeling to Predict Grain Morphology in $\beta$-Titanium during Simulated Additive Manufacturing

The continued development of metal additive manufacturing (AM) has expanded the engineering metallic alloys for which these processes may be applied, including beta-titanium alloys with desirable strength-to-density ratios. To understand the response of beta-titanium alloys to AM processing, solidification and microstructure evolution needs to be investigated. In particular, thermal gradients (Gs) and solidification velocities (Vs) experienced during AM are needed to link processing to microstructure development, including the columnar-to-equiaxed transition (CET). In this work, in situ synchrotron X-ray radiography of the beta-titanium alloy Ti-10V-2Fe-3Al (wt.%) (Ti-1023) during simulated laser-powder bed fusion (L-PBF) was performed at the Advanced Photon Source at Argonne National Laboratory, allowing for direct determination of Vs. Two different computational modeling tools, SYSWELD and FLOW-3D, were utilized to investigate the solidification conditions of spot and raster melt scenarios. The predicted Vs obtained from both pieces of computational software exhibited good agreement with those obtained from in situ synchrotron X-ray radiography measurements. The model that accounted for fluid flow also showed the ability to predict trends unobservable in the in situ synchrotron X-ray radiography, but are known to occur during rapid solidification. A CET model for Ti-1023 was also developed using the Kurz–Giovanola–Trivedi model, which allowed modeled Gs and Vs to be compared in the context of predicted grain morphologies. Both pieces of software were in agreement for morphology predictions of spot-melts, but drastically differed for raster predictions. The discrepancy is attributable to the difference in accounting for fluid flow, resulting in magnitude-different values of Gs for similar Vs.

36 MATERIALS SCIENCE↗

Ag(111) Remains Significantly Reduced In Situ under Simulated Ethylene Epoxidation Conditions

Direct ethylene epoxidation is among the highest value processes in the chemical industry, yet the reaction mechanism remains debated. A central question is whether the unpromoted Ag catalyst is metallic or oxidized under reaction conditions, as this determines the active oxidant species. Using ambient pressure X-ray photoelectron spectroscopy at chemical potentials simulating industrial conditions, we find that under oxidizing environments, nucleophilic oxygen (∼80% surface coverage) and some carbonate impurities (∼20% coverage) form on Ag(111). Upon switching to an industrially relevant 5:2 ethylene-to-oxygen ratio at 433 K, nucleophilic oxygen is consumed, leaving mostly surface carbonate and bare Ag. The Ag(111) surface maintains ∼50% exposed metallic sites under these conditions. This indicates that proposed mechanisms involving a fully oxidized surface may not represent the state of the surface under relevant reaction conditions and that bare Ag sites, which are necessary to form the oxametallacycle intermediate thought to drive selective epoxidation, are available.

36 MATERIALS SCIENCE↗

Ice Nucleation Processes in Upper Tropospheric Wave-Clouds Observed During SUCCESS

We have compared in situ measurements near the leading-edges of wave-clouds observed during the SUCCESS experiment with numerical modeling of ice nucleation. Observations of high supersaturations with respect to ice (\geq 150\%) near the leading edge of a very cold wave cloud (T < --60^\circC) are consistent with recent theoretical and laboratory studies suggesting that large supersaturations are required to homogeneously freeze sulfate aerosols. Also, the peak ice crystal number densities observed in this cloud (about 4cm -3/sup>) are consistent with the number densities calculated in our model. The consistency between model results (using homogeneous freezing and the observations indicates that the number density of effective heterogeneous ice nuclei must be no more than about 2 cm -3 . In the warmer wave-cloud (T (approx.)eq --37^\circC) relatively large ice number densities were observed (20--40 cm -3 . Our model calculations suggest that these large number densities are only possible if liquid droplets were activated at the cloud leading-edge, followed by subsequent homogeneous freezing. If sulfate aerosols had frozen before liquid droplets could be activated, then the peak ice crystal number density should have been less than 10 cm -3 .

Jensen, E. J.↗

Preliminary System Analysis of In Situ Resource Utilization for Mars Human Exploration

We carried out a system analysis of processes for utilization of Mars resources to support human exploration of Mars by production of propellants from indigenous resources. Seven ISRU processes were analyzed to determine mass. power and propellant storage volume requirements. The major elements of each process include C02 acquisition, chemical conversion, and storage of propellants. Based on a figure of merit (the ratio of the mass of propellants that must be brought from Earth in a non-ISRU mission to the mass of the ISRU system. tanks and feedstocks that must be brought from Earth for a ISRU mission) the most attractive process (by far); is one where indigenous Mars water is accessible and this is processed via Sabatier/Electrolysis to methane and oxygen. These processes are technically relatively mature. Other processes with positive leverage involve reverse water gas shift and solid oxide electrolysis.

Mars↗

Uneven Strain Distribution Induces Consecutive Dislocation Slipping, Plane Gliding, and Subsequent Detwinning of Penta-Twinned Nanoparticles

Twin structures possess distinct physical and chemical properties by virtue of their specific twin configuration. However, twinning and detwinning processes are not fully understood on the atomic scale. Integrating in situ high resolution transmission electron microscopy and molecular dynamic simulations, here, we find tensile strain in the asymmetrical 5-fold twins of Au nanoparticles leads to twin boundary migration through dislocation sliding (slipping of an atomic layer) along twin boundaries and dislocation reactions at the 5-fold axis under an electron beam. Migration of one or two layers of twin planes is governed by energy barriers, but overall, the total energy, including surface, lattice strain, and twin boundary energy, is relaxed after consecutive twin boundary migration, leading to a detwinning process. In addition, surface rearrangement of 5-fold twinned nanoparticles can aid in the detwinning process.

36 MATERIALS SCIENCE↗

Measuring a Precise Ultra-Lightweight Spaceflight Mirror on Earth: The Analysis of the SHARPI PM Mirror Figure Data during Mirror Processing at GSFC

The SHARPI (Solar High Angular Resolution Photometric Imager) primary mirror is a 5kg, 0.5m paraboloid, diffraction limited at FUV wavelengths when placed in a 0-G environment. The ULE sandwich honeycomb mirror and the attached mount pads were delivered by ITT (then Kodak) in 2003 to NASA s Goddard Space Flight Center (GSFC). At GSFC, we accepted, coated, mounted, and vibration tested this mirror in preparation for flight on the PICTURES (Planet Imaging Concept Testbed Using a Rocket Experiment) mission. At each step, the integrated analysis of interferometer data and FEA models was essential to quantify the 0-G mirror figure. This task required separating nanometer sized variations from hundreds of nanometers of gravity induced distortion. The ability to isolate such features allowed in-situ monitoring of mirror figure, diagnosis of perturbations, and remediation of process errors. In this paper, we describe the technical approach used to achieve these measurements and overcome the various difficulties maintaining UV diffraction-limited performance with this aggressively lightweighted mirror.

Antonille, Scott↗

In Situ Insights into Cathode Calcination for Predictive Synthesis: Kinetic Crystallization of LiNiO 2 from Hydroxides

Abstract Calcination is a solid‐state synthesis process widely deployed in battery cathode manufacturing. However, its inherent complexity associated with elusive intermediates hinders the predictive synthesis of high‐performance cathode materials. Here, correlative in situ X‐ray absorption/scattering spectroscopy is used to investigate the calcination of nickel‐based cathodes, focusing specifically on the archetypal LiNiO 2 from Ni(OH) 2 . Combining in situ observation with data‐driven analysis reveals concurrent lithiation and dehydration of Ni(OH) 2 and consequently, the low‐temperature crystallization of layered LiNiO 2 alongside lithiated rocksalts. Following early nucleation, LiNiO 2 undergoes sluggish crystallization and structural ordering while depleting rocksalts; ultimately, it turns into a structurally‐ordered layered phase upon full lithiation but remains small in size. Subsequent high‐temperature sintering induces rapid crystal growth, accompanied by undesired delithiation and structural degradation. These observations are further corroborated by mesoscale modeling, emphasizing that, even though calcination is thermally driven and favors transformation towards thermodynamically equilibrium phases, the actual phase propagation and crystallization can be kinetically tuned via lithiation, providing freedom for structural and morphological control during cathode calcination.

36 MATERIALS SCIENCE↗

Near Infrared In-situ Measurements for the Detection of Keyhole Porosity in Autogenous Ti-6AL-4V Welds

Certification of additive manufactured metal parts requires nondestructive evaluation (NDE) to ensure build quality. NDE can be performed during the build process or post build. For large parts with complex geometries, post build NDE can be challenging. In-situ NDE potentially provides a way to perform the inspection layer by layer. This work explores the use of a high speed near infrared (NIR) camera that is focused in-line with a laser to obtain high spatial and temporal resolution thermal imagery of the melt pool and associated cooling areas. The thermal data is obtained during a laser melting process using a Ti-6Al-4V plate and of particular interest is the detection of keyhole porosity. Keyhole porosity can result from non-optimal build conditions, such as excessive laser power at a given laser scanning speed, that creates an entrapped bubble. The NIR measured melt pool and cooling areas are processed to detect keyhole porosity. The results are compared to X-ray CT results for validation. Small keyhole pores buried deep were not detectable with this technique, however, some larger subsurface elongated pores along with some open surface pores did show some promise for detectability.

additive manufacturing↗

In situ laser profilometry for material segmentation and digital reconstruction of a multicomponent additively manufactured part

In addition to its ability to produce geometrically complex parts, additive manufacturing offers a unique opportunity to collect data about a component while it is being fabricated. However, there has only been limited effort to characterize parts morphologically and compositionally in situ. In this article, we present a layer-by-layer, laser profilometry-based in situ characterization technique as a method to digitally reconstruct a multi-material part. Data collected by the laser profilometer yields height maps and grayscale images which are voxelized using purpose-built software to volumetrically reconstruct the part. Additionally, the same part was also analyzed using X-ray computed tomography (CT) which was not able to resolve the different compositional regions within the part, but captured the filament morphology. The part was then bisected to compare the digital reconstruction to the actual part morphology and composition. Overall, the digital reconstruction was in good agreement with both the CT and bisected images. Deviations between the digital reconstruction and the CT/bisected images are likely the result of image segmentation settings or material shifts after data was collected. The in situ characterization method demonstrated here sets the stage for real time process monitoring and paves the way for additively manufactured parts that are “born qualified.”

36 MATERIALS SCIENCE↗

Selective butene formation in direct ethanol-to-C3+-olefin valorization over Zn-Y/Beta and single-atom alloy composite catalysts using in situ generated hydrogen

The selective production of C3+ olefins from renewable feedstocks, especially via C1 and C2 platform chemicals, is a critical challenge for obtaining economically viable low-carbon middle distillate transportation fuels (i.e., jet and diesel). Here, we report a multifunctional catalyst system composed of Zn-Y/Beta and “single-atom” alloy (SAA) Pt-Cu/Al2O3 which selectively catalyzes ethanol-to-olefins (C3+, ETO) valorization in the absence of cofed hydrogen, forming butenes as the primary olefin products. Beta zeolites containing predominately isolated Zn and Y metal sites catalyze ethanol upgrading steps (588 K, 3.1 kPa ethanol, ambient pressure) regardless of cofed hydrogen partial pressure (0-98.3 kPa H2), forming butadiene as the primary product (60% selectivity at 87% conversion). The Zn-Y/Beta catalyst possesses site-isolated Zn and Y Lewis acid sites (at ~7 wt% Y) and Brønsted acidic Y sites, the latter of which has been previously uncharacterized. A secondary bed of SAA Pt-Cu/Al2O3 selectively hydrogenates butadiene to butene isomers at a consistent reaction temperature using hydrogen generated in situ from ethanol-to-butadiene (ETB) conversion. This unique hydrogenation reactivity at near-stoichiometric hydrogen and butadiene partial pressures is not observed over monometallic Pt or Cu catalysts, highlighting these operating conditions as a critical SAA catalyst application area for conjugated diene selective hydrogenation at high reaction temperatures (>573 K) and low H2/diene ratios (e.g., 1:1). Single-bed steady state selective hydrogenation rates, associated apparent hydrogen and butadiene reaction orders, and DFT calculations of the Horiuti-Polanyi reaction mechanisms indicate that the unique butadiene selective hydrogenation reactivity over SAA Pt-Cu/Al2O3 reflects lower hydrogen scission barriers relative to monometallic Cu surfaces and limited butene binding energies relative to monometallic Pt surfaces. DFT calculations further indicate the preferential desorption of butene isomers over SAA Pt-Cu(111) and Cu(111) surfaces while Pt(111) surface favors subsequent butene hydrogenation reactions to form butane over butene desorption events. Under operating conditions without of hydrogen cofeeding, this combination of Zn-Y/Beta and SAA Pt-Cu catalysts can selectively form butenes (65% butenes, 78% C3+ selectivity at 94% conversion) and avoid butane formation using only in situ generated hydrogen, avoiding costly hydrogen cofeeding requirements that hinder many renewable energy processes.

Cordon, Michael↗

Data-Driven Optimization of the Processing Window for 316H Components Fabricated Using Laser Powder Bed Fusion

The Advanced Materials and Manufacturing Technologies Program is focused on accelerating the development and deployment of advanced materials and components fabricated via additive manufacturing with a specific focus on laser powder bed fusion (LPBF). As an initial case study, the program has selected 316H stainless steel (SS) as an initial material around which to develop a code case development strategy. This strategy involves two parallel approaches: (1) an equivalency approach whereby round-robin testing across multiple collaborating laboratories demonstrates repeatability in processing and direct comparisons with conventional wrought 316H material and (2) a revolutionary approach to code qualification combining in situ data collection and high-fidelity modeling to capture, predict, and bound the performance of LPBF 316HSS components. As part of this campaign, this work package has initiated an extensive process optimization campaign across three laboratories, each printing variations of LPBF 316HSS using three different LPBF units (Concept Laser, EOS, and Renishaw). In FY23, ORNL has focused on unique experimental designs spanning wide ranges in energy inputs and turning knobs such as scan speed, laser power, hatch spacing, layer thickness, spot size, scan rotation, and more. On the Concept Laser M2, 72 different combinations of processing variables were investigated with duplicate samples and different powder compositions. In total, 252 samples were printed with combined in situ sensing data. A parallel design of experiments was conducted on the Renishaw AM400 with an additional 390 printed specimens for analysis. All 642 miniature specimens, each with unique features included in each print to capture geometry-related heterogeneity, were subjected to high-throughput x-ray computed tomography (XCT) analysis to enable the downselection of specific processing parameters of interest. Then, using electrical discharge machining (EDM), miniature tensile specimens were extracted for mechanical testing and microscopy investigations. From the analysis performed in FY23, it was found that powder composition drastically affects the resulting microstructure and mechanical performance of 316SS. Specifically, changing from 316L to 316HSS powder results in a wide range of grain sizes with varying degrees of preferred grain orientation, which increases as a function of energy density. It was also found that due to stored heat in thin fin–type features, large microstructural differences can be seen within one part printed with one set of processing parameters. These variations in microstructure features, including grain size, the nanoscale dislocation structure, and grain texture, will all affect the irradiation performance and high-temperature mechanical performance of LPBF 316HSS parts. Two sets of concept laser processing parameters, spanning both refined and columnar grain structures, were scaled to print larger 316H builds for campaign testing (high-temperature creep and irradiation). In addition, at least two optimized processing parameter sets were identified for the Renishaw AM400 for round-robin testing in FY24 with Argonne National Laboratory. Future work includes printing samples using identical parameters identified by partner institutions, providing material for corrosion and high-temperature mechanical testing, and continuing evaluations of heterogeneity in larger printed parts.

36 MATERIALS SCIENCE↗

Data-Driven Optimization of the Processing Window for 316H Components Fabricated Using Laser Powder Bed Fusion

The Advanced Materials and Manufacturing Technologies Program is focused on accelerating the development and deployment of advanced materials and components fabricated via additive manufacturing with a specific focus on laser powder bed fusion (LPBF). As an initial case study, the program has selected 316H stainless steel (SS) as an initial material around which to develop a code case development strategy. This strategy involves two parallel approaches: (1) an equivalency approach whereby round-robin testing across multiple collaborating laboratories demonstrates repeatability in processing and direct comparisons with conventional wrought 316H material and (2) a revolutionary approach to code qualification combining in situ data collection and high-fidelity modeling to capture, predict, and bound the performance of LPBF 316HSS components. As part of this campaign, this work package has initiated an extensive process optimization campaign across three laboratories, each printing variations of LPBF 316HSS using three different LPBF units (Concept Laser, EOS, and Renishaw). In FY23, ORNL has focused on unique experimental designs spanning wide ranges in energy inputs and turning knobs such as scan speed, laser power, hatch spacing, layer thickness, spot size, scan rotation, and more. On the Concept Laser M2, 72 different combinations of processing variables were investigated with duplicate samples and different powder compositions. In total, 252 samples were printed with combined in situ sensing data. A parallel design of experiments was conducted on the Renishaw AM400 with an additional 390 printed specimens for analysis. All 642 miniature specimens, each with unique features included in each print to capture geometry-related heterogeneity, were subjected to high-throughput x-ray computed tomography (XCT) analysis to enable the downselection of specific processing parameters of interest. Then, using electrical discharge machining (EDM), miniature tensile specimens were extracted for mechanical testing and microscopy investigations. From the analysis performed in FY23, it was found that powder composition drastically affects the resulting microstructure and mechanical performance of 316SS. Specifically, changing from 316L to 316HSS powder results in a wide range of grain sizes with varying degrees of preferred grain orientation, which increases as a function of energy density. It was also found that due to stored heat in thin fin–type features, large microstructural differences can be seen within one part printed with one set of processing parameters. These variations in microstructure features, including grain size, the nanoscale dislocation structure, and grain texture, will all affect the irradiation performance and high-temperature mechanical performance of LPBF 316HSS parts. Two sets of concept laser processing parameters, spanning both refined and columnar grain structures, were scaled to print larger 316H builds for campaign testing (high-temperature creep and irradiation). In addition, at least two optimized processing parameter sets were identified for the Renishaw AM400 for round-robin testing in FY24 with Argonne National Laboratory. Future work includes printing samples using identical parameters identified by partner institutions, providing material for corrosion and high-temperature mechanical testing, and continuing evaluations of heterogeneity in larger printed parts.

36 MATERIALS SCIENCE↗

In situ x-ray photoelectron spectroscopy analysis of electrochemical interfaces in battery: Recent advances and remaining challenges

An in-depth understanding of charge transfer processes at the electrochemical interfaces is a critical knowledge gap impeding the design of energy storage materials. X-ray photoelectron spectroscopy plays an important role in analyzing electronic structures of heterogeneous interfaces, such as electrode-electrolyte interphases. Correspondingly, ex situ studies based on postmortem analysis of electrode materials using x-ray techniques are widely reported in the literature but often fail to capture intermediate and transient species, which are critical for a predictive understanding of the charge transfer process. The lack of extensive in situ/operando x-ray analysis of buried interfaces in energy storage systems can be mainly attributed to technical limitations, such as the requirement of high vacuum conditions. However, in the past decade, considerable efforts have been devoted to overcoming these technical barriers and enable investigation of the solid/solid and solid/liquid interfaces. This review catalogs some of the recent progresses and new experimental designs in the application of in situ and operando x-ray photoelectron spectroscopy toward characterizing interfacial processes and emergent properties, which can help build the design strategy for advanced batteries. The remaining challenges and future research directions are also discussed, as potential paths forward in this field.

Wi, Sungun↗