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At least 73 records · Page 4

Accurate and efficient predictions of keyhole dynamics in laser materials processing using machine learning-aided simulations

The keyhole phenomenon has been widely observed in laser materials processing, including laser welding, remelting, cladding, drilling, and additive manufacturing. Keyhole-induced defects, primarily pores, dramatically affect the performance of final products, impeding the broad use of these laser-based technologies. The formation of these pores is typically associated with the dynamic behavior of the keyhole. So far, the accurate characterization and prediction of keyhole features, particularly keyhole depth, as a function of time, has been a challenging task. In situ characterization of keyhole dynamic behavior using the synchrotron X-ray technique is informative but complicated and expensive. Current simulations are generally hindered by their poor accuracy and generalization abilities in predicting keyhole depths due to the lack of accurate laser absorptance data. In this study, we develop a machine learning-aided simulation method that accurately predicts keyhole dynamics, especially in keyhole depth fluctuations, over a wide range of processing parameters. In two case studies involving titanium and aluminum alloys, we achieve keyhole depth prediction with a mean absolute percentage error of 10 %, surpassing those simulated using the ray-tracing method with an error margin of 30 %, while also reducing computational time. This exceptional fidelity and efficiency empower our model to serve as a cost-effective alternative to synchrotron experiments. Our machine learning-aided simulation method is affordable and readily deployable for a large variety of materials, opening new doors to eliminate or reduce defects for a wide range of laser materials processing techniques.

Computational fluid dynamics

Active Sites in the Dealuminated Beta Zeolite-Supported Cobalt Catalyst for Non-Oxidative Ethane Dehydrogenation

Dispersed metal species in siliceous zeolites have been actively studied for non-oxidative dehydrogenation of ethane (NDE). Fundamental insights into the dynamics of metal species in zeolites under reaction conditions have rarely been explored. Herein, we report an atomic level understanding of the dynamics and activity of cobalt (Co) sites in dealuminated Beta zeolite (DeAl-BEA) for NDE during induction and reaction conditions with extensive characterization techniques such as diffuse reflectance UV–vis, solid state nuclear magnetic resonance and X-ray photoelectron, X-ray diffraction along with in situ Fourier transform infrared and X-ray absorption spectroscopy. For a catalyst with 0.5 mass % Co loading, tetrahedral Co 2+ mononuclear sites, di-coordinated to the zeolite framework and with two silanol groups in vicinity (i.e., (≡SiO) 2 Co(HO–Si≡) 2 ), form upon exposure to hydrogen during induction and persist through the NDE reaction. Increasing the Co loading to 3.0 mass % yielded Co sites with similar electronic and coordination structures but slightly elongated Co–O bonds. Upon cooling to room temperature, the Co sites persisted in the same coordination environment, though the disappearance of a feature in the Co K-edge near-edge region revealed changes in the active site’s electronic structure coinciding with modest shifts in bond lengths. The electronic structure and activity of (≡SiO) 2 Co(HO–Si≡) 2 sites were studied comparatively to a few other hypothetical Co 2+ coordination structures, using electronic structure calculations and microkinetic simulations. The simulations showed that NDE is controlled by β-hydride elimination following C–H bond activation and that Co-sites possessing flexibility because of neighboring silanol defects are more active. Interestingly, dinuclear Co–O–Co sites (i.e., (≡SiO)Co(HO–Si≡) 2 –O–(HO–Si≡) 2 Co(≡SiO)) were more active than the mononuclear (≡SiO) 2 Co(HO–Si≡) 2 sites because of favorable hydrogen bonding with the vicinal silanol groups. In conclusion, the present study bridges the gap between the knowledge acquired by ex-situ characterizations and the active sites under the reaction conditions in alkane dehydrogenation chemistry.

36 MATERIALS SCIENCE

Experimental trends and theoretical descriptors for electrochemical reduction of carbon dioxide to formate over Sn-based bimetallic catalysts

The electrochemical carbon dioxide reduction reaction (CO 2 RR) using renewable energy sources is a promising solution for mitigating CO 2 emissions. In particular, CO 2 RR to formate represents a commercially profitable target. However, a comprehensive understanding of the catalytic mechanisms of Sn-based catalysts under reaction conditions, including the real-time structural evolution of catalysts and the role of all key reaction intermediates in influencing the CO 2 RR selectivity, is still lacking. The current study reports a framework to study the selectivity preference of Sn-based bimetallic catalysts using a combination of electrochemical measurements, in situ characterization, and density functional theory (DFT) calculations. The addition of a second metal (Co, Ni, Ag, Zn, Ga, Bi) was found to play a vital role in affecting the CO 2 RR performance. In situ X-ray absorption near edge structure (XANES) measurements revealed a dynamic evolution in the Sn valence state induced by different secondary metals. A multidimensional descriptor involving all the key reaction intermediates was developed to assess formate selectivity using a 2-dimensional volcano plot. Finally, this research offers an effective framework for understanding CO 2 RR catalytic selectivity by considering both the real-time structural evolution of catalysts and all the key intermediates involved.

58 GEOSCIENCES

Image-Based Fracture Surface Defect Characterization Methods for Additively Manufactured Ti-6Al-4V Tested in Fatigue

Abstract Fatigue initiation in additively manufactured samples/parts often occurs at processed-induced defects such as lack-of-fusion (LoF), keyhole, or other morphological/microstructural defects that have unique characteristics and measurable qualities. Attempts at identifying and minimizing such defects have utilized optimized processing conditions along with in situ and ex situ characterization that includes metallography and/or X-ray computed tomography (XCT). This paper highlights the benefits of using fracture surface analyses to detect and quantify defects that may not be detected by metallography/XCT due to sectioning and resolution limits. In addition to using manual quantification of fatigue initiating LoF and keyhole defects on fracture surfaces, image-based machine learning using convolutional neural networks such as U-Net were also used to automate the process. Statistical analyses were used to identify the extreme cases of defects that initiated and accelerated fatigue and to model the distribution of defect size and shape characteristics to distinguish the type of defect. Initial results show agreement between trained machine learning models and ground truth data in defect segmentation, and the distributions of defect characteristics are distinguishable to particular process-induced defect types.

Materials Science

Crossflow membrane filtration system for operando fouling characterization using transmission x-ray scattering

Membrane-based separations are widely used for wastewater treatment due to their low cost and efficiency. However, membrane fouling, which is the unwanted deposition or attachment of contaminants on membrane surfaces and/or within membrane pores, remains a major challenge as it increases the mass transfer resistance and reduces membrane productivity. Membrane fouling is typically probed by macroscopic performance metrics, such as flux decline, and ex situ characterization. However, this does not capture the membrane and fouling layer evolution under operating conditions, potentially masking important mechanisms and nonequilibrium pathways that impact fouling. Here, we present a remotely controlled crossflow membrane system and a custom membrane cell for operando fouling characterization using transmission small/wide angle x-ray scattering (SAXS/WAXS). This approach allows direct observation of the nanoscale changes occurring at the membrane surface during pressurized water treatment processes, enabling a new way to understand the connections between dynamic fouling behaviors and membrane performance. Nanoparticle fouling of porous membranes during ultrafiltration was investigated using operando SAXS, and mineral scaling of reverse osmosis membranes was investigated using operando WAXS. Furthermore, this system allows for tracking membrane fouling in real time and under realistic conditions, providing fundamental physical insights into how water chemistry and operating conditions affect macroscopic membrane performance. Moreover, this system opens the door for future in situ and operando studies, and it serves as a testbed for evaluating novel materials/processes for membrane-based separations.

36 MATERIALS SCIENCE

In-situ ETEM study of plasma-facing tungsten nanofuzz oxidation at atmospheric pressure: Microstructure evolution and substrate-free oxidation kinetics

To enable sustainable carbon-free fusion energy, managing reactor structural material degradation during normal operation as well as accident scenarios is vital. Tungsten (W) plasma-facing materials (PFMs) are susceptible to aggressive high-temperature oxidation during air-ingress fusion reactor accidents, yet there's a lack of oxidation kinetic data for irradiated tungsten. Here, in this study, we utilize atmospheric environmental transmission electron microscopy (ETEM) to present the first kinetic data for substrate-free W nanofuzz oxidation at 400 ºC and 500 ºC in 1 bar dry air. Comparison with pristine bulk W during the early parabolic stage suggests an irradiationdecelerated oxidation for W nanofuzz. Our time-resolved in-situ characterization reveals a durable amorphous surface oxide, likely promoted by high-flux He + irradiation-induced surface defects, serving as an effective passivating layer that impedes nanofuzz oxidation onset. This surface oxide layer also interfaces well with newly formed orthorhombic WO 3 , facilitated by stress relief through He bubble shrinkage, providing lasting passivating protection throughout the nanofuzz parabolic oxidation. This new finding challenges conventional notions of irradiation's negative impact on metal oxidation, and calls for advanced characterization to enhance our understanding of fusion energy materials degradation, informed by further accident modeling.

36 MATERIALS SCIENCE

Characterization of Synthetic and Natural Manganese Oxides as Martian Analogues

Recent discoveries of highly concentrated manganese oxides in Gale Crater and on the rim of Endeavour Crater by the Mars Science Laboratory Curiosity and Mars Exploration Rover Opportunity, respectively, imply more highly oxidizing aqueous conditions than previously recognized. Manganese oxides are a significant environmental indicator about ancient aqueous conditions, provided the phases can be characterized reliably. Manganese oxides are typically fine-grained and poorly crystalline, making the mineral structures difficult to determine, and they generally have very low visible reflectance with few distinctive spectral features in the visible to near infrared, making them a challenge for interpretation from remote sensing data. Therefore, these recent discoveries motivate better characterization using methods available on Mars, particularly visible to near infrared (VNIR) spectroscopy, X-ray diffractometry (XRD), and compositional measurements. Both rovers have complementary instruments in this regard. Opportunity is equipped with its multispectral visible imager, Pancam, and an Alpha Particle X-ray Spectrometer (APXS), and Curiosity has the multispectral Mastcam, ChemCam (laser-induced breakdown spectroscopy and passive spectroscopy), and APXS for in situ characterization, and ChemMin (XRD) for collected samples.

Fox, V. K.

Facile Tensile Testing Platform for In Situ Transmission Electron Microscopy of Nanomaterials

In situ tensile testing using transmission electron microscopy (TEM) is a powerful technique to probe structure-property relationships of materials at the atomic scale. In this work, a facile tensile testing platform for in situ characterization of materials inside a transmission electron microscope is demonstrated. The platform consists of: 1) a commercially available, flexible, electron-transparent substrate (e.g., TEM grid) integrated with a conventional tensile testing holder, and 2) a finite element simulation providing quantification of specimen-applied strain. The flexible substrate (carbon support film of the TEM grid) mitigates strain concentrations usually found in free-standing films and enables in situ straining experiments to be performed on materials that cannot undergo localized thinning or focused ion beam lift-out. The finite element simulation enables direct correlation of holder displacement with sample strain, providing upper and lower bounds of expected strain across the substrate. The tensile testing platform is validated for three disparate material systems: sputtered gold-palladium, few-layer transferred tungsten disulfide, and electrodeposited lithium, by measuring lattice strain from experimentally recorded electron diffraction data. The results show good agreement between experiment and simulation, providing confidence in the ability to transfer strain from holder to sample and relate TEM crystal structural observations with material mechanical properties.

2D materials

Efficient on-chip terahertz generation and detection with GaN photoconductive emitters

Photoconductive emitters for terahertz generation hold promise for highly efficient down-conversion of optical photons because it is not constrained by the Manley-Rowe relation. Existing terahertz photoconductive devices, however, faces limits in efficiency due to the semiconductor properties of commonly used GaAs materials. Here, we demonstrate that large bandgap semiconductor GaN, characterized by its high breakdown electric field, facilitates the highly efficient generation of terahertz waves in a coplanar stripline waveguide. Towards this goal, we investigated the excitonic contribution to the electro-optic response of GaN under static electric field both through experiments and first-principles calculations, revealing a robust excitonic Stark shift. Using this electro-optic effect, we developed a novel ultraviolet pump-probe spectroscopy for in-situ characterization of the terahertz electric field strength generated by the GaN photoconductive emitter. Our findings show that terahertz power scales quadratically with optical excitation power and applied electric field over a broad parameter range. We achieved an optical-to-terahertz conversion efficiency approaching 100% within the 0.03–1 THz bandwidth at the highest bias field (116 kV/cm) in our experiment. Further optimization of GaN-based terahertz generation devices could achieve even greater optical-to-terahertz conversion efficiencies.

Uzundal, Can B

In-Situ Investigation of Advanced Structural Coatings and Composites

The premise of this project is a comprehensive study that involves the in-situ characterization of advanced coatings and composites by employing both neutron and x-ray diffraction techniques in a complementary manner. The diffraction data would then be interpreted and used in developing or validating advanced micromechanics models with life prediction capability. In the period covered by this report, basic work was conducted to establish the experimental conditions for various specimens and techniques. In addition, equipment was developed that will allow the in-situ studies under a range of conditions (stress, temperature, atmosphere, etc.).

Ustundag, Ersan

Technology Gaps for Rapid Response Missions to Near-Earth Objects, Interstellar Objects, and Long-Period Comets

The last several years has seen the discovery of the first two interstellar objects, the first ever planetary defense mission, recommendation for a rapid reconnaissance planetary defense demonstration, and the continued emergence of a robust commercial small satellite industry. The present and near future also consist of emerging next-generation observatories including Vera Rubin and NEO Surveyor. These seemingly disparate events converge in the context of rapid response: a cross-cutting capability that would enable NASA and the international community to quickly discover and respond to an emerging target such as a near-Earth object (NEO), interstellar object (ISO), or long-period comet (LPC) either for rapid characterization of a potential threat, or revolutionary science that would inform early solar system formation and evolution. In late October 2022, subject matter experts gathered at the California Institute of Technology in a week-long workshop sponsored by the Keck Institute for Space Studies (KISS) to address enabling mission concepts for rapid response and key technology gaps (final report in progress). These experts concurred that the ability to respond on the order of a few months is necessary for rapid in-situ characterization of a NEO, ISO, or LPC, and that while there are several technology gaps, this capability could be realized in the near future.

Technology gaps

Tracking the dynamics of catalytic Pt/CeO2 active sites during water-gas-shift reaction

Abstract Understanding the atomistic structure of the active site during catalytic reactions is of paramount importance in both fundamental studies and practical applications, but such studies are challenging due to the complexity of heterogeneous systems. Here, we use Pt/CeO 2 as an example to study the dynamic nature of active sites during the water-gas-shift reaction (WGSR) by combining multiple in situ characterization tools. We show that the different concentrations of interfacial Pt δ+ – O – Ce 4+ moieties at Pt/CeO 2 interfaces are responsible for the rank of catalytic performance of Pt/CeO 2 catalysts: Pt/CeO 2 -rod > Pt/CeO 2 -cube > Pt/CeO 2 -oct. For all the catalysts, metallic Pt is formed during the WGSR, leading to the transformation of the active sites to Pt 0 – O v – Ce 3+ and interface reconstruction. These findings shed light on the nature of the active site for the WGSR on Pt/CeO 2 and highlight the importance of combining complementary in situ techniques for establishing structure-performance relationships.

36 MATERIALS SCIENCE

PLANETARY DEFENSE: FINDINGS AND RECOMMENDATIONS FROM THE NATIONAL ACADEMIES PLANETARY SCIENCE AND ASTROBIOLOGY DECADAL SURVEY 2023 - 2032

The National Academies of Sciences, Engineering, and Medicine was chartered by the NASA Science Mission Directorate (SMD), with support from the National Science Foundation, to conduct a new decadal survey to develop a comprehensive science and mission strategy for planetary science (1). The survey was tasked to determine the current state of knowledge and to identify the most important scientific questions to be addressed in astrobiology and planetary science during the upcoming decade of 2023 - 2032. For the first time, the decadal survey also included and addressed the topic of planetary defense, now recognized as a key element of NASA’s planetary science activities under the direction of NASA’s SMD Planetary Defense Coordination Office. The topic of planetary defense was included in the decadal survey as a dedicated chapter, divided into five sections based on the framework from the U.S. National NEO Preparedness Strategy and Action Plan (2). These sections discussed: NEO Detection, Tracking, and Characterization NEO Modelling, Prediction, and Integration NEO Deflection and Disruption Missions International Cooperation on NEO Preparation NEO Impact Emergency Procedures and Action Protocols Content of these sections included identifying the activities, ground- and space-based assets, facilities, resources, technologies, and missions that should be considered to enable NEO preparedness over the next decade. Supporting inputs to this chapter involved contributions from submitted white papers authored by many members of the NEO science and planetary defense communities. In addition, a planetary defense rapid mission architecture study commissioned by the decadal survey small bodies panel and led by the Jet Propulsion Laboratory examined several different types of in-situ characterization and mitigation demonstration missions. All of this input contributed to the formulation of 42 findings and 11 recommendations that suggest a path forward for increasing our understanding of the NEO population and their associated physical characteristics, modelling the impact probabilities and hazard potential of these objects, and implementing plans to develop and test NEO impact mitigation capabilities. Including planetary defense in the decadal survey has helped sharpen the focus on this international issue and provided key inputs for stakeholders and decision makers to consider when developing future planetary defense-related activities. Such information is vital for developing a long-term integrated planetary defense capability able to protect humanity in the decades to come.

NEO Detection and Characterization

Characterizing degraded visual environments with scanning lenses to improve contrast recovery

Atmospheric aerosols, such as fog and smoke, degrade optical signals via the scattering and absorption of light, making it difficult to recover information from the surrounding environment. Here, we present a technique that measures the angular distribution of light in scattering environments to help recover these degraded optical signals. This is done by passing a collimated beam through the aerosol environment and collecting the scattered and unscattered light with an f-theta scan lens. The lens transforms the angular distribution of the scattered light into the linear domain, mapping the collected light onto a detector. The measured angular scattering distribution is then used to estimate the point spread function of the environment at an arbitrary stand-off distance. This point spread function can be used to deconvolve images blurred by the aerosol environment in which the angular scattering distribution was initially measured. With this approach, we demonstrate improvements in the effective resolution of deblurred images up to 26% over a 120-cm stand-off distance. Experimentation was performed in the Sandia National Laboratories tabletop fog chamber, a platform that generates aerosol environments analogous to real-world fogs. We intend to leverage this technique in future work to develop a low-SWaP system for the in situ characterization of aerosol environments.

Aerosols

Real-Time Optical Monitoring of Flow Kinetics and Gas Phase Reactions Under High-Pressure OMCVD Conditions

This contribution addresses the real-time optical characterization of gas flow and gas phase reactions as they play a crucial role for chemical vapor phase depositions utilizing elevated and high pressure chemical vapor deposition (HPCVD) conditions. The objectives of these experiments are to validate on the basis of results on real-time optical diagnostics process models simulation codes, and provide input parameter sets needed for analysis and control of chemical vapor deposition at elevated pressures. Access to microgravity is required to retain high pressure conditions of laminar flow, which is essential for successful acquisition and interpretation of the optical data. In this contribution, we describe the design and construction of the HPCVD system, which include access ports for various optical methods of real-time process monitoring and to analyze the initial stages of heteroepitaxy and steady-state growth in the different pressure ranges. To analyze the onset of turbulence, provisions are made for implementation of experimental methods for in-situ characterization of the nature of flow. This knowledge will be the basis for the design definition of experiments under microgravity, where gas flow conditions, gas phase and surface chemistry, might be analyzed by remote controlled real-time diagnostics tools, developed in this research project.

Dietz, N.

In situ Raman investigation of Dy complexation in Cl-bearing aqueous solutions at 20–300 °C

Raman spectroscopy provides a versatile tool for in situ characterization of aqueous rare earth elements (REE) speciation at the molecular level. Complexation of REE with ligands such as Cl – and OH – is of particular interest for understanding the mobility of REE in NaCl-bearing hydrothermal fluids responsible for enriching REE to economic levels in nature. Raman spectroscopic studies of REE speciation in Cl-bearing aqueous fluids are primarily conducted at ambient temperature, whereas natural systems indicate temperatures of >100–600 °C. In this study, the speciation of Dy in acidic chloride-bearing hydrothermal solutions was investigated using confocal Raman spectroscopy with a new capillary Raman heating stage at 20–300 °C. Background solutions (pure water, NaCl-solutions) and solutions with 0.14–1.8 mol kg –1 dissolved DyCl 3 were sealed in quartz capillary cells. Comparison of the spectra for Dy chloride solutions with those for background solutions and the spectra for reference Dy-bearing solids was used to identify Raman bands specific to Dy–O and Dy–Cl bonds. The Raman band for the Dy–O stretching mode of hydrated Dy 3+ aqua ions was measured at 365–384 cm –1 and a Raman band for the Dy–Cl stretching modes of Dy chloride complexes was measured near 240 cm –1 . The Dy–O band decreases systematically with temperature, whereas the Dy–Cl band systematically increases, indicating a systematic increase in the stability of Dy chloride complexes with temperature. Here, this study provides the framework for expanding the use of in situ Raman spectroscopy to investigate the speciation of REE in aqueous solutions to hydrothermal conditions.

58 GEOSCIENCES

Controlling Reaction Pathways of Ethylene Hydroformylation Using Isolated Bimetallic Rhodium–Cobalt Sites

Designing efficient ligand-free heterogeneous catalysts for ethylene hydroformylation to produce C 3 oxygenates is of importance for both fundamental research and practical applications, but it is often hindered by insufficient catalytic activity and selectivity. Here, this work designs isolated rhodium–cobalt (Rh–Co) sites confined within a ZSM-5 zeolite to enhance ethylene hydroformylation rates and selectivity while maintaining catalyst stability. By adjusting the Co/Al ratio in Co-ZSM-5, different sizes of Co are formed; subsequent Rh introduction produces isolated Rh 1 Co x clusters with different Rh–Co coordination numbers (CNs). In-situ characterizations and density functional theory calculations reveal that a Rh–Co CN of 3, corresponding to an isolated Rh 1 Co 3 site, provides optimal bindings to reaction intermediates and thus achieves the highest hydroformylation rates among supported Rh-based catalysts. This study demonstrates the role of coordination-tuning via a secondary metal in effectively controlling the reaction pathway over single Rh atom catalysts.

03 NATURAL GAS

Electrochemical Control of the Ultrafast Lattice Response of a Layered Semimetal

The unique layer-stacking in two-dimensional (2D) van der Waals materials facilitates the formation of nearly degenerate phases of matter and opens novel routes for the design of low-power, reconfigurable functional materials. Electrochemical ion intercalation between stacked layers offers a promising approach to stabilize bulk metastable phases and to explore the effects of extreme carrier doping and strain. However, in situ characterization methods to study the structural evolution and dynamical functional properties of these intercalated materials remains limited. Here a novel experimental platform is presented capable of simultaneously performing electrochemical lithium-ion intercalation and multimodal ultrafast characterization of the lattice using both electron diffraction and nonlinear optical techniques. Using the layered semimetal WTe 2 as a model system, the interlayer shear phonon mode that modulates stacking between 2Dlayers is probed, showing that small amounts of lithiation enhance the amplitude and lifetime of the phonon, contrary to expectations. This results from the dynamically fluctuating and anharmonic structure between nearly degenerate phases at room temperature, which can be stabilized by electronic carriers accompanying the inserted lithium ions. At high lithiation, the T d ’ structure emerges and quenches the phonon response. This work defines new approaches for using electrochemistry to engineer the dynamic structure of 2D materials.

36 MATERIALS SCIENCE