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At least 649 records · Page 36

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts

Abstract The complex structure of the catalytic active phase, and surface‐gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na 2 WO 4 /SiO 2 catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H 2 ‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na 2 WO 4 active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WO x sites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that ( i ) surface Na‐WO x sites are responsible for selectively activating CH 4 to C 2 H x and over‐oxidizing CH y to CO and ( ii ) molten Na 2 WO 4 phase is mainly responsible for over‐oxidation of CH 4 to CO 2 and also assists in oxidative dehydrogenation of C 2 H 6 to C 2 H 4 . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na 2 WO 4 /SiO 2 catalysts.

Sourav, Sagar↗

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts

Abstract The complex structure of the catalytic active phase, and surface‐gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na 2 WO 4 /SiO 2 catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H 2 ‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na 2 WO 4 active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WO x sites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that ( i ) surface Na‐WO x sites are responsible for selectively activating CH 4 to C 2 H x and over‐oxidizing CH y to CO and ( ii ) molten Na 2 WO 4 phase is mainly responsible for over‐oxidation of CH 4 to CO 2 and also assists in oxidative dehydrogenation of C 2 H 6 to C 2 H 4 . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na 2 WO 4 /SiO 2 catalysts.

Sourav, Sagar↗

Effects of shielding gas and spot reduction on humping suppression in high-speed laser welding

High-speed laser welding is a crucial process to enhance the production rate of fuel cell fabrication. However, exceeding a critical welding speed leads to defect formation such as humps and root concavities, which degrade weld quality and mechanical performance. This study employed shielding gas and spot reduction approaches to suppress these defects. The relationships between individual defect types and their influence on weld strength were systematically examined. Moreover, in situ high-speed synchrotron X-ray imaging was employed to comprehend the mechanisms of humping mitigation by shielding gas through analysis of instantaneous keyhole and melt pool dynamics. The observations reveal that shielding gas mitigates humping by shortening the molten pool through enhanced surface heat convection and by altering surface tension to prevent melt flow collisions. The effects of shielding gas and spot reduction were further incorporated into the dimensionless humping index (π h ) that describes the humping formation tendency. These findings provide mechanistic insights and quantitative guidance for defect control strategies in high-speed laser welding.

08 HYDROGEN↗

Crack Front Segmentation and Facet Coarsening in Mixed-Mode Fracture

A planar crack generically segments into an array of “daughter cracks” shaped as tilted facets when loaded with both a tensile stress normal to the crack plane (mode I) and a shear stress parallel to the crack front (mode III). We investigate facet propagation and coarsening using in situ microscopy observations of fracture surfaces at different stages of quasistatic mixed-mode crack propagation and phase-field simulations. The results demonstrate that the bifurcation from propagating a planar to segmented crack front is strongly subcritical, reconciling previous theoretical predictions of linear stability analysis with experimental observations. As a result, they further show that facet coarsening is a self-similar process driven by a spatial period-doubling instability of facet arrays.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Robust Solar Receivers Using MAX Phase Materials

This work was supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy under the Solar Energy Technologies Office Award Number 35928. The objective of the proposed effort was to develop and optimize additive manufacturing technologies for low-cost fabrication of high-temperature receivers using MAX phase-based materials (Ti 3 SiC 2 and Ti 3 AlC 2 ). MAX phase materials are a group of ternary metal carbides and nitrides where M stands for an early transition metal element, A is a group 13–16 element, and X is C and/or N. In Phase 1, the binder jetting additive manufacturing process was used to synthesize and characterize the Ti 3 SiC 2 MAX phase material. The typical process involved first producing a TiC preform using binder jetting followed by infiltration of the preform with silicon melt to form Ti 3 SiC 2 in situ. The reaction-infiltrated samples showed formation of MAX phase in the sample core; however, the surface showed cracking. Various process conditions—cooling rates, hold times, Si proportion, etc.—were varied to minimize the surface cracking. The fabricated MAX phase core was characterized by microstructure analysis and evaluations of mechanical properties such as hardness and thermal shock. In Phase 2, the focus included fabrication of Ti 3 SiC 2 MAX phase materials by spark plasma sintering (SPS) and synthesis of Ti 3 AlC 2 MAX phase materials by the Al melt infiltration process. It is expected that Al infiltration will not cause sample cracking, since Al does not expand during solidification. In addition, other processing approaches were investigated to fabricate the MAX phase materials, such as SPS with a graphite bedding approach for producing short-length Ti 3 AlC 2 MAX phase tubes for demonstration of prototypical Concentrating Solar Power receiver tubes. Fabricated samples underwent thermo-mechanical testing to validate the materials for the solar receiver application at temperatures >1000°C. In Phase 3, the effort focused on the development and optimization of the Ti-Al-C MAX phase composite material using the Al melt infiltration approach. We started with optimization of precursor powders and making preform structures by either pressing them in a die or using the binder jetting additive manufacturing process followed by Al melt infiltration. In addition, we investigated the formation of preform structures by cold isostatic pressing followed by Al melt infiltration for making Ti-Al-C MAX phase composite. Thermo-mechanical characterizations, such as creep, strength, and thermal shock, were conducted to establish the structures’ performance.

36 MATERIALS SCIENCE↗

Air-sea interactions yielding rapid Beaufort Sea ice losses during the 2021 ONR THINICE Pilot Field Campaign

Seasonal sea ice coverage has declined in the Pacific Arctic region. Losses of the ice cover have modified the region’s surface heat and momentum fluxes providing weather systems more direct interaction with the upper ocean. For example, recent cyclones that have passed over these waters have initiated multiple air-sea interactions and have impacted mixed layer depth, wave properties, and sea ice mass budgets due to diabatic and/or advective processes. As a United States Office of Naval Research (ONR) Departmental Research initiative, one key component of the ONR THINICE program was to advance knowledge on Arctic cyclone coupling with the ocean surface, its ice cover, and understand how such coupling can lead to rapid ice loss. Leading up to the primary field campaign in August 2022, a pilot field campaign from 19 August to 13 September 2021 focused in Utqiagvik, Alaska and Longyearbyen, Svalbard was carried out. This period was marked by frequent Arctic cyclones, periods of strong low-level winds, and stints of extreme short-term Beaufort Sea ice area losses. Cyclones traversed these waters much more frequently than usual during this 26-day period, but did not exhibit extreme central pressures indicative of high intensity and impactful storms. Using ERA5 atmospheric reanalysis fields, CERES and AIRS surface flux retrievals, and in situ sensor data collected from ice-tethered profilers and ice mass balance buoys, we highlight air-sea-ice interactions in the Beaufort Sea during and between these cyclones leading up to extreme ice loss events. Our case study analysis is aimed at understanding how Arctic cyclones, including air-sea interactions prompted by their passage over the marginal ice zone, influence the end-of-summer ice conditions and ice loss events. This study provides an example where frequent, yet weak storms drive rather large marginal sea-scale losses albeit with heterogenous sea ice effects at local scales.

Ballinger, Thomas [International Arctic Research C↗

Petrology of lunar rocks and implication to lunar evolution

Recent advances in lunar petrology, based on studies of lunar rock samples available through the Apollo program, are reviewed. Samples of bedrock from both maria and terra have been collected where micrometeorite impact penetrated the regolith and brought bedrock to the surface, but no in situ cores have been taken. Lunar petrogenesis and lunar thermal history supported by studies of the rock sample are discussed and a tentative evolutionary scenario is constructed. Mare basalts, terra assemblages of breccias, soils, rocks, and regolith are subjected to elemental analysis, mineralogical analysis, trace content analysis, with studies of texture, ages and isotopic composition. Probable sources of mare basalts are indicated.

Ridley, W. I.↗

On the maintenance of the Marine boundary layer-free tropospheric gradient of transient tracers

A simple model of the marine boundary layer is used to arrive at a steady-state budget for trace gases in this layer. Five processes maintain the tracer balance in the layer. The first is a large-scale horizontal convergence of the tracer; the second is the pumping by clouds of the tracer out of the boundary layer into the free troposphere; the third is penetration by the tracer from the free troposphere into the marine boundary from compensating subsidence in the cloud-free air surrounding cumulus clouds; the fourth is sea surface emission or deposition of the tracer; and the fifth is in situ photochemical production or loss of the tracer within the marine boundary layer. The budget equation is used in deriving an expression for the mixing ratio difference between the two regions. A scale analysis suggests that the mixing ratio difference between the marine boundary layer and the free troposphere can be an order of magnitude smaller in disturbed weather conditions than in suppressed conditions, showing that the difference in chemical concentrations between the free troposphere and the marine boundary layer cannot be rationalized solely on the basis of chemical measurements.

Gidel, L. T.↗

Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

Sermon, Paul A.↗

Investigating Surface Mineralogy, Alteration Processes, and Biomarkers on Mars Using Laser Raman Spectroscopy

Despite a wealth of information from past and ongoing missions to Mars, the capability to determine the mineralogy of surface materials and to connect mineralogy with lithologic characteristics that are diagnostic of the environment in which those materials formed remains inadequate. The 2003 Mars Exploration Rovers (MER) will carry a Mini-TES and a Mossbauer spectrometer, which will provide some detailed mineralogy information. For general characterization of minerals and/or biogenic phases (reduced carbon, PAHs, etc) on the surface of Mars, we have been developing a miniaturized laser Raman spectrometer for in situ analyses -- the Mars Microbeam Raman Spectrometer, MMRS. We are also developing strategies to use Raman spectroscopy as a stand-alone technique and to be used synergistically with other in situ analysis methods in future planetary missions. Through studies of Martian meteorites and terrestrial analogs, we are gaining experience of what compositional and structural information can be obtained on key mineral groups using in-situ Raman measurements. We are developing methods for determining mineral proportions in rocks or soils and identifying rock types from sets of closely spaced, rapidly acquired spectra. We are studying how weathering and alteration affect the Raman and luminescence features of minerals and rocks, and we are investigating the Raman characteristics of biogenic organisms and their remains. These studies form the scientific basis for in-situ planetary Raman spectroscopy, and they are being done in parallel with instrument development towards a flight version of the MMRS.

Alian Wang↗

Lake Anna Water Resources: Using NASA Earth Observations to Identify Algal Event Risk Factors in Lake Anna and Help Inform Future Management Practices

Lake Anna is a man-made reservoir and popular recreation destination that spans over 13,000 acres-9,600 public and 3,400 private-in the Piedmont region of Virginia. The Lake has recently seen a rise in documented harmful algal blooms (HABs), which pose a variety of community and ecological concerns and are often exacerbated by anthropogenic factors, such as excess nutrient loads from agricultural runoff. NASA DEVELOP has partnered with the Virginia Department of Environmental Quality (DEQ) to help monitor cyanobacteria and nutrient pollution indicators across Lake Anna. The team utilized Earth observations (EO) and in situ ancillary data to identify and monitor algal bloom trends. The team used Landsat 8 Operational Land Imager (OLI), Landsat 9 OLI-2, Sentinel-2 Multispectral Instrument (MSI), and Sentinel-3 Ocean and Land Color Instrument (OLCI) to analyze water quality variables such as chlorophyll-a, turbidity, surface temperature, and cyanobacteria. Due to the lack of comprehensive in situ data and historic HAB event records, our ability to compare and validate EOs was limited. Additionally, deficient spatial resolutions, along with a geographically complicated shoreline, accentuated the spatial constraints we faced in our analysis. After examining EOs, our results indicated conditions conducive to the formation of HABs within the upper reaches of Lake Anna. Yet, spatially dependent limiting factors may have also influenced where these phenomena developed. When used in concert with existing in situ datasets, NASA EOs provide relevant stakeholders with more comprehensive analyses with which to engage in enhanced monitoring and watershed management.

cyanobacteria↗

Determining Remaining Useful Life of Aging Cables in Nuclear Power Plants using Non-destructive Evaluation

License renewal of existing nuclear power plants (NPPs) to extend operation from 40 to 60 to 80 years will require effective aging management programs for the 100’s of kilometers of electric power, control and instrumentation cables installed in each plant. Degradation of jacket, insulation and other cable components can reduce the ability of cables to withstand design-basis accidents. The groundwork for a research and development roadmap to address aging cable management in NPPs was laid at a July 2012 workshop1 that brought together subject matter experts from the U.S. Nuclear Regulatory Commission (NRC), the U.S. Department of Energy (DOE) national laboratories, the Electric Power Research Institute (EPRI), universities, and cable manufacturers and inspectors. The most common nondestructive evaluation (NDE) methods for gauging cable status include indentation and visual inspection. These methods are limited to evaluation of the surface easily accessed cable assemblies. Other current methods (such as time and frequency domain analysis, inductance and capacitance measurements, tan d, etc.) provide flaw detection, but are not predictive. The workshop identified the need to advance and develop new NDE methods to enable in-situ cable condition assessment. Key chemical, physical, and electrical indicators of cable aging with exposure to heat, radiation, moisture, chemicals, and mechanical stress need to be determined. Finally, models correlating the key cable indicators with NDE signals need to be developed that can aging cable remaining useful life.

NDE, Nuclear Cables, Polymer Aging↗

Particle beam experiments for the analysis of reactive sputtering processes in metals and polymer surfaces

A beam experiment is presented to study heterogeneous reactions relevant to plasma-surface interactions in reactive sputtering applications. Atom and ion sources are focused onto the sample to expose it to quantified beams of oxygen, nitrogen, hydrogen, noble gas ions, and metal vapor. The heterogeneous surface processes are monitored in situ by means of a quartz crystal microbalance and Fourier transform infrared spectroscopy. Two examples illustrate the capabilities of the particle beam setup: oxidation and nitriding of aluminum as a model of target poisoning during reactive magnetron sputtering, and plasma pre-treatment of polymers (PET, PP)

36 MATERIALS SCIENCE↗

Quantifying the Role of Snowmelt in Stream Discharge in an Alaskan Watershed: An Analysis Using a Spatially Distributed Surface Hydrology Model

Here, this study uses a spatially distributed surface hydrology model to investigate the role of snowmelt in stream discharge for the Tanana Flats Basin in interior Alaska. The Parameter ESTimation code is used to calibrate the model with observed stream discharge data. The model was further evaluated using remote sensing-based snow cover product and in situ snowpack water equivalent (SWE) observations. A 36 year (1980–2015) U.S. Geological Survey Precipitation-Runoff Modeling System simulation shows (1) the monthly stream discharge from the Tanana Flats Basin in April decreased by 44%; (2) snow cover area at high altitudes (above 2000 m) decreased in summer, both SWE and snowmelt also decreased significantly, especially in spring; (3) the timings of snowmelt onset and ending shifted by 2 (earlier) and 5 (later) days per decade, respectively; and (4) snowmelt accounts for 40% of the annual stream discharge. This study provides a quantitative tool to investigating hydrological systems considering the impacts of snow dynamics in cold regions. Additionally, this study suggests that future warming will further decrease snow coverage, advance snow melting time, and hereafter change the stream discharge dynamics in the Arctic.

58 GEOSCIENCES↗

An Investigation into the Effects of Mn Promotion on the Activity and Selectivity of Co/SiO 2 for Fischer - Tropsch Synthesis: Evidence for Enhanced CO Adsorption and Dissociation

Mn is an effective promoter for improving the activity and selectivity of Co-based Fischer-Tropsch synthesis (FTS) catalysts, but the mechanism by which this promoter functions is poorly understood. The work reported here was aimed at defining the manner in which Mn interacts with Co and determining how these interactions affect the activity and selectivity of Co. Detailed measurements are reported for the kinetics of FTS as a function of Mn/Co ratio, temperature, and reactant partial pressure. These data are described by a single, two-parameter rate expression. Mn promotion was found to increase both the apparent rate constant for CO consumption and the CO adsorption constant. Further evidence for enhanced CO adsorption and dissociation was obtained from measurements of temperature-programmed desorption of CO and CO disproportionation rates, respectively. Our quantitative analysis of elemental maps obtained by STEM-EDS revealed that the promoter accumulates preferentially on the surface of Co nanoparticles at low Mn loadings, resulting in a rapid onset of improvements in the product selectivity as the Mn loading increases. For catalysts prepared with loadings higher than Mn/Co = 0.1, the additional Mn accumulates in the form of nanometer-scale particles of MnO on the support. In situ IR spectra of adsorbed CO show that Mn promotion increases the abundance of adsorbed CO with weakened C-O bonds. Furthermore, it is proposed that the cleavage of the C-O bond is promoted through Lewis acid-base interactions between the Mn 2+ cations located at the edges of MnO islands covering the Co nanoparticles and the O atom of CO adsorbates adjacent to the MnO islands. The observed decrease in selectivity to CH 4 and the increased selectivity to C 5+ products with increasing Mn/Co ratio are attributed to a decrease in the ratio of adsorbed H to CO on the surface of the supported Co nanoparticles.

Johnson, Gregory R.↗

THE LONGITUDINAL PROPERTIES OF A SOLAR ENERGETIC PARTICLE EVENT INVESTIGATED USING MODERN SOLAR IMAGING

We use combined high-cadence, high-resolution, and multi-point imaging by the Solar-Terrestrial Relations Observatory (STEREO) and the Solar and Heliospheric Observatory to investigate the hour-long eruption of a fast and wide coronal mass ejection (CME) on 2011 March 21 when the twin STEREO spacecraft were located beyond the solar limbs. We analyze the relation between the eruption of the CME, the evolution of an Extreme Ultraviolet (EUV) wave, and the onset of a solar energetic particle (SEP) event measured in situ by the STEREO and near-Earth orbiting spacecraft. Combined ultraviolet and white-light images of the lower corona reveal that in an initial CME lateral 'expansion phase', the EUV disturbance tracks the laterally expanding flanks of the CME, both moving parallel to the solar surface with speeds of {approx}450 km s{sup -1}. When the lateral expansion of the ejecta ceases, the EUV disturbance carries on propagating parallel to the solar surface but devolves rapidly into a less coherent structure. Multi-point tracking of the CME leading edge and the effects of the launched compression waves (e.g., pushed streamers) give anti-sunward speeds that initially exceed 900 km s{sup -1} at all measured position angles. We combine our analysis of ultraviolet and white-light images with a comprehensive study of the velocity dispersion of energetic particles measured in situ by particle detectors located at STEREO-A (STA) and first Lagrange point (L1), to demonstrate that the delayed solar particle release times at STA and L1 are consistent with the time required (30-40 minutes) for the CME to perturb the corona over a wide range of longitudes. This study finds an association between the longitudinal extent of the perturbed corona (in EUV and white light) and the longitudinal extent of the SEP event in the heliosphere.

79 ASTRONOMY AND ASTROPHYSICS↗

The integrated sounding system: Description and preliminary observations from TOGA COARE

An Integrated Sounding System (ISS) that combines state-of-the-art remote and in situ sensors into a single transportable facility has been developed jointly by the National Center for Atmospheric Research (NCAR) and the Aeronomy Laboratory of the National Oceanic and Atmospheric Administration (NOAA/AL). The instrumentation for each ISS includes a 915-MHz wind profiler, a Radio Acoustic Sounding System (RASS), an Omega-based NAVAID sounding system, and an enhanced surface meteorological station. The general philosophy behind the ISS is that the integration of various measurement systems overcomes each system's respective limitations while taking advantage of its positive attributes. The individual observing systems within the ISS provide high-level data products to a central workstation that manages and integrates these measurements. The ISS software package performs a wide range of functions: real-time data acquisition, database support, and graphical displays; data archival and communications; and operational and posttime analysis. The first deployment of the ISS consists of six sites in the western tropical Pacific--four land-based deployments and two ship-based deployments. The sites serve the Coupled Ocean-Atmosphere Response Experiment (COARE) of the Tropical Ocean and Global Atmosphere (TOGA) program and TOGA's enhanced atmospheric monitoring effort. Examples of ISS data taken during this deployment are shown in order to demonstrate the capabilities of this new sounding system and to demonstrate the performance of these in situ and remote sensing instruments in a moist tropical environment. In particular, a strong convective outflow with a pronounced impact of the atmospheric boundary layer and heat fluxes from the ocean surface was examined with a shipboard ISS. If these strong outflows commonly occur, they may prove to be an important component of the surface energy budget of the western tropical Pacific.

Parsons, David↗

In situ grain fracture mechanics during uniaxial compaction of granular solids

Grain fracture and crushing are known to influence the macroscopic mechanical behavior of granular materials and be influenced by factors such as grain composition, morphology, and microstructure. In this paper, we investigate grain fracture and crushing by combining synchrotron x-ray computed tomography and three-dimensional x-ray diffraction to study two granular samples undergoing uniaxial compaction. Our measurements provide details of grain kinematics, contacts, average intra-granular stresses, inter-particle forces, and intra-grain crystal and fracture plane orientations. Our analyses elucidate the complex nature of fracture and crushing, showing that: (1) the average stress states of grains prior to fracture vary widely in their relation to global and local trends; (2) fractured grains experience inter-particle forces and stored energies that are statistically higher than intact grains prior to fracture; (3) fracture plane orientations are primarily controlled by average intra-granular stress and contact fabric rather than the orientation of the crystal lattice; (4) the creation of new surfaces during fracture accounts for a very small portion of the energy dissipated during compaction; (5) mixing brittle and ductile grain materials alters the grain-scale fracture response. The results highlight an application of combined x-ray measurements for non-destructive in situ analysis of granular solids and provide details about grain fracture that have important implications for theory and modeling.

42 ENGINEERING↗