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At least 703 records · Page 39

Growth of Au on Ni(110): a BFS Modelling of Surface Alloy Phases

Recent experiments using scanning tunneling microscopy show evidence for the formation of surface alloys of otherwise immiscible metals. Such is the case for Au deposited in Ni(11), where experiments by Pleth Nielsen et al. indicate that at low Au coverage (less than 0.5 ML), Au atoms replace Ni atoms in the surface layer forming a surface alloy while the Ni atoms form islands on the surface. In this work, we present results of a theoretical modeling of this phenomenon using the recently developed BFS method for alloys. We provide results of an extensive analysis of the growth process which strongly support the conclusions drawn from the experiment; at very low coverages, there is tendency for dimer formation on the overlayer, which later exchange positions with Ni atoms in the surface layer, thus accounting for the large number of substituted dimers. Ni island formations as well as other alternative short range order patterns are discussed.

Bozzolo, Guillermo↗

Surface Protected Organozirconium Catalyzes C─H Alumination of Saturated Hydrocarbons

Surface grafted organozirconium catalyzes C─H/Et─Al exchange reactions, involving saturated hydrocarbons and AlEt 3 , to afford organoaluminum compounds and ethane. The Zr(O t Bu) 3 @SiO 2 -Al 2 O 3 –700 (1) catalyst contains monopodal ≡SiO─Zr(O t Bu) 3 and only a few residual silanols (<5%). Nonetheless, these silanols are the Achille's heel of 1, providing a pathway for surface and catalyst degradation during catalysis, limiting the alkylaluminum yield and catalyst turnover. Support degradation, involving the cleavage of Si─O bonds by activated surface organometallics, is inhibited by capping silanols with ─SiMe 3 . Residual silanols in 1 react with allyltrimethylsilane, as determined by solid-state 13 C and 29 Si nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and reaction stoichiometry, to form Zr(O t Bu) 3 /SiMe 3 @SiO 2 -Al 2 O 3–700 (2), which is resistant to degradation by AlEt 3 . C─H alumination of dodecane catalyzed by 2 produces higher yields of the 1-dodecylaluminum product in comparison to 1, and in >95% selectivity. Additionally, methane undergoes 2-catalyzed C─H alumination, providing a route to AlMe 3 .

Banerjee, Sayak [Iowa State Univ., Ames, IA (Unite↗

Water Ice Cloud Opacities and Temperatures Derived from the Viking IRTM Data Set

The degree to which water ice clouds play a role in the Mars climate is unknown. Latent heating of water ice clouds is small and since most hazes appeared to be thin (tau less than or = 1) their radiative effects have been neglected. Condensation likely limits the vertical extent of water vapor in the water column and a lowering of the condensation altitude, as seen in the northern spring and summer, could increase the seasonal exchange of water between the atmosphere and the surface. It has been suggested that water ice cloud formation is more frequent and widespread in the aphelic hemisphere (currently the northern). This may limit water to the northern hemisphere through greater exchange with the regolith and through restricted southward transport of water vapor by the Mars Hadley circulation. In addition, it has been suggested that water ice cloud formation also controls the vertical distribution of atmospheric dust in some seasons. This scavenging of dust may Continuing from the IRTM cloud maps, derived cloud opacities and cloud temperatures for several locations and seasons will be presented. Sensitivities to cloud particle sizes, surface temperature, and dust opacity will be discussed.

TamppariL. K.↗

Controlling Infrared Plasmon Resonances in Inverse-Spinel Cadmium Stannate Nanocrystals via Site-Selective Cation-Exchange Reactions

Doped metal oxide nanocrystals (NCs) exhibit tunable localized surface plasmon resonances (LSPRs) in the infrared spectral region. Compared to the binary oxides commonly studied, plasmonic NCs derived from ternary oxides remain far less explored primarily due to the difficulty of controlling NC phase-purity and stoichiometry. Here, we report the synthesis of inverse spinel-type cadmium stannate (Cd 2 SnO 4 ) NCs, for which cation-exchange reactions were developed to tailor their composition and LSPR properties. X-ray absorption spectroscopy studies revealed that the inequivalent tetrahedrally and octahedrally coordinated Cd 2+ can be selectively exchanged for Cu + and In 3+ ions, respectively, enabling broadband tunable LSPR and Cu-mediated cation-exchange with lanthanide ions that are otherwise difficult to incorporate. Here, our work paves the way for systematic compositional engineering to accelerate the design of complex metal oxide NCs with emerging plasmonic, electronic, and magnetic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Temperature on Flow Fouling of Smooth and Nonwetting Surfaces

Mineral fouling (scaling) of heat transfer surfaces is a pervasive problem in heat exchangers, chemical reactors, and other equipment in energy, environmental, and process industrial applications. Many of the applications involve dynamic flow of fluids with the impurity minerals and, furthermore, operate at elevated temperature. Strategies to mitigate fouling under these conditions are of much value in industrial applications. This paper presents a comparative study of temperature-dependent mineral fouling deposition on smooth surfaces and nonwetting superhydrophobic and lubricant-infused surfaces under dynamic flow conditions. The surfaces are represented in a unified manner using the viscosity ratio of the infused material within the porous asperities on a surface to that of the flowing fluid such that the spectrum of surfaces from superhydrophobic to smooth is captured by the range of viscosity ratios from 0 to ∞. Using a forced convection experimental setup, deposition of calcium sulfate on the surfaces is quantified in terms of asymptotic fouling resistance over a range of temperature, Reynolds number, and mineral foulant supersaturation. Through a systematic set of accelerated fouling experiments, an empirical relationship for the asymptotic fouling resistance is developed in terms of Reynolds number, foulant concentration, temperature, and surface type. The empirical model is validated with a comprehensive set of experimental data from this study as well as from the literature. Optimum nonwetting surface designs for minimizing fouling resistance compared to conventional smooth surfaces are developed as a function of temperature. The results of the study offer insight into the temperature-dependent fouling of surfaces under flow conditions and a rational design of fouling-resistant nonwetting surfaces that can be readily translated to practice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Growth of Au on Ni(110): A Semiempirical Modeling of Surface Alloy Phases

Recent experiments using scanning tunneling microscopy show evidence for the formation of surface alloys of otherwise immiscible metals. Such is the case for Au deposited in Ni(110), where experiments by Pleth Nielsen el al.indicate that at low Au coverage (less than 0. 5 ML), Au atoms replace Ni atoms in the surface layer forming a surface alloy while the Ni atoms form islands on the surface. In this paper, we present results of a theoretical modeling of this phenomenon using the recently developed Bozzolo-Ferrante-Smith method for alloys. We provide results of an extensive analysis of the growth process that strongly support the conclusions drawn from the experiment: at very low coverages, there is a tendency for dimer formation on the overlayer, which later exchange positions with Ni atoms in the surface layer, thus accounting for the large number of substituted dimers. Ni island formation as well as other alternative short-range-order patterns are discussed.

Bozzolo, Guillermo↗

Spaceborne microwave remote sensing of seasonal freeze-thaw processes in theterrestrial high l atitudes : relationships with land-atmosphere CO2 exchange

Landscape transitions between seasonally frozen and thawed conditions occur each year over roughly 50 million square kilometers of Earth's Northern Hemisphere. These relatively abrupt transitions represent the closest analog to a biospheric and hydrologic on/off switch existing in nature, affecting surface meteorological conditions, ecological trace gas dynamics, energy exchange and hydrologic activity profoundly. We utilize time series satellite-borne microwave remote sensing measurements from the Special Sensor Microwave Imager (SSM/I) to examine spatial and temporal variability in seasonal freeze/thaw cycles for the pan-Arctic basin and Alaska. Regional measurements of spring thaw timing are derived using daily brightness temperature measurements from the 19 GHz, horizontally polarized channel, separately for overpasses with 6 AM and 6 PM equatorial crossing times. Spatial and temporal patterns in regional freeze/thaw dynamics show distinct differences between North America and Eurasia, and boreal forest and Arctic tundra biomes. Annual anomalies in the timing of thawing in spring also correspond closely to seasonal atmospheric CO2 concentration anomalies derived from NOAA CMDL arctic and subarctic monitoring stations. Classification differences between AM and PM overpass data average approximately 5 days for the region, though both appear to be effective surrogates for monitoring annual growing seasons at high latitudes.

Sensor Microwave Imager (SSM/I)carbon cycle↗

Spaceborne Microwave Remote Sensing of Seasonal Freeze-Thaw Processes in the Terrestrial High Latitudes: Relationships with Land-Atmosphere CO2 exchange

Landscape transitions between seasonally frozen and thawed conditions occur each year over roughly 50 million square kilometers of Earth's Northern Hemisphere. These relatively abrupt transitions represent the closest analog to a biospheric and hydrologic on/off switch existing in nature, affecting surface meteorological conditions, ecological trace gas dynamics, energy exchange and hydrologic activity profoundly. We utilize time series satellite-borne microwave remote sensing measurements from the Special Sensor Microwave Imager (SSM/I) to examine spatial and temporal variability in seasonal freeze/thaw cycles for the pan-Arctic basin and Alaska. Regional measurements of spring thaw timing are derived using daily brightness temperature measurements from the 19 GHz, horizontally polarized channel, separately for overpasses with 6 AM and 6 PM equatorial crossing times. Spatial and temporal patterns in regional freeze/thaw dynamics show distinct differences between North America and Eurasia, and boreal forest and Arctic tundra biomes. Annual anomalies in the timing of thawing in spring also correspond closely to seasonal atmospheric CO2 concentration anomalies derived from NOAA CMDL arctic and subarctic monitoring stations. Classification differences between AM and PM overpass data average approximately 5 days for the region, though both appear to be effective surrogates for monitoring annual growing seasons at high latitudes.

net primary products↗

Synthesis of a planar, multicomponent catalytic surface of Na 2 CO 3 /MnO

Here, O 2 adsorption on MnO(100) precovered with sodium (Na) multilayers was investigated by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Deposition of Na multilayers leads to a first monolayer of oxidic Na followed by metallic Na island growth. XPS results for the oxidation of the metallic Na islands indicate an incomplete oxidation of Na at 125 K. Oxidation at 350 K completely oxidizes the metallic islands producing a mixture of Na 2 O and Na 2 O 2 . Thermal evolution of the oxidation products was examined. After oxidation at 350 K and flashing to 750 K, Na 2 O and Na 2 O 2 are the primary oxides on MnO(100). After flashing to 850 K, a solid state reaction of Na 2 O 2 /Na 2 O and the MnO(100) substrate forms a NaMnO 2 -like surface compound which decomposes above 850 K. Oxygen exchange between CO 2 and Na oxides is observed. The strong interaction between CO 2 and Na oxide islands forms Na 2 CO 3 on MnO(100). Heating the Na 2 CO 3 covered MnO(100) surface to 600 K for 10 min drives oxidic Na in the first monolayer into the MnO subsurface, and produces a surface exposing islands of Na 2 CO 3 on MnO(100).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of particle transport for the P80-1 spacecraft

Charged and neutral particle transport from an 8-cm mercury ion thruster to the surfaces of the P80-1 spacecraft, the Teal Ruby sensor and the ECOM-501 sensor was examined. Evaluation of particle transport modes utilized both laboratory measurements and analysis. Line-of-sight particle transport considered deposition of Group II (high energy-high angle mercury charge exchange) ions and neutral mercury on solar array surfaces. Nonline-of-sight transport modes studied were recirculation/reinterception of mercury ions in magnetic fields and refraction of low energy mercury charge exchange (Group IV) ions by local electric fields.

Sellen, J. M., Jr.↗

Investigation of Effectiveness of Air-Heating a Hollow Steel Propeller for Protection Against Icing. 3: 25% Partitioned Blades

The icing protection obtained from an internally air-heated propeller blade partitioned to confine the heated air forward of 25-percent chord was investigated in the NACA Cleveland icing research tunnel. A production-model hollow steel propeller was modified with an Internal radial partition at 25-percent chord and with shank and tip openings to admit and exhaust the heated air. Temperatures were measured on the blade surfaces and in the heated-air system during tunnel icing conditions. Heat-exchanger effectiveness and photographs of Ice formations on the blades were obtained. Surface temperature measurements indicated that confining the heated air forward of the 25-percent chord gave.a more economical distribution of the applied heat as compared with unpartitioned and 50-percent partitioned blades, by dissipating a greater percentage of the available heat at the leading edge. At a propeller speed of 850 rpm, a heating rate of 7000 Btu per hour per blade at a shank air temperature of 400 F provided adequate Icing protection at ambient-air temperatures of 23 F but not at temperatures as low as 15 F. With the heating rate used, a heat-exchanger effectiveness of 77 percent was obtained as compared to 56 percent for 50-percent partitioned and 47 percent for unpartitioned blades.

Mulholland, Donald R.↗

Erosion rate diagnostics in ion thrusters using laser-induced fluorescence

We have used laser-induced fluorescence (LIF) to monitor the charge-exchange ion erosion of the molybdenum accelerator electrode in ion thrusters. This real-time, nonintrusive method was implemented by operating a 30cm-diam ring-cusp thruster using xenon propellant. With the thruster operating at a total power of 5 kW, laser radiation at a wavelength of 390 nm (corresponding to a ground state atomic transition of molybdenum) was directed through the extracted ion beam adjacent to the downstream surface of the molybdenum accelerator electrode. Molybdenum atoms, sputtered from this surface as a result of charge-exchange ion erosion, were excited by the laser radiation. The intensity of the laser-induced fluorescence radiation, which is proportional to the sputter rate of the molybdenum atoms, was measured and correlated with variations in thruster operating conditions such as accelerator electrode voltage, accelerator electrode current, and test facility background pressure. We also demonstrated that the LIF technique has sufficient sensitivity and spatial resolution to evaluate accelerator electrode lifetime in ground-based test facilities.

Gaeta, C. J.↗

Falling particle impact erosion testing for particle based CSP systems

CSP systems are currently being examined as an effective method for using solar energy to generate electricity. While much of this research has been conducted using molten salt as the heat transfer medium, in recent years, solid particles have been posited as a cheaper and more energy efficient heat transfer medium for use in CSP systems. Many researchers have looked into the effectiveness of solid particles as a heat transfer medium. However, a concern with the use of particles is that the falling particles will impact various components within the CSP system, such as the hopper, the heat exchanger, and the insulating material, resulting in surface erosion and damage. With repeated impacts from falling particles, material from the surfaces under impact is removed. The degree of erosion depends on whether the substrate is made of brittle or ductile material. Furthermore, factors such as particle shape, size, hardness, concentration, impact angle, particle velocity, and substrate hardness will contribute to the erosion process and determine how much and how quickly erosion will takes place in a system. Three types of erosion will be observed simultaneously: impact erosion from particle impact on receiver, particle storage, and heat exchanger walls, abrasion erosion from particle sliding motion along walls, and attrition erosion as the particles breakdown from particle-to-particle contact and particle-to-wall interactions. It is imperative to understand each of these erosions individually for a more comprehensive understanding and prediction of CSP system durability. In this work, we developed an experimental test setup capable of measuring impact erosion at conditions relevant to 1MW CSP plant. Subsequently, Impact erosion measurements were performed for three different candidate substrate materials at low particle velocities using HSP 40/70 ceramic particles.

14 SOLAR ENERGY↗

Vacancy surface migration mechanisms in dilute nickel-chromium alloys

We investigate the unitary mechanisms related to the surface migration of vacancies in dilute Ni-Cr alloys via first-principle calculations. We survey a complete set of surface and sub-surface migration paths for vacancies near the (100) free surface and calculate the corresponding migration barriers. Our results show that a vacancy migrating towards the free surface will face lower energy barriers to migrate via atomic exchange with a neighboring Cr atom rather than with a Ni atom. Once a vacancy reaches the free surface, it will be trapped there. Our results also reveal that, when a Cr atom sits in the atomic plane just below the free surface, any in-plane vacancy hopping jump that would result in the vacancy sitting on top a subsurface Cr atom is energetically unfavorable. Taken together, these fundamental unitary surface migration mechanisms offer insights into the complex interactions between surface segregation and vacancy migration phenomena in Ni-Cr-based alloys.

36 MATERIALS SCIENCE↗

Benchmarking the AirSquared All-Metal Scroll Pump Against the Normetex 15 - Preliminary report

Tritium operations require specialized equipment for material compatibility, safety, and waste considerations. Non-metallic pump materials (polymer, oil, or grease) on a tritium-wetted surface can absorb tritium and/or undergo isotope exchange between tritium and more common protium, creating tritiated compounds that can result in material property modification via beta-radiolysis, inventory loss, reduced performance and special waste considerations, all of which increase the operating cost for a facility. Vacuum pumps move gas via a pressure differential between volumes of an operation. Several types of all-metal vacuum pumps exist for this application including metal bellows, diaphragm and scroll pumps. A metal bellows pump incorporates only metal components at the wetted surfaces. The common metal bellows pump employed in tritium facilities, the MB601 (Senior Metal Bellows, Sharon, PA, USA) creates a gas-motive force with a vacuum pressure between 30-40 torr. These pumps can efficiently move gas from one process step to another, as long as sub-30 torr pressures are not required. However, for higher vacuum demand, an all-metal scroll pump can be used with the bellows pump serving as a “backing” pump. This configuration typically provides an achievable vacuum of less than 20 mTorr. All-metal scroll pumps are a technology uniquely applicable to tritium gas handling. The industry standard all-metal scroll pump for glovebox-scale tritium operations is the Normetex 15 m 3 /hr, typically referred to as the Normetex 15 (Normetex Pompes, Pont Audemer, France). However, the final Normetex pumps were manufactured in 2012, rendering them no longer available. Eumeca SaRL (formerly Normetex) has developed and is marketing a scroll pump based on the design of the Normetex 15. A US company, AirSquared (Broomfield, Colorado), has developed and is marketing a potential alternative to the Normetex 15. The Gas Transfer Systems group (Q-7) of the Los Alamos National Laboratory (LANL) procured serial number 0001 of the AirSquared All Metal Vacuum Scroll pump model number V16H034A-C01 in 2019. The LANL Hydrogen Processing Laboratory (HPL) has been evaluating the performance of the pump compared to a Normetex pump as a potential replacement in tritium and fusion facilities requiring this type of pump.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Charge-exchange plasma generated by an ion thruster

The use of high voltage solar arrays greatly reduces or eliminates power processing requirements in space electric propulsion systems. This use also requires substantial areas of solar array to be at high positive potential relative to space and most of the spacecraft. The charge exchange plasma conducts electrons from the ion beam to such positive surfaces, and thereby electrically load the high voltage solar array. To evaluate this problem, the charge-exchange plasma generated by an ion beam was investigated experimentally. Based upon the experimental data, a simple model was derived for the charge-exchange plasma. This model is conservative in the sense that both the electron/ion density and the electron current density should be equal to, or less than, the preducted value for all directions in the hemisphere upstream of the ion beam direction. Increasing the distance between a positive potential surface (such as a high voltage solar array) and the thruster is the simplest way to control interactions. Both densities and currents vary as the inverse square of this distance.

Kaufman, H. R.↗

Surface heat flux and its association with the MJO in the tropical western Pacific using ARM observations

The Madden-Julian oscillation (MJO) is a major atmospheric phenomenon in the tropics that moves eastward every 20 to 100 days. It brings heavy rain and strong winds, influencing extreme weather events far beyond the tropics – including flooding, hurricanes, tornadoes and heavy snow in the United States. Therefore, an improved understanding of the MJO is critical for enhancing weather forecasts and supporting better decision-making for communities, emergency managers, and the private sector. Past studies, based on short-term observations or long-term model data, have emphasized the dominant role of atmospheric humidity in driving the MJO. Our research, using long-term observations (2000-2014) from three U.S. Department of Energy’s Atmospheric Radiation Measurement (ARM) sites in the tropical western Pacific (Manus, Nauru, and Darwin) confirms those past findings. However, we also show that atmospheric temperature, especially in the mid and upper troposphere, also plays a key role in the MJO’s evolution from its quiet (suppressed) to convective (active) phase. These findings provide valuable insights into how the MJO evolves and may help evaluate and improve weather and climate models. Our study also examined how the exchange of heat between the Earth's surface and the atmosphere, called surface heat flux, interacts with the MJO. This flux includes components such as latent heat (related to evaporation), sensible heat (related to temperature difference between surface and atmosphere), and radiation. We found that modulation in MJO convection is well connected to surface heat flux over the tropical western Pacific. One surface heat flux component often overlooked is the sensible heat flux due to precipitation (Q P ). Since falling raindrops are typically cooler than the land or ocean surface, they can cool the surface and affect local weather. To test the impact of Q P on convection during MJO, we incorporated it into a weather model, and ran simulations for two periods: April 2009 (when the MJO was active) and June 2006 (when it was not). Including Q P reduced errors in simulating the daily peak of rainfall—by 83% during the strong MJO and 23% during the inactive phase. It also improved the timing of peak daily rainfall and reduced the overall precipitation error by about 10%. These improvements were especially noticeable during periods of heavy rainfall. Our results suggest that even small heat exchanges from rainfall can play a significant role in shaping local weather. Accounting for these effects, particularly in regions like the tropical islands, can lead to more accurate simulations of the MJO-associated precipitation.

54 ENVIRONMENTAL SCIENCES↗