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At least 1,477 records · Page 82

Non-compact oxide-island growth induced by surface phase transition of the intermetallic NiAl during vacuum annealing

Crystal structure and composition are inter-dependent and decoupling their effects on surface reactivity is challenging. Using low-energy electron microscopy to spatially and temporally resolve the oxide film growth during the oxidation of NiAl(100), we differentiate such coupled effects by monitoring oxide growth while simultaneously fine-tuning the surface structure and composition during oxidation. We demonstrate that the oxidation of chemically ordered surfaces results in compact oxide island growth whereas non-compact oxide growth during the surface phase transition. By incorporating the surface phase transition induced chemical disordering into kinetic Monte Carlo simulations, we illustrate that the non-compact oxide growth is induced by the composition effect on the surface diffusion of oxygen, which can be described by the concept of “ant in the labyrinth”.

36 MATERIALS SCIENCE↗

Epitaxial Thin Film Growth on Recycled SrTiO 3 Substrates Toward Sustainable Processing of Complex Oxides

Complex oxide thin films cover a range of physical properties and multifunctionalities that are critical for logic, memory, and optical devices. Typically, the high‐quality epitaxial growth of these complex oxide thin films requires single crystalline oxide substrates such as SrTiO 3 (STO), MgO, LaAlO 3 , a‐Al 2 O 3, and many others. Recent successes in transferring these complex oxides as free‐standing films not only offer great opportunities in integrating complex oxides on other devices, but also present enormous opportunities in recycling the deposited substrates after transfer for cost‐effective and sustainable processing of complex oxide thin films. In this work, the surface modification effects introduced on the recycled STO are investigated, and their impacts on the microstructure and properties of subsequently grown epitaxial oxide thin films are assessed and compared with those grown on the pristine substrates. Detailed analyses using high‐resolution scanning transmission electron microscopy and geometric phase analysis demonstrate distinct strain states on the surfaces of the recycled STO versus the pristine substrates, suggesting a pre‐strain state in the recycled STO substrates due to the previous deposition layer. These findings offer opportunities in growing highly mismatched oxide films on the recycled STO substrates with enhanced physical properties. Specifically, yttrium iron garnet (Y 3 Fe 5 O 12 ) films grown on recycled STO present different ferromagnetic responses compared to that on the pristine substrates, underscoring the effects of surface modification. The study demonstrates the feasibility of reuse and redeposition using recycled substrates. Via careful handling and preparation, high‐quality epitaxial thin films can be grown on recycled substrates with comparable or even better structural and physical properties toward sustainable process of complex oxide devices.

pre-strained STO surfaces↗

Breakup of Droplets in an Accelerating Gas Flow

A study of droplet breakup phenomena by an accelerating gas flow is described. The phenomena are similar to what propellant droplets experience when exposed to accelerating combustion gas flow in a rocket engine combustion zone. Groups of several dozen droplets in the 100-10 750-micron-diameter range were injected into a flowing inert gas in a transparent rectangular nozzle. Motion photography of the behavior of the droplets at various locations in the accelerating gas flow has supplied quantitative and qualitative data on the breakup phenomena which occur under conditions similar to those found in large rocket engine combustors. A blowgun injection device, used to inject very small amounts of liquid at velocities of several hundred feet per second into a moving gas stream, is described. The injection device was used to inject small amounts of liquid RP-1 and water into the gas stream at a velocity essentially equal to the gas velocity where the group of droplets was allowed to stabilize its formation in a constant area section before entering the convergent section of the transparent nozzle. Favorable comparison with the work of previous investigators who have used nonaccelerating gas flow is found with the data obtained from this study with accelerating gas flow. The criterion for the conditions of minimum severity required to produce shear-type droplet breakup in an accelerating gas flow is found to agree well with the criterion previously established at Rocketdyne for breakup in nonaccelerating flow. An extension of the theory of capillary surface wave effects during droplet breakup is also presented. Capillary surface waves propagating in the surface of the droplet, according to classical hydrodynamical laws, are considered. The waves propagate tangentially over the surface of the droplet from the forward stagnation point to the major diameter. Consideration of the effects of relative gas velocity on the amplitude growth of these waves allows conclusions to be made regarding rates of the droplet breakup processes and total time of the breakup process.

Dickerson, R. A.↗

Pathways Following Electron Injection: Medium Effects and Cross-Surface Electron Transfer in a Ruthenium-Based, Chromophore–Catalyst Assembly on TiO 2

Interfacial dynamics following photoexcitation of the water oxidation assembly [((PO 3 H 2 ) 2 bpy) 2 Ru II (bpy-bimpy)Ru II (tpy)(OH 2 )] 4+ , -[Ru a II –Ru b II –OH 2 ] 4+ , on nanocrystalline TiO 2 electrodes, starting from either -[Ru a II –Ru b II –OH 2 ] 4+ or -[Ru a II –Ru b III –OH 2 ] 5+ , have been investigated. Transient absorption measurements for TiO 2 –[Ru a II –Ru b II –OH 2 ] 4+ in 0.1 M HPF 6 or neat trifluoroethanol reveal that electron injection occurs with high efficiency but that hole transfer to the catalyst, which occurs on the electrochemical time scale, is inhibited by local environmental effects. Back electron transfer occurs to the oxidized chromophore on the microsecond time scale. Photoexcitation of the once-oxidized assembly, TiO 2 –[Ru a II –Ru b III –OH 2 ] 5+ , in a variety of media, generates -[Ru a III –Ru b III –OH 2 ] 6+ . The injected electron randomly migrates through the surface oxide structure reducing an unreacted -[Ru a II –Ru b III –OH 2 ] 5+ assembly to -[Ru a II –Ru b II –OH 2 ] 4+ . In a parallel reaction, -[Ru a III –Ru b III –OH 2 ] 6+ formed by electron injection undergoes proton loss giving -[Ru a II –Ru b IV $=$O] 4+ with possible conversion to -[Ru a II –Ru b II –OH 2 ] 4+ by an electrolyte-mediated reaction. In the following slow step, re-equilibration on the surface occurs either by reaction with added Fe III/II or by cross-surface electron transfer between spatially separated -[Ru a II –Ru b IV $=$O] 4+ and -[Ru a II –Ru b II –OH 2 ] 4+ assemblies to give -[Ru a II –Ru b III –OH 2 ] 5+ with a half-time of t 1/2 ~ 68 μs. Finally, these results and analyses show that the transient surface behavior of the assembly and cross-surface reactions play important roles in producing and storing redox equivalents on the surface that are used for water oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the effect of flux-surface shaping on trapped-electron modes in quasi-helically symmetric stellarators

Using a novel optimization procedure, it has been shown that the Helically Symmetric eXperiment stellarator can be optimized for reduced trapped-electron-mode (TEM) instability [Gerard et al., Nucl. Fusion 63, (2023) 056004]. Presently, with a set of 563 experimental candidate configurations, gyrokinetic simulations are performed to investigate the efficacy of available energy EA, quasi-helical symmetry, and flux-surface shaping parameters as metrics for TEM stabilization. It is found that lower values of EA correlate with reduced growth rates, but only when separate flux-surface shaping regimes are considered. Moreover, configurations with improved quasi-helical symmetry demonstrate a similar reduction in growth rates and less scatter compared to EA. Regarding flux-surface shaping, a set of helical shaping parameters is introduced that show increased elongation is strongly correlated with reduced TEM growth rates, however, only when the quasi-helical symmetry is preserved. Using a newly derived velocity-space-averaged TEM resonance operator, these trends are analyzed to provide insights into the physical mechanism of the observed stabilization. For elongation, stabilization is attributed to geometric effects that reduce the destabilizing particle drifts across the magnetic field. Regarding quasi-helical symmetry, the TEM resonance in the maximally resonant trapping well is shown to increase as the quasi-helical symmetry is broken, and breaking quasi-helical symmetry increases the prevalence of highly resonant trapping wells. While these results demonstrate the limitations of using any single metric as a linear TEM proxy, it is shown that quasi-helical symmetry and plasma elongation are highly effective metrics for reducing TEM growth rates in helical equilibria.

Physics↗

Life of Pennzane and 815Z-Lubricated Instrument Bearings Cleaned with Non-CFC Solvents

This report takes the form of two papers: (1) "Life of Pennzane and 815Z-Lubricated Instrument Bearings cleaned with Non-CFC Solvents" and (2) a published paper, entitled "Instrument bearing life with NON-CFC cleaners". Abstract for paper # 1 : Bearings used in spacecraft mechanisms have historically been cleaned with chlorofluorocarbon CFC-1 13 (Freon) solvents and lubricated with a perfluorinated polyalkylether (PFPE) oils like 815-Z. Little full-scale bearing life test data exists to evaluate the effects of the newer class environmental-friendly bearing cleaners or improved synthetic hydrocarbon space oils like Pennzane. To address the lack of data, a cooperative, bearing life test program was initiated between NASA, Lockheed Martin and MPB. The objective was to obtain comparative long-term, life test data for flight-quality bearings, cleaned with non-CFC solvents versus CFC-1 13 under flight-like conditions with two space oils. A goal was to gain a better understanding of the lubricant surface chemistry effects with such solvents. A second objective was to obtain well-controlled, full-scale bearing life test data with a relatively new synthetic oil (Pennzane), touted as an improvement to Bray 815Z, an oil with considerable space flight history. The second paper, which serves as an attachment, is abstracted below: Bearings used in spacecraft mechanisms have historically been cleaned with chlorofluorocarbon CFC-113 (Freon) solvents and lubricated with a perfluorinated polyalkylether (PFPE) oils like 815-Z. Little full-scale bearing life test data exists to evaluate the effects of the newer class environmental-friendly bearing cleaners or improved synthetic hydrocarbon space oils like Pennzane. To address the lack of data, a cooperative, bearing life test program was initiated between NASA, Lockheed Martin and MPB. The objective was to obtain comparative long-term, life test data for flight-quality bearings, cleaned with non-CFC solvents versus CFC-1 13 under flight-like conditions with two space oils. A goal was to gain a better understanding of the lubricant surface chemistry effects with such solvents. A second objective was to obtain well-controlled, full-scale bearing life test data with a relatively new synthetic oil (Pennzane), touted as an improvement to Bray 815Z, an oil with considerable space flight history.

Loewenthal, Stuart↗

Effects of load, speed, and surface roughness on sliding EHD contact temperatures

An infrared technique has been used to determine the effects of load, speed and surface roughness on temperature in a sliding elastohydrodynamic (EHD) point contact. Ball surface temperatures are reported for sliding speeds of 0.35 to 5.08 m/s at 0.52 to 2.03 GN/per sq m maximum pressure with surface roughness in the range 0.01 to 0.38 micron c.l.a. The relationship between asperity interaction, as measured by relocation surface profilimetry and high frequency temperature measurements, and the ratio of film thickness to surface roughness has also been studied.

Nagaraj, H. S.↗

Increased importance of methane reduction for a 1.5 degree target

To understand the importance of methane on the levels of carbon emission reductions required to achieve temperature goals, a processed-based approach is necessary rather than reliance on the transient climate response to emissions. We show that plausible levels of methane (CH 4 ) mitigation can make a substantial difference to the feasibility of achieving the Paris climate targets through increasing the allowable carbon emissions. This benefit is enhanced by the indirect effects of CH 4 on ozone (O 3 ). Here the differing effects of CH 4 and CO 2 on land carbon storage, including the effects of surface O 3 , lead to an additional increase in the allowable carbon emissions with CH 4 mitigation. We find a simple robust relationship between the change in the 2100 CH 4 concentration and the extra allowable cumulative carbon emissions between now and 2100 (0.27 ± 0.05 GtC per ppb CH 4 ). This relationship is independent of modelled climate sensitivity and precise temperature target, although later mitigation of CH 4 reduces its value and thus methane reduction effectiveness. Up to 12% of this increase in allowable emissions is due to the effect of surface ozone. We conclude early mitigation of CH 4 emissions would significantly increase the feasibility of stabilising global warming below 1.5 °C, alongside having co-benefits for human and ecosystem health.

54 ENVIRONMENTAL SCIENCES↗

The Effect of Diffusional Transport and Surface Catalysis on the Aerothermodynamic Heating for Martian Atmospheric Entry

For the reentry heating of 70-degree blunt sphere-cones entering Mars at velocities in excess of 6 km/sec, a study was performed to determine the magnitude of both convective and catalytic heating on the cone forebody. Case studies of the peak heating conditions for the current NASA Mars Pathfinder entry probe, as well as the peak heating conditions of the proposed NASA Mars 2001 aerobraking orbiter mission were performed. Since the actual behavior of the chemical recombination of Mars atmosphere hypersonic shock layer species on heat shield materials is not known, and no experimental studies of any consequence have been done to determine surface reaction rates for the CO2 system, a parametric analysis of various reaction schemes and surface catalytic mechanistic models was performed. In many cases the actual Mars entry probe will have a heat shield composed of an ablative material which can either partially or completely preclude the existence of catalytic surface recombination phenomena. The extent of this blockage effect has not been examined at this time and is not considered in this effort. Instead only non-ablative computations are performed to separately evaluate the full extent of the surface catalysis and related diffusional phenomena. Parametric studies include peak heating point comparisons of non-catalytic, partially catalytic and fully catalytic total surface heat transfer for three difference surface recombination catalytic mechanisms (with and without simultaneous CO + O and O + O recombination) as well as with different species diffusion models. Diffusion model studies include constant Schmidt number (equal diffusivities) and the bifurcation, approximate multi-component diffusion model. Since the gas phase reaction kinetics for the Mars CO2 based atmosphere have also not been validated, the effect of two different (fast and slow) sets of gas kinetics on heat transfer is presented.

Henline, William D.↗

Adjacency effects on imaging by surface reflection and atmospheric scattering - Cross radiance to zenith

The paper discusses an analytical solution for the nadir radiance as measured from a satellite, based on a simplified single-scattering approximation in which the scattered radiation is not subject to extinction. In the solution, terms can be identified as due to a reflection from the vicinity of the object pixel, and respectively, (1) upward scattering to zenith above the object pixel (cross radiance), and (2) downward scattering from the entire atmosphere to the object pixel (cross irradiance). It is shown that the cross radiance is proportional to the forward scattering optical thickness, as defined, and the cross irradiance to the backscattering optical thickness. In addition, explicit expressions and computer solutions for the cross radiance from annular or from rectangular reflecting areas are presented. It is concluded that the effect depends on the height distribution and on the sharpness of the forward peak of the scattering particles.

Otterman, J.↗

Effect of non-equilibrium flow chemistry and surface catalysis on surface heating to AFE

The effect of nonequilibrium flow chemistry on the surface temperature distribution over the forebody heat shield on the Aeroassisted Flight Experiment (AFE) vehicle was investigated using a reacting boundary-layer code. Computations were performed by using boundary-layer-edge properties determined from global iterations between the boundary-layer code and flow field solutions from a viscous shock layer (VSL) and a full Navier-Stokes solution. Surface temperature distribution over the AFE heat shield was calculated for two flight conditions during a nominal AFE trajectory. This study indicates that the surface temperature distribution is sensitive to the nonequilibrium chemistry in the shock layer. Heating distributions over the AFE forebody calculated using nonequilibrium edge properties were similar to values calculated using the VSL program.

Stewart, David A.↗

A time variable model of Earth's albedo

A time variable model of Earth's albedo was prepared for use in climate studies and as an aid to the interpretation of satellite Earth radiation budget data. The features of the model include: a 10 deg latitude 10 deg longitude grid for numerical integration, surface albedo specified at 1 month intervals, calculation of zenith angle effect for surface albedo and of the additional effect of the atmosphere on the albedo. Percent cloud cover is specified for 29 different climatological cloud type regions at 8 times of the day for 12 months of the year. Cloud albedos were specified for each of the cloud climatological types. Diurnal and monthly variations of this model are described and results are compared with a model which is based on satellite measurements. A computer program was also written for use in studying the sampling effects in satellite radiation budget measurements. An example of the results of calculations with this program are compared with a previous study of the sampling effects. This program for satellite orbit characteristics is to be combined with the time-variable albedo model for further study of the sampling problem.

Bartman, F. L.↗

Engineered Surfaces for Mitigation of Insect Residue Adhesion

Maintenance of laminar flow under operational flight conditions is being investigated under NASA s Environmentally Responsible Aviation (ERA) Program. Among the challenges with natural laminar flow is the accretion of residues from insect impacts incurred during takeoff or landing. Depending on air speed, temperature, and wing structure, the critical residue height for laminar flow disruption can be as low as 4 microns near the leading edge. In this study, engineered surfaces designed to minimize insect residue adhesion were examined. The coatings studied included chemical compositions containing functional groups typically associated with abhesive (non-stick) surfaces. To reduce surface contact by liquids and enhance abhesion, the engineered surfaces consisted of these coatings doped with particulate additives to generate random surface topography, as well as coatings applied to laser ablated surfaces having precision patterned topographies. Performance evaluation of these surfaces included contact angle goniometry of pristine coatings and profilometry of surfaces after insect impacts were incurred in laboratory scale tests, wind tunnel tests and flight tests. The results illustrate the complexity of designing antifouling surfaces for effective insect contamination mitigation under dynamic conditions and suggest that superhydrophobic surfaces may not be the most effective solution for preventing insect contamination on aircraft wing leading edges.

Siochi, Emilie J.↗

Gas sorption and non-Darcy flow in shale reservoirs

Gas sorption and non-Darcy flow are two important issues for shale gas reservoirs. The sorption consists of dissolution and adsorption. Dissolved gas and adsorbed gas are different. The former is dissolved in the shale matrix, while the latter is concentrated near the solid walls of pores. In this paper, the Langmuir equation is used to describe adsorption and Henry’s law is used to describe dissolution. The K coefficient in Henry’s law of 0.052 mmol/(MPa g TOC) is obtained by matching experimental data. The amount of dissolved gas increases linearly when pressure increases. Using only the Langmuir equation without considering dissolution can lead to a significant underestimation of the amount of sorbed gas in shales. For non-Darcy gas flow, the apparent permeability model for free gas is established by combining slip flow and Knudsen flow. For adsorbed gas, the surface diffusion effect is also considered in this model. Here, the surface diffusion coefficient is suggested to be of the same scale as the gas self-diffusion coefficient, and the corresponding effective permeability is derived. When

02 PETROLEUM↗

Radiative forcing perturbation due to observed increases in tropospheric ozone at Hohenpeissenberg

The effect on surface temperature due to changes in atmospheric O3 depends highly on the latitude where the change occurs. Previous sensitivity calculations indicate that ozone changes in the upper troposphere and lower stratosphere are more effective in causing surface temperature change (Wang et al., 1980). Long term ground-based observations show that tropospheric ozone, especially at the tropopause region, has been increasing at middle and high latitudes in the Northern Hemisphere (NATO, 1988; Quadrennial Ozone Symposium, 1992). These increases will enhance the greenhouse effect and increase the radiative forcing to the troposphere-surface system, which is opposite to the negative radiative forcing calculated from the observed stratospheric ozone depletion recently reported in WMO (1992). We used more than two thousands regularly measured ozonesondes providing reliable vertical O3 distribution at Hohenpeissenberg (47N; 11E) for the 1967-1990 to study the instantaneous solar and longwave radiative forcing the two decades 1971-1990 and compare the forcing with those caused by increasing CO2, CH4, N2O, and CFCs. Calculations are also made to compare the O3 radiative forcing between stratospheric depletion and tropospheric increase. Results indicate that the O3 changes will induce a positive radiative forcing dominated by tropospheric O3 increase and the magnitude of the forcing is comparable to that due to CO2 increases during the two decades. The significant implications of the tropospheric O3 increase to the global climate are discussed.

Wang, Wei-Chyung↗