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DOE OSTI2020

Surface Termination of CsPbBr 3 Perovskite Quantum Dots Determined by Solid-State NMR Spectroscopy

Cesium lead halide perovskite quantum dots (QDs) have gained significant attention as next-generation optoelectronic materials; however, their properties are highly dependent on their surface chemistry. The surfaces of cuboidal CsPbBr 3 QDs have been intensively studied by both theoretical and experimental techniques, but fundamental questions still remain about the atomic termination of the QDs. The surface binding sites and modes of ligands at the surface remain unproven. Herein, we demonstrate that solid-state NMR spectroscopy allows the unambiguous assignment of organic surface ligands via 1 H, 13 C, and 31 P NMR. Surface-selective 133 Cs solid-state NMR spectra show the presence of an additional 133 Cs NMR signal with a unique chemical shift that is attributed to Cs atoms terminating the surface of the particle and which are likely coordinated by carboxylate ligands. Dipolar dephasing curves that report on the distance between the surface ammonium ligands and Cs and Pb were recorded using double resonance 1 H{ 133 Cs} and 1 H{ 207 Pb} RESPDOR experiments. Model QD surface slabs with different possible surface terminations were generated from the CsPbBr 3 crystal structure and theoretical RESPDOR dipolar dephasing curves considering all possible 1 H- 133 Cs/ 207 Pb spin pairs were then calculated. Comparison of the calculated and experimental RESPDOR curves indicates the particles are CsBr terminated (not PbBr 2 terminated) with alkylammonium ligands substituting into some surface Cs sites, consistent with the surface-selective 133 Cs NMR experiments. Lastly, these results highlight the utility of high-resolution solid-state NMR spectroscopy for studying ligand binding and the surface structure of nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Effect of graphitic anode surface functionalization on the structure and dynamics of electrolytes at the interface

Surface termination on a graphitic surface and the type of electrolytes in lithium-ion batteries (LIBs) play an important part in determining the structure, composition, and thus, the quality of the emergent solid electrolyte interphase. In this paper, we analyze the structure and dynamics of electrolyte molecules in multi-component electrolyte with varying species compositions combinatorially paired with four different graphitic surfaces terminated with hydrogen, hydroxyl, carbonyl, and carboxyl to explore the interplay between surface chemistry and electrolyte dynamics at electrode/electrolyte interfaces. Addition of dimethyl carbonate and fluoroethylene carbonate brought substantial changes in the ethylene carbonate (EC) and LiPF6 surface population density for hydroxyl and carbonyl surfaces. Strong density oscillation and drastic slowing of the dynamics of the electrolyte molecules at the interface are reported for all the systems. While these observations are universal, carboxyl surfaces have the strongest local and long-range effects. Characterization of the average dipole direction at the interface shows strong orientational preferences of ethylene carbonate molecules. EC molecules are preferred to be oriented either almost parallel or perpendicular to the hydroxyl surface, are tilted between parallel and perpendicular with a higher angle of incidence of the dipole vs surface normal on the carbonyl surface than on the hydroxyl surface, and are oriented perpendicularly against the carboxyl surface. These differences highlight the significant effect of graphite surface termination on the dynamics of the electrolytes and provide insight into the complex interplays between electrolyte species and graphite anode in LIBs.

Rustam, Sabiha (ORCID:0000000224248153)↗

DOE OSTI2025

Competition between roughness and strength for scale-dependent surfaces

Rocks famously have scale-dependent strength, yet the actual dependence is notoriously hard to measure or incorporate into any theoretical framework. Natural rough surfaces present an opportunity to solve the problem. Surfaces sliding in shear evolve as protrusions collide. These asperities can deform or break, thus creating a new surface shape. In particular, natural surfaces have roughness at all scales as well as scale-dependent strength. Based on a scaling analysis, we have previously suggested that the scale-dependent aspect ratio of steady-state surfaces should be proportional to the scale-dependent shear strain at yield. If true, scale-dependent strength could easily be inferred from natural surfaces. Thus, moving beyond the scaling argument to a rigorous treatment of scale-dependent strength for multiscale rough surfaces in shear is important. However, analytic frameworks for analyzing multiscale problems are challenging, as conventional continuum mechanics typically involves a single value for a material property across scales. Here, in this work, we build on the formalism of Persson (2001) that presents a method to compute contact area for rough surfaces with a prescribed topographic spectrum using a stochastic differential equation. The Persson formalism allows for plastic yield under normal loading of otherwise elastic materials and leaves open the possibility of scale-dependent yield stress. In this study, we pursue this route to develop a theory and numerical results for the yielding of a rough, elastoplastic surface with scale-dependent yield stress. Here, we examine surfaces for which the power spectrum of the topography 𝐶 and yield stress 𝑌 follow power laws as a function of scale 𝜆, such that 𝐶∼𝜆 −𝑚 and 𝑌∼𝜆 −𝑛 , respectively. In this formal treatment of the problem, we focus on surfaces in contact and the resulting yield and do not impose shear. Numerical solutions show that the deviation from the elastic scaling solution is bounded as expected by the prior 1D heuristic scaling argument that anticipates the Hurst exponent as 1−𝑛. We also show that the plasticity is expected to erode the contacts if 𝑚 is lower than 𝑛−3, which corresponds to a Hurst exponent lower than 1−𝑛/2. This result is rigorously sound for 2D, i.e., realistic surfaces, and quantitatively different than the prior scaling argument. The theory now permits a correspondingly quantitative approach to interpreting natural surfaces.

elasticity↗

DOE OSTI2021

A Comprehensive Investigation into the Effect of a Low Surface Energy Treatment on Gas Hydrate, Asphaltene, and Wax Formation, Deposition, and Adhesion

The formation/precipitation and deposition of pipeline solids, such as gas hydrates, asphaltenes, and waxes have long plagued production fields. Given the vast differences in chemistries of these solids, any current prevention or mitigation strategy, particularly for cases in which multiple issues are a concern, is likely to involve an extensive assortment of chemical additives that are both costly and add complexity to the system. Surface treatments (coatings), on the other hand, present a relatively viable option for management strategies. A chemically and physically robust surface treatment with the ability to address deposition issues for multiple pipeline solids could not only decrease the operating expenditures for a field through material cost savings and obviation of downstream separation, but could also simplify produced fluids by eliminating additional chemicals from the mixture. The purpose of this study was to explore the feasibility of a particular surface treatment as part of a solids management strategy. This work used an omniphobic surface treatment to probe its effects on gas hydrate, asphaltene, and wax deposition. Specifically, an interfacial tensiometer (IFT) collected contact angle measurements for wettability studies. High-pressure rocking cells studied gas hydrate nucleation and deposition. A bench-scale flow loop quantified the deposition of oil and asphaltenes after a set time period. Finally, a mechanical shear device measured the adhesion force of wax deposits on untreated/treated surfaces. Static contact angle results showed that the omniphobic surface treatment had reduced surface interaction with water droplets in air, altering from the complete wetting on corroded surfaces to slightly hydrophobic conditions of greater than 100°. In addition, rocking-cell tests indicated that these omniphobic surface treatments may prevent gas hydrate deposition for up to 72 hours. The gas hydrate rocking-cell tests also demonstrated possible increases in induction time and occasional elimination of hydrate nucleation with the surface treatment. Finally, the surface treatment application, which also decreased surface roughness, showed that crude oil and asphaltene particles deposition, as well as the shear required to remove solidified wax deposits, could be reduced by a large factor. Overall, promising results were recorded for all major flow-assurance solids in the presence of the surface treatment.

Engineering↗

NASA NTRS1972

Optical polarimetric properties of the Echo 2 and PAGEOS 1 engineering surfaces

Experimental investigations of the percent polarization of sunlight reflected from the surfaces of each of the Echo 2 Satellite and PAGEOS (Passive Geodetic Earth Orbiting Satellite) were performed to determine the stability of their surfaces in the space environment. The Echo 2 surface material was amorphous phosphate chemically bonded to a rolled aluminum substrate while the PAGEOS 1 surface material is vapor deposited aluminum on a poly (ethylene terephthalate) film. The stability of the satellites' surfaces was analyzed by comparing the light polarizing properties of the satellites, to those of test surfaces representative of the satellites' surfaces. The properties of flat test surfaces were measured experimentally in the laboratory, and the effects of surface strain, surface geometry, and vacuum upon these properties were examined. The laboratory analyses revealed that the polarization properties of the Echo 2 surface were significantly affected by surface geometry and vacuum, and that the properties of the PAGEOS 1 surface were not significantly altered by any of the above mechanisms.

Lee, R. B., III↗

NASA NTRS1993

Synergism of active and passive microwave data for estimating bare surface soil moisture

Active and passive microwave sensors were applied effectively to the problem of estimating the surface soil moisture in a variety of environmental conditions. Research to date has shown that both types of sensors are also sensitive to the surface roughness and the vegetation cover. In estimating the soil moisture, the effect of the vegetation and roughness are often corrected either by acquiring multi-configuration (frequency and polarization) data or by adjusting the surface parameters in order to match the model predictions to the measured data. Due to the limitations on multi-configuration spaceborne data and the lack of a priori knowledge of the surface characteristics for parameter adjustments, it was suggested that the synergistic use of the sensors may improve the estimation of the soil moisture over the extreme range of naturally occurring soil and vegetation conditions. To investigate this problem, the backscattering and emission from a bare soil surface using the classical rough surface scattering theory were modeled. The model combines the small perturbation and the Kirchhoff approximations in conjunction with the Peak formulation to cover a wide range of surface roughness parameters with respect to frequency for both active and passive measurements. In this approach, the same analytical method was used to calculate the backscattering and emissivity. Therefore, the active and passive simulations can be combined at various polarizations and frequencies in order to estimate the soil moisture more actively. As a result, it is shown that (1) the emissivity is less dependent on the surface correlation length, (2) the ratio of the backscattering coefficient (HH) over the surface reflectivity (H) is almost independent of the soil moisture for a wide range of surface roughness, and (3) this ratio can be approximated as a linear function of the surface rms height. The results were compared with the data obtained by a multi-frequency radiometer-scatterometer system working at frequencies between 3.0 GHz to 11.0 GHz. The data were acquired over bare soil surfaces with moisture variations due to freezing and thawing and roughness changes due to rain and erosion. The model predictions are shown to be in reasonable agreement with the data. In addition, it was shown that the same ratio when calculated from the data shows almost no dependence on the soil moisture. Finally, a simple technique which combines the backscattering coefficient at HH polarization (active sensing) with the emissivity at H polarization (passive sensing) is suggested for retrieving the soil moisture from bare soil surfaces.

Saatchi, Sasan S.↗

NASA NTRS1996

A Numerical Simulation of Scattering from One-Dimensional Inhomogeneous Dielectric Random Surfaces

In this paper, an efficient numerical solution for the scattering problem of inhomogeneous dielectric rough surfaces is presented. The inhomogeneous dielectric random surface represents a bare soil surface and is considered to be comprised of a large number of randomly positioned dielectric humps of different sizes, shapes, and dielectric constants above an impedance surface. Clods with nonuniform moisture content and rocks are modeled by inhomogeneous dielectric humps and the underlying smooth wet soil surface is modeled by an impedance surface. In this technique, an efficient numerical solution for the constituent dielectric humps over an impedance surface is obtained using Green's function derived by the exact image theory in conjunction with the method of moments. The scattered field from a sample of the rough surface is obtained by summing the scattered fields from all the individual humps of the surface coherently ignoring the effect of multiple scattering between the humps. The statistical behavior of the scattering coefficient sigma(sup 0) is obtained from the calculation of scattered fields of many different realizations of the surface. Numerical results are presented for several different roughnesses and dielectric constants of the random surfaces. The numerical technique is verified by comparing the numerical solution with the solution based on the small perturbation method and the physical optics model for homogeneous rough surfaces. This technique can be used to study the behavior of scattering coefficient and phase difference statistics of rough soil surfaces for which no analytical solution exists.

Sarabandi, Kamal↗

NASA NTRS1999

Surface Emissivity Maps for Use in Satellite Retrievals of Longwave Radiation

Accurate accounting of surface emissivity is essential for the retrievals of surface temperature from remote sensing measurements, and for the computations of longwave (LW) radiation budget of the Earth?s surface. Past studies of the above topics assumed that emissivity for all surface types, and across the entire LW spectrum is equal to unity. There is strong evidence, however, that emissivity of many surface materials is significantly lower than unity, and varies considerably across the LW spectrum. We have developed global maps of surface emissivity for the broadband LW region, the thermal infrared window region (8-12 micron), and 12 narrow LW spectral bands. The 17 surface types defined by the International Geosphere Biosphere Programme (IGBP) were adopted as such, and an additional (18th) surface type was introduced to represent tundra-like surfaces. Laboratory measurements of spectral reflectances of 10 different surface materials were converted to corresponding emissivities. The 10 surface materials were then associated with 18 surface types. Emissivities for the 18 surface types were first computed for each of the 12 narrow spectral bands. Emissivities for the broadband and the window region were then constituted from the spectral band values by weighting them with Planck function energy distribution.

Wilber, Anne C.↗

NASA NTRS1999

Comparison of Continuous Wave CO2 Doppler Lidar Calibration Using Earth Surface Targets in Laboratory and Airborne Measurements

Routine backscatter, beta, measurements by an airborne or space-based lidar from designated earth surfaces with known and fairly uniform beta properties can potentially offer lidar calibration opportunities. This can in turn be used to obtain accurate atmospheric aerosol and cloud beta measurements on large spatial scales. This is important because achieving a precise calibration factor for large pulsed lidars then need not rest solely on using a standard hard target procedure. Furthermore, calibration from designated earth surfaces would provide an inflight performance evaluation of the lidar. Hence, with active remote sensing using lasers with high resolution data, calibration of a space-based lidar using earth's surfaces will be extremely useful. The calibration methodology using the earth's surface initially requires measuring beta of various earth surfaces simulated in the laboratory using a focused continuous wave (CW) CO2 Doppler lidar and then use these beta measurements as standards for the earth surface signal from airborne or space-based lidars. Since beta from the earth's surface may be retrieved at different angles of incidence, beta would also need to be measured at various angles of incidences of the different surfaces. In general, Earth-surface reflectance measurements have been made in the infrared, but the use of lidars to characterize them and in turn use of the Earth's surface to calibrate lidars has not been made. The feasibility of this calibration methodology is demonstrated through a comparison of these laboratory measurements with actual earth surface beta retrieved from the same lidar during the NASA/Multi-center Airborne Coherent Atmospheric Wind Sensor (MACAWS) mission on NASA's DC8 aircraft from 13 - 26 September, 1995. For the selected earth surface from the airborne lidar data, an average beta for the surface was established and the statistics of lidar efficiency was determined. This was compared with the actual lidar efficiency determined with the standard calibrating hard target.

Jarzembski, Maurice A.↗

NASA NTRS2000

Remobilizing the Interfaces of Thermocapillary Driven Bubbles Retarded by the Adsorption of a Surfactant Impurity on the Bubble Surface

Thermocapillary migration is a method for moving bubbles in space in the absence of buoyancy. A temperature gradient is applied to the continuous phase in which a bubble is situated, and the applied gradient impressed on the bubble surface causes one pole of the drop to be cooler than the opposite pole. As the surface tension is a decreasing function of temperature, the cooler pole pulls at the warmer pole, creating a flow which propels the bubble in the direction of the warmer fluid. A major impediment to the practical use of thermocapillarity to direct the movement of bubbles in space is the fact that surfactant impurities which are unavoidably present in the continuous phase can significantly reduce the migration velocity. A surfactant impurity adsorbed onto the bubble interface is swept to the trailing end of the bubble. When bulk concentrations are low (which is the case with an impurity), diffusion of surfactant to the front end is slow relative to convection, and surfactant collects at the back end of the bubble. Collection at the back lowers the surface tension relative to the front end setting up a reverse tension gradient. For buoyancy driven bubble motions in the absence of a thermocapillarity, the tension gradient opposes the surface flow, and reduces the surface and terminal velocities (the interface becomes more solid-like). When thermocapillary forces are present, the reverse tension gradient set up by the surfactant accumulation reduces the temperature tension gradient, and decreases to near zero the thermocapillary velocity. The objective of our research is to develop a method for enhancing the thermocapillary migration of bubbles which have been retarded by the adsorption onto the bubble surface of a surfactant impurity, Our remobilization theory proposes to use surfactant molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher concentrations than the impurity, it adsorbs to the bubble much faster than the impurity when the bubble is formed, and thereby prevents the impurity from adsorbing onto the surface. In addition the rapid kinetic exchange and high bulk concentration maintain a saturated surface with a uniform surface concentrations. This prevents retarding surface tension gradients and keeps the velocity high. In our first report last year, we detailed experimental results which verified the theory of remobilization in ground based experiments in which the steady velocity of rising bubbles was measured in a continuous phase consisting of a glycerol/water mixture containing a polyethylene glycol surfactant C12E6 (CH3(CH2)11(OCH2CH2)6OH). In our report this year, we detail our efforts to describe theoretically the remobilization observed. We construct a model in which a bubble rises steadily by buoyancy in a continuous (Newtonian) viscous fluid containing surfactant with a uniform far field bulk concentration. We account for the effects of inertia as well as viscosity in the flow in the continuous phase caused by the bubble motion (order one Reynolds number), and we assume that the bubble shape remains spherical (viscous and inertial forces are smaller than capillary forces, i e. small Weber and capillary numbers). The surfactant distribution is calculated by solving the mass transfer equations including convection and diffusion in the bulk, and finite kinetic exchange the bulk and the surface. Convective effects dominate diffusive mass transfer in the bulk of the liquid (high Peclet numbers) except in a thin boundary layer near the surface. A finite volume method is used to numerically solve the hydrodynamic and mass transfer equations on a staggered grid which accounts specifically for the thin boundary layer. We present the results of the nondimensional drag as a function of the bulk concentration of surfactant for different rates of kinetic exchange, from which we develop criteria for the concentration necessary to develop a prescribed degree of remobilization. The criteria compare favorably with the experimental results.

Palaparthi, Ravi↗

NASA NTRS2001

The Development of Surface Roughness and Implications for Cellular Attachment in Biomedical Applications

The application of a microscopic surface texture produced by ion beam sputter texturing to the surfaces of polymer implants has been shown to result in significant increases in cellular attachment compared to smooth surface implants in animal studies. A collaborative program between NASA Glenn Research Center and the Cleveland Clinic Foundation has been established to evaluate the potential for improving osteoblast attachment to surfaces that have been microscopically roughened by atomic oxygen texturing. The range of surface textures that are feasible depends upon both the texturing process and the duration of treatment. To determine whether surface texture saturates or continues to increase with treatment duration, an effort was conducted to examine the development of surface textures produced by various physical and chemical erosion processes. Both experimental tests and computational modeling were performed to explore the growth of surface texture with treatment time. Surface texturing by means of abrasive grit blasting of glass, stainless steel, and polymethylmethacry I ate surfaces was examined to measure the growth in roughness with grit blasting duration by surface profilometry measurements. Laboratory tests and computational modeling was also conducted to examine the development of texture on Aclar(R) (chlorotfifluoroethylene) and Kapton(R) polyimide, respectively. For the atomic oxygen texturing tests of Aclar(R), atomic force microscopy was used to measure the development of texture with atomic oxygen fluence. The results of all the testing and computational modeling support the premise that development of surface roughness obeys Poisson statistics. The results indicate that surface roughness does not saturate but increases as the square root of the treatment time.

Banks, Bruce↗

NASA NTRS2001

Remobilizing the Interface of Thermocapillary Driven Bubbles Retarded By the Adsorption of a Surfactant Impurity on the Bubble Surface

Thermocapillary migration is a method for moving bubbles in space in the absence of buoyancy. A temperature gradient is the continuous phase in which a bubble is situated, and the applied gradient impressed on the bubble surface causes one pole of the drop to be cooler than the opposite pole. As the surface tension is a decreasing function of temperature, the cooler pole pulls at the warmer pole, creating a flow that propels the bubble in the direction of the warmer fluid. A major impediment to the practical use of thermocapillary to direct the movement of bubbles in space is the fact that surfactant impurities, which are unavoidably present in the continuous phase, can significantly reduce the migration velocity. A surfactant impurity adsorbed onto the bubble interface is swept to the trailing end of the bubble. When bulk concentrations are low (which is the case with an impurity), diffusion of surfactant to the front end is slow relative to convection, and surfactant collects at the back end of the bubble. Collection at the back lowers the surface tension relative to the front end setting up a reverse tension gradient. (This can also be the case if kinetic desorption of surfactant at the back end of the bubble is much slower than convection.) For buoyancy driven bubble motions in the absence of a thermocapillarity, the tension gradient opposes the surface flow, and reduces the surface and terminal velocities (the interface becomes more solid-like and bubbles translate as solid particles). When thermocapillary forces are present, the reverse tension gradient set up by the surfactant accumulation reduces the temperature-induced tension gradient, and can decrease to near zero the bubble's thermocapillary velocity. The objective of our research is to develop a method for enhancing the thermocapillary migration of bubbles which have be retarded by the adsorption onto the bubble surface of a surfactant impurity. Our remobilization theory proposes to use surfactant molecules which kinetically rapidly exchange between the bulk and the surface and are at high bulk concentrations. Because the remobilizing surfactant is present at much higher concentrations than the impurity, it adsorbs to the bubble surface much faster than the impurity when the bubble is formed, and thereby prevents the impurity from adsorbing onto the surface. In addition, the rapid kinetic exchange and high bulk concentration maintain a saturated surface with uniform surface concentrations. This prevents retarding surface tension gradients and keeps the thermocapillary velocity high. In our reports over the first 2 years, we presented numerical simulations of the bubble motion and surfactant transport which verified theoretically the concept of remobilization, and the development of an apparatus to track and measure the velocity of rising bubbles in a glycerol/water surfactant solution. This year, we detail experimental observations of remobilization. Two polyethylene oxide surfactants were studied, C12E6 (CH3(CH2)11(OCH2)6OH) and C10E8 (CH3(CH2)4(OCH2CH2)8OH). Measurements of the kinetic exchange for these surfactants show that the one with the longer hydrophobe chain C12E6 has a lower rate of kinetic exchange. In addition, this surfactant is much less soluble in the glycerol/water mixture because of the shorter ethoxylate chain. As a result, we found that C12E6 had only a very limited ability to remobilize rising bubbles because of the limited kinetic exchange and reduced solubility. However, C10E8, with its higher solubility and more rapid exchange was found to dramatically remobilize rising bubbles. We also compared our theoretical calculations to the experimental measurements of velocity for both the non-remobilizing and remobilizing surfactants and found excellent agreement. We further observed that for C10E8 at high concentrations, which exceeded the critical micelle concentrations, additional remobilization was measured. In this case the rapid exchange of monomer between micelle and surfactant provides an additional mechanism for maintaining a uniform surface concentrations.

Palaparthi, Ravi↗

NASA NTRS2002

Urban Surface Radiative Energy Budgets Determined Using Aircraft Scanner Data

It is estimated that by the year 2025, 80% of the world's population will live in cities. The extent of these urban areas across the world can be seen in an image of city lights from the Defense Meteorological Satellite Program. In many areas of North America and Europe, it is difficult to separate individual cities because of the dramatic growth and sprawl of urbanized areas. This conversion of the natural landscape vegetation into man-made urban structures such as roads and buildings drastically alter the regional surface energy budgets, hydrology, precipitation patterns, and meteorology. One of the earliest recognized and measured phenomena of urbanization is the urban heat island (UHI) which was reported as early as 1833 for London and 1862 for Paris. The urban heat island results from the energy that is absorbed by man-made materials during the day and is released at night resulting in the heating of the air within the urban area. The magnitude of the air temperature difference between the urban and surrounding countryside is highly dependent on the structure of the urban area, amount of solar immolation received during the day, and atmospheric conditions during the night. These night time air temperature differences can be in the range of 2 to 5 C. or greater. Although day time air temperature differences between urban areas and the countryside exists during the day, atmospheric mixing and stability reduce the magnitude. This phenomena is not limited to large urban areas, but also occurs in smaller metropolitan areas. The UHI has significant impacts on the urban air quality, meteorology, energy use, and human health. The UPI can be mitigated through increasing the amount of vegetation and modification of urban surfaces using high albedo materials for roofs and paved surfaces. To understand why the urban heat island phenomenon exists it is useful to define the surface in terms of the surface energy budget. Surface temperature and albedo is a major component of the surface energy budget. Knowledge of it is important in any attempt to describe the radiative and mass fluxes which occur at the surface. Use of energy terms in modeling surface energy budgets allows the direct comparison of various land surfaces encountered in a urban landscape, from vegetated (forest and herbaceous) to non-vegetated (bare soil, roads, and buildings). These terms are also easily measured using remote sensing from aircraft or satellite platforms allowing one to examine the spacial variability. The partitioning of energy budget terms depends on the surface type. In natural landscapes, the partitioning is dependent on canopy biomass, leaf area index, aerodynamic roughness, and moisture status, all of which are influenced by the development stage of the ecosystem. In urban landscapes, coverage by man-made materials substantially alters the surface face energy budget. The remotely sensed data obtained from aircraft and satellites, when properly calibrated allows the measurement of important terms in the radiative surface energy budget a urban landscape scale.

Luvall, Jeffrey C.↗

NASA NTRS2002

Motion of Drops on Surfaces with Wettability Gradients

A liquid drop present on a solid surface can move because of a gradient in wettability along the surface, as manifested by a gradient in the contact angle. The contact angle at a given point on the contact line between a solid and a liquid in a gaseous medium is the angle between the tangent planes to the liquid and the solid surfaces at that point and is measured within the liquid side, by convention. The motion of the drop occurs in the direction of increasing wettability. The cause of the motion is the net force exerted on the drop by the solid surface because of the variation of the contact angle around the periphery. This force causes acceleration of an initially stationary drop, and leads to its motion in the direction of decreasing contact angle. The nature of the motion is determined by the balance between the motivating force and the resisting hydrodynamic force from the solid surface and the surrounding gaseous medium. A wettability gradient can be chemically induced as shown by Chaudhury and Whitesides who provided unambiguous experimental evidence that drops can move in such gradients. The phenomenon can be important in heat transfer applications in low gravity, such as when condensation occurs on a surface. Daniel et al have demonstrated that the velocity of a drop on a surface due to a wettability gradient in the presence of condensation can be more than two orders of magnitude larger than that observed in the absence of condensation. In the present research program, we have begun to study the motion of a drop in a wettability gradient systematically using a model system. Our initial efforts will be restricted to a system in which no condensation occurs. The experiments are performed as follows. First, a rectangular strip of approximate dimensions 10 x 20 mm is cut out of a silicon wafer. The strip is cleaned thoroughly and its surface is exposed to the vapor from an alkylchlorosilane for a period lasting between one and two minutes inside a desiccator. This is done using an approximate line source of the vapor in the form of a string soaked in the alkylchlorosilane. Ordinarily, many fluids, including water, wet the surface of silicon quite well. This means that the contact angle is small. But the silanized surface resists wetting, with contact angles that are as large as 100 degs. Therefore, a gradient of wettability is formed on the silicon surface. The region near the string is highly hydrophobic, and the contact angle decreases gradually toward a small value at the hydrophilic end away from this region. The change in wettability occurs over a distance of several mm. The strip is placed on a platform within a Plexiglas cell. Drops of a suitable liquid are introduced on top of the strip near the hydrophobic end. An optical system attached to a video camera is trained on the drop so that images of the moving drop can be captured on videotape for subsequent analysis. We have performed preliminary experiments with water as well as ethylene glycol drops. Results from these experiments will be presented in the poster. Future plans include the refinement of the experimental system so as to permit images to be recorded from the side as well as the top, and the conduct of a systematic study in which the drop size is varied over a good range. Experiments will be conducted with different fluids so as to obtain the largest possible range of suitably defined Reynolds and Capillary numbers. Also, an effort will be initiated on theoretical modeling of this motion. The challenges in the development of the theoretical description lie in the proper analysis of the region in the vicinity of the contact line, as well as in the free boundary nature of the problem. It is known that continuum models assuming the no slip condition all the way to the contact line fail by predicting that the stress on the solid surface becomes singular as the contact line is approached. One approach for dealing with this issue has been to relax the no-slip boundary condition using the Navier model. Molecular dynamics simulations of the contact line region show that for a non-polar liquid on a solid surface, the no-slip boundary condition is in fact incorrect near the contact line. Furthermore, the same simulations also show that the usual relationship between stress and the rate of deformation breaks down in the vicinity of the contact line. In developing continuum theoretical models of the system, we shall accommodate this knowledge to the extent possible.

Subramanian, R. Shankar↗

NASA NTRS2001

Atomically Flat Surfaces Developed for Improved Semiconductor Devices

New wide bandgap semiconductor materials are being developed to meet the diverse high temperature, -power, and -frequency demands of the aerospace industry. Two of the most promising emerging materials are silicon carbide (SiC) for high-temperature and high power applications and gallium nitride (GaN) for high-frequency and optical (blue-light-emitting diodes and lasers) applications. This past year Glenn scientists implemented a NASA-patented crystal growth process for producing arrays of device-size mesas whose tops are atomically flat (i.e., step-free). It is expected that these mesas can be used for fabricating SiC and GaN devices with major improvements in performance and lifetime. The promising new SiC and GaN devices are fabricated in thin-crystal films (known as epi films) that are grown on commercial single-crystal SiC wafers. At this time, no commercial GaN wafers exist. Crystal defects, known as screw defects and micropipes, that are present in the commercial SiC wafers propagate into the epi films and degrade the performance and lifetime of subsequently fabricated devices. The new technology isolates the screw defects in a small percentage of small device-size mesas on the surface of commercial SiC wafers. This enables atomically flat surfaces to be grown on the remaining defect-free mesas. We believe that the atomically flat mesas can also be used to grow GaN epi films with a much lower defect density than in the GaN epi films currently being grown. Much improved devices are expected from these improved low-defect epi films. Surface-sensitive SiC devices such as Schottky diodes and field effect transistors should benefit from atomically flat substrates. Also, we believe that the atomically flat SiC surface will be an ideal surface on which to fabricate nanoscale sensors and devices. The process for achieving atomically flat surfaces is illustrated. The surface steps present on the "as-received" commercial SiC wafer is also illustrated. because of the small tilt angle between the crystal "basal" plane and the polished wafer surface. These steps are used in normal SiC epi film growth in a process known as stepflow growth to produce material for device fabrication. In the new process, the first step is to etch an array of mesas on the SiC wafer top surface. Then, epi film growth is carried out in the step flow fashion until all steps have grown themselves out of existence on each defect-free mesa. If the size of the mesas is sufficiently small (about 0.1 by 0.1 mm), then only a small percentage of the mesas will contain an undesired screw defect. Mesas with screw defects supply steps during the growth process, allowing a rough surface with unwanted hillocks to form on the mesa. The improvement in SiC epi surface morphology achievable with the new technology is shown. An atomic force microscope image of a typical SiC commercial epilayer surface is also shown. A similar image of an SiC atomically flat epi surface grown in a Glenn laboratory is given. With the current screw defect density of commercial wafers (about 5000 defects/cm2), the yield of atomically free 0.1 by 0.l mm mesas is expected to be about 90 percent. This is large enough for many types of electronic and optical devices. The implementation of this new technology was recently published in Applied Physics Letters. This work was initially carried out in-house under a Director's Discretionary Fund project and is currently being further developed under the Information Technology Base Program.

Powell, J. Anthony↗

NASA NTRS2005

The Influence of Roughness on Gear Surface Fatigue

Gear working surfaces are subjected to repeated rolling and sliding contacts, and often designs require loads sufficient to cause eventual fatigue of the surface. This research provides experimental data and analytical tools to further the understanding of the causal relationship of gear surface roughness to surface fatigue. The research included evaluations and developments of statistical tools for gear fatigue data, experimental evaluation of the surface fatigue lives of superfinished gears with a near-mirror quality, and evaluations of the experiments by analytical methods and surface inspections. Alternative statistical methods were evaluated using Monte Carlo studies leading to a final recommendation to describe gear fatigue data using a Weibull distribution, maximum likelihood estimates of shape and scale parameters, and a presumed zero-valued location parameter. A new method was developed for comparing two datasets by extending the current methods of likelihood-ratio based statistics. The surface fatigue lives of superfinished gears were evaluated by carefully controlled experiments, and it is shown conclusively that superfinishing of gears can provide for significantly greater lives relative to ground gears. The measured life improvement was approximately a factor of five. To assist with application of this finding to products, the experimental condition was evaluated. The fatigue life results were expressed in terms of specific film thickness and shown to be consistent with bearing data. Elastohydrodynamic and stress analyses were completed to relate the stress condition to fatigue. Smooth-surface models do not adequately explain the improved fatigue lives. Based on analyses using a rough surface model, it is concluded that the improved fatigue lives of superfinished gears is due to a reduced rate of near-surface micropitting fatigue processes, not due to any reduced rate of spalling (sub-surface) fatigue processes. To complete the evaluations, surface inspection were completed. The surface topographies of the ground gears changed substantially due to running, but the topographies of the superfinished gears were essentially unchanged with running.

Krantz, Timothy↗

NASA NTRS2006

Airport Surface Network Architecture Definition

Currently, airport surface communications are fragmented across multiple types of systems. These communication systems for airport operations at most airports today are based dedicated and separate architectures that cannot support system-wide interoperability and information sharing. The requirements placed upon the Communications, Navigation, and Surveillance (CNS) systems in airports are rapidly growing and integration is urgently needed if the future vision of the National Airspace System (NAS) and the Next Generation Air Transportation System (NGATS) 2025 concept are to be realized. To address this and other problems such as airport surface congestion, the Space Based Technologies Project s Surface ICNS Network Architecture team at NASA Glenn Research Center has assessed airport surface communications requirements, analyzed existing and future surface applications, and defined a set of architecture functions that will help design a scalable, reliable and flexible surface network architecture to meet the current and future needs of airport operations. This paper describes the systems approach or methodology to networking that was employed to assess airport surface communications requirements, analyze applications, and to define the surface network architecture functions as the building blocks or components of the network. The systems approach used for defining these functions is relatively new to networking. It is viewing the surface network, along with its environment (everything that the surface network interacts with or impacts), as a system. Associated with this system are sets of services that are offered by the network to the rest of the system. Therefore, the surface network is considered as part of the larger system (such as the NAS), with interactions and dependencies between the surface network and its users, applications, and devices. The surface network architecture includes components such as addressing/routing, network management, network performance and security.

Nguyen, Thanh C.↗

NASA NTRS2011

In Situ Surface Characterization

Operation of in situ space assets, such as rovers and landers, requires operators to acquire a thorough understanding of the environment surrounding the spacecraft. The following programs help with that understanding by providing higher-level information characterizing the surface, which is not immediately obvious by just looking at the XYZ terrain data. This software suite covers three primary programs: marsuvw, marsrough, and marsslope, and two secondary programs, which together use XYZ data derived from in situ stereo imagery to characterize the surface by determining surface normal, surface roughness, and various aspects of local slope, respectively. These programs all use the Planetary Image Geometry (PIG) library to read mission-specific data files. The programs themselves are completely multimission; all mission dependencies are handled by PIG. The input data consists of images containing XYZ locations as derived by, e.g., marsxyz. The marsuvw program determines surface normals from XYZ data by gathering XYZ points from an area around each pixel and fitting a plane to those points. Outliers are rejected, and various consistency checks are applied. The result shows the orientation of the local surface at each point as a unit vector. The program can be run in two modes: standard, which is typically used for in situ arm work, and slope, which is typically used for rover mobility. The difference is primarily due to optimizations necessary for the larger patch sizes in the slope case. The marsrough program determines surface roughness in a small area around each pixel, which is defined as the maximum peak-to-peak deviation from the plane perpendicular to the surface normal at that pixel. The marsslope program takes a surface normal file as input and derives one of several slope-like outputs from it. The outputs include slope, slope rover direction (a measure of slope radially away from the rover), slope heading, slope magnitude, northerly tilt, and solar energy (compares the slope with the Sun s location at local noon). The marsuvwproj program projects a surface normal onto an arbitrary plane in space, resulting in a normalized 3D vector, which is constrained to lie in the plane. The marsuvwrot program rotates the vectors in a surface normal file, generating a new surface normal file. It also can change coordinate systems for an existing surface normal file. While the algorithms behind this suite are not particularly unique, what makes the programs useful is their integration into the larger in situ image processing system via the PIG library. They work directly with space in situ data, understanding the appropriate image metadata fields and updating them properly. The secondary programs (marsuvwproj, marsuvwrot) were originally developed to deal with anomalous situations on Opportunity and Spirit, respectively, but may have more general applicability.

Deen, Robert G.↗