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DOE OSTI2018

Fabrication of hierarchical meso/macroporous TiO2 scaffolds by evaporation-induced self-assembly technique for bone tissue engineering applications

Highlights: • Hierarchical meso/macroporous TiO{sub 2} scaffolds were produced. • TiO{sub 2} formation mechanism was investigated. • The scaffolds had a pore size of 150–300 μm and meso pores of 6–12 nm. • The specific surface area obtained from BET theory was 67.89 m{sup 3} g{sup −1}. - Abstract: This paper reports the synthesis of hierarchical meso/macroporous TiO{sub 2} scaffolds by mimicking bone structure. Evaporation-induced self-assembly (EISA) method along with foamy method was utilized to produce TiO{sub 2} scaffolds in situ. Simultaneous thermal analysis (STA), small angle X-ray diffraction (SAXD), wide-angle X-ray diffraction (WAXD), nitrogen adsorption–desorption isotherm analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques were applied to characterize the scaffolds. The results showed that TiO{sub 2} scaffolds can be produced after sintering the specimens at 550 °C for 2 h. The obtained scaffolds had a pore size in the range of 150–300 μm and meso pores in the range of 6–12 nm. The specific surface area was obtained from the Brunauer–Emmett–Teller theory, the total volume and mean diameter of pores were 67.89 m{sup 3} g{sup −1}, 0.1245 cm{sup 3} g{sup −1} and 7.3 nm, respectively.

36 MATERIALS SCIENCE↗

NASA NTRS2021

Thermal Analysis of Landers using Radioisotope Power Systems on Ice Worlds

The surfaces of Ice Worlds record evidence of interior processes, chemical potential, habitability, and potentially life within the interior. Volatile and organic chemistry at the surface is critical in determining habitability and detecting the presence of past or extant life. Radioisotope Power Systems (RPS) could be an enabling technology for in situ missions to ice worlds, providing both power and heat for long durations where solar power would not be feasible. However, it is necessary to understand the potential impact of RPS upon the local environment, to ensure that the rejected heat from RPS does not compromise science measurements or planetary protection requirements. To address these concerns, an RPS Ice World Lander Study was carried out in 2019 to investigate possible requirements on RPS surface mission concepts and approaches to excess heat management. The study focused on two destinations that are representative of the range of potential environments: Europa and Enceladus.Initial analysis showed that, due to the very low pressures on the surfaces of most ice world targets, surface melting does not occur because the water ice does not meet the triple-point. A 4 kW heat source suspended above the surface of Europa or Enceladus would not cause any melting, only sublimation.The study used a surface sublimation limit of 10 cm over a two-year period (the baseline for the recent Europa Lander study). To stay within this limit, Europa, with its relatively warm surface, could tolerate only 10 W/m2 of surface heat flux. Enceladus, with its relatively cold pure ice composition, could tolerate up to 100 W/m2.Various lander and heat shield configurations were analyzed for their heat flux radiated from the RPS to the surface. For a given heat shield configuration, the study team determined the minimum height of the RPS above the surface for which the heat flux would be within the accepted parameters for Europa and for Enceladus. Based on these thermal analyses, such RPS-powered landers could remain compliant with science investigation and planetary protection requirements with only modest mass allocated to spacecraft thermal accommodations.

Perl, Scott↗

DOE OSTI2013

Surface characterization of nanomaterials and nanoparticles: Important needs and challenging opportunities

This review examines characterization challenges inherently associated with understanding nanomaterials and the roles surface and interface characterization methods can play in meeting some of the challenges. In parts of the research community, there is growing recognition that studies and published reports on the properties and behaviors of nanomaterials often have reported inadequate or incomplete characterization. As a consequence, the true value of the data in these reports is, at best, uncertain. With the increasing importance of nanomaterials in fundamental research and technological applications, it is desirable that researchers from the wide variety of disciplines involved recognize the nature of these often unexpected challenges associated with reproducible synthesis and characterization of nanomaterials, including the difficulties of maintaining desired materials properties during handling and processing due to their dynamic nature. It is equally valuable for researchers to understand how characterization approaches (surface and otherwise) can help to minimize synthesis surprises and to determine how (and how quickly) materials and properties change in different environments. Appropriate application of traditional surface sensitive analysis methods (including x-ray photoelectron and Auger electron spectroscopies, scanning probe microscopy, and secondary ion mass spectroscopy) can provide information that helps address several of the analysis needs. In many circumstances, extensions of traditional data analysis can provide considerably more information than normally obtained from the data collected. Less common or evolving methods with surface selectivity (e.g., some variations of nuclear magnetic resonance, sum frequency generation, and low and medium energy ion scattering) can provide information about surfaces or interfaces in working environments (operando or in situ) or information not provided by more traditional methods. Although these methods may require instrumentation or expertise not generally available, they can be particularly useful in addressing specific questions, and examples of their use in nanomaterial research are presented.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRS1986

F-106 data summary and model results relative to threat criteria and protection design analysis

The NASA F-106 has acquired considerable data on the rates-of-change of electromagnetic parameters on the aircraft surface during 690 direct lightning strikes while penetrating thunderstorms at altitudes ranging from 15,000 to 40,000 feet. These in-situ measurements have provided the basis for the first statistical quantification of the lightning electromagnetic threat to aircrat appropriate for determining lightning indirect effects on aircraft. The data are presently being used in updating previous lightning criteria and standards developed over the years from ground-based measurements. The new lightning standards will, therefore, be the first which reflect actual aircraft responses measured at flight altitudes. The modeling technique developed to interpret and understand the direct strike electromagnetic data acquired on the F-106 provides a means to model the interaction of the lightning channel with the F-106. The reasonable results obtained with the model, compared to measured responses, yield confidence that the model may be credibly applied to other aircraft types and uses in the prediction of internal coupling effects in the design of lightning protection for new aircraft.

Pitts, F. L.↗

NASA NTRS2008

Proceedings of the 39th Lunar and Planetary Science Conference

Sessions with oral presentations include: A SPECIAL SESSION: MESSENGER at Mercury, Mars: Pingos, Polygons, and Other Puzzles, Solar Wind and Genesis: Measurements and Interpretation, Asteroids, Comets, and Small Bodies, Mars: Ice On the Ground and In the Ground, SPECIAL SESSION: Results from Kaguya (SELENE) Mission to the Moon, Outer Planet Satellites: Not Titan, Not Enceladus, SPECIAL SESSION: Lunar Science: Past, Present, and Future, Mars: North Pole, South Pole - Structure and Evolution, Refractory Inclusions, Impact Events: Modeling, Experiments, and Observations, Mars Sedimentary Processes from Victoria Crater to the Columbia Hills, Formation and Alteration of Carbonaceous Chondrites, New Achondrite GRA 06128/GRA 06129 - Origins Unknown, The Science Behind Lunar Missions, Mars Volcanics and Tectonics, From Dust to Planets (Planetary Formation and Planetesimals):When, Where, and Kaboom! Astrobiology: Biosignatures, Impacts, Habitability, Excavating a Comet, Mars Interior Dynamics to Exterior Impacts, Achondrites, Lunar Remote Sensing, Mars Aeolian Processes and Gully Formation Mechanisms, Solar Nebula Shake and Bake: Mixing and Isotopes, Lunar Geophysics, Meteorites from Mars: Shergottite and Nakhlite Invasion, Mars Fluvial Geomorphology, Chondrules and Chondrule Formation, Lunar Samples: Chronology, Geochemistry, and Petrology, Enceladus, Venus: Resurfacing and Topography (with Pancakes!), Overview of the Lunar Reconnaissance Orbiter Mission, Mars Sulfates, Phyllosilicates, and Their Aqueous Sources, Ordinary and Enstatite Chondrites, Impact Calibration and Effects, Comparative Planetology, Analogs: Environments and Materials, Mars: The Orbital View of Sediments and Aqueous Mineralogy, Planetary Differentiation, Titan, Presolar Grains: Still More Isotopes Out of This World, Poster sessions include: Education and Public Outreach Programs, Early Solar System and Planet Formation, Solar Wind and Genesis, Asteroids, Comets, and Small Bodies, Carbonaceous Chondrites, Chondrules and Chondrule Formation, Chondrites, Refractory Inclusions, Organics in Chondrites, Meteorites: Techniques, Experiments, and Physical Properties, MESSENGER and Mercury, Lunar Science Present: Kaguya (SELENE) Results, Lunar Remote Sensing: Basins and Mapping of Geology and Geochemistry, Lunar Science: Dust and Ice, Lunar Science: Missions and Planning, Mars: Layered, Icy, and Polygonal, Mars Stratigraphy and Sedimentology, Mars (Peri)Glacial, Mars Polar (and Vast), Mars, You are Here: Landing Sites and Imagery, Mars Volcanics and Magmas, Mars Atmosphere, Impact Events: Modeling, Experiments, and Observation, Ice is Nice: Mostly Outer Planet Satellites, Galilean Satellites, The Big Giant Planets, Astrobiology, In Situ Instrumentation, Rocket Scientist's Toolbox: Mission Science and Operations, Spacecraft Missions, Presolar Grains, Micrometeorites, Condensation-Evaporation: Stardust Ties, Comet Dust, Comparative Planetology, Planetary Differentiation, Lunar Meteorites, Nonchondritic Meteorites, Martian Meteorites, Apollo Samples and Lunar Interior, Lunar Geophysics, Lunar Science: Geophysics, Surface Science, and Extralunar Components, Mars, Remotely, Mars Orbital Data - Methods and Interpretation, Mars Tectonics and Dynamics, Mars Craters: Tiny to Humongous, Mars Sedimentary Mineralogy, Martian Gullies and Slope Streaks, Mars Fluvial Geomorphology, Mars Aeolian Processes, Mars Data and Mission,s Venus Mapping, Modeling, and Data Analysis, Titan, Icy Dwarf Satellites, Rocket Scientist's Toolbox: In Situ Analysis, Remote Sensing Approaches, Advances, and Applications, Analogs: Sulfates - Earth and Lab to Mars, Analogs: Remote Sensing and Spectroscopy, Analogs: Methods and Instruments, Analogs: Weird Places!. Print Only Early Solar System, Solar Wind, IDPs, Presolar/Solar Grains, Stardust, Comets, Asteroids, and Phobos, Venus, Mercury, Moon, Meteorites, Mars, Astrobiology, Impacts, Outer Planets, Satellites, and Rings, Support for Mission Operations, Analog Education and Public Outreach.

Source record↗

NASA NTRS2013

Surface Reflectance of Mars Observed by CRISM-MRO: 1. Multi-angle Approach for Retrieval of Surface Reflectance from CRISM Observations (mars-reco)

This article addresses the correction for aerosol effects in near-simultaneous multiangle observations acquired by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) aboard the Mars Reconnaissance Orbiter. In the targeted mode, CRISM senses the surface of Mars using 11 viewing angles, which allow it to provide unique information on the scattering properties of surface materials. In order to retrieve these data, however, appropriate strategies must be used to compensate the signal sensed by CRISM for aerosol contribution. This correction is particularly challenging as the photometric curve of these suspended particles is often correlated with the also anisotropic photometric curve of materials at the surface. This article puts forward an innovative radiative transfer based method named Multi-angle Approach for Retrieval of Surface Reflectance from CRISM Observations (MARS-ReCO). The proposed method retrieves photometric curves of surface materials in reflectance units after removing aerosol contribution. MARS-ReCO represents a substantial improvement regarding previous techniques as it takes into consideration the anisotropy of the surface, thus providing more realistic surface products. Furthermore, MARS-ReCO is fast and provides error bars on the retrieved surface reflectance. The validity and accuracy of MARS-ReCO is explored in a sensitivity analysis based on realistic synthetic data. According to experiments, MARS-ReCO provides accurate results (up to 10 reflectance error) under favorable acquisition conditions. In the companion article, photometric properties of Martian materials are retrieved using MARS-ReCO and validated using in situ measurements acquired during the Mars Exploration Rovers mission.

CRISM/MRO↗

DOE OSTI2013

Coupled alkai fieldspar dissolution and secondary mineral precipatation in batch systems-2: New experiments with supercritical CO2 and implications for carbon sequestration

In order to evaluate the extent of CO{sub 2}–water–rock interactions in geological formations for C sequestration, three batch experiments were conducted on alkali feldspars–CO{sub 2}–brine interactions at 150–200 °C and 300 bars. The elevated temperatures were necessary to accelerate the reactions to facilitate attainable laboratory measurements. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. SEM, TEM and XRD analysis of reaction products showed extensive dissolution features (etch pits, channels, kinks and steps) on feldspars and precipitation of secondary minerals (boehmite, kaolinite, muscovite and paragonite) on feldspar surfaces. Therefore, these experiments have generated both solution chemistry and secondary mineral identity. The experimental results show that partial equilibrium was not attained between secondary minerals and aqueous solutions for the feldspar hydrolysis batch systems. Evidence came from both solution chemistry (supersaturation of the secondary minerals during the entire experimental duration) and metastable co-existence of secondary minerals. The slow precipitation of secondary minerals results in a negative feedback in the dissolution–precipitation loop, reducing the overall feldspar dissolution rates by orders of magnitude. Furthermore, the experimental data indicate the form of rate laws greatly influence the steady state rates under which feldspar dissolution took place. Negligence of both the mitigating effects of secondary mineral precipitation and the sigmoidal shape of rate–ΔG{sub r} relationship can overestimate the extent of feldspar dissolution during CO{sub 2} storage. Finally, the literature on feldspar dissolution in CO{sub 2}-charged systems has been reviewed. The data available are insufficient and new experiments are urgently needed to establish a database on feldspar dissolution mechanism, rates and rate laws, as well as secondary mineral information at CO{sub 2} storage conditions.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Bridging Nano- and Microscale X-Ray Tomography for Battery Research by Leveraging Artificial Intelligence

X-ray computed tomography (CT) is a non-destructive imaging technique in which contrast originates from the materials' absorption coefficient. The recent development of laboratory nanoscale CT (nano-CT) systems has pushed the spatial resolution for battery material imaging to voxel sizes of 50 nm, a limit previously achievable only with synchrotron facilities. Given the non-destructive nature of CT, in situ and operando studies have emerged as powerful methods to quantify morphological parameters, such as tortuosity factor, porosity, surface area and volume expansion, during battery operation or cycling. Combined with artificial intelligence and machine learning analysis techniques, nano-CT has enabled the development of predictive models to analyse the impact of the electrode microstructure on cell performances or the influence of material heterogeneities on electrochemical responses. In this Review, we discuss the role of X-ray CT and nano-CT experimentation in the battery field, discuss the incorporation of artificial intelligence and machine learning analyses and provide a perspective on how the combination of multiscale CT imaging techniques can expand the development of predictive multiscale battery behavioural models.

diagnostics↗

DOE OSTI2013

Volmer-Weber growth of AlSb on Si(111)

AlSb is grown by molecular beam epitaxy. The evolution and the relaxation of the deposited AlSb layer is investigated by synchrotron-based in situ grazing incidence x-ray diffraction (GID), and the analysis of the real space distribution is performed by atomic force microscopy. AlSb forms islands with (111)A polarity and {l_brace}110{r_brace} surface orientations with different side facets following the Volmer-Weber growth mode. GID investigations reveal facet rods originating from AlSb{l_brace}110{r_brace} islands. It is shown that a concentration of only 0.7% AlSb{l_brace}110{r_brace} oriented domains influences the diffraction pattern in such a way that additional crystal truncation rods parallel to the surface appear.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Development of a Portable In Situ Phosphorous Sensor

While phosphorus is a critical nutrient for all forms of life, runoff leads to phosphorus accumulation in surface water where it can cause a variety of health, environmental, and economic problems. The Department of Energy is interested in conducting long-term field experiments to monitor the impact of phosphorus in terrestrial and aquatic environments, and to better understand a cost vs. benefit analysis of reducing phosphorus pollution. Performing such long-term experiments requires affordable sensors capable of monitoring low-level phosphorus concentrations under challenging environmental conditions. However, such sensors are currently not available. The goal of this proposed project is to develop and demonstrate a low-cost portable phosphorus sensor suitable for in situ measurements. We will determine the technical requirements for a Raman-based sensor system, design and build a signal amplifier, integrate it with a Raman-based sensor, and demonstrate a proof-of-concept level sensor system. The expected accomplishments for Phase I include the identification of the technical requirements of a combined Raman laser/spectrometer and cavity enhancement system, building a proof-of-concept level sensor system capable of detecting orthophosphate compounds at the desired level of 0.25 mg P/L and organic P compounds, and verification of the sensor performance under laboratory and field conditions. In addition, we will identify initial hardening requirements that will need to be implemented during Phase II. While we plan to develop an integrated sensor system for monitoring phosphorus, the cavity-based enhancement system can also be used in combination with other (non-phosphorus) Raman sensors that we plan to develop or that are already commercially available. A recent market report highlights the increasing demand for such environmental monitoring applications, with the market for chemical detection anticipated to grow at a compound annual growth rate of 6.5% (2020-2025). Wide-spread monitoring of phosphorus could reduce the damage from eutrophication in freshwater, which is estimated to be $2.2 billion annually, thereby increasing biodiversity, reducing costs required for drinking water treatment, and decreasing economic losses related to recreation and angling and lake property values.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Determining the hydration energetics on carbon-supported Ru catalysts: An adsorption calorimetry and density functional theory study

Fundamental knowledge on the energetics at the interface between a water layer and a metal catalyst is essential so as to understand the roles that water can play in the synthesis, activation and regeneration of noble metal-based catalysts. Here, we report the direct measurement of the enthalpy of water adsorption (Δh ads ) on activated carbon (C) and activated C-supported Ru nanoparticles, which are promising catalyst as applied to the hydrogenation/hydrodeoxygenation (HDO) of oxygenates (phenolics, aldehydes, etc.). Specifically, the near-zero coverage enthalpy of water adsorption on a C-supported Ru catalyst is -75.3 ± 0.4 kJ/(mol water), suggesting favorable water–metal binding. This is much more exothermic than that on C, which has an enthalpy of adsorption of -50.3 ± 1.3 kJ/(mol water). Despite the favorable initial binding, the magnitudes of enthalpies of water condensation on C and Ru-C indicate that overall, their surfaces are both hydrophobic. Moreover, the experimentally-measured near-zero coverage water adsorption enthalpy at the Ru sites is in very good agreement with our density functional theory based calculations. At low coverages, we obtain a water binding energy of -61.7 kJ/(mol water), which increases to -78.1 kJ/(mol water) at saturation. Complementary results are also obtained from a thermal analysis, which employed a thermogravimetric analysis–differential scanning calorimetry–mass spectrometry (TG-DSC-MS), a spectroscopic investigation using ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a morphological evaluation with transmission electron microscopy (TEM). We point out that in carbon-supported metal catalysts, such as Ru-C, a strong hydration at near-zero coverage and relative weak water-surface interactions occurs upon saturation. Such heterogeneity is essential and crucial for catalytic hydrogenation/HDO reactions that involve balanced interactions among the water-rich reactant mixture and nonpolar organic products.

09 BIOMASS FUELS↗

NASA NTRS1998

Evidence for Microfossils in Ancient Rocks and Meteorites

The McKay et all. detection of chemical biomarkers and possible microfossils in an ancient meteorite from Mars (ALH84001) stimulated research in several areas of importance to the newly emerging field of Astrobiology. Their report resulted in a search for additional evidence of microfossils in ancient terrestrial rocks and meteorites. These studies of ancient rocks and meteorites were conducted independently (and later collaboratively) in the United States and Russia using the SEM, Environmental Scanning Electron Microscope (ESEM), and Field Emission Scanning Electron Microscope (FESEM). We have encountered in-situ in freshly broken carbonaceous chondrites a large number of complex microstructures that appear to be lithified microbial forms. The meteoritic microstructures have characteristics similar to the lithified remains of filamentous cyanobacteria and bacterial microfossils we have found in ancient phosphorites, ancient graphites and oil shales. Energy Dispersive Spectroscopy (EDS) and Link microprobe analysis shows the possible microfossils have a distribution of chemical elements characteristic of the meteorite rock matrix, although many exhibit a superimposed carbon enhancement. We have concluded that the mineralized bodies encountered embedded in the rock matrix of freshly fractured meteoritic surfaces can not be dismissed as recent surface contaminants. Many of the forms found in-situ in the Murchison, Efremovka, and Orgueil carbonaceous meteorites are strikingly similar to microfossils of coccoid bacteria, cyanobacteria and fungi such as we have found in the Cambrian phosphorites of Khubsugul, Mongolia and high carbon Phanerozoic and Precambrian rocks of the Siberian and Russian Platforms.

Hoover, Richard B.↗

NASA NTRS2014

Organics Exposure in Orbit (OREOcube): A Next-Generation Space Exposure Platform

The OREOcube (ORganics Exposure in Orbit cube) experiment on the International Space Station (ISS) will investigate the effects of solar and cosmic radiation on organic thin films supported on inorganic substrates. Probing the kinetics of structural changes and photomodulated organic− inorganic interactions with real-time in situ UV−visible spectroscopy, this experiment will investigate the role played by solid mineral surfaces in the (photo)chemical evolution, transport, and distribution of organics in our solar system and beyond. In preparation for the OREOcube ISS experiment, we report here laboratory measurements of the photostability of thin films of the 9,10-anthraquinone derivative anthrarufin (51 nm thick) layered upon ultrathin films of iron oxides magnetite and hematite (4 nm thick), as well as supported directly on fused silica. During irradiation with UV and visible light simulating the photon flux and spectral distribution on the surface of Mars, anthrarufin/iron oxide bilayer thin films were exposed to CO2 (800 Pa), the main constituent (and pressure) of the martian atmosphere. The time-dependent photodegradation of anthrarufin thin films revealed the inhibition of degradation by both types of underlying iron oxides relative to anthrarufin on bare fused silica. Interactions between the organic and inorganic thin films, apparent in spectral shifts of the anthrarufin bands, are consistent with presumed free-electron quenching of semiquinone anion radicals by the iron oxide layers, electively protecting the organic compound from photodegradation. Combining such in situ real-time kinetic measurements of thin films in future space exposure experiments on the ISS with postflight sample return and analysis will provide time-course studies complemented by in-depth chemical analysis. This will facilitate the characterization and modeling of the chemistry of organic species associated with mineral surfaces in astrobiological contexts.

Organics↗

NASA NTRS2004

Titan Ice and Dust Experiment (TIDE): Detection and Analysis of Compounds of Interest to Astrobiology in the Lower Atmosphere and Surface of Titan

The Titan Orbiter Aerorover Mission (TOAM) is a proposed concept for the Solar System Exploration Visions Mission, Titan Explorer, a follow-on to the Cassini-Huygens mission. TOAM would use a Titan polar orbiter and a lighter-than-air aerorover to investigate the surface and atmosphere of Titan. Astrobiology issues will be addressed though TOAM investigations including, for example: Distribution and composition of organics (atmospheric, aerosol, surface); Organic chemical processes, their chemical context and energy sources; and Seasonal variations and interactions of the atmosphere and surface. The TIDE instrument will perform in-situ analyses to obtain comprehensive and sensitive molecular and elemental assays of volatile organics in the atmosphere, oceans and surface. TIDE chemical analyses are conducted by a Gas Chromatograph-Ion Mobility Spectrometer (GC-IMS). This TIDE GC-IMS was a component of the mini-Cometary Ice and Dust Experiment (mini-CIDEX) developed for the chemical analysis of a cometary environment. Both the GC and helium IMS of mini-CIDEX have been further developed to better meet the analytical and operational requirements of the TOAM. application. A Micro-ElectroMechanical System (MEMS) GC and Mini-Cell helium IMS are under development to replace their respective mini-CIDEX components, providing similar or advanced analytical capabilities.

Kojiro, Daniel R.↗

DOE OSTI2017

Is an electric field always a promoter of wetting? Electro-dewetting of metals by electrolytes probed by in situ X-ray nanotomography

We developed a special electrochemical cell enabling quantitative analysis and in situ X-ray nanotomography of metal/electrolyte interfaces subject to corrosion. Using this cell and applying the nodoid model to describe menisci formed on tungsten wires during anodization, the evolution of the electrolyte surface tension, the concentration of reaction products, and the meniscus contact angle were studied. In contrast to the electrowetting effect, where the applied electric field decreases the contact angle of electrolytes, anodization of the tungsten wires increases the contact angle of the meniscus. Hence, an electric field favors dewetting rather than wetting of the newly formed surface. Finally, the discovered effect opens up new opportunities for the control of wetting phenomena and calls for the revision of existing theories of electrowetting.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Interpreting inorganic compositional depth profiles to understand the rate-limiting step in vapor phase infiltration processes

Vapor phase infiltration (VPI) is a post-polymerization modification technique that infuses inorganics into polymers to create organic–inorganic hybrid materials with new properties. Much is yet to be understood about the chemical kinetics underlying the VPI process. The aim of this study is to create a greater understanding of the process kinetics that govern the infiltration of trimethyl aluminum (TMA) and TiCl 4 into PMMA to form inorganic-PMMA hybrid materials. To gain insight, this paper initially examines the predicted results for the spatiotemporal concentrations of inorganics computed from a recently posited reaction–diffusion model for VPI. This model provides insight on how the Damköhler number (reaction versus diffusion rates) and non-Fickian diffusional processes (hindering) that result from the material transforming from a polymer to a hybrid can affect the evolution of inorganic concentration depth profiles with time. Subsequently, experimental XPS depth profiles are collected for TMA and TiCl 4 infiltrated PMMA films at 90 °C and 135 °C. The functional behavior of these depth profiles at varying infiltration times are qualitatively compared to various computed predictions and conclusions are drawn about the mechanisms of each of these processes. TMA infiltration into PMMA appears to transition from a diffusion-limited process at low temperatures (90 °C) to a reaction-limited process at high temperatures (135 °C) for the film thicknesses investigated here (200 nm). While TMA appears to fully infiltrate these 200 nm PMMA films within a few hours, TiCl 4 infiltration into PMMA is considerably slower, with full saturation not occurring even after 2 days of precursor exposure. Infiltration at 90 °C is so slow that no clear conclusions about mechanism can be drawn; however, at 135 °C, the TiCl 4 infiltration into PMMA is clearly a reaction-limited process, with TiCl 4 permeating the entire thickness (at low concentrations) within only a few minutes, but inorganic loading continuously increasing in a uniform manner over a course of 2 days. Near-surface deviations from the uniform-loading expected for a reaction-limited process also suggest that diffusional hindering is high for TiCl 4 infiltration into PMMA. In conclusion, these results demonstrate a new, ex situ analysis approach for investigating the rate-limiting process mechanisms for vapor phase infiltration.

36 MATERIALS SCIENCE↗

NASA NTRS2009

Climatological Features of the Upper Troposphere and Stratosphere in the GEOS-5 "MERRA" Analyses (1979-2008)

The realism of various aspects of the upper troposphere and stratosphere in the "Modern Era Retrospective-analysis for Research and Applications" (MERRA) dataset will be examined. The MERRA reanalysis extends from 1979 until the present, using the Goddard Earth Observing System, Version 5 (GEOS-5) data assimilation system. The model and analysis have a half-degree spatial resolution with 72 layers that are constrained by observations between the Earth's surface and the stratopause. A comprehensive, time-evolving suite of meteorological observations (e.g., in-situ temperature, moisture, wind and pressure measurements and space-based infrared and microwave radiances) is assimilated. Results show realistic depiction of dominant features, such as the quasi-biennial oscillation, jet structures (including interannual variaficns) and tropopause characteristics, as validated using independent observations and system statistics. Challenges for such reanalyses include the stability to transitions in the observing system, such as the replacement of MSU/SSU by the AMSU-A data in the middle atmosphere. The paper will discuss the use of satellite radiances and examine impacts of satellite drifts and instrument changes on the analyses.

Pawson, S.↗

NASA NTRS1986

Global duricrust on Mars - Analysis of remote-sensing data

A study is conducted of the infrared thermal emission, radio thermal emission, and radar reflection data sets with the objective to obtain a simple and self-consistent model for the Mars surface. The results are compared with in situ observations at the Viking Lander sites. Attention is given to thermal inertia values, the abundance of surface rocks, radar/thermal correlations, diurnal temperature deviations, and radio emission data. It is suggested that all of the global remote-sensing data sets considered can be reconciled on the basis of variations in the degree of formation of a case-hardened crust or duricrust. On the other hand, no other model which has been proposed in conjunction with any individual data set can satisfy all of the constraints discussed.

Jakosky, B. M.↗