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At least 523 records · Page 29

Applications of surface analysis and surface theory in tribology

Tribology, the study of adhesion, friction and wear of materials, is a complex field which requires a knowledge of solid state physics, surface physics, chemistry, material science, and mechanical engineering. It has been dominated, however, by the more practical need to make equipment work. With the advent of surface analysis and advances in surface and solid-state theory, a new dimension has been added to the analysis of interactions at tribological interfaces. In this paper the applications of tribological studies and their limitations are presented. Examples from research at the NASA Lewis Research Center are given. Emphasis is on fundamental studies involving the effects of monolayer coverage and thick films on friction and wear. A summary of the current status of theoretical calculations of defect energetics is presented. In addition, some new theoretical techniques which enable simplified quantitative calculations of adhesion, fracture, and friction are discussed.

Ferrante, John↗

Exploitation of Pore Structure for Increased CO 2 Selectivity in Type 3 Porous Liquids

CO 2 capture requires materials with high adsorption selectivity and an industrial ease of implementation. To address these needs, a new class of porous materials was recently developed that combines the fluidity of solvents with the porosity of solids. Type 3 porous liquids (PLs) composed of solvents and metal–organic frameworks (MOFs) offer a promising alternative to current liquid carbon capture methods due to the inherent tunability of the nanoporous MOFs. However, the effects of MOF structural features and solvent properties on CO 2 –MOF interactions within PLs are not well understood. Herein experimental and computational data of CO 2 gas adsorption isotherms were used to elucidate both solvent and pore structure influences on ZIF-based PLs. The roles of the pore structure including solvent size exclusion, structural environment, and MOF porosity on PL CO 2 uptake were examined. A comparison of the pore structure and pore aperture was performed using ZIF-8, ZIF-L, and amorphous-ZIF-8. Adsorption experiments here have verified our previously proposed solvent size design principle for ZIF-based PLs (1.8× ZIF pore aperture). Furthermore, the CO 2 adsorption isotherms of the ZIF-based PLs indicated that judicious selection of the pore environment allows for an increase in CO 2 selectivity greater than expected from the individual PL components or their combination. This nonlinear increase in the CO 2 selectivity is an emergent behavior resulting from the complex mixture of components specific to the ZIF-L + 2'-hydroxyacetophenone-based PL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deuterium plasma induced preferential erosion in ultra-high temperature ceramics TiB 2 and ZrB 2 *

Abstract Steady-state deuterium plasma exposures were performed on ultra-high temperature ceramics titanium diboride (TiB 2 ) and zirconium diboride (ZrB 2 ) using the PISCES-RF linear plasma device (LPD) as early screening for first wall, plasma-facing applications. Deuterium plasma exposures were performed using 40 eV ion energies at 240, 525, and 800 °C sample temperatures and 90 eV ion energies at 240 °C sample temperatures to analyze TiB 2 and ZrB 2 surface morphology and chemistry evolution behavior. Post-plasma exposure chemistry characterization of the near surface ( < 50 nm) region of the samples all show transition metal enrichment, indicating boron preferential erosion. Transition metal to boron fractions vary with plasma exposure temperature under the 40 eV ion energy; metal enrichment is maximized at 800 °C and then minimized at 525 °C. SEM micrographs of all plasma exposed sample surfaces show no significant or noticeable plasma induced damage from cracking or blistering.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Surface-atmosphere interactions on Titan compared with those on the pre-biotic Earth

The surface and atmosphere of Titan constitute a system which is potentially as complex as that of the Earth, with the possibility of precipitation, surface erosion due to liquids, chemistry in large surface or subsurface hydrocarbon resevoirs, surface expressions of internal activity, and occasional major impacts leading to crustal melting. While none of the above have been observed as yet, the composition, density and thermal properties of Titan's atmosphere make it uniquely suited in the outer solar system as a place where such processes may occur. The one attribute of the Earth not expected on Titan is biological activity, which has had a profound effect on the evolution of the Earth's surface-atmosphere system. The earliest environment of Titan could have been warm enough for liquid ammonia-water solutions to exist on or near surface; pre-biotic organic processes may have taken place in such an environment. After a few hundred million years surface ammonia-water would have disappeard. Therefore, study of Titan through Cassini/Huygens mission, planned for launch in 1997, primarily affords the opportunity to understand planet-side surface-atmophsre interactions in the presence of fluids but in the absence of life. More speculative is the possibility that endogenic and exogenic heating continue to provide short-lived environments on Titan wherein pre-biotic organic processes in the presence of water happen.

Lunine, J. I.↗

EFRC Accomplishments: Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)

The vision of IMASC is to advance the fundamental science necessary to alter fundamental aspects of the chemical industries sector and its carbon footprint. The IMASC mission is to develop design principles for increasing the efficiency of key chemical syntheses using dilute alloy catalysts by quantitatively scaling from model studies to catalytic operation using advanced experiment and theory. One of the major challenges in catalysis is predicting catalytic behavior—especially selectivity. The IMASC team developed a methodology for obtaining critical information for selected catalytic processes using dilute alloy catalysts, that is widely applicable to modeling catalytic processes.

36 MATERIALS SCIENCE↗

Correlating structure, self-assembly chemistry and conductivity of trithiocyanuric acid on Au(111)

The majority of candidates for simple model molecular-electronic components consist of a conductive π-conjugated hydrocarbon linker attached to at least two anchoring groups, such as thiols or isocyanides. It has been found that select molecules self-assemble on gold surfaces, creating one-dimensional conductive structures that act as “molecular wires”. Furthermore, these oligomers can form molecular bridges between gold nanoparticles, leading to the creation of simple molecular-electronic devices. This raises the question whether other π-conjugated molecular linkers could exhibit similar behavior that might offer a broader range of candidates for fabricating electronic devices. Trithiocyanuric acid (1,3,5-triazine-2,4,6-trithiol, TTCA) provides a possible candidate. TTCA (C3N3(SH)3) can exist as a trithiol or as a trithione in which hydrogens transfer to the sulfurs so that they are present with three C=N groups within the ring. TTCA exists naturally in the trithione form but converts into a trithiol when adsorbed onto an Ag(111) where it is vertically oriented. The structure of TTCA adsorbed on Au(111) is studied here using reflection-absorption infrared spectroscopy (RAIRS) where it is found to remain as the trithione isomer, but changes orientation as the coverage increases. Scanning-tunneling microscopy (STM) reveals that TTCA oligomerizes on Au(111) to form chains and triangular structures. The influence on molecular conductivity due to the differences in the adsorbate's isomeric structure was investigated using devices comprising either silver or gold nanoparticles deposited in the gap between gold nanoelectrodes. Both devices were found to conduct when dosed with TTCA, but the devices fabricated using silver were about 13 time more conductive than those made from gold nanoparticles, consistent with the π-conjugated structure formed on silver but not on gold. This implies that oligomers form both on silver and on gold and potentially increases the range of molecule-metal combinations that might be used to fabricate molecular-electronic devices.

Molecular electronics↗

NASA’s High-Resolution GEOS Forecasting and Reanalysis Products: Impact of Stratospheric Intrusions on Surface Ozone Air Quality

A new approach to the study of stratospheric intrusions (SIs)? the introduction of ozone-rich lower stratospheric air into the troposphere ? uses NASA's Goddard Earth Observing System Model (GEOS) model and assimilation products with an objective feature tracking algorithm to investigate the atmospheric dynamics in the UTLS region that generate SIs and the different mechanisms through which SIs may influence tropospheric chemistry and surface air quality. In particular, SIs have been linked with surface ozone air quality exceedances, especially at the high elevations in the western USA in springtime. However, the impact of SIs in the remaining seasons and over the rest of the USA is less clear. Improved understanding of the connections between large-scale climate variability and local-scale dynamically-driven air quality events may support improved seasonal prediction of SI events. While the spring over the western USA does exhibit the largest number of SIs affecting the lower troposphere, we demonstrate that the number of intrusions in the remaining seasons and over the eastern USA is sizable. Using a multitude of observational datasets, including lidar data, ozonesondes and air quality monitoring surface sites, in combination with GEOS forecast and reanalysis products, the transport of ozone from the stratosphere toward the surface is assessed. By focusing on recent reports of high ozone at monitoring station sites likely associated with SIs, we aim to provide the public with tools which are available in near-real time to enhance their capability to identify the impact of stratospheric air on surface ozone concentrations separate from anthropogenic sources.

Knowland, K. Emma↗

Regioselective Hydrosilylation Catalysis with Supported Well-Defined Pt(0) Complexes: Effects of Surface Anions and Phosphenium Ligands

Achieving stable, selective single-atom catalysts is challenging because localsurface-site structures are difficult to control. Surface organometallic chemistry and organic−inorganic hybrid materials offer partial solutions, but applications to supporting zero-valent metals are limited. We demonstrate that well-defined, ionically bound N-heterocyclic phosphenium ([NHP] + ) ligands can be generated on silylium-functionalized sulfated zirconia ([ i Pr 3 Si][SZO]). These surface-bound [NHP][SZO] ligands coordinate Pt(0) centers, forming [(NHP)Pt(0)L][SZO] precatalysts that are highly active for alkyne hydrosilylation. Systematic studies reveal that sterically bulky aromatic ligands enhance regioselectivity, achieving performances comparable to molecular Pt catalysts. Further, more-coordinating anions support more-regioselective precatalysts; therefore, SZO supports more-selective species than weaker-coordinating Al(OC(CF 3 ) 3 ) 3 - functionalized silica, a trend confirmed by molecular analogues. These results demonstrate that both the ligand and support control catalytic behavior and enable solid-state structure− activity relationships.

Catalysts↗

The structure of ion plated films in relation to coating properties

Ion plating is an ion assisted or glow discharge deposition technique, where ions or energetic atoms transfer energy, momentum and charge to the substrate and the growing film in a manner which can be controlled to favorably modify surface, subsurface chemistry, and microstructure. The glow discharge energizing effects from the initial nucleation stages to the final film growth are discussed. As a result, adherence, coherence, internal stresses, density and morphology of the coatings are significantly improved, over the conventional (nonion-assisted) techniques which in turn favorably affect the surface initiated failures caused by friction, wear, erosion, corrosion and fatigue. Ion plated films because of their graded coating/substrate interface, fine, uniform, densely packed film structure also induce a surface strengthening effect which improved the mechanical properties such as yield, tensile strength and fatigue life. Since a uniform, continuous film can be obtained at lower nominal film thickness, this effect is of great importance in solid film lubrication and in corrosion protection.

Spalvins, T.↗

Probing Alkylpolyglycoside Hydrogen Bonding and Its Destabilization by Sulfonate Hydrotropes with X‑ray and Vibrational Spectroscopy

It has been proposed that intersurfactant H-bonding networks can produce highly stable foams, specifically those generated from solutions containing alkylpolyglycoside surfactants. In this work, we aim to characterize the presence and destabilization of these networks by introducing a hydrotrope (sodium p-toluene sulfate) at various concentrations into an alkylpolyglycoside (Glucopon 225 DK) surfactant containing solution. Solution surface properties are probed by using aerosol velocity map imaging X-ray photoelectron spectroscopy (A-VMI-XPS) and tensiometer measurements. Bulk properties below the surface are probed using Fourier transform infrared spectroscopy (FTIR) and C-edge near-edge X-ray fine structure spectroscopy (NEXAFS). The surface measurements provide the framework to describe the destabilization of the solution H-bonding network, while the bulk solution measurements provide hints about the disruption of the hydrogen bonding network upon hydrotrope addition. The collected data support the hypothesis that the destabilization of the intersurfactant H-bonding network frees surfactant molecules from the bulk, increasing surfactant population at the air/water interface. This was quantified through an increase in peak area and width in XPS measurements as well as a decrease in surfactant critical micelle concentration. Three regimes with increasing amounts of hydrotrope addition are suggested, described as (1) a hydrotrope affecting only surfactant surface properties, (2) a hydrotrope affecting surfactant surface and bulk properties, and (3) hydrotrope-dominated surface and bulk properties. Future studies will characterize foam stability across the hydrotrope concentration regimes to better define correlations between intersurfactant H-bonding networks and foam stability.

Molecules↗

Surface Water Quality Data from Beaver-Impacted Streams; Trail Creek and East River, Colorado 2025

This data package contains surface water chemistry measurements collected in 2025 to evaluate how beaver damming and low-tech process-based stream restoration influence water quality and metal mobility in mountainous headwater systems of the Upper Colorado River Basin. Sampling was conducted at Trail Creek (Taylor Park watershed, Colorado), a tributary undergoing restoration through installation of low-tech process-based structures (i.e., beaver dam analogs), and at off-channel beaver ponds within the East River floodplain (East River watershed, Colorado). Samples were collected along longitudinal transects spanning upstream control reaches, beaver-influenced ponded reaches, and downstream segments. Additional samples were collected from near-surface pore waters within a beaver dam seepage face. The dataset includes concentrations of major and trace elements measured by inductively coupled plasma–mass spectrometry (ICP-MS) and inductively coupled plasma–optical emission spectrometry (ICP-OES), major anions measured by ion chromatography (IC), and dissolved organic carbon (DOC; reported as non-purgeable organic carbon, NPOC). Samples were size-fractionated at 0.45 micrometers (µm), 0.22 µm, and 0.02 µm to distinguish particulate (>0.45 µm), colloidal (0.22–0.02 µm), and dissolved (<0.02 µm) fractions. The data package consists of comma-separated value (.csv) files containing tabulated chemical concentration data, sample metadata (site identifiers, geographic coordinates, sampling dates, fraction type), and quality control flags. All files are provided in open, non-proprietary formats that can be accessed using standard data analysis software such as Microsoft Excel, R, Python, MATLAB, or other programs capable of reading .csv files. Units, detection limits, and analytical methods are documented in accompanying metadata files. The dataset is designed to support analyses of (1) how beaver impoundment and restoration structures alter elemental partitioning and transport, (2) the role of iron and organic carbon in mediating trace metal mobility, and (3) reach-scale changes in water quality across restoration gradients. This work was supported by the Watershed Function Science Focus Area at Lawrence Berkeley National Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-05CH11231. Part of this work was performed at SLAC Accelerator Laboratory funded by the US Department of Energy, Office of Science, Biological and Environmental Research under Contract No. DE-AC02-76SF00515.

Anions↗

Investigating CO2 Reservoirs at Gale Crater and Evidence for a Dense Early Atmosphere

One of the most compelling features of the Gale landing site is its age. Based on crater counts, the formation of Gale crater is dated to be near the beginning of the Hesperian near the pivotal Hesperian/Noachian transition. This is a time period on Mars that is linked to increased fluvial activity through valley network formation and also marks a transition from higher erosion rates/clay mineral formation to lower erosion rates with mineralogies dominated by sulfate minerals. Results from the Curiosity mission have shown extensive evidence for fluvial activity within the crater suggesting that sediments on the floor of the crater and even sediments making up Mt. Sharp itself were the result of longstanding activity of liquid water. Warm/wet conditions on early Mars are likely due to a thicker atmosphere and increased abundance of greenhouse gases including the main component of the atmosphere, CO2. Carbon dioxide is minor component of the Earth's atmosphere yet plays a major role in surface water chemistry, weathering, and formation of secondary minerals. An ancient martian atmosphere was likely dominated by CO2 and any waters in equilibrium with this atmosphere would have different chemical characteristics. Studies have noted that high partial pressures of CO2 would result in increased carbonic acid formation and lowering of the pH so that carbonate minerals are not stable. However, if there were a dense CO2 atmosphere present at the Hesperian/Noachian transition, it would have to be stored in a carbon reservoir on the surface or lost to space. The Mt. Sharp sediments are potentially one of the best places on Mars to investigate these CO2 reservoirs as they are proposed to have formed in the early Hesperian, from an alkaline lake, and record the transition to an aeolian dominated regime near the top of the sequence. The total amount of CO2 in the Gale crater soils and sediments is significant but lower than expected if a thick atmosphere was present at the Hesperian/Noachian boundary. Likewise, the absence of carbonates suggests that CO2- weathering processes similar to those present on Earth were not dominant. Instead it is possible that more exotic CO2 deposition has occurred driven by atmospheric photochemistry and/or degradation of organic carbon.

Niles, P. B.↗

Stratospheric Instrusion Catalog: A 10-Year Compilation of Events Identified by using TRACK with NASA's MERRA-2 Reanalysis

Stratospheric intrusions "the introduction of ozone-rich stratospheric air into the troposphere" have been linked with surface ozone air quality exceedances, especially at the high elevations in the western USA in springtime. However, the impact of stratospheric intrusions in the remaining seasons and over the rest of the USA is less clear. A new approach to the study of stratospheric intrusions uses NASA's Goddard Earth Observing System Model (GEOS) model and assimilation products with an objective feature tracking algorithm to investigate the atmospheric dynamics that generate stratospheric intrusions and the different mechanisms through which stratospheric intrusions may influence tropospheric chemistry and surface air quality seasonally over both the western and the eastern USA. A catalog of stratospheric intrusions identified in the MERRA-2 reanalysis was produced for the period 2004-2015 and validated against surface ozone observations (focusing on those which exceed the national air quality standard) and a recent data set of stratospheric intrusion-influenced air quality exceedance flags from the US Environmental Protection Agency (EPA). Considering not all ozone exceedances have been flagged by the EPA, a collection of stratospheric intrusions can support air quality agencies for more rapid identification of the impact of stratospheric air on surface ozone and demonstrates that future operational analyses may aid in forecasting such events. An analysis of the spatiotemporal variability of stratospheric intrusions over the continental US was performed, and while the spring over the western USA does exhibit the largest number of stratospheric intrusions affecting the lower troposphere, the number of intrusions in the remaining seasons and over the eastern USA is sizable. By focusing on the major modes of variability that influence weather in the USA, such as the Pacific North American (PNA) teleconnection index, predicative meteorological patterns associated with stratospheric intrusions and their regional effects on tropospheric ozone were identified. Improved understanding of the connections between large-scale climate variability and local-scale dynamically-driven air quality events may support improved seasonal prediction of such events.

PN↗

The Discharging of Roving Objects in the Lunar Polar Regions

In 2007, the National Academy of Sciences identified the lunar polar regions as special environments: very cold locations where resources can be trapped and accumulated. These accumulated resources not only provide a natural reservoir for human explorers, but their very presence may provide a history of lunar impact events and possibly an indication of ongoing surface reactive chemistry. The recent LCROSS impacts confirm that polar crater floors are rich in material including approx 5%wt of water. An integral part of the special lunar polar environment is the solar wind plasma. Solar wind protons and electrons propagate outward from the Sun, and at the Moon's position have a nominal density of 5 el/cubic cm, flow speed of 400 km/sec, and temperature of 10 eV (approx. equal 116000K). At the sub-solar point, the flow of this plasma is effectively vertically incident at the surface. However, at the poles and along the lunar terminator region, the flow is effectively horizontal over the surface. As recently described, in these regions, local topography has a significant effect on the solar wind flow. Specifically, as the solar wind passes over topographic features like polar mountains and craters, the plasma flow is obstructed and creates a distinct plasma void in the downstream region behind the obstacle. An ion sonic wake structure forms behind the obstacle, not unlike that which forms behind a space shuttle. In the downstream region where flow is obstructed, the faster moving solar wind electrons move into the void region ahead of the more massive ions, thereby creating an ambipolar electric field pointing into the void region. This electric field then deflects ion trajectories into the void region by acting as a vertical inward force that draws ions to the surface. This solar wind 'orographic' effect is somewhat analogous to that occurring with terrestrial mountains. However, in the solar wind, the ambipolar E-field operating in the collision less plasma replaces the gradient in pressure that would act in a collisional neutral gas. Human systems (roving astronauts or robotic systems created by humans) may be required to gain access to the crater floor to collect resources such as water and other cold-trapped material. However, these human systems are also exposed to the above-described harsh thermal and electrical environments in the region. Thus, the objective of this work is to determine the nature of charging and discharging for a roving object in the cold, plasma-starved lunar polar regions. To accomplish this objective, we first define the electrical charging environment within polar craters. We then describe the subsequent charging of a moving object near and within such craters. We apply a model of an astronaut moving in periodic steps/cadence over a surface regolith. In fact the astronaut can be considered an analog for any kind of moving human system. An astronaut stepping over the surface accumulates charge via contact electrification (tribocharging) v.lith the lunar regolith. We present a model of this tribo-charge build-up. Given the environmental plasma in the region, we determine herein the dissipation time for the astronaut to bleed off its excess charge into the surrounding plasma.

Jackson, T. L.↗

Gerischer Electrochemistry Today

Semiconductor photoelectrochemistry is a dynamic and interdisciplinary field at the forefront of research in solar fuels, energy conversion, and catalysis. Here, this Perspective captures the collective insights from the second Gerischer Electrochemistry Today Symposium, held at Colorado State University in Fort Collins, CO, in August 2024, which convened leading researchers, early-career scientists, and industry partners to define the critical next steps for the field. Through interactive sessions, technical talks, panel discussions, and training initiatives─including a Semiconductor Electrochemistry Bootcamp─the symposium emphasized three pillars of advancement: (i) facilitating the exchange of new ideas in semiconductor electrochemistry and charge separation; (ii) fostering the development of future researchers, research topics, and participation in the semiconductor workforce; and (iii) building community. This Energy Focus distills key themes from the meeting and identifies major knowledge gaps in the following areas: mechanisms of charge separation and recombination, role of defects and disorder, dynamic and operando characterization methods, interfacial chemistry and surface passivation, theoretical and modeling limitations, and standardization and benchmarking. The inclusive and collaborative structure of the symposium enabled the generation of this comprehensive report that will serve as a roadmap for fundamental and applied research in the rapidly evolving field of semiconductor electrochemistry over the next decade.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Meteorite organics in planetary environments: hydrothermal release, surface activity, and microbial utilization

Up to 50% of the organics in the Murchison meteorite, possibly including some of the polymer, is released in high temperature and pressure aqueous environments, to 350 degrees C and 250 bar, that simulate submarine volcanic, hydrothermal or impact-induced conditions. Meteorite organics of prebiotic significance, such as nonanoic acid, glycine, and pyrene survive the hydrothermal conditions. The released material is surface active with surface pressures up to 19.8 x 10(-3) N m-1, and exhibits an extended surface tension isotherm which suggests a mixture of amphiphilic components. One component, nonanoic acid, is shown to form vesicles. The materials extracted under mild conditions, at 120 degrees C, are nutrients for the humic acid bacterium Pseudomonas maltophilia and efficient nutrients for the oligotroph Flavobacterium oryzihabitans, demonstrating the capability of microorganisms to metabolize extraterrestrial organics.

NASA Program Exobiology↗

The Aquarius Mission: Sea Surface Salinity from Space

Aquarius is a new satellite mission concept to study the impact of the global water cycle on the ocean, including the response of the ocean to buoyancy forcing and the subsequent feedback of the ocean on the climate. The measurement objective of Aquarius is sea surface salinity, which reflects the concentration of freshwater at the ocean surface. Salinity affects the dielectric constant of sea water and, consequently, the radiometric emission of the sea surface to space. Rudimentary space observations with an L-band radiometer were first made from Skylab in the mid-70s and numerous aircraft missions of increasing quality and improved technology have been conducted since then. Technology is now available to carry out a global mission, which includes both an accurate L band (1.413 Ghz) radiometer and radar system in space and a global array of in situ observations for calibration and validation, in order to address key NASA Earth Science Enterprise questions about the global cycling of water and the response of the ocean circulation to climate change. The key scientific objectives of Aquarius examine the cycling of water at the ocean's surface, the response of the ocean circulation to buoyancy forcing, and the impact of buoyancy forcing on the ocean's thermal feedback to the climate. Global surface salinity will also improve our ability to model the surface solubility chemistry needed to estimate the air-sea exchange of CO2. In order to meet these science objectives, the NASA Salinity Sea Ice Working Group over the past three years has concluded that the mission measurement goals should be better than 0.2 practical salinity units (psu) accuracy, 100 km resolution, and weekly to revisits. The Aquarius mission proposes to meet these measurement requirements through a real aperture dual-polarized L band radiometer and radar system. This system can achieve the less than 0.1 K radiometric temperature measurement accuracy that is required. A 3 m antenna at approx. 600km altitude in a sun-synchronous orbit and 300 km swath can provide the desired 100 km resolution global coverage every week. Within this decade, it may be possible to combine satellite sea surface salinity measurements with ongoing satellite observations of temperature, surface height, air-sea fluxes; vertical profiles of temperature and salinity from the Argo program; and modern ocean/atmosphere modeling and data assimilation tools, in order to finally address the complex influence of buoyancy on the ocean circulation and climate.

Koblinsky, Chester↗

Vapor-Phase Heteroatom Incorporation into Semiconductive Molecular-Scale Magic-Size Clusters

Magic-size metal chalcogenide clusters of molecular size exhibit well-defined structure and unique properties that might be further expanded with the incorporation or substitution of a second metal. Here, we report the postmodification of magic-size clusters synthesized in polymer thin films via exposure to volatile metal organic precursors commonly utilized for atomic layer deposition. Exposure of In 6 S 6 (CH 3 ) 6 clusters to dimethylcadmium results in exposure-dependent incorporation of Cd 2+ , which extends the optical absorbance of the clusters into the visible spectrum. The mechanism for Cd 2+ incorporation is consistent with Cd 2+ replacement of In 3+ that includes methyl ligand removal to maintain charge neutrality. Even for clusters embedded in a polymer matrix, ligand loss leads to sintering and transformation into larger nanoscale aggregates with zinc blende-type structure. The extent of Cd incorporation can be modulated by varying the process temperature and volatile metal organic exposure as well as the choice of volatile metal organic precursor. A computational thermodynamic analysis of heteroatom incorporation for several metals and chemistries reveals that both the stability of the substituted cluster and the favorability of reaction byproducts jointly determine the favorability of cation incorporation.

atomic layer deposition↗