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At least 1,045 records · Page 58

Robust silane self-assembled monolayer coatings on plasma-engineered copper surfaces promoting dropwise condensation

Dropwise condensation is well known to result in better heat transfer performance owing to efficient condensate/droplet removal, which can be harnessed in various industrial heat/mass transfer applications such as power generation and conversion, water harvesting/desalination, and electronics thermal management. The key to enhancing condensation via the dropwise mode is thin low surface energy coatings (<100 nm) with low contact angle hysteresis. Ultrathin (<5 nm) silane self-assembled monolayers (or SAMs) have been widely studied to promote dropwise condensation due to their minimal thermal resistance and scalable integration processes. Such thin coatings typically degrade within an hour during condensation of water vapor. After coating failure, water vapor condensation transitions to the inefficient filmwise mode with poor heat transfer performance. We enhance silane SAM quality and durability during water vapor condensation on copper compared to state-of-the-art silane coatings on metal surfaces. We achieve this via (i) surface polishing to sub-10 nm levels, (ii) pure oxygen plasma surface treatment, and (iii) silane coating integration with the copper substrate in an anhydrous/moisture-free environment. The resulting silane SAM has low contact angle hysteresis (≈20°) and promotes efficient dropwise condensation of water for >360 hours without any visible sign of coating failure/degradation in the absence of non-condensable gases. We further demonstrate enhanced heat transfer performance (≈5-7× increase over filmwise condensation) over an extended period of time. Surface characterization data post-condensation leads us to propose that in the absence of non-condensable gases in the vapor environment, the silane SAM degrades due to reduction and subsequent dissolution of copper oxide at the oligomer-substrate interface. The experiments also indicate that the magnitude of surface subcooling (or condensation rate) affects the rate of coating degradation. Finally, this work identifies a pathway to durable dropwise promoter coatings that will enable efficient heat transfer in industrial applications.

42 ENGINEERING↗

Brittle-to-Ductile Transitions of Polyelectrolyte Complexes: Humidity, Temperature, and Salt

Polyelectrolyte complexation is an entropically driven, associative phase separation that results in a polymer-rich polyelectrolyte complex (PEC) and a polymer-poor supernatant. PECs show promise as a new class of sustainable materials since they can be processed using aqueous solutions rather than organic solvents. Previous reports have looked at the mechanical properties and glass transitions of PECs as a function of temperature, relative humidity (rH), and salt concentration (CS), but establishing a universal understanding of how these parameters affect PEC mechanics has yet to be achieved. We examined the effects of temperature, rH, and CS on the mechanical properties of PECs formed from poly(methacrylic acid) and poly(trimethyl aminoethyl methacrylate) with a goal of establishing design rules for their mechanical response. Relative humidity was shown to have the most dramatic effect on the mechanical properties, with temperature and salt concentration having far less of an impact. Furthermore, we observed that the glass transition of PECs is tied to both temperature and relative humidity, creating a glass transition rH g /T g line that can be modulated by added salt. Finally, we looked at the thermodynamics behind the glass transition of PECs, which yielded similar energies as the condensation of water. Here, we propose the use of water and/or salt as a low energy and efficient method of processing PECs for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas Production from Hot Water Circulation through Hydraulic Fractures in Methane Hydrate-Bearing Sediments: THC-Coupled Simulation of Production Mechanisms

Methane hydrates, widely found in permafrost and deep marine sediments, have great potential as a future energy 6 source. Conventional production schemes perform poorly for challenging hydrate reservoirs with low permeability. We propose an 7 efficient production scheme by combining hydraulic fracturing from horizontal wells and hot water circulation through fractures. A 8 fully coupled thermo-hydro-chemical (THC) model is developed to simulate the key physical processes during gas production from 9 a hydrate reservoir representative of typical geological settings in Shenhu, South China Sea. We found that the gas production 10 process has two distinct stages divided by thermal breakthrough: a relatively short prebreakthrough stage and a postbreakthrough 11 stage yielding stable gas production. Heat advection along and near the hydraulic fracture dominates the prebreakthrough stage, 12 whereas conduction-driven thermal recovery in the volume around fractures dominates the postbreakthrough stage. We identified 13 that the steady-state injection temperature has a strong effect on the performance of the proposed scheme while the fluid mass 14 circulation rate has a moderate impact beyond a threshold. The proposed scheme proves to be efficient and robust over a range of 15 reservoir conditions with respect to initial hydrate saturation and intrinsic permeability, including their spatial heterogeneities, 16 thereby offering a promising solution for challenging reservoir conditions.

gas hydrate, fracture flow, gas production, numeri↗

Diffuse reflectance of the ocean - The theory of its augmentation by chlorophyll a fluorescence at 685 nm

The radiative transfer equation is modified to include the effect of fluorescent substances and solved in the quasi-single scattering approximation for a homogeneous ocean containing fluorescent particles with wavelength independent quantum efficiency and a Gaussian shaped emission line. The results are applied to the in vivo fluorescence of chlorophyll a (in phytoplankton) in the ocean to determine if the observed quantum efficiencies are large enough to explain the enhancement of the ocean's diffuse reflectance near 685 nm in chlorophyll rich waters without resorting to anomalous dispersion. The computations indicate that the required efficiencies are sufficiently low to account completely for the enhanced reflectance. The validity of the theory is further demonstrated by deriving values for the upwelling irradiance attenuation coefficient at 685 nm which are in close agreement with the observations.

Gordon, H. R.↗

Monochromatic calculations of atmospheric radiative transfer due to molecular line absorption

Sensitivity studies related to the effects of line cutoff, spectral resolution, and temperature and pressure interpolations in radiative transfer have been performed so that a data set of absorption coefficients for water vapor, CO2, and O3 may be created efficiently. Results show that computations of absorption coefficients are affected only slightly by cutting a line off at a wave number 190 times the Lorentz half width from the center, or equivalently, cutting off 0.33 percent of the line intensity from the wings. To achieve a relative cooling rate error smaller than 2 percent, it is sufficient to precompute the absorption coefficient at three temperatures (210, 250, and 290 K) and 19 pressures with Delta (log 10 p) = 0.2. The absorption coefficient at other conditions can be interpolated linearly with pressure and exponentially with a quadratic in temperature. For the spectral resolution the absorption coefficients can be adequately computed at 0.01, 0.002, 0.005, and 0.025/cm intervals in the thermal water vapor, the CO2 and O3 bands, and the solar water vapor bands, respectively, which limits the error to only a few percent in the cooling and heating rates. Using the precomputed absorption coefficients, repeated monochromatic calculations of atmospheric heating/cooling rates for radiation model developments and for comparison with less detailed calculations are no longer difficult.

Chou, M.-D.↗

Leveraging High Resolution Remotely Sensed Evapotranspiration Data to Assess Water Availability and Vulnerability in the Memphis Aquifer Area in West Tennessee

The Memphis aquifer is an indispensable source of water for municipal, agricultural, and industrial use across west Tennessee. The aquifer's water is thousands of years old and in pristine condition due to the natural geological filtering by the aquifer’s confining clay layers. To sustain the aquifer’s water supply, recharge must happen at a rate efficient enough to keep up with pumping from the aquifer. In partnership with Protect Our Aquifer and the University of Memphis Center for Applied Earth Science and Engineering Research, this project examined multiple factors to discover thriving areas of recharge in west Tennessee. The team used Integrated Multi-satellite Retrievals for GPM (IMERG) precipitation data, ECOsystem Spaceborne Thermal Radiometer on Space Station (ECOSTRESS) evapotranspiration data, Landsat 8 and National Land Cover Database (NLCD) to track landcover change, and the North American Land Data Assimilation System (NLDAS) Noah land surface model to estimate monthly runoff. These factors were averaged seasonally from 2019 to 2022 to understand seasonal relationships within the study area. Precipitation and evapotranspiration data were used to create water balance maps and with the evaporative stress index (ESI), landcover, and runoff maps, the team pinpointed locations that are most conducive to recharge. The team determined that areas where the water balance is low, ESI is high, and where there is sufficient pervious landcover are locations where recharge happens most effectively. Identification of effective recharge locations may be used by the partners to prioritize areas in need of protection before they become impacted by industrialization and urbanization.

Lauren Webster↗

Performance and Regulation of Photosystem II Energy Conversion in Oxygenic Phototrophs: From PSII Crystals to Living Cells

New information not previously accessible to answer remaining questions about the mechanism of PSII catalyzed water oxidation, its intrinsic inefficiencies and the regulation of PSII in living cells were obtained. This effort was done in collaboration with an expert in PSII crystallography (led by Prof. Petra Fromme, ASU). We applied a set of tools for fluorometric, oximetric, potentiometric and absorbance measurements. Transformational knowledge from PSII crystals and a powerful new fluorescence technique were developed. Three aims were addressed and 18 peer-reviewed publications were generated.

59 BASIC BIOLOGICAL SCIENCES↗

Exploring the potential of high entropy perovskite oxides as catalysts for water oxidation

Electrochemical water splitting is a promising technology to renewably generate hydrogen from water with no carbon footprint. However, the catalytic efficiency is hindered by the sluggishness of the oxygen evolution reaction (OER) at the anode. Therefore, developing earth-abundant, stable, and efficient OER catalysts is of keen interest. Recent studies have demonstrated that high entropy perovskite oxides (HEPOs) can exhibit superior OER activity and excellent electrochemical stability due to the synergistic effects of the multiple cations and the high entropy configuration effect. In this opinion paper, we point out the strengths and discuss the challenges and future prospects for HEPO-based electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Implications of reduced-complexity aerosol thermodynamics on organic aerosol mass concentration and composition over North America

Atmospheric organic aerosol (OA) mass concentrations can be affected by water uptake through its impact on the gas–particle partitioning of semi-volatile compounds. Current chemical transport models (CTMs) neglect this process. We have implemented the Binary Activity Thermodynamics model coupled to a volatility basis set partitioning scheme in the GEOS-Chem CTM, providing an efficient reduced-complexity OA model that predicts relative-humidity-dependent mixing and partitioning thermodynamics, while limiting the impact on computational efficiency. We provide a quantitative assessment of this water-sensitive OA treatment, focusing on a subdomain over North America. The updated OA scheme predicts a spatiotemporal mean enhancement in surface-level OA mass concentration of 145 % for January 2019 and 76 % for July 2019 compared to GEOS-Chem's most advanced OA scheme. The temporal mean surface-level OA organic mass concentration can increase by up to ∼590 % for January 2019 and ∼280 % for July 2019, with the greatest enhancements occurring over the ocean. The updated OA scheme also quantifies the OA-associated water content. The simulations show how different OA precursors and related OA surrogates contribute and respond to water uptake, including that due to changes in temperature and relative humidity over the diurnal cycle in selected winter and summer months. These results are independent of future CTM improvements involving updates to chemical reaction schemes and emission inventories. Our water-sensitive OA scheme allows for a better representation of the seasonal and regional variations in OA mass concentration in CTMs.

54 ENVIRONMENTAL SCIENCES↗

Simulation Helps Improve Atmosphere Revitalization Systems for Manned Spacecraft

Life support systems for manned spacecraft must provide breathable air and drinkable water for the astronauts. Through the Atmosphere Revitalization Recovery and Environmental Monitoring (ARREM) project, engineers at NASA are developing atmosphere control devices for the safety of the onboard crew. The atmosphere in a manned spacecraft needs to be regularly revitalized in order to ensure the safety of the astronauts and the success of the space mission. For missions lasting a few months, this means air is continuously dehumidified, water collected for re-use, and carbon dioxide (CO2) ejected. One component of the onboard atmosphere control system is a water-saving device that Jim Knox, aerospace engineer at NASA, is optimizing through the Atmosphere Revitalization Recovery and Environmental Monitoring (ARREM) project. He is leading a team at the Marshall Space Flight Center (Huntsville, Alabama) that is aiming to make the assembly more cost-effective and efficient by reducing its power usage and maximizing the water saved; their goal is to save 80-90% of the water in the air. They hope to offer flight system developers at NASA an integrated approach to atmosphere revitalization and water collection that will ultimately increase the time and distance space missions can travel.

Knox, James C.↗

Evaluation of active thermal control options for Space Station

An analysis of various Space Station (MSS) active thermal control systems options under consideration because of their potential low weight, efficiency and reliability is reported. The study addressed ordinary and diode-action body mounted radiators, thermal storage, the area and pumping power requirements for single-phase cooling of cold plates, and single-phase and two-phase active cooling loops. The base configuration considered was a core MSS formed by four habitable modules on which are mounted heat pipe radiators articulated to be always edge-on to the sun. A simulation was performed which accounted for the available heat sinks, several thermal loads and the heat rejection capability. No benefits were found with diode-action radiators if the solar absorption is 0.1 or less, although diode-action heat pipes will maintain a higher level of performance in the presence of coating degradation. Thermal storage becomes important only with radiator coating degradation. Water can be up to three times as efficient as Freon as a heat transfer medium. Finally, single-phase cooling offers a lower system mass than two-phase cooling if varying temperature heat loads can be accommodated.

Schuster, J. R.↗

Dielectric surface properties of Venus

It has been known for over a decade that certain high-altitude regions on Venus exhibit bizarre radar-scattering and radiothermal-emission behavior. For example, observed values for normal-incidence power reflection coefficients in these areas can exceed 0.5; enhanced back scatter in some mountainous areas in the Magellan SAR images creates a bright surface with the appearance of snow; and reduced thermal emission in the anomalous areas makes the surface there appear hundreds of degrees cooler than the corresponding physical surface temperatures. The inferred radio emissivity in several of these regions falls to 0.3 for horizontal linear polarization at viewing angles in the range 20 deg - 40 deg. Several explanations have been offered for these linked phenomena. One involves single-surface reflection from a sharp discontinuity separating two media that have extremely disparate values of electromagnetic propagation. The mismatch may occur in either or both the real (associated with propagation velocity) or imaginary (associated with absorption) components of the relevant indices of refraction, and the discontinuity must take place over a distance appreciably shorter than a wavelength. An example of such an interaction of Earth would occur at the surface of a body of water. At radio wavelengths, water has an index of refraction of 9 (dielectric permittivity of about 80), and an associated loss factor that varies strongly with the amount of dissolved salts, but is generally significant. Its single-surface radar reflectivity at normal incidence is about 0.65, and the corresponding emissivity (viewed at the same angle) is therefore 0.35. Both these values are similar to the extremes found on Venus, but in the absence of liquid water, the process on Venus requires a different explanation. Two of the present authors (Pettengill and Ford) have suggested that scattering from a single surface possessing a very high effective dielectric permittivity could explain many of the unusual characteristics displayed by the Venus surface. A second explantion relates to the volume scattering that results from successive interactions with one or more interfaces interior to the planetary surface. If the near-surface material has a moderately low index of refraction (to ensure that a substantial fraction of the radiation incident from outside is not reflected, but rather penetrates into the surface), and a very low internal propagation loss, successive internal reflections can eventually redirect much of the energy back through the surface toward the viewer. The necessary conditions for this process to be effective are a low internal propagation loss coupled with efficient internal reflection. At sufficiently low temperatures, fractured water ice displays both the necessary low loss and near-total internal reflection. The possibility that this mechanism might be acting on Venus has recently been put forward.

Pettengill, G. H.↗

Significant Role of Oxygen Dopants in Photocatalytic PFCA Degradation over h-BN

The activation of the C(sp 3 )–F bond is extremely difficult due to its unreactive nature. The importance of this bond activation is recently highlighted because extensive distribution of perfluorocarboxylic acids (PFCAs) (C n F 2n+1 COOH) has emerged as a challenging environmental issue. Photocatalytic degradation of PFCAs over a few semiconducting light absorbers is known to remove these water and soil resilient contaminants but with limited efficiency. This work reports density functional theory calculations, through which we present a detailed mechanistic study of photocatalytic degradation of CF 3 COOH (the shortest member of the PFCA family) over hexagonal boron nitride (h-BN). Here, our results clearly demonstrate that the existence of point defects is necessary to activate the h-BN plane for photocatalytic dissociation of the C–F bond. Specifically, we show that vacancies create strong Lewis acid or base sites (B or N vacancy, respectively) that facilitate the activation of the C(sp 3 )–F bond considerably. Furthermore, this study presents vivid theoretical evidence for the significant role of oxygen dopants, which mitigate the strength of the active sites and promote PFCA degradation over h-BN. Our calculations suggest that while the very stable intermediates generated during the reaction, in the case of h-BN with B or N vacancies, practically poison the catalyst, oxygen dopants make the degradation much more plausible and controllable. This work thus provides both an explanation for recently observed photocatalytic activity of h-BN to decompose PFCAs and valuable insights for exploring defected two-dimensional materials for activating and removing the fluorine-containing contaminants from water and soil.

54 ENVIRONMENTAL SCIENCES↗

Covalent Triazine-Based Frameworks with Ru-tda Based Catalyst Anchored via Coordination Bond for Photoinduced Water Oxidation

Light-induced water splitting (hν-WS) for the production of hydrogen as a solar fuel is considered a promising sustainable strategy for the replacement of fossil fuels. An efficient system for hν-WS involves a photoactive material that, upon shining light, is capable of separating and transferring charges to catalysts for the hydrogen and oxygen evolution processes. Covalent triazine-based frameworks (CTFs) represent an interesting class of 2D organic light-absorbing materials that have recently emerged thanks to their tunable structural, optical and morphological properties. Typically, catalysts (Cat) are metallic nanoparticles generated in situ after photoelectroreduction of metal precursors or directly drop-casted on top of the CTF material to generate Cat-CTF assemblies. Here, in this work, the synthesis, characterization and photocatalytic performance of a novel hybrid material, Ru-CTF, is reported, based on a CTF structure featuring dangling pyridyl groups that allow the Ru-tda (tda is [2,2':6',2'“-terpyridine]-6,6'”-dicarboxylic acid) water oxidation catalyst (WOC) unit to coordinate via covalent bond. The Ru-CTF molecular hybrid material can carry out the light-induced water oxidation reaction efficiently at neutral pH, reaching values of maximum TOF of 17 h -1 and TONs in the range of 220 using sodium persulfate as a sacrificial electron acceptor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nova Analysis: Holistically Valuing the Contributions of Residential Efficiency, Solar and Storage

Policies to address climate change and grid modernization, in combination with cost reductions and technological advancements in energy efficiency (EE) and distributed energy resources (DER), are driving rapid deployment of building electrification and energy efficiency retrofits, rooftop solar photovoltaics (PV), smart thermostats, smart water heaters, and battery energy storage. In residential buildings, there are multiple stakeholders (occupant, utility, aggregator, society at large) that are each focused on different value streams. This project uses a suite of metrics intended to all of these value streams to try to holistically analyze the benefits that come from solar, storage, and energy efficiency. To demonstrate the value of these metrics, a semi annual study was performed simulating hundreds of homes across the U.S. under several different upgrade scenarios.

14 SOLAR ENERGY↗

The exercise and environmental physiology of extravehicular activity

Extravehicular activity (EVA), i.e., exercise performed under unique environmental conditions, is indispensable for supporting daily living in weightlessness and for further space exploration. From 1965-1996 an average of 20 h x yr(-1) were spent performing EVA. International Space Station (ISS) assembly will require 135 h x yr(-1) of EVA, and 138 h x yr(-1) is planned for post-construction maintenance. The extravehicular mobility unit (EMU), used to protect astronauts during EVA, has a decreased pressure of 4.3 psi that could increase astronauts' risk of decompression sickness (DCS). Exercise in and repeated exposure to this hypobaria may increase the incidence of DCS, although weightlessness may attenuate this risk. Exercise thermoregulation within the EMU is poorly understood; the liquid cooling garment (LCG), worn next to the skin and designed to handle thermal stress, is manually controlled. Astronauts may become dehydrated (by up to 2.6% of body weight) during a 5-h EVA, further exacerbating the thermoregulatory challenge. The EVA is performed mainly with upper body muscles; but astronauts usually exercise at only 26-32% of their upper body maximal oxygen uptake (VO2max). For a given ground-based work task in air (as opposed to water), the submaximal VO2 is greater while VO2max and metabolic efficiency are lower during ground-based arm exercise as compared with leg exercise, and cardiovascular responses to exercise and training are also different for arms and legs. Preflight testing and training, whether conducted in air or water, must account for these differences if ground-based data are extrapolated for flight requirements. Astronauts experience deconditioning during microgravity resulting in a 10-20% loss in arm strength, a 20-30% loss in thigh strength, and decreased lower-body aerobic exercise capacity. Data from ground-based simulations of weightlessness such as bed rest induce a 6-8% decrease in upper-body strength, a 10-16% loss in thigh extensor strength, and a 15-20% decrease in lower-body aerobic exercise capacity. Changes in EVA support systems and training based on a greater understanding of the physiological aspects of exercise in the EVA environment will help to insure the health, safety, and efficiency of working astronauts.

Review↗

Investigation of the benefits of diabatic microreactors for process intensification of the water-gas shift reaction within the steam reforming process

Presently, the steam reforming process is the largest industrial source of hydrogen. Improving its efficiency can help to reduce associated carbon emissions and hydrogen production costs. Intensifying the water-gas shift reaction using microreactors with integrated cooling is one way of achieving this. In this study, a 2-D computational model of one of these microreactors is developed, validated with experimental data, and then used to demonstrate how microreactors can enhance the conversion of the water-gas shift reaction beyond what can be achieved using conventional packed bed reactors. These results are then generalized into a full system model of the steam reforming process to demonstrate how microreactors can reduce hydrogen production costs. The results suggest that microreactors can significantly reduce the required reactor volume and catalyst loading for the water-gas shift reaction and can similarly reduce the hydrogen production costs associated with the steam reforming process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Factors influencing organic carbon preservation in marine sediments

The organic matter that escapes decomposition is buried and preserved in marine sediments, with much debate as to whether the amount depends on bottom-water O2 concentration. One group argues that decomposition is more efficient with O2, and hence, organic carbon will be preferentially oxidized in its presence, and preserved in its absence. Another group argues that the kinetics of organic matter decomposition are similar in the presence and absence of O2, and there should be no influence of O2 on preservation. A compilation of carbon preservation shows that both groups are right, depending on the circumstances of deposition. At high rates of deposition, such as near continental margins, little difference in preservation is found with varying bottom-water O2. It is important that most carbon in these sediments decomposes by anaerobic pathways regardless of bottom-water O2. Hence, little influence of bottom-water O2 on preservation would, in fact, be expected. As sedimentation rate drops, sediments deposited under oxygenated bottom water become progressively more aerobic, while euxinic sediments remain anaerobic. Under these circumstances, the relative efficiencies of aerobic and anaerobic decomposition could affect preservation. Indeed, enhanced preservation is observed in low-O2 and euxinic environments. To explore in detail the factors contributing to this enhanced carbon preservation, aspects of the biochemistries of the aerobic and anaerobic process are reviewed. Other potential influences on preservation are also explored. Finally, a new model for organic carbon decomposition, the "pseudo-G" model, is developed. This model couples the degradation of refractory organic matter to the overall metabolic activity of the sediment, and has consequences for carbon preservation due to the mixing together of labile and refractory organic matter by bioturbation.

Non-NASA Center↗