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At least 523 records · Page 29

Analyzers Provide Water Security in Space and on Earth

Resourcefulness is a key quality for living in space, and on the International Space Station (ISS), that means making the most of water supplies. In 2008, the installation of the Water Processing Assembly (WPA) onboard the ISS allowed the space station s crew to do just that. The WPA purifies moisture from nearly every possible source - sweat, water vapor, wastewater, and even urine - for drinking and oxygen generation. Capable of producing 35 gallons of potable, recycled water a day, the system has reduced the need for water delivered to the ISS by over 1,000 gallons a year, saving significant payload costs in the process. As with any drinking water, quality is a concern, particularly when that water has been recycled. This is an issue of particular interest in space, where ISS crewmembers would have to deal with any illness far from the nearest medical personnel and facilities. The WPA employs sensors that monitor water quality by measuring its conductivity, and rounding out the system s quality assurance methods is a device developed for NASA by a private industry partner. That company has now made the technology available for ensuring the purity of water for consumption and industrial uses on Earth.

Source record↗

The Doubly Labeled Water Method for Measuring Human Energy Expenditure: Adaptations for Spaceflight

It is essential to determine human energy requirements in space, and the doubly labeled water method has been identified as the most appropriate means of indirect calorimetry to meet this need. The method employs naturally occurring, stable isotopes of hydrogen (H-2, deuterium) and oxygen (O-18) which, after dosing, mix with body water. The deuterium is lost from the body as water while the O-18 is eliminated as both water and CO2. The difference between the two isotope elimination rates is therefore a measure of CO2 production and hence energy expenditure. Spaceflight will present a unique challenge to the application of the doubly labeled water method. Specifically, interpretation of doubly labeled water results assumes that the natural abundance or 'background' levels of the isotopes remain constant during the measurement interval. To address this issue, an equilibration model will be developed in an ongoing ground-based study. As energy requirements of women matched to counterparts in the Astronauts Corps are being determined by doubly labeled water, the baseline isotope concentration will be changed by consumption of 'simulated Shuttle water' which is artificially enriched. One group of subjects will be equilibrated on simulated Shuttle water prior to energy determinations by doubly labeled water while the others will consume simulated Shuttle water after dosing. This process will allow us to derive a prediction equation to mathematically model the effect of changing background isotope concentrations.

Schulz, Leslie O.↗

Understanding Anomalous Gas-Phase Peak Shifts in Dip-and-Pull Ambient Pressure XPS Experiments

Dip-and-pull ambient pressure X-ray photoelectron spectroscopy (AP-XPS) holds promise to uncover elementary processes of (photo)electrochemistry. We show, however, that the sample for such experiments should preferably be nonporous and the potential on the surface homogeneous. We carried out dip-and-pull AP-XPS experiments on a hematite thin film sample under the photoelectrochemical oxygen evolution reaction (OER) and find unexpected O 1s core level shifts. Upon electrochemical biasing under simulated solar light illumination, the gas-phase water peak shifted more than the electrolyte peak. To uncover the origin of the unexpected larger shift of the gas-phase peak, we performed electrostatic simulations using COMSOL, to map the potential field in the relevant volume between the sample and the first aperture of the XPS spectrometer. A number of geometric models were considered. We find that when the potential on the sample surface is inhomogeneous, e.g., with ionically isolated electrolyte patches, the gas-phase peak of the spectrum can shift more than the peak due to the electrolyte film. This suggests that at the measured sample position, the local potential was not as set by the potentiostat. Despite this, we find reversible consumption and replenishment of hydroxide in the spectra, which, due to OH– being the reactant of the OER in alkaline electrolyte, makes sense chemically. We propose that this is linked to OH– diffusion across the measured sample position, driven by the potential dependent consumption and replenishment of OH– at the nearby well-connected surface regions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Process Considerations for the Production of Hydrogen via Steam Reforming of Oxygenated Gases from Biomass Pyrolysis and Other Conversion Processes

Abstract In 2021, average CO 2 emissions was 9.7 g CO 2 /g H 2 produced, primarily based on steam methane reforming (SMR) technology that currently dominates hydrogen production. The substitution of natural gas (NG) and other fossil feedstocks in SMRs with renewable gases may be considered as an option for reducing greenhouse gas emissions. This analysis explores process impacts and constraints associated with the potential introduction of biogenic gases into SMRs. The results indicate that replacing NG in the fuel train of the SMR, followed by partial replacement of NG in the feed train may be a feasible approach. For the CO‐ and CO 2 ‐rich gas compositions assumed in this analysis the results indicate that feed train may accommodate up to 25 mole % of biogenic gases using allowances in existing designs and/or with small modifications, while maintaining similar hydrogen output. NG substitution in higher proportions require more major changes because of increased flow rates and heat exchange requirements in the system. Biogenic gases with lower CO 2 and higher calorific values are advantageous for NG substitution, and dry reforming using the CO 2 present in the feed gas can reduce steam consumption and increase process efficiency within limits where coking does not become a new constraint.

08 HYDROGEN↗

Hydrogen and its Vital Role in a Clean Energy Future

Large-scale, low -cost hydrogen production can enable an economically competitive, secure, and environmentally beneficial future energy system across multiple sectors. Furthermore, clean hydrogen can address specific sectors that are hard to decarbonize (e.g., heavy-duty trucking, load-following electricity, iron, steel, and cement) and can help the U.S. meet the net zero carbon goal by 2050. To achieve this goal, tens of millions of metric tons of clean, reliable, and affordable hydrogen will be needed annually1. In 2021, the Hydrogen Energy Earthshot was launched, and its goal is to reduce the cost of clean hydrogen to $1 per $1 kilogram in 1 decade (1 1 1) 2. One very promising pathway for large-scale hydrogen production is water splitting. Water splitting technologies range from commercial technologies such as electrolyzers to approaches that are at a much earlier stage of development, such as photoelectrochemical (PEC) and thermochemical (TCH) processes. All these water splitting pathways offer diverse benefits in energy storage, grid services, and cross-sector emissions reductions while taking advantage of the diverse domestic resources. However, critical materials-, component- and system-level challenges must be addressed to improve efficiency and durability and reduce cost. To address these barriers and move these promising and high impact technologies forward, the HydroGEN Advanced Water Splitting Materials (AWSM) and the H2 from the Next-generation of Electrolyzers of Water (H2NEW) consortia were formed and supported by the Department of Energy (DOE) EERE Hydrogen and Fuel Cell Technologies Office (HFTO). HydroGEN (https://www.energy.gov/eere/h2awsm/) consortium, established in 2016, is an Energy Materials Network (EMN) that aims to accelerate the materials R&D of low technology readiness level (TRL) advanced water splitting (AWS) technologies. The consortium comprises five core national laboratories and focuses on four early-stage AWS pathways: alkaline exchange membrane (AEM) electrolysis, proton conducting solid oxide electrolysis (p-SOEC), photoelectrochemical, and thermochemical water splitting. Liquid alkaline and PEM electrolyzers are already commercial and significant advancements in oxygen conducting solid oxide electrolysis cells (o-SOECs) have been realized. Yet, these systems are still too expensive and not sufficiently durable for wide-scale commercialization. To enable high-volume manufacturing of affordable, durable, efficient electrolyzers, H2NEW (https://h2new.energy.gov/), another multi-lab consortium, was established in 2020. This comprehensive, concerted effort is focused on overcoming barriers related to components and materials integration and scale-up to achieve performance, durability, with an initial focus to achieve $2/kg H2 by 2026.

AEM↗

Electrocatalytic alkene epoxidation at disrupted metal ensembles in blended electrolytes

The project aims to achieve a molecular understanding of oxygen-atom transfer from water to alkenes at electrocatalytic interfaces. Molecular oxygen is the most common oxygen-atom source for epoxidations, and our group is developing sustainable routes through which epoxidation of olefins is achieved using water as the oxygen source. This route can improve the safety of the reaction while also co-producing hydrogen, demonstrating the relevance of this reaction to the energy transition. If successful in our efforts, we may enable oxygen-atom transfer reactions at the anode of water electrolyzers in the place of conventional oxygen evolution, allowing for the synthesis of sustainable value-added co-products. In this vein, we explore several approaches to acquiring high selectivity toward epoxidation over competing reactions, such as oxygen evolution. One of our aims is to allow for rational control of epoxide selectivity by disrupting contiguous metal ensembles at the surface of catalytic metal oxide nanoparticles. Specifically, we aim to synthesize single-atom, few-atom, and many-atom clusters supported on metal oxides and study the mechanism of oxygen evolution and alkene epoxidation on these materials. Thus, this approach will determine the impact of disrupting metal ensembles on the selectivity for alkene epoxidation versus oxygen evolution in blended electrolytes. Another aim is to develop a molecular-level understanding of how a blended electrolyte (i.e., a mixture of aqueous and organic solvents) influences rates of alkene epoxidation versus oxygen evolution. In other words, we are interested in understanding the catalytic influence of the solvent, as our preliminary work shows that the selectivity and reactivity of epoxidation depend strongly on the solvent composition. This investigation includes blended electrolytes and electrolytes containing redox mediator species that improve selectivity toward the desired epoxidation reaction. Overall, our proposed work will help to provide a detailed molecular-level picture of how solvents interact with substrates at the electrode-electrolyte interface, including their involvement in proton transfer reactions and screening of electric fields.

14 SOLAR ENERGY↗

Distributed Sapphire Fiber Bragg Gratings Based Thermal Profiling of Submerged Entry Nozzles

This research focuses on the application of sapphire fiber Bragg gratings (FBGs) for instrumentation in submerged entry nozzles (SEN) within the steelmaking industry. The SEN is pivotal for transferring molten steel from a tundish to a mold, while preventing the infiltration of oxygen and nitrogen from the surrounding environment. Maintaining optimal flow conditions in the mold is crucial for ensuring casting process stability and maintaining high quality steel. Sapphire FBG sensors have been instrumented in SENs to enable distributed thermal mapping for monitoring the health of the SEN. The optical sensor comprises three cascaded sapphire FBGs inscribed using femtosecond laser technology into a one-meter-long sapphire crystalline fiber. The sensor underwent characterization in a laboratory setting up to 1600°C and was tested for long-term stability over 40 hours under extreme environmental conditions. The coupling between silica and sapphire fibers was investigated and implemented during sensor packaging. Here, the sensor successfully captured the pre-heat sequence of the SEN in real-world steelmaking operations. Compared to conventional thermocouples, sapphire FBG sensors demonstrated exceptional efficiency and precision. They offer potential benefits such as increased productivity, reduced energy consumption, and minimized carbon footprint in the steel industry.

Sapphire Fiber Bragg Grating↗

Iron-Tolerant Cyanobacteria: Ecophysiology and Fingerprinting

Although the iron-dependent physiology of marine and freshwater cyanobacterial strains has been the focus of extensive study, very few studies dedicated to the physiology and diversity of cyanobacteria inhabiting iron-depositing hot springs have been conducted. One of the few studies that have been conducted [B. Pierson, 1999] found that cyanobacterial members of iron depositing bacterial mat communities might increase the rate of iron oxidation in situ and that ferrous iron concentrations up to 1 mM significantly stimulated light dependent consumption of bicarbonate, suggesting a specific role for elevated iron in photosynthesis of cyanobacteria inhabiting iron-depositing hot springs. Our recent studies pertaining to the diversity and physiology of cyanobacteria populating iron-depositing hot springs in Great Yellowstone area (Western USA) indicated a number of different isolates exhibiting elevated tolerance to Fe(3+) (up to 1 mM). Moreover, stimulation of growth was observed with increased Fe(3+) (0.02-0.4 mM). Molecular fingerprinting of unialgal isolates revealed a new cyanobacterial genus and species Chroogloeocystis siderophila, an unicellular cyanobacterium with significant EPS sheath harboring colloidal Fe(3+) from iron enriched media. Our preliminary data suggest that some filamentous species of iron-tolerant cyanobacteria are capable of exocytosis of iron precipitated in cytoplasm. Prior to 2.4 Ga global oceans were likely significantly enriched in soluble iron [Lindsay et al, 2003], conditions which are not conducive to growth of most contemporary oxygenic cyanobacteria. Thus, iron-tolerant CB may have played important physiological and evolutionary roles in Earths history.

Brown, I. I.↗

Structural and mechanistic basis for redox sensing by the cyanobacterial transcription regulator RexT

Abstract Organisms have a myriad of strategies for sensing, responding to, and combating reactive oxygen species, which are unavoidable consequences of aerobic life. In the heterocystous cyanobacterium Nostoc sp. PCC 7120, one such strategy is the use of an ArsR-SmtB transcriptional regulator RexT that senses H 2 O 2 and upregulates expression of thioredoxin to maintain cellular redox homeostasis. Different from many other members of the ArsR-SmtB family which bind metal ions, RexT has been proposed to use disulfide bond formation as a trigger to bind and release DNA. Here, we present high-resolution crystal structures of RexT in the reduced and H 2 O 2 -treated states. These structures reveal that RexT showcases the ArsR-SmtB winged-helix-turn-helix fold and forms a vicinal disulfide bond to orchestrate a response to H 2 O 2 . The importance of the disulfide-forming Cys residues was corroborated using site-directed mutagenesis, mass spectrometry, and H 2 O 2 -consumption assays. Furthermore, an entrance channel for H 2 O 2 was identified and key residues implicated in H 2 O 2 activation were pinpointed. Finally, bioinformatics analysis of the ArsR-SmtB family indicates that the vicinal disulfide “redox switch” is a unique feature of cyanobacteria in the Nostocales order, presenting an interesting case where an ArsR-SmtB protein scaffold has been evolved to showcase peroxidatic activity and facilitate redox-based regulation.

54 ENVIRONMENTAL SCIENCES↗

Development of Microfabricated Chemical Gas Sensors and Sensor Arrays for Aerospace Applications

Aerospace applications require the development of chemical sensors with capabilities beyond those of commercially available sensors. In particular, factors such as minimal sensor size, weight, and power consumption are particularly important. Development areas which have potential aerospace applications include launch vehicle leak detection, engine health monitoring, fire detection, and environmental monitoring. Sensor development for these applications is based on progress in three types of technology: 1) Micromachining and microfabrication (Microsystem) technology to fabricate miniaturized sensors. 2) The use of nanocrystalline materials to develop sensors with improved stability combined with higher sensitivity. 3) The development of high temperature semiconductors, especially silicon carbide. However, due to issues of selectivity and cross-sensitivity, individual sensors are limited in the amount of information that they can provide in environments that contain multiple chemical species. Thus, sensor arrays are being developed to address detection needs in such multi-species environments. This paper discusses the needs of space applications as well as the point-contact sensor technology and sensor arrays being developed to address these needs. Sensors to measure hydrogen, hydrocarbons, hydrazine, nitrogen oxides (NO,), carbon monoxide, oxygen, and carbon dioxide are being developed as well as arrays for leak, fire, and emissions detection. Demonstrations of the technology will also be discussed. It is concluded that microfabricated sensor technology has significant potential for use in a range of aerospace applications.

Hunter, G. W.↗

Characterization of the Benefit of APS Flash Coatings in Improving TBC Lifetime

The addition of an air plasma sprayed (APS) “flash” layer on top of a high velocity oxygen fuel (HVOF) bond coating has been shown to extend the lifetime of thermal barrier coatings. A series of furnace cycle tests (FCTs) has been conducted at 1100 °C in air + 10% H 2 O to study the benefit of flash coatings on rod and disk alloy 247 specimens and provide a better mechanistic understanding of their benefit. Flash coatings of NiCoCrAlY and NiCoCrAlYHfSi both improved the FCT lifetime of rod specimens tested in 100-h cycles and disk specimens tested in 1-h cycles. In 1-h cycles, the NiCoCrAlY flash coating significantly outperformed an HVOF-only NiCoCrAlYHfSi bond coating and a NiCoCrAlYHfSi flash coating. Both flash coatings increased the bond coating roughness compared to HVOF. During exposure, the flash layer formed an intermixed alumina-metal layer that appeared to inhibit crack formation. Using a time series of observations, the lower Y + Hf content in the Y-only flash coating appeared to reduce Al consumption. The HVOF layer acted as a source of Al for the adjacent mixed zone. A second series of specimens included a fully APS bond coating where oxide had penetrated through the entire coating to the substrate after only 100, 1-h cycles and lifetime was similar to an HVOF-only bond coating. The inner HVOF layer with the outer APS flash coating prevented this complete penetration from occurring.

Pint, Bruce↗

Hydrogen Recovery by Methane Pyrolysis to Elemental Carbon

Use of a Sabatier reactor to recover the oxygen from the carbon dioxide exhaled by the crew on the International Space Station has been limited by the loss of the hydrogen contained in the methane it generates. Maximizing the oxygen recovered requires the hydrogen to be recovered from the methane product and recycled back to the Sabatier reactor. We describe the use of a tailored methane pyrolysis reactor to completely recover this hydrogen. The carbon-containing byproduct is elemental carbon, which is generated in the form of easily handled, non-sooty material that may have various uses. The process of creating this tailored carbon vapor deposition process involved exploration of the effects of temperature, pressure, substrate design and other variables to develop a high yield process that cleanly generates the desired products. Reaction kinetics and kinetics modelling were used to specify the temperature, pressure and reactor volume required to achieve the target conversion and to assure that the final average density was as high as possible. Reactor design included the selection of materials that will survive the high temperatures and environment in the pyrolysis reactor, and thermal modeling to achieve the required temperatures with minimum power consumption. The successful construction and demonstration of a brassboard prototype will allow the results of the chemical, thermal and mechanical models to be validated and should provide a useful alternative for a completely closed loop ECLS system. Integration of this technology with state-of-the-art (SOA) Sabatier hardware on ISS requires a complete understanding of the effects of impurities in the product hydrogen on the Sabatier catalyst. SOA Sabatier catalyst was evaluated over short and long-term exposure to anticipated contaminants to identify effects.

Yates, Stephen F.↗

Hydrogen Recovery by Methane Pyrolysis to Elemental Carbon

Use of a Sabatier reactor to recover the oxygen from the carbon dioxide exhaled by the crew on the International Space Station has been limited by the loss of the hydrogen contained in the methane it generates. Maximizing the oxygen recovered requires the hydrogen to be recovered from the methane product and recycled back to the Sabatier reactor. We describe the use of a tailored methane pyrolysis reactor to completely recover this hydrogen. The carbon-containing byproduct is elemental carbon, which is generated in the form of easily handled, non-sooty material that may have various uses. The process of creating this tailored carbon vapor deposition process involved exploration of the effects of temperature, pressure, substrate design and other variables to develop a high yield process that cleanly generates the desired products. Reaction kinetics and kinetics modelling were used to specify the temperature, pressure and reactor volume required to achieve the target conversion and to assure that the final average density was as high as possible. Reactor design included the selection of materials that will survive the high temperatures and environment in the pyrolysis reactor, and thermal modeling to achieve the required temperatures with minimum power consumption. The successful construction and demonstration of a brassboard prototype will allow the results of the chemical, thermal and mechanical models to be validated and should provide a useful alternative for a completely closed loop ECLS system. Integration of this technology with state-of-the-art (SOA) Sabatier hardware on ISS requires a complete understanding of the effects of impurities in the product hydrogen on the Sabatier catalyst. SOA Sabatier catalyst was evaluated over short and long-term exposure to anticipated contaminants to identify effects.

Yates, Stephen F.↗

Retrofitting stoves with forced jets of primary air improves speed, emissions, and efficiency: Evidence from six types of biomass cookstoves

Incorporating jets of forced air into biomass cookstove combustion has been shown to potentially decrease harmful emissions, leading to a variety of designs in recent years. These have shown mixed success in terms of real-world performance, usability, and durability. The Jet-Flame forced draft retrofit accessory was recently developed to implement forced jets of primary air at a low cost into a wide range of types of cookstoves using a small 1.5-W fan housed in a low-cost cast iron body to be inserted beneath the fuel bed of a biomass cooking fire. This research sought to quantify the potential efficiency and emissions performance impacts of the Jet-Flame when installed in six different types of biomass cookstoves (three open or shielded fires and three rocket stoves) versus the natural draft performance of each. The effect of the operating fan voltage was also measured. A series of tests following a modified ISO 19867-1:2018 protocol were performed in the laboratory using the Aprovecho Laboratory Emissions Measurement System (LEMS) equipped with additional oxygen and temperature sensors. Results for each stove carefully tended with a single layer of sticks showed that the global average PM 2.5 reduction with the Jet-Flame was 89 % relative to the natural draft cases, with larger relative improvements seen in the most rudimentary stoves. CO was reduced by a global average of 74 %, reaching tier 4 or 5 for all stoves. Thermal efficiency was also improved by 34 % when calculated without taking into account the energy content of the remaining char (or 21 % with char), illustrating the value of burning char to provide cooking energy rather than leaving it unburned in the combustion chamber as is common in many natural draft stoves. Time to boil was also reduced by 8 %. In addition, adjusting the voltage of the jet-flame assisted in modulating firepower, improving the usability of the stove. These results indicate a strong potential for the Jet-Flame to help reduce emissions and fuel consumption in a wide range of cookstove designs at a relatively low cost or need for changes in behavior, fuel, or cooking device. The unit also provides enhanced usability in terms of ease of startup, cooking speed, low PM emissions at high power, and burning char. Additional studies are needed to measure performance in the field and under a variety of operational conditions.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Uptake of polystyrene nanospheres by wheat and Arabidopsis roots in agar, hydroponics, and soil

Plant uptake of micro- and nanoplastics can lead to contamination of food with plastic particles and subsequent human consumption of plastics. There is evidence that plant roots can take up micro and nanoplastics; however, most of this evidence stems from experiments conducted with plants grown in hydroponics or agar systems where uptake of nanoparticles by roots is more favorable than when plants were grown in soil. Here, we discern the root uptake and accumulation of polystyrene nanospheres in plants grown in different growth media: agar, hydroponics, and soil. In addition, we tested the impacts of nanospheres on plant biomass and plant stress. Wheat and Arabidopsis thaliana were grown in agar, hydroponics, and soil media and exposed to polystyrene nanospheres. Three different nanospheres were used (40 nm and 200 nm carboxylate-modified and 200 nm amino-modified polystyrene) and uniformly mixed into the growth media. Plants were grown for 7 to 10 days and the roots were then examined for the presence of nanospheres by confocal laser scanning microscopy and scanning electron microscopy. Plant stress was evaluated by measuring reactive oxygen species (ROS). We observed the 40 nm nanospheres inside the plant roots, but the 200 nm nanospheres only adhered to the root cap cells showing no uptake into the roots. Furthermore, confocal images indicated that root uptake of nanospheres was favored in hydroponic solutions as compared to agar and soil media. Plant biomass was generally not affected by the nanospheres, except for hydroponically grown Arabidopsis thaliana, where biomass was significantly reduced. Small sized (40 nm) and positively charged (200 nm amino-modified) nanospheres showed higher ROS accumulation in plants than negatively charged 200 nm carboxylate-modified nanospheres. In conclusion, this study provides evidence that polystyrene nanospheres can be taken up into the interior of plant roots and cause plant stress, but these impacts are less pronounced in media where the plastic particles are less mobile, like in agar and soil media as compared to hydroponic systems.

54 ENVIRONMENTAL SCIENCES↗

Catalytic processes for space station waste conversion

Catalytic techniques for processing waste products onboard space vehicles were evaluated. The goal of the study was the conversion of waste to carbon, wash water, oxygen and nitrogen. However, the ultimate goal is conversion to plant nutrients and other materials useful in closure of an ecological life support system for extended planetary missions. The resulting process studied involves hydrolysis at 250 C and 600 psia to break down and compact cellulose material, distillation at 100 C to remove water, coking at 450 C and atmospheric pressure, and catalytic oxidation at 450 to 600 C and atmospheric pressure. Tests were conducted with a model waste to characterize the hydrolysis and coking processes. An oxidizer reactor was sized based on automotive catalytic conversion experience. Products obtained from the hydrolysis and coking steps included a solid residue, gases, water condensate streams, and a volatile coker oil. Based on the data obtained, sufficient component sizing was performed to make a preliminary comparison of the catalytic technique with oxidation for processing waste for a six-man spacecraft. Wet oxidation seems to be the preferred technique from the standpoint of both component simplicity and power consumption.

Schoonover, M. W.↗

The Decompression Sickness and Venous Gas Emboli Consequences of Air Breaks During 100% Oxygen Prebreathe

Not enough is known about the increased risk of hypobaric decompression sickness (DCS) and production of venous (VGE) and arterial (AGE) gas emboli following an air break in an otherwise normal 100% resting oxygen (O2) prebreathe (PB), and certainly a break in PB when exercise is used to accelerate nitrogen (N2) elimination from the tissues. Current Aeromedical Flight Rules at the Johnson Space Center about additional PB payback times are untested, possibly too conservative, and therefore not optimized for operational use. A 10 min air break at 90 min into a 120 min PB that includes initial dual-cycle ergometry for 10 min will show a measurable increase in the risk of DCS and VGE after ascent to 4.3 psia compared to a 10 min break at 15 min into the PB, or when there is no break in PB. Data collection with humans begins in 2005, but here we first evaluate the hypothesis using three models of tissue N2 kinetics: Model I is a simple single half-time compartment exponential model, Model II is a three compartment half-time exponential model, and Model III is a variable half-time compartment model where the percentage of maximum O2 consumption for the subject during dual-cycle ergometry exercise defines the half-time compartment. Model I with large rate constants to simulate an exercise effect always showed a late break in PB had the greatest consequence. Model II showed an early break had the greatest consequence. Model III showed there was no difference between early or late break in exercise PB. Only one of these outcomes will be observed when humans are tested. Our results will favor one of these models, and so advance our understanding of tissue N2 kinetics, and of altitude DCS after an air break in PB.

Conkin, J.↗

Enhanced Light Outcoupling from OLEDs Fabricated on Novel Low-Cost Patterned Plastic Substrates of Varying Periodicity

OLEDs continue to make strides in display applications, but their commercial utilization in solid-state lighting (SSL) is lagging. An ongoing challenge, in particular for manufacturing, is the need for enhanced efficiency and hence the necessity to increase in an inexpensive approach the extraction of the light generated inside the OLED into the forward (viewing) hemisphere. In conventional OLEDs fabricated on a transparent flat anode coated on glass, the external quantum efficiency (EQE) is only ~20%. About 50% of the light is lost to internal waveguiding in the high refractive index (RI) organic + ITO anode layers and to surface plasmon polaritons (SPPs) at the organic/metal cathode interface. Another ~30% of the light is externally waveguided in the substrate to its edges. While extraction of the externally waveguided light is commonly addressed by adding a microlens array (MLA) or a scattering layer at the substrate’s air-side, light outcoupling increases by only ~1.6-1.7x (vs up to 2.5x in improving from ~20% to ~50%). The use of a hemispherical lens or an index matching fluid (IMF) at the substrate/photodetector (PD) interface increases the outcoupling by at least 2x; these approaches however, are not viable industrially, and even a MLA is sometimes undesirable due to its non-planar, scattering structure. In multi-stack tandem OLEDs, where the metal cathode is far from the emitting zone(s), the impact of photons loss to SPPs decreases. Our project addressed the ~50% loss to the internally waveguided light and SPPs. We evaluated OLEDs fabricated on patterned or planarized plastic substrates manufactured in a cost-effective approach compatible with a roll-to-roll (R2R) process. The OLEDs were either (i) patterned to various degrees depending on the pitch a and height or depth h of the pattern features or (ii) planar, with a pattern buried under a flat high RI planarization layer. We demonstrated that the outcoupling from green patterned OLEDs reaches ~50% by mitigating plasmon–related loss and internal waveguiding, even without the addition of a MLA, a hemispherical lens, or IMF. Simulations conducted in parallel with the experimental effort demonstrated how diffraction by conformally corrugated OLEDs increases the outcoupling to >60%. Structures with varying pitch values were also simulated indicating that combining domains of varying pitch could increase outcoupling to 55-60%. Experimentally, we additionally assessed the role a and h in determining not only the OLED efficiencies, but also their structural properties, i.e., the uniformity and conformality throughout the OLED stack. As planar OLEDs are preferred over corrugated devices, we studied different patterns in plastic substrates that were planarized by a high RI formulation. Planar green OLEDs on such structures showed enhanced efficiencies with EQEs larger than 60% with the addition of an IMF (to extract the substrate mode) at the substrate/Si PD interface. White OLEDs showed EQEs of 45.5%. Plastic substrates are currently less attractive than glass substrates due to drawbacks such as permeability to water vapor and oxygen, and in some cases thermal instability. Plastic substrates however, are flexible and easy to handle unlike thin flexible glass, and once transparent thin barrier films are available, they will become more attractive; they are already of interest in medical applications. Importantly, as it is easy to generate various patterns in different plastic materials, they provide excellent means for assessing and optimizing enhancing extracting structures. Such structures can also be transferred to glass substrates with some process modifications. The technical effectiveness and economic feasibility of the project lie in the patterning of the extracting plastic substrates in an approach that is scalable to R2R manufacturing. R2R processes are of drastically lower-cost than batch or single-unit fabrication. The patterned plastic can be a part of an integrated substrate either plastic or glass, which includes also a MLA or a planar layer with embedded scattering particles, as well as a conductive metal mesh/electrode design. SSL is environmentally-friendly and as OLED SSL becomes more efficient it will reduce electricity consumption, and hence lighting cost, as well as produce less expensive attractive lighting fixtures. Our university-industry collaboration is hence of major benefit to the public as it demonstrates the feasibility of manufacturing optimized extracting substrates for highly efficient OLEDs for SSL in a future R2R process, which would drastically reduce the manufacturing cost and increase production in the USA. Moreover, newly developed methods by our team allow low-cost roll manufactured substrates to be transferred to flexible or rigid glass substrates, which solves the plastic substrate barrier issues, and when combined with device encapsulation will increase the OLEDs’ environmental stability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗