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Mo/Ti Diffusion Bonding for Making Thermoelectric Devices

An all-solid-state diffusion bonding process that exploits the eutectoid reaction between molybdenum and titanium has been developed for use in fabricating thermoelectric devices based on skutterudite compounds. In essence, the process is one of heating a flat piece of pure titanium in contact with a flat piece of pure molybdenum to a temperature of about 700 C while pushing the pieces together with a slight pressure [a few psi (of the order of 10 kPa)]. The process exploits the energy of mixing of these two metals to form a strong bond between them. These two metals were selected partly because the bonds formed between them are free of brittle intermetallic phases and are mechanically and chemically stable at high temperatures. The process is a solution of the problem of bonding hot-side metallic interconnections (denoted hot shoes in thermoelectric jargon) to titanium-terminated skutterudite n and p legs during the course of fabrication of a unicouple, which is the basic unit cell of a thermoelectric device (see figure). The hot-side operating temperature required for a skutterudite thermoelectric device is 700 C. This temperature precludes the use of brazing to attach the hot shoe; because brazing compounds melt at lower temperatures, the hot shoe would become detached during operation. Moreover, the decomposition temperature of one of the skutterudite compounds is 762 C; this places an upper limit on the temperature used in bonding the hot shoe. Molybdenum was selected as the interconnection metal because the eutectoid reaction between it and the titanium at the ends of the p and n legs has characteristics that are well suited for this application. In addition to being suitable for use in the present bonding process, molybdenum has high electrical and thermal conductivity and excellent thermal stability - characteristics that are desired for hot shoes of thermoelectric devices. The process takes advantage of the chemical potential energy of mixing between molybdenum and titanium. These metals have a strong affinity for each other. They are almost completely soluble in each other and remain in the solid state at temperatures above the eutectoid temperature of 695 C. As a result, bonds formed by interdiffusion of molybdenum and titanium are mechanically stable at and well above the original bonding temperature of about 700 C. Inasmuch as the bonds are made at approximately the operating temperature, thermomechanical stresses associated with differences in thermal expansion are minimized.

Sakamoto, Jeffrey

Phonon modulation of strongly coupled gold tetrahedral plasmonic nanoparticles and a carbocyanine J-aggregate

Coupling exciton and plasmon excitations to form polaritons are of great interest for manipulating energy transfer at the nanoscale via the formation of hybrid light–matter states. In this study, we successfully couple gold tetrahedral nanoparticles with the J-aggregate forming dye 5,5′,6,6′-tetrachloro-1,1′-diethyl-3,3′-di(4-sulfobutyl)-benzimidazolocarbocyanine (TDBC) to form a strongly coupled colloidal polariton system with a Rabi splitting energy of ∼206 meV. These gold tetrahedra exhibit coherent phonon modes upon photoexcitation, which produce transient oscillations of the LSPR energy for isolated tetrahedra. Transient absorption measurements of the polariton system were performed and show how these coherent phonon modes influence the polariton states’ extinction. We found that the oscillation period increases by 0.5 ± 0.14 ps upon surface deposition of TDBC dye, demonstrating LSPR sensitivity to the refractive index environment. Shifts in the plasmon resonance due to the coherent phonon modes transiently alters LSPR alignment with the J-aggregate exciton peak, resulting in shifts of the hybrid polariton states’ oscillator strength.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Adhesion in ceramics and magnetic media

When a ceramic is brought into contact with a metal or a polymeric material such as a magnetic medium, strong bonds form between the materials. For ceramic-to-metal contacts, adhesion and friction are strongly dependent on the ductility of the metals. Hardness of metals plays a much more important role in adhesion and friction than does the surface energy of metals. Adhesion, friction, surface energy, and hardness of a metal are all related to its Young's modulus and shear modulus, which have a marked dependence on the electron configuration of the metal. An increase in shear modulus results in a decrease in area of contact that is greater than the corresponding increase in surface energy (the fond energy) with shear modulus. Consequently, the adhesion and friction decrease with increasing shear modulus. For ceramics in contact with polymeric magnetic tapes, environment is extremely important. For example, a nitrogen environment reduces adhesion and friction when ferrite contacts polymeric tape, whereas a vacuum environment strengthens the ferrite-to-tape adhesion and increases friction. Adhesion and friction are strongly dependent on the particle loading of the tape. An increase in magnetic particle concentration increases the complex modulus of the tape, and a lower real area of contact and lower friction result.

Miyoshi, Kazuhisa

Extreme Emission Line Galaxies in CANDELS: Broad-Band Selected, Star-Bursting Dwarf Galaxies at Z greater than 1

We identify an abundant population of extreme emission line galaxies (EELGs) at redshift z approx. 1.7 in the Cosmic Assembly Near-IR Deep Extragalactic Legacy Survey (CANDELS) imaging from Hubble Space Telescope/Wide Field Camera 3 (HST/WFC3). 69 EELG candidates are selected by the large contribution of exceptionally bright emission lines to their near-infrared broad-band magnitudes. Supported by spectroscopic confirmation of strong [OIII] emission lines . with rest-frame equivalent widths approx. 1000A in the four candidates that have HST/WFC3 grism observations, we conclude that these objects are galaxies with approx.10(exp 8) Solar Mass in stellar mass, undergoing an enormous starburst phase with M*/M* of only approx. 15 Myr. These bursts may cause outflows that are strong enough to produce cored dark matter profiles in low-mass galaxies. The individual star formation rates and the co-moving number density (3.7x10(exp -4) Mpc(sup -3) can produce in approx.4 Gyr much of the stellar mass density that is presently contained in 10(exp 8) - 10(exp 9) Solar Mass dwarf galaxies. Therefore, our observations provide a strong indication that many or even most of the stars in present-day dwarf galaxies formed in strong, short-lived bursts, mostly at z > 1.

vanderWel, A.

Mechanisms of Basalt-plains Ridge Formation

The morphologic similarities between the Columbia Plateau ridges and ridges on the Moon, Mercury and Mars form a strong basis for the interpretation of basalt-plains ridges as compressional folds. The basalt-plains ridges appear to have formed on competent flood basalt units deformed at the surface with essentially no confining pressure. Estimates of compressive strain for planetary ridges range from a few tenths of a percent on the Moon to up to 0.4% on Mars, to as high as 35% for Columbia Plateau folds with associated thrust faults. Such values have strong implications for both deformational mechanisms as well as for the source of stress. Deformational mechanisms that will attempt to account for the morphology, fold geometry, possible associated thrust faulting and regular spacing of the basalt-plains ridges on the terrestrial planets are under investigation.

Watters, T. R.

Particle simulation of auroral double layers

Work on the simulation of auroral double layers (DLs) with realistic particle-in-cell models is presented. An early model simulated weak DLs formed in a self-consistent circuit but under conditions subject to the ion-acoustic instability. Recent work has focused on strong DLs formed when currentless jets are injected into a dipole magnetic field.

Smith, Bruce L.

MAVEN Observations of Energy-Time Dispersed Electron Signatures in Martian Crustal Magnetic Fields

Energy-time dispersed electron signatures are observed by the Mars Atmosphere and Volatile EvolutioN (MAVEN) mission in the vicinity of strong Martian crustal magnetic fields. Analysis of pitch angle distributions indicates that these dispersed electrons are typically trapped on closed field lines formed above strong crustal magnetic sources. Most of the dispersed electron signatures are characterized by peak energies decreasing with time rather than increasing peak energies. These properties can be explained by impulsive and local injection of hot electrons into closed field lines and subsequent dispersion by magnetic drift of the trapped electrons. In addition, the dispersed flux enhancements are often bursty and sometimes exhibit clear periodicity, suggesting that the injection and trapping processes are intrinsically time dependent and dynamic. These MAVEN observations demonstrate that common physical processes can operate in both global intrinsic magnetospheres and local crustal magnetic fields.

martian

Moonrise: Sampling the South Pole-Aitken Basin to Address Problems of Solar System Significance

A mission to land in the giant South Pole-Aitken (SPA) Basin on the Moon's southern farside and return a sample to Earth for analysis is a high priority for Solar System Science. Such a sample would be used to determine the age of the SPA impact; the chronology of the basin, including the ages of basins and large impacts within SPA, with implications for early Solar System dynamics and the magmatic history of the Moon; the age and composition of volcanic rocks within SPA; the origin of the thorium signature of SPA with implications for the origin of exposed materials and thermal evolution of the Moon; and possibly the magnetization that forms a strong anomaly especially evident in the northern parts of the SPA basin. It is well known from studies of the Apollo regolith that rock fragments found in the regolith form a representative collection of many different rock types delivered to the site by the impact process (Fig. 1). Such samples are well documented to contain a broad suite of materials that reflect both the local major rock formations, as well as some exotic materials from far distant sources. Within the SPA basin, modeling of the impact ejection process indicates that regolith would be dominated by SPA substrate, formed at the time of the SPA basin-forming impact and for the most part moved around by subsequent impacts. Consistent with GRAIL data, the SPA impact likely formed a vast melt body tens of km thick that took perhaps several million years to cool, but that nonetheless represents barely an instant in geologic time that should be readily apparent through integrated geochronologic studies involving multiple chronometers. It is anticipated that a statistically significant number of age determinations would yield not only the age of SPA but also the age of several prominent nearby basins and large craters within SPA. This chronology would provide a contrast to the Imbrium-dominated chronology of the nearside Apollo samples and an independent test of the timing of the lunar cataclysm.

Zeigler, R. A.

Adhesion, friction, and wear behavior of clean metal-ceramic couples

When a clean metal is brought into contact with a clean, harder ceramic in ultrahigh vacuum, strong bonds form between the two materials. The interfacial bond strength between the metal and ceramic surfaces in sliding contact is generally greater than the cohesive bond strength in the metal. Thus, fracture of the cohesive bonds in the metal results when shearing occurs. These strong interfacial bonds and the shearing fracture in the metal are the main causes of the observed wear behavior and the transfer of the metal to the ceramic. In the literature, the surface energy (bond energy) per unit area of the metal is shown to be related to the degree of interfacial bond strength per unit area. Because the two materials of a metal-ceramic couple have markedly different ductilities, contact can cause considerable plastic deformation of the softer metal. It is the ductility of the metal, then, that determines the real area of contact. In general, the less ductile the metal, the smaller the real area of contact. The coefficient of friction for clean surfaces of metal-ceramic couples correlates with the metals total surface energy in the real area of contact gamma A (which is the product of the surface energy per unit area of the metal gamma and the real area of contact (A)). The coefficient of friction increases as gamma A increases. Furthermore, gamma A is associated with the wear and transfer of the metal at the metal-ceramic interface: the higher the value of gamma A, the greater the wear and transfer of the metal.

Miyoshi, Kazuhisa

Numerical simulation of viscous-inviscid interactions on indented nose tips

An implicit numerical algorithm to solve the unsteady thin-layer Navier-Stokes equations in a strong conservative form has been used to compute the viscous flow over indented nose tips placed in a supersonic free stream. Numerical solutions are presented for axisymmetric and three-dimensional indented configurations for laminar flow conditions. Results demonstrate the capability of the present numerical procedure to predict flow fields that contain strong viscous-inviscid interactions, including boundary-layer separation, reattachment, and embedded discontinuities. Comparisons with available experimental data for the shock shape and surface pressure are also given.

Rizk, Y. M.

An improved stochastic weighted particle method for boundary driven flows

Here, the stochastic weighted particle method (SWPM) is a generalization of the Direct Simulation Monte Carlo (DSMC) method where particle weights are variable and dynamic. SWPM is backed by a strong theoretical foundation but has not been critically evaluated for problems of practical interest. A thorough assessment of SWPM for boundary-driven flows reveals significant numerical artifacts near the boundary, notably a diverging heat flux. To correct the boundary heat flux, two modifications to SWPM are proposed: separated grouping and a spatially-dependent weight transfer function. To gauge the relative efficiency of SWPM in comparison to DSMC, a high-Mach-number wheel flow which forms a strong density gradient is also simulated.

97 MATHEMATICS AND COMPUTING

Ag Intercalation in Layered Cs 3 Bi 2 Br 9 Perovskite for Enhanced Light Emission with Bound Interlayer Excitons

Cesium bismuth bromide (CBB) has garnered considerable attention as a vacancy-ordered layered perovskite with notable optoelectronic applications. However, its use as a light source has been limited due to its weak photoluminescence (PL). Here, we demonstrate metal intercalation as a novel approach to engineer the room-temperature PL of CBB using experimental and computational methods. Ag, when introduced into CBB, occupies vacant sites in the spacer region, forming octahedral coordination with surrounding Br anions. First-principles density functional theory calculations reveal that intercalated Ag represents the most energetically stable Ag species compared to other potential forms, such as Ag substituting Bi. The intercalated Ag forms a strong polaronic trap state close to the conduction band minimum and quickly captures photoexcited electrons with holes remaining in CBB layers, leading to the formation of a bound interlayer exciton, or BIE. The radiative recombination of this BIE exhibits bright room-temperature PL at 600 nm and a decay time of 38.6 ns, 35 times greater than that of free excitons, originating from the spatial separation of photocarriers by half a unit cell separation distance. The BIE as a new form of interlayer exciton is expected to inspire new research directions for vacancy-ordered perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Investigation of Machine Design for Friction Stir Welding

The process of joining two pieces of metal together has not significantly changed over the last few decades. The basic idea used is to bring the pieces together and apply enough heat to melt the metal at the interface. The molten metal mixes and after cooling forms a strong joint. This process is called the fusion process. The most significant difference between the many fusion processes is how the heat is generated and applied. The Welding Institute (TWI), in Great Britain, has recently patented an innovative application of mechanical friction. TWI designed a tool and process called Friction Stir Welding (FSW) that uses friction to heat the metal to within a few hundred degrees Fahrenheit of melting, just to the point of being plastic-like. The tool then stirs the plasticized metal together forming a joint that has been shown to be as good or better than an equivalent fusion joint. The FSW process is well suited for the joining of the aluminum alloys used in the aerospace industry. The relatively low melting point of aluminum eliminates the requirements for exotic materials for pin tool design. The FSW process has been successfully used to join alloys such as 7075 which were before considered "unweldable", and aluminum-lithium 2195 which exhibits many problems when fusion welded. The objective this summer was to investigate the design of a FSW system that could take this process from the laboratory to the manufacturing floor. In particular, it was the goal of my NASA colleague to develop a concept for applying the FSW process to the manufacturing of aluminum cryogenic oxygen and hydrogen tanks, of the sort used to make the Shuttle External Tank.

Romine, Peter L.

The Earliest Ion Channels in Protocellular Membranes

Cellular membranes with their hydrophobic interior are virtually impermeable to ions. Bulk of ion transport through them is enabled through ion channels. Ion channels of contemporary cells are complex protein molecules which span the membrane creating a cylindrical pore filled with water. Protocells, which are widely regarded as precursors to modern cells, had similarly impermeable membranes, but the set of proteins in their disposal was much simpler and more limited. We have been, therefore, exploring an idea that the first ion channels in protocellular membranes were formed by much smaller peptide molecules that could spontaneously selfassemble into short-lived cylindrical bundles in a membrane. Earlier studies have shown that a group of peptides known as peptaibols is capable of forming ion channels in lipid bilayers when they are exposed to an electric field. Peptaibols are small, non-genetically encoded peptides produced by some fungi as a part of their system of defense against bacteria. They are usually only 14-20 residues long, which is just enough to span the membrane. Their sequence is characterized by the presence of non-standard amino acids which, interestingly, are also expected to have existed on the early earth. In particular, the presence of 2-aminoisobutyric acid (AIB) gives peptaibols strong helix forming propensities. Association of the helices inside membranes leads to the formation of cylindrical bundles, typically containing 4 to 10 monomers. Although peptaibols are excellent candidates for models of the earliest ion channels their structures, which are stabilized only by van der Waals forces and occasional hydrogen bonds between neighboring helices, are not very stable. Although it might properly reflect protobiological reality, it is also a major obstacle in studying channel behavior. For this reason we focused on two members of the peptaibol family, trichotoxin and antiamoebin, which are characterized by a single conductance level. This indicates that their structures are unique and stable. In addition, it is also believed that the trichotoxin channel displays some selectivity between potassium and chloride ions. This makes trichotoxin and antiamoebin ideal models of the earliest ion channels that could provide insight into the origins of ion conductance and selectivity. In the absence of crystal structure of the trichotoxin and antiamoebin channels, we propose their molecular models based on experimentally determined number of monomers forming the bundles. We use molecular dynamics simulations to validate the models in terms of their conductance and selectivity. On the basis of our simulations we show that the emergence of channels built of small, alpha-helical peptides was protobiologically plausible and did not require highly specific amino acid sequences, which is a convenient evolutionary trait. Despite their simple structure, such channels could possess properties that, at the first sight, appear to require markedly larger complexity. To this end, we will discuss how the amino acid sequence and structure of primitive channels give rise to the phenomena of ionic conductance and selectivity across the earliest cell walls, which were essential functions for the emergence and early evolution of protocells. Furthermore, we will argue that even though architectures of membrane proteins are not nearly as diverse as those of water-soluble proteins, they are sufficiently flexible to adapt readily to the functional demands arising during evolution.

Mijajlovic, Milan

Experiments and analysis concerning the use of external burning to reduce aerospace vehicle transonic drag

The external combustion of hydrogen to reduce transonic drag was investigated. A control volume analysis is developed and indicates that the specific impulse performance of external burning is competitive with other forms of airbreathing propulsion and depends on the fuel-air ratio, freestream Mach number, and the severity of the base drag. A method is presented for sizing fuel injectors for a desired fuel-air ratio in the unconfined stream. A two-dimensional Euler analysis is also presented which indicates that the total axial force generated by external burning depends on the total amount of energy input and is independent of the transverse and streamwise distribution of heat addition. Good agreement between the Euler and control volume analysis is demonstrated. Features of the inviscid external burning flowfield are discussed. Most notably, a strong compression forms at the sonic line within the burning stream which may induce separation of the plume and prevent realization of the full performance potential. An experimental program was conducted in a Mach 1.26 free-jet to demonstrate drag reduction on a simple expansion ramp geometry, and verify hydrogen-air stability limits at external burning conditions. Stable combustion appears feasible to Mach number of between 1.4 and 2 depending on the vehicle flight trajectory. Drag reduction is demonstrated on the expansion ramp at Mach 1.26; however, force levels showed little dependence on fuel pressure or altitude in contrast to control volume analysis predictions. Various facility interference mechanisms and scaling issues were studied and are discussed.

Trefny, Charles J.

Requirements and Challenges for CFD Validation within the High-Lift Common Research Model Ecosystem

The High-Lift Common Research Model (CRM-HL) ecosystem is envisioned to become an industry standard set of test cases for high-lift aerodynamics prediction, with data generated providing a strong foundation for CFD validation. Since its original development, preliminary wind tunnel tests have been conducted to further understand and configure the geometry, and several more are in the planning phases. It is anticipated that the data generated in these tests will be used extensively by the CFD community for research, development, and validation of new techniques that yield more accurate results. To derive the maximum benefit from planned wind tunnel testing, data acquisition will be focused in several key areas to address specific shortcomings in CFD predictive capabilities. Significant challenges currently exist in areas including, but not limited to, characterizing high-lift flow phenomena, quantifying effects due to configuration changes, understanding wind tunnel and model installation effects, and establishing data uncertainty. This paper will discuss the current state-of-the-art in high-lift CFD prediction, key limitations of current CFD methods and tools, establishing a validation dialog between test and CFD practitioners, and the flow phenomena of highest interest, in an effort to begin to address these challenges. To this end, it is expected that the data generated from CRM-HL tests will form a strong foundation for future predictive capability.

Adam M Clark

NASA Electric Vertical Takeoff and Landing (eVTOL) Aircraft Technology for Public Services – A White Paper

History has shown that our personal life is highly dependent on the technology that people have developed. A strategic scan of the aerospace environment at the beginning of the 21st century strongly suggests that the world might be approaching a new age of airpower—the era of electrified/hybrid aircraft propulsion. Undeniably, starting from the Montgolfier Brothers balloon flight in 1783, to the Wright Brothers piston engine flight in 1903, and the jet engine of the 1960s, or the space age of today, one can say that leaps in propulsion technology have marked the different ages of human flight. The technological advancements, brought at the beginning of 21st century by the revolution in data exchange, computational power, sensors, wireless communication, internet, and autonomy, contributed to the vision of this new age of propulsion we are approaching. Historically, conventional vertical takeoff and landing (VTOL) aircraft have been equipped with propulsion units relying on complex internal combustion machines (turbines, piston engines, for example), and complex mechanical arrangements (gearboxes, shafts, variable pitch propeller). By contrast, electric VTOL aircraft (eVTOL)1 rely on simpler propulsion units (electric motors and in some cases fixed-pitch propellers). This promotes redundancy and improves tolerance to failures, in turn improving safety. The use of simpler electric propulsion units should also allow significant acquisition and operating cost reductions. Whether full-electric (relying solely on batteries) or hybrid-electric (relying on a combination of batteries, fuel-powered engines, and generators.), eVTOLs are also expected to generate less noise and air pollution than conventional aircraft with similar payloads. According to the 2019 Annual Review of IATA (International Air Transport Association) [ref.1], due to an expected increase in air transport traffic by 5% every year and a doubling of air transport passenger numbers to 8.2 billion by 2037 significant challenges are posed to the aviation industry. Furthermore, this report does not factor in the expected demand for short-range (intra-city) air transportation, which is in development and yet to be operational. The increased demand to fly creates a responsibility to expand in a sustainable manner and an endeavor to develop more environmentally-friendly aircraft. eVTOL aircraft, either piloted or autonomous, is gathering considerable interest worldwide. Modern and novel full-electric or hybrid-electric eVTOL configurations enable a new paradigm shift in air transportation as the aviation industry remains committed to its goals of carbon-neutral growth from 2020 onwards and cutting CO2 emissions to half 2005 levels by 2050. While electric power has been used for decades, recent developments in mobile electric/hybrid propulsion coupled with advanced materials and autonomous systems may create the possibility to transition into the next age of air mobility propelled by electric/hybrid VTOL aircraft technology. Although eVTOL aircraft might seem like an incremental improvement or even a counterintuitive regression with regard to past VTOL development, it has in fact the potential to transform air mobility across a wide range of government applications. Previous transformations in aviation generated dramatic leaps in performance, but the cost was commensurate with performance, limiting quantity produced. This next age appears to take a different approach. Performance may not increase, but at this moment technology is poised for future urban mobility that will spawn commercial passenger drone services, that is, autonomous (pilotless) air taxis and thereby add a new dimension to the urban transportation mix of the future [ref. 2]. Advances in electric propulsion, autonomous flight technology, and 5G communication networks will enable this fast new-growing market to become a reality. It is now time to envision the introduction of electric/hybrid eVTOL aircraft for Public Services2. We believe that in the next decades eVTOL aircraft will have the potential to become an essential tool to Public Service agencies around the world in applications such as firefighting, public safety, search and rescue, disaster relief and law enforcement. This is due to several major factors. • First, with the increasing popularity of small, unmanned aircraft vehicles (UAVs) or drones, many companies today are focusing on the development of passenger UAVs designed to accommodate up to five passengers or equivalent cargo payload. Many such configurations are electric or hybrid-electric designs with VTOL capabilities. Several of these projects have started a flight test program and many more are expected to be in the experimental and development phase in 2020. Such revolutionary vehicles could be in commercial operations by 2030. These eVTOL systems could be ready for selected Public Services missions even sooner. • Second, although these advanced eVTOL vehicles under development still need access to fuel (hybrid) and/or electric charging capability, they can take off and land from almost anywhere. Therefore, such vehicles, both manned and unmanned can be successfully integrated for the critical missions of the Public Services with extra deployment flexibilities. • Third, advancement in electric propulsion systems in the automotive industry together with NASA’s leading efforts in electrification of aircraft propulsion systems, FAA’s ongoing active eVTOL certification programs, and EASA’s proposed framework for the certification of electric/hybrid small category VTOL aircraft in Europe [ref. 3] will help accelerate industry electric propulsion system development and integration. • Finally, eVTOL vehicles could be deployed for Public Services sooner than air taxi or other commercial applications, since Public Services missions may be more easily approved based on specific mission criteria, localized airworthiness authority for public-use aircraft3, and are normally operating under centralized airspace management and control by the theater command. Moreover, public perception and acceptance are generally less of a concern when operations save lives and benefit the wider community. The prioritized introduction of eVTOL aircraft in Public Services is ambitious, but we believe it is achievable in the coming decades if fundamental enablers (people and technologies) are engaged in defining the objectives and needs of these missions. The revolution that is currently taking place in eVTOL aircraft represents an unprecedented opportunity to develop a safer, more affordable, more available and more environmentally friendly future of vertical flight. To ensure that these novel aircraft meet the future expectations of Public Services, it is essential to take a collaborative and multi-disciplinary approach to their development, across engineering disciplines, policy-making, program management, business case development, manufacturing, and flight demonstrations. It should be noted that the term eVTOL (in the near term) used throughout this publication implies aircraft capable of transporting up to 5 persons which may or may not include a pilot if operated fully autonomously, assuming an average of 200 pounds (91 kg) per person or equivalent payload and a range up to 60 miles plus a suitable reserve. Hybrid or hydrogen powered eVTOLs would have greater range. For example, a “3-seat” eVTOL aircraft may only be able to carry two fully equipped firemen, and payload capacity is more relevant when used for the supply mission. Moreover, this paper concentrates on the “last-mile” solutions with a deployment time of no more than 6 hours. Although not specifically discussed in this document, it is understood that the future of Transformative Vertical Flight in general and Public Services, in particular, will also involve smaller UAVs that will undoubtedly play a crucial role in future aerial operations. For example, smaller unmanned aircraft may be used to dispatch medical supplies, portable filtration systems or perform the Search task of future Search and Rescue (SAR) operations. Close collaboration between the aircraft industry, the Civil Aviation Authorities (CAA), e.g., Federal Aviation Administration (FAA), European Aviation Safety Agency (EASA), Transport Canada Civil Aviation (TCCA) and the Department of Defense (DoD) certifiers, will help identify Public Services requirements, define expectations and limit development cost and timescales. Take the US Air Force Agility Prime as an example, the majority of the eVTOL application opportunities and mission elements identified are in line with the NASA TVF WG-4 objectives and use cases. Together, it forms a strong partnership to accelerate the development, certification, and practical deployment for public service missions. The US Air Force Agility Prime has been a collaboration partner on this white paper, and provided valuable input and recommendations. Most of the eVTOL public service mission elements discussed in this paper and additional use cases envisioned by the NASA TVF WG-4 team are shared by the Agility Prime program. The focus and efforts of the Agility Prime in product and system development, industry and government partnership, accelerated certifications as well as early test and deployment are totally in sync with the path forward recommended by this white paper. This kind of collaboration and partnership will help enable the practical use of the eVTOL for public service missions, benefit the eVTOL public acceptance, and accelerate the eVTOL industry revolution.

Johnny T. Doo

2,5‐Dimercapto‐1,3,4‐Thiadiazole (DMCT)‐Based Polymers for Rechargeable Metal–Sulfur Batteries

Organosulfur materials are a sustainable alternative to the present-day layered oxide cathodes in lithium-based batteries. One such organosulfur material that was intensely explored from the 1990s to early 2010s is 2,5-dimercapto-1,3,4-thiadiazole (DMCT). However, research interest declined as the electrode reactions with DMCT were assumed to be too sluggish to be practical. Armed with the advances in metal–sulfur batteries, we revisit DMCT-based materials in the form of poly[tetrathio-2,5-(1,3,4-thiadiazole)], referred to as pDMCT-S. With an appropriate choice of electrode design and electrolyte, pDMCT-S cathode paired with a Li-metal anode shows a capacity of 715 mA h g −1 and a Coulombic efficiency of 97.7% at a C/10 rate, thus quelling the concerns of sluggish reactions. Surprisingly, pDMCT-S shows significantly improved long-term cyclability compared to a sulfur cathode. Investigations into the origin of the stability reveals that the discharge product Li-DMCT in its mesomeric form can strongly bind to polysulfides, preventing their dissolution into the electrolyte and shuttling. This unique mechanism solves a critical problem faced by sulfur cathodes. Encouragingly, this mechanism results in a stable performance of pDMCT-S with Na-metal cells as well. In conclusion, this study opens the potential for exploring other organic materials that have inherent polysulfide sequestering capabilities, enabling long-life metal–sulfur batteries.

2,5-dimercapto-1,3,4-thiadiazole