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At least 343 records · Page 19

Improved hybrid rocket fuel

McDonnell Douglas Aerospace, as part of its Independent R&D, has initiated development of a clean burning, high performance hybrid fuel for consideration as an alternative to the solid rocket thrust augmentation currently utilized by American space launch systems including Atlas, Delta, Pegasus, Space Shuttle, and Titan. It could also be used in single stage to orbit or as the only propulsion system in a new launch vehicle. Compared to solid propellants based on aluminum and ammonium perchlorate, this fuel is more environmentally benign in that it totally eliminates hydrogen chloride and aluminum oxide by products, producing only water, hydrogen, nitrogen, carbon oxides, and trace amounts of nitrogen oxides. Compared to other hybrid fuel formulations under development, this fuel is cheaper, denser, and faster burning. The specific impulse of this fuel is comparable to other hybrid fuels and is between that of solids and liquids. The fuel also requires less oxygen than similar hybrid fuels to produce maximum specific impulse, thus reducing oxygen delivery system requirements.

Dean, David L.↗

A Novel Unitized Regenerative Proton Exchange Membrane Fuel Cell

A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel single cell unitized regenerative fuel cell and results obtained on testing it are presented.

Murphy, O. J.↗

History of Ozone Research: From Schonbein to the Present

In 1840, C.F. Schonbein recognized that the smell generated in several different electrical and chemical processes was a single substance. He named this substance "ozein" from the Greek for "to smell". This substance we know today as ozone. Several periods can be distinguished in the continued development of our understanding of ozone. Throughout the late 19th century, the identity and properties of ozone were established and described. Ozone was recognized to be a constituent of normal air and tests were established to measure its concentration. Its disinfectant properties were recognized. New methods were developed for making ozone in the laboratory. In 1879, ultraviolet spectroscopic techniques were applied to the measurement of the solar spectrum and it was discovered by Comu that the spectrum was cut off at about 300 nm wavelength. Hartley suggested, based on laboratory measurements, that this cutoff was due to ozone in the atmosphere which he correctly asserted was somewhere in the upper atmosphere. This began the period of development of the amount and distribution of ozone throughout the atmosphere. In 1930, Chapman put forward the first theory of the formation and destruction of ozone. By the mid-1960s it was becoming obvious that the description of the chemical loss term was inadequate. By the early 1970s the chemical destruction of ozone by the oxides of hydrogen, nitrogen, chlorine, and bromine was recognized as an essential element in the chemical balance determining the ozone concentration. Today, ozone is a broad research project which crosses the boundaries of traditional disciplines. Stratospheric ozone loss due to chlorofluorocarbons is a newsworthy item. The Antarctic ozone hole opens up every spring. The provisions of the Montreal Protocol were agreed upon by countries around the world and promise to reduce the future levels of ozone-destroying chlorine in the stratosphere. Ozone concentrations in polluted cities are a subject of local and national regulations to limit its potential for causing health problems and corrosive effects on materials. A lot is known about ozone but many new questions are still being developed.

Stolarski, Richard S.↗

Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF

We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These studies form the necessary precursors to the development of compact, lightweight stable isotope/trace gas sensors for future planetary missions.

Blake, Geoffrey A.↗

Corrosive Space Gas Restores Artwork, Promises Myriad Applications

Atomic oxygen's unique characteristic of oxidizing primarily hydrogen, carbon, and hydrocarbon polymers at surface levels has been applied in the restoration of artwork, detection of document forgeries, and removal of bacterial contaminants from surgical implants. The Electro-Physics Branch at Glenn Research Center built on corrosion studies of long-duration coatings for use in space, and applied atomic oxygen's selectivity to instances where elements need to be removed from a surface. Atomic oxygen is able to remove organic compounds high in carbon (mostly soot) from fire-damaged artworks without causing a shift in the paint color. First successfully tested on oil paintings, the team then applied the restoration technique to acrylics, watercolors, and ink. The successful art restoration process was well-publicized, and soon a multinational, nonprofit professional organization dedicated to the art of forensic analysis of documents had successfully applied this process in the field of forgery detection. The gas has biomedical applications as well-Atomic Oxygen technology can be used to decontaminate orthopedic surgical hip and knee implants prior to surgery, and additional collaborative research between the Cleveland Clinic Foundation and the Glenn team shows that this gas's roughening of surfaces improves cell adhesion, which is important for the development of new drugs.

Source record↗

Miniaturized Hollow-Waveguide Gas Correlation Radiometer (GCR) for Trace Gas Detection in the Martian Atmosphere

Gas correlation radiometry (GCR) has been shown to be a sensitive and versatile method for detecting trace gases in Earth's atmosphere. Here, we present a miniaturized and simplified version of this instrument capable of mapping multiple trace gases and identifying active regions on the Mars surface. Reduction of the size and mass of the GCR instrument has been achieved by implementing a lightweight, 1 mm inner diameter hollow-core optical fiber (hollow waveguide) for the gas correlation cell. Based on a comparison with an Earth orbiting CO2 gas correlation instrument, replacement of the 10 meter mUltipass cell with hollow waveguide of equivalent pathlength reduces the cell mass from approx 150 kg to approx 0.5 kg, and reduces the volume from 1.9 m x 1.3 m x 0.86 m to a small bundle of fiber coils approximately I meter in diameter by 0.05 m in height (mass and volume reductions of >99%). This modular instrument technique can be expanded to include measurements of additional species of interest including nitrous oxide (N2O), hydrogen sulfide (H2S), methanol (CH3OH), and sulfur dioxide (SO2), as well as carbon dioxide (CO2) for a simultaneous measure of mass balance.

Wilson, Emily L.↗

Miniaturized Gas Correlation Radiometer for the Detection of Trace Gases in the Martian Atmosphere

We present a miniaturized and simplified version of a gas correlation radiometer (GCR) capable of simultaneously mapping multiple trace gases and identifying active regions on the Mars surface. Gas correlation radiometry (GCR) has been shown to be a sensitive and versatile method for detecting trace gases in Earth's atmosphere. Reduction of the size and mass of the GCR was achieved by implementing compact, light-weight 1 mm inner diameter hollow-core optical fibers (hollow waveguides) as the gas correlation cells. In a comparison with an Earth orbiting CO2 GCR instrument, exchanging the 10 m multipass cells with hollow waveguide gas correlation cells of equivalent path length reduces the mass from approximately 150 kg to approximately 0.5 kg, and reduces the volume from 1.9 m x 1.3 m x 0.86 m to a small bundle of fiber coils approximately 1 meter in diameter by 0.05 m in height (mass and volume reductions of greater than 99%). A unique feature of this instrument is its stackable module design, with a single module for each trace gas. Each of the modules is self-contained, and fundamentally identical; differing by the bandpass filter wavelength range and gas mixtures inside the hollow-waveguide absorption cells. The current configuration contains four stacked modules for simultaneous measurements of methane (CH4), formaldehyde (H2CO), water vapor (H2O), and deuterated water vapor (HDO) but could easily be expanded to include measurements of additional species of interest including nitrous oxide (N2O), hydrogen sulfide (H2S), methanol (CH3OH), and sulfur dioxide (SO2), as well as carbon dioxide (CO2) for a simultaneous measure of mass balance. Preliminary results indicate that a 1 ppb detection limit is possible for both formaldehyde and methane with one second of averaging. Using non-optimized components, we have demonstrated an instrument sensitivity equivalent to approximately 30 ppb for formaldehyde, and approximately 500 ppb for methane. We expect custom bandpass filters and 6 m long waveguides to significantly improve these promising results. Ongoing testing is being conducted on water vapor and deuterated water vapor.

Melroy, Hilary R.↗

Novel Catalysts and Processing Technologies for Production of Aerospace Fuels from Non-Petroleum Raw Materials

Transportation fuels production (including aerospace propellants) from non-traditional sources (gases, waste materials, and biomass) has been an active area of research and development for decades. Reducing terrestrial waste streams simultaneous with energy conversion, plentiful biomass, new low-cost methane sources, and/or extra-terrestrial resource harvesting and utilization present significant technological and business opportunities being realized by a new generation of visionary entrepreneurs. We examine several new approaches to catalyst fabrication and new processing technologies to enable utilization of these non-traditional raw materials. Two basic processing architectures are considered: a single-stage pyrolysis approach that seeks to basically re-cycle hydrocarbons with minimal net chemistry or a two-step paradigm that involves production of supply or synthesis gas (mainly carbon oxides and hydrogen) followed by production of fuel(s) via Sabatier or methanation reactions and/or Fischer-Tropsch synthesis. Optimizing the fraction of product stream relevant to targeted aerospace (and other transportation) fuels via modeling, catalyst fabrication and novel reactor design are described. Energy utilization is a concern for production of fuels for either terrestrial or space operations; renewable sources based on solar energy and/or energy efficient processes may be mission enabling. Another important issue is minimizing impurities in the product stream(s), especially those potentially posing risks to personnel or operations through (catalyst) poisoning or (equipment) damage. Technologies being developed to remove (and/or recycle) heteroatom impurities are briefly discussed as well as the development of chemically robust catalysts whose activity are not diminished during operation. The potential impacts on future missions by such new approaches as well as balance of system issues are addressed.

propellants↗

Impact Delivery of Reduced Greenhouse Gases on Early MARS

While there is abundant evidence for flowing liquid water on the ancient Martian surface, a widely accepted greenhouse mechanism for explaining this in the presence of a faint young sun has yet to emerge. Gases such as NH3, CO2 alone, SO2, clouds, and CH4, have sustainability issues or limited greenhouse power. Recently, Ramirez et al. proposed that CO2-H2 atmospheres, through collision induced absorptions (CIA), could solve the problem if large amounts are present (1.3-4 bars of CO2, 50-20% H2). However, they had to estimate the strength of the H2- CO2 interaction from the measured strength of the H2- N2 interaction. Recent ab initio calculations show that the strength of CO2-H2 CIA is greater than Ramirez et al. assumed. Wordsworth et al. also calculated the absorption coefficients for CO2-CH4 CIA and show that on early Mars a 0.5 bar CO2 atmosphere with percent levels of H2 or CH4 can raise mean annual temperatures by tens of degrees Kelvin. Freezing temperatures can be reached in atmospheres containing 1-2 bars of CO2 and 2-10% H2 and CH4. The new work demonstrates that less CO2 and reduced gases are needed than Ramirez et al. originally proposed, which improves prospects for their hypothesis. If thick weakly reducing atmospheres are the solution to the faint young sun paradox, then plausible mechanisms must be found to generate and sustain the required concentrations of H2 and CH4. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolysis, oxidation, and hydrogen escape. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks.

Martian surface↗

Single Atom Catalysis: An Analogy between Heterogeneous and Homogeneous Catalysts

In recent years, enormous efforts have been invested to improve the atom-efficiency of metal catalysts by decrease the size of metal particles to the limit of isolated atoms in heterogenous catalysis, termed single atom catalysts (SACs). In addition to being atom-efficient, these SACs are increasingly gaining attention due to the unique reactivity and selectivity they have exhibited in industrially relevant reactions, including both oxidation and hydrogenation reactions. Clear parallels can be drawn between heterogeneous SACs and their analogous homogeneous catalysts. In this chapter, we highlight SACs that demonstrate this relationship and report on relevant, recent developments in the field of single atom catalysis.

Yuk, Simuck F.↗

Ultrastable rechargeable manganese battery with solid-liquid-gas reactions

A rechargeable manganese battery includes: (1) a first electrode including a porous, conductive support; (2) a second electrode including a catalyst support and a catalyst disposed over the catalyst support; and (3) an electrolyte disposed between the first electrode and the second electrode to support reversible precipitation and dissolution of manganese at the first electrode and reversible evolution and oxidation of hydrogen at the second electrode.

Chen, Wei↗

Ultrastable rechargeable manganese battery with solid-liquid-gas reactions

A rechargeable manganese battery includes: (1) a first electrode including a porous, conductive support; (2) a second electrode including a catalyst support and a catalyst disposed over the catalyst support; and (3) an electrolyte disposed between the first electrode and the second electrode to support reversible precipitation and dissolution of manganese at the first electrode and reversible evolution and oxidation of hydrogen at the second electrode.

Chen, Wei↗

Oxidizer Selection for the ISTAR Program (Liquid Oxygen versus Hydrogen Peroxide)

This paper discusses a study of two alternate oxidizers, liquid oxygen and hydrogen peroxide, for use in a rocket based combined cycle (RBCC) demonstrator vehicle. The flight vehicle is baselined as an airlaunched self-powered Mach 0.7 to 7 demonstration of an RBCC engine through all or its air breathing propulsion modes. Selection of an alternate oxidizer has the potential to lower overall vehicle size, system complexity/ cost and ultimately the total program risk. This trade study examined the oxidizer selection effects upon the overall vehicle performance, safety and operations. After consideration of all the technical and programmatic details available at this time, 90% hydrogen peroxide was selected over liquid oxygen for use in this program.

Quinn, Jason Eugene↗

PtRu Catalysts on Nitrogen-Doped Carbon Nanotubes with Conformal Hydrogenated TiO 2 Shells for Methanol Oxidation

The methanol oxidation reaction (MOR) is the limiting factor in direct methanol fuel cells (DMFC). There is an urgent need to improve the catalytic activity and stability of MOR catalysts. This study reports a highly active PtRu catalyst for MOR based on a hybrid multifunctional catalyst support consisting of a conformal amorphous hydrogenated TiO 2 shell wrapped around the oxygenated N-doped carbon nanotube core, denoted as PtRu/TiO 2 / ONCNT-400. Both the TiO 2 shell and the subsequent PtRu nanoparticles are deposited by a rapid microwave-assisted synthesis processes. The hydrogenated TiO 2 shell is found to exhibit a strong interaction with the deposited PtRu catalyst nanoparticles and effectively prevent them from agglomeration during the postdeposition thermal annealing to form more active crystalline PtRu alloy catalysts. In addition, the defective hydrogenated TiO 2 shell enhances the PtRu catalyst activity by the synergistic effects of partial charge transfer from TiO 2 to PtRu and high oxophilicity, which improves the kinetics of oxidation of poisonous CO intermediate to CO 2 . The mass activity for MOR and long-cycling stability of the PtRu/TiO 2 /ONCNT-400 catalyst surpass the two benchmark commercial PtRu/C catalysts from Johnson Matthey (JM) and Tanaka KiKinzoku (TKK), respectively. Furthermore, the results demonstrate that PtRu/TiO 2 /ONCNT-400 can serve as an efficient catalyst for MOR in DMFC.

36 MATERIALS SCIENCE↗

A surface acoustic wave hydrogen sensor with tin doped indium oxide layers for intermediate temperatures

We report high temperature surface acoustic wave (SAW) gas sensors with conducting sensing layers require tuning of the sheet conductivity for optimal response. Conducting metal oxides are attractive sensing materials for their tunable electronic properties and high thermal stability, amongst others. Here, we have investigated the application of indium oxide (IO) and indium tin oxide (ITO) films on langasite (LGS)-based SAW reflective delay line sensor devices for monitoring hydrogen at 350 °C. Specifically, we modeled the effect of the IO and ITO sensing layer thickness on the wave velocity, attenuation, and effective electromechanical coefficient. This was followed by an experimental demonstration of tuning of the ITO film sheet conductivity by controlling the dopant concentration and yielding an improvement in the sensor sensitivity. The current study provides a pathway towards the development of conductivity-based sensing layers for high temperature SAW gas sensors with improved sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cost analysis of hydrogen production by high-temperature solid oxide electrolysis

In this study, we estimate construction and operation costs of gigawatt-scale solid oxide electrolysis (SOE) facilities for producing high purity hydrogen gas from water. Manufacturing and assembly costs for two types of SOE cell stacks are estimated using a detailed design for manufacture and assembly (DFMA®) analysis. Modular balance of plant (BOP) process equipment is designed and sized with Aspen®, and cost estimated using equipment vendor quotes. Factory and on-site assembly and installation costs for SOEC stack and BOP equipment integration into modular SOE process units are calculated using a simplified DFMA® method. Total stack costs on a stack input power (SIP) basis reduce to <$100/kW e DC SIP for >500 MW e DC SIP /year production rates with electrode cermet, interconnects, and high-temperature heat treatments dominating the total cost. Integration of stacks with larger BOP equipment operating at higher pressures offers ~36% cost reduction in total facility capital cost due to an economies of physical scale effect since BOP equipment comprises >50% of facility costs. Optimized H 2 prices decrease from ~$\$$4/kgH 2 to ~$\$$2/kgH 2 for 1 GWe DCSIP facilities using $\$$0.025/kWh electricity price. All costs are reported in 2021 US dollars.

08 HYDROGEN↗

Surface Processes Control the Fate of Reactive Oxidants Generated by Electrochemical Activation of Hydrogen Peroxide on Stainless-Steel Electrodes

Low-cost stainless-steel electrodes can activate hydrogen peroxide (H 2 O 2 ) by converting it into a hydroxyl radical ( • OH) and other reactive oxidants. At an applied potential of +0.020 V, the stainless-steel electrode produced • OH with a yield that was over an order of magnitude higher than that reported for other systems that employ iron oxides as catalysts under circumneutral pH conditions. Decreasing the applied potential at pH 8 and 9 enhanced the rate of H 2 O 2 loss by shifting the process to a reaction mechanism that resulted in the formation of an Fe(IV) species. Significant metal leaching was only observed under acidic pH conditions (i.e., at pH <6), with the release of dissolved Fe and Cr occurring as the thickness of the passivation layer decreased. Despite the relatively high yield of • OH production under circumneutral pH conditions, most of the oxidants were scavenged by the electrode surface when contaminant concentrations comparable to those expected in drinking water sources were tested. The stainless-steel electrode efficiently removed trace organic contaminants from an authentic surface water sample without contaminating the water with Fe and Cr. With further development, stainless-steel electrodes could provide a cost-effective alternative to other H 2 O 2 activation processes, such as those by ultraviolet light.

42 ENGINEERING↗

Ultra-high efficiency hydrogen production using a large-scale solid oxide electrolysis cell system

Efficient and cost-effective production of clean hydrogen is key to decarbonizing the production of hard-to-abate industries, such as chemicals, fuels, steel, cement and many other commodities that form the basis of modern societies. High-temperature steam electrolysis (HTSE) has recently become commercially available and offers opportunities for producing hydrogen at higher efficiency and lower cost than competing low temperature technologies. In this work, we report world record setting hydrogen production efficiency from large-scale prototype HTSE systems based on solid oxide electrolysis cell (SOEC) technology. Independent tests performed at Idaho National Laboratory (INL) employed a Bloom Energy 100 kW SOEC system to achieve a hydrogen production direct current specific electric energy consumption as low as 36.7 kWh per kilogram of hydrogen. Remarkably, similar high efficiencies in the range of 36–39 kW/kg-H2 were obtained over a wide range of hydrogen production rates and even during dynamic ramping as the hydrogen production and electric power consumption of the system were varied between 20 % and 100 % of nominal conditions. Furthermore, these test results validate previous projections that commercial SOEC systems can produce clean hydrogen at efficiencies approaching 100 % for less than 2 U S. dollars per kilogram when located near sources of inexpensive, low-grade heat and clean electricity.

08 HYDROGEN↗