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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 199 records · Page 11

Conceptual design study of an improved gas turbine powertrain

The conceptual design for an improved gas turbine (IGT) powertrain and vehicle was investigated. Cycle parameters, rotor systems, and component technology were reviewed and a dual rotor gas turbine concept was selected and optimized for best vehicle fuel economy. The engine had a two stage centrifugal compressor with a design pressure ratio of 5.28, two axial turbine stages with advanced high temperature alloy integral wheels, variable power turbine nozzle for turbine temperature and output torque control, catalytic combustor, and annular ceramic recuperator. The engine was rated at 54.81 kW, using water injection on hot days to maintain vehicle acceleration. The estimated vehicle fuel economy was 11.9 km/l in the combined driving cycle, 43 percent over the 1976 compact automobile. The estimated IGT production vehicle selling price was 10 percent over the comparable piston engine vehicle, but the improved fuel economy and reduced maintenance and repair resulted in a 9 percent reduction in life cycle cost.

Chapman, W. I.↗

Observations of Ozone-aerosol Correlated Behaviour in the Lower Stratosphere During the EASOE Campaign

The question of possible interactions between ozone and stratospheric aerosol has been open for a long time. Measurements carried out after the Mt. Agung and El Chicon eruptions showed evidence of negative correlations between the presence of volcanic stratospheric aerosols and ozone concentration. Evidence for negative correlations in the polar winter has been also found. It is only after the discovery of the Antarctic ozone hole that catalytic effects related to low temperature heterogeneous chemistry have become the object of much investigation, now extended to the role of volcanic aerosol in the ozone reduction. These phenomena can be the object of various interpretations, not mutually exclusive, including the effect of transport, diffuse radiation as well as heterogeneous chemistry. The present paper provides preliminary results of simultaneous measurements of ozone and aerosol, carried out at Thule, Greenland, during the winter 1991-92. The European Stratospheric Ozone Experiment (EASOE) was aimed at monitoring the winter Arctic stratosphere in order to obtain a deeper insight of the ozone destruction processes taking place in the polar regions. A large amount of aerosol was injected into the lower stratosphere by the recent eruption of Volcano Pinatubo. A lidar system, already operational in Thule since November 1990, has provided detailed measurements of the stratospheric aerosol concentration during EASOE. In the same period, a large number of ozonesondes were launched. Although no PSC formation was detected over Thule, the simultaneous measurement of the stratospheric aerosol and ozone profiles give the possibility to study interactions occurring in the stratosphere between these two constituents.

Digirolamo, P.↗

Thermal Protection Materials for Reentry and Planetary Applications

Thermal protection materials and systems (TPS) are used to protect spacecraft during reentry into Earth's atmosphere or entry into planetary atmospheres. As such, these materials are subject to severe environments with high heat fluxes and rapid heating. Catalytic effects can increase the temperatures substantially. These materials are also subject to impact damage from micrometeorites or other debris during ascent, orbit, and descent, and thus must be able to withstand damage and function following damage. Thermal protection materials and coatings used in reusable launch vehicles will be reviewed, including the needs and directions for new materials to enable new missions that require faster turnaround and much greater reusability. The role of ablative materials for use in high heat flux environments, especially for non-reusable applications and upcoming planetary missions, will be discussed. New thermal protection system materials may enable the use of sharp nose caps and leading edges on future reusable space transportation vehicles. Vehicles employing this new technology would have significant increases in maneuverability and out-of-orbit cross range compared to current vehicles, leading to increased mission safety in the event of the need to abort during ascent or from orbit. Ultrahigh temperature ceramics, a family of materials based on HfB2and ZrB2 with SiC, will be discussed. The development, mechanical and thermal properties, and uses of these materials will be reviewed.

Johnson, Sylvia M.↗

Thermal Protection Materials for Reentry Applications

Thermal protection materials and systems (IRS) are used to protect spacecraft during reentry into Earth's atmosphere or entry into planetary atmospheres. As such, these materials are subject to severe environments with high heat fluxes and rapid heating. Catalytic effects can increase the temperatures substantially. These materials are also subject to impact damage from micrometeorites or other debris during ascent, orbit, and descent, and thus must be able to withstand damage and to function following damage. Thermal protection materials and coatings used in reusable launch vehicles will be reviewed, including the needs and directions for new materials to enable new missions that require faster turnaround and much greater reusability. The role of ablative materials for use in high heat flux environments, especially for non-reusable applications and upcoming planetary missions, will be discussed. New thermal protection system materials may enable the use of sharp nose caps and leading edges on future reusable space transportation vehicles. Vehicles employing this new technology would have significant increases in maneuverability and out-of-orbit cross range compared to current vehicles, leading to increased mission safety in the event of the need to abort during ascent or from orbit. Ultrahigh temperature ceramics, a family of materials based on HfB2 and ZrB2 with SiC, will be discussed. The development, mechanical and thermal properties, and uses of these materials will be reviewed.

Johnson, Sylvia M.↗

Stabilized tin-oxide-based oxidation/reduction catalysts

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Jordan, Jeffrey D.↗

Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

Jordan, Jeffrey D.↗

Low-temperature dechlorination of polyvinyl chloride (PVC) for production of H 2 and carbon materials using liquid metal catalysts

Polyvinyl chloride (PVC) is ubiquitous in everyday life; however, it is not recycled because it degrades uncontrollably into toxic products above 250°C. Therefore, it is of interest to controllably dechlorinate PVC at mild temperatures to generate narrowly distributed carbon materials. We present a catalytic route to dechlorinate PVC (~90% reduction of Cl content) at mild temperature (200°C) to produce gas H 2 (with negligible coproduction of corrosive gas HCl) and carbon materials using Ga as a liquid metal (LM) catalyst. A LM was used to promote intimate contact between PVC and the catalytic sites. During dechlorination of PVC, Cl is sequestrated in the carbonaceous solid product. Later, chlorine is easily removed with an acetone wash at room temperature. The Ga LM catalyst is reusable, outperforms a traditional supported metal catalyst, and successfully converts (untreated) discarded PVC pipe.

36 MATERIALS SCIENCE↗

Process of forming catalytic surfaces for wet oxidation reactions

A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

Jagow, R. B.↗

Stability of Titanium Nitride and Titanium Carbide When Exposed to Hydrogen Atoms from 298 to 1950 K

Titanium nitride and titanium carbide deposited on tungsten wires were exposed to hydrogen atoms (10(exp -4) atm pressure) produced by the action of microwave radiation on molecular hydrogen. The results of these experiments in the temperature range 298 to 1950 K indicate that no appreciable reaction takes place between atomic hydrogen and TiN or TiC. The formation of reaction products (NH3, CH4, C2H2) should be favored at lower temperatures. However, because of the high catalytic activity of Ti for H atom recombination, the rate of such reactions with H atoms is controlled by the rate of evaporation of Ti from the surface, this rate being low at temperatures below 1200 K. In order to interpret the stability of TiN and TiC in H atoms more fully, the stability of TiN and TiC in vacuum and H2 gas was also studied. The thermodynamic computations conform in order of magnitude to the experimentally found rates of decomposition of TiN and TiC in vacuum and are also consistent with the fact that no appreciable reaction is found with these compounds in molecular H2 at a pressure of 10(exp -3) atmosphere in the temperature range 2980 to 2060 K. When TiN or TiC was heated in atomic H or molecular H2, no reaction products other than those obtained from the simple decomposition of the nitride and carbide were observed. The gaseous products were analyzed in a mass spectrometer.

Philipp, Warren H.↗

Thermally stable porous catalyst systems and methods to produce the same

This disclosure provides compositions and methods directed to thermally stable catalyst systems, which display stable physical properties and/or stable catalytic properties after thermal pretreatment at a temperature in the range of about 600° C. to about 1000° C. The catalyst systems include metal particles which contain a stable metal and a catalytic metal deposited on a porous support. Embodiments of the disclosure include catalyst systems that can be used in high temperature applications such as the hybrid sulfur cycle. The hybrid sulfur cyclic is an elevated temperature and high acid reaction that may be conducted using concentrated sulfuric acid heated to 800° C. Embodiments of the disclosure can provide thermally stable catalysts and methods to produce thermally stable catalysts that remain active for at least 80 hours' exposure to these harsh conditions.

Monnier, John↗

Catalytic Microtube Rocket Igniter

Devices that generate both high energy and high temperature are required to ignite reliably the propellant mixtures in combustion chambers like those present in rockets and other combustion systems. This catalytic microtube rocket igniter generates these conditions with a small, catalysis-based torch. While traditional spark plug systems can require anywhere from 50 W to multiple kW of power in different applications, this system has demonstrated ignition at less than 25 W. Reactants are fed to the igniter from the same tanks that feed the reactants to the rest of the rocket or combustion system. While this specific igniter was originally designed for liquid methane and liquid oxygen rockets, it can be easily operated with gaseous propellants or modified for hydrogen use in commercial combustion devices. For the present cryogenic propellant rocket case, the main propellant tanks liquid oxygen and liquid methane, respectively are regulated and split into different systems for the individual stages of the rocket and igniter. As the catalyst requires a gas phase for reaction, either the stored boil-off of the tanks can be used directly or one stream each of fuel and oxidizer can go through a heat exchanger/vaporizer that turns the liquid propellants into a gaseous form. For commercial applications, where the reactants are stored as gases, the system is simplified. The resulting gas-phase streams of fuel and oxidizer are then further divided for the individual components of the igniter. One stream each of the fuel and oxidizer is introduced to a mixing bottle/apparatus where they are mixed to a fuel-rich composition with an O/F mass-based mixture ratio of under 1.0. This premixed flow then feeds into the catalytic microtube device. The total flow is on the order of 0.01 g/s. The microtube device is composed of a pair of sub-millimeter diameter platinum tubes connected only at the outlet so that the two outlet flows are parallel to each other. The tubes are each approximately 10 cm long and are heated via direct electric resistive heating. This heating brings the gasses to their minimum required ignition temperature, which is lower than the auto-thermal ignition temperature, and causes the onset of both surface and gas phase ignition producing hot temperatures and a highly reacting flame. The combustion products from the catalytic tubes, which are below the melting point of platinum, are injected into the center of another combustion stage, called the primary augmenter. The reactants for this combustion stage come from the same source but the flows of non-premixed methane and oxygen gas are split off to a secondary mixing apparatus and can be mixed in a near-stoichiometric to highly lean mixture ratio. The primary augmenter is a component that has channels venting this mixed gas to impinge on each other in the center of the augmenter, perpendicular to the flow from the catalyst. The total crosssectional area of these channels is on a similar order as that of the catalyst. The augmenter has internal channels that act as a manifold to distribute equally the gas to the inward-venting channels. This stage creates a stable flame kernel as its flows, which are on the order of 0.01 g/s, are ignited by the combustion products of the catalyst. This stage is designed to produce combustion products in the flame kernel that exceed the autothermal ignition temperature of oxygen and methane.

Schneider, Steven J.↗

Linking low and high temperature NO oxidation mechanisms over Brønsted acidic chabazite to dynamic changes of the active site

The oxidation of NO over Brønsted acid sites in chabazite (CHA) zeolites shows an atypical temperature dependence; at low temperature the apparent activation energy is negative, but it becomes positive as the temperature exceeds a transition temperature. To explain this behavior we used density functional theory and statistical mechanics to investigate high and low temperature mechanisms for this reaction and propose a dynamic active site change in response to temperature variation. Our simulations show that the apparent activation barrier in the low temperature regime is more negative over Brønsted acidic CHA as compared to the siliceous zeolite framework. This effect is attributed to further enthalpic stabilization of the transition states by physical interaction with the H-CHA Brønsted acid sites. At elevated temperature, our calculations support both the existence and the significant catalytic role of NO+ in providing a modified active site. The temperature dependent transformation of the active site from H-CHA to NO-CHA sites may occur via two plausible ion-exchange mechanisms that define a transition temperature for the reaction. This transition temperature can be tuned by incorporating different trivalent metal atoms (B, Al, Ga or In) within the CHA framework. We found the lowest transition temperature for H-[In] CHA and H-[Ga]CHA. Here, the ability to control the dynamic response of the active site and the associated switch between low and high temperature mechanism with negative and positive apparent activation energy, respectively, is of fundamental interest for the design of zeolite catalysts operating in the presence of NO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The effect of catalyst length and downstream reactor distance on catalytic combustor performance

A study was made to determine the effects on catalytic combustor performance which resulted from independently varying the length of a catalytic reactor and the length available for gas-phase reactions downstream of the catalyst. Monolithic combustion catalysts from three manufacturers were tested in a combustion test rig with no. 2 diesel fuel. Catalytic reactor lengths of 2.5 and 5.4 cm, and downstream gas-phase reaction distances of 7.3, 12.4, 17.5, and 22.5 cm were evaluated. Measurements of carbon monoxide, unburned hydrocarbons, nitrogen oxides, and pressure drop were made. The catalytic-reactor pressure drop was less than 1 percent of the upstream total pressure for all test configurations and test conditions. Nitrogen oxides and unburned hydrocarbons emissions were less than 0.25 g NO2/kg fuel and 0.6 g HC/kg fuel, respectively. The minimum operating temperature (defined as the adiabatic combustion temperature required to obtain carbon monoxide emissions below a reference level of 13.6 g CO/kg fuel) ranged from 1230 K to 1500 K for the various conditions and configurations tested. The minimum operating temperature decreased with increasing total (catalytic-reactor-plus-downstream-gas-phase-reactor-zone) residence time but was independent of the relative times spent in each region when the catalytic-reactor residence time was greater than or equal to 1.4 ms.

Anderson, D.↗

Low-Temperature Processing of Pyrolysis Bio-Oil for Sustainable Biographite Production

Catalytic graphitization of pyrolysis bio-oil with iron (Fe) can produce an anode material for lithium-ion batteries (LIBs) at a moderate temperature. The key challenge to scaling up the process is foaming, which occurs due to the oxidation of Fe by the organic acids present in bio-oil. This study explored five different pathways to control foaming in bio-oil upon Fe addition, including (i) defoamers use, (ii) use of iron oxide (Fe2O3) as graphitization catalyst, (iii) pH adjustment of bio-oil, (iv) bio-oil coking (300-500 degrees C), and (v) low-temperature pretreatment of bio-oil (150-200 degrees C). The low-temperature pretreatment successfully avoided foaming by removing the volatile acids in bio-oil. The bio-oil was solidified and powdered for even mixing with the Fe catalyst. The biographite catalytically prepared at 1500 degrees C following this pathway demonstrated nearly theoretical specific gravimetric capacity (~370 mAh/g), high initial Coulombic efficiency (90.03%), and minimal capacity fading after 50 cycles in LIB half-cells. The low-temperature pretreatment pathway also addressed the viscosity, swelling, and aging issues associated with bio-oil processing and will make scale-up endeavors more attainable.

09 BIOMASS FUELS↗

Thermochemical Instabilities at High Temperature Ceramic Surfaces

The surface of silicon-based high temperature ceramics exhibits thermochemical instabilities when exposed to oxygen-rich high enthalpy flows. These instabilities manifest as sudden temperature jumps of several hundred degrees and rapid material failure, when temperatures exceed 2000 K. Understanding and predicting these phenomena is critical to the design of thermal protection systems for sustained high speed flight vehicles. In this talk we review a series of test cases where surface temperature jumps were observed during plasmatron wind tunnel testing of ceramic materials, including ZrB2-SiC ultra-high temperature ceramics, C/SiC ceramic matrix composites, and silicone-based coatings for low-density carbon phenolic ablators. The underlying physical processes occurring when Si-containing ceramics are exposed to high enthalpy air flow include formation of passivating scales at low temperatures, passive to active oxidation transition, melting of oxide scales, changes in surface radiative properties, formation of porosity and changes in effective conductivity, surface catalytic recombination and transitions in catalytic properties, as well as high-temperature phase changes. The role of these processes in promoting thermochemical instabilities for the different material systems is discussed.

Ultra High Temperature Ceramics, UHTC↗

Catalytic trimerization of aromatic nitriles and triaryl-s-triazine ring cross-linked high temperature resistant polymers and copolymers made thereby

Triazine compounds and cross-linked polymer compositions are made by heating aromatic nitriles to a temperature in the range of from about 100 C to about 700 C, and preferably in the range of from about 200 C to about 350 C, in the presence of a catalyst or mixture of catalysts selected from one or more of the following groups: (1) organic sulfonic and sulfinic acids, (2) organic phosphonic and phosphinic acids, and (3)metallic acetylacetonates, at a pressure in the range of from about atmospheric pressure to about 10,000 psi and preferably in the range of from about 200 psi to about 750 psi. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers are made which are trimerized with or without a filler by the aforementioned catalytic trimerization process into triaryl-s-triazine ring containing or cross-linked polymeric or copolymeric products useful in applications requiring high thermal-oxidative stability and high performance structural properties at elevated temperatures.

Hsu, L. C.↗

Divanadium substituted keggin [PV 2 W 10 O 40 ] on non-reducible supports-Al 2 O 3 and SiO 2 : synthesis, characterization, and catalytic properties for oxidative dehydrogenation of propane

Molecular metal oxide cluster, K 5 [α-1,2-PV 2 W 10 O 40 ] (PV 2 W 10 ), was found to have intrinsic catalytic activity for the oxidative dehydrogenation of propane with high selectivity (> 80%) to propylene at low propane conversion (0.3%). Synthesis of dispersed PV 2 W 10 in non-reducible supports, γ-Al 2 O 3 and SiO 2 , was done by incipient wetness impregnation. The supported catalysts were characterized by IR, Raman spectroscopy, nitrogen adsorption, x-ray powder diffraction (PXRD), elemental analysis, hydrogen temperature-programmed reduction (H 2 –TPR), and ammonia temperature-programmed desorption (NH 3 –TPD). Catalytic testing of the supported PV 2 W 10 at equimolar cluster concentration revealed that when supported in γ-Al 2 O 3 it is more active (sevenfold increase in propane conversion) but in SiO 2 it is more selective to propylene (94%). The observed performance was due to both an increase in reducibility and higher concentration of strong acid sites for PV 2 W 10 supported in γ-Al 2 O 3 versus SiO 2 . Lastly, PV 2 W10 was shown to remain intact under reaction conditions indicating its thermal and oxidative stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multivariate Bayesian Optimization of CoO Nanoparticles for CO 2 Hydrogenation Catalysis

The hydrogenation of CO 2 holds promise for transforming the production of renewable fuels and chemicals. However, the challenge lies in developing robust and selective catalysts for this process. Transition metal oxide catalysts, particularly cobalt oxide, have shown potential for CO 2 hydrogenation, with performance heavily reliant on crystal phase and morphology. Achieving precise control over these catalyst attributes through colloidal nanoparticle synthesis could pave the way for catalyst and process advancement. Yet, navigating the complexities of colloidal nanoparticle syntheses, governed by numerous input variables, poses a significant challenge in systematically controlling resultant catalyst features. We present a multivariate Bayesian optimization, coupled with a data-driven classifier, to map the synthetic design space for colloidal CoO nanoparticles and simultaneously optimize them for multiple catalytically relevant features within a target crystalline phase. The optimized experimental conditions yielded small, phase-pure rock salt CoO nanoparticles of uniform size and shape. These optimized nanoparticles were then supported on SiO 2 and assessed for thermocatalytic CO 2 hydrogenation against larger, polydisperse CoO nanoparticles on SiO 2 and a conventionally prepared catalyst. The optimized CoO/SiO 2 catalyst consistently exhibited higher activity and CH 4 selectivity (ca. 98%) across various pretreatment reduction temperatures as compared to the other catalysts. This remarkable performance was attributed to particle stability and consistent H* surface coverage, even after undergoing the highest temperature reduction, achieving a more stable catalytic species that resists sintering and carbon occlusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗