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At least 181 records · Page 10

Miniaturized metal (metal alloy)/ PdO.sub.x/SiC hydrogen and hydrocarbon gas sensors

A miniaturized Schottky diode hydrogen and hydrocarbon sensor and the method of making same is disclosed and claimed. The sensor comprises a catalytic metal layer, such as palladium, a silicon carbide substrate layer and a thin barrier layer in between the catalytic and substrate layers made of palladium oxide (PdO.sub.x ). This highly stable device provides sensitive gas detection at temperatures ranging from at least 450 to 600.degree. C. The barrier layer prevents reactions between the catalytic metal layer and the substrate layer. Conventional semiconductor fabrication techniques are used to fabricate the small-sized sensors. The use of a thicker palladium oxide barrier layer for other semiconductor structures such as a capacitor and transistor structures is also disclosed.

Hunter, Gary W.↗

Onboard hydrogen generation for automobiles

Problems concerning the use of hydrogen as a fuel for motor vehicles are related to the storage of the hydrogen onboard a vehicle. The feasibility is investigated to use an approach based on onboard hydrogen generation as a means to avoid these storage difficulties. Two major chemical processes can be used to produce hydrogen from liquid hydrocarbons and methanol. In steam reforming, the fuel reacts with water on a catalytic surface to produce a mixture of hydrogen and carbon monoxide. In partial oxidation, the fuel reacts with air, either on a catalytic surface or in a flame front, to yield a mixture of hydrogen and carbon monoxide. There are many trade-offs in onboard hydrogen generation, both in the choice of fuels as well as in the choice of a chemical process. Attention is given to these alternatives, the results of some experimental work in this area, and the combustion of various hydrogen-rich gases in an internal combustion engine.

Houseman, J.↗

Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

Sermon, Paul A.↗

Review of HxPyOz-Catalyzed H + OH Recombination in Scramjet Nozzle Expansions; and Possible Phosphoric Acid Enhancement of Scramjet Flameholding, from Extinction of H3PO4 + H2 - Air Counterflow Diffusion Flames

Recent detailed articles by Twarowski indicate that small quantities of phosphorus oxides and acids in the fuel-rich combustion products of H2 + phosphine (PH3) + air should significantly catalyze H, OH and O recombination kinetics during high-speed nozzle expansions -- to reform H2O, release heat, and approach equilibrium more rapidly and closely than uncatalyzed kinetics. This paper is an initial feasibility study to determine (a) if addition of phosphoric acid vapor (H3PO4) to a H2 fuel jet -- which is much safer than using PH3 -- will allow combustion in a high-speed scramjet engine test without adverse effects on localized flameholding, and (b) if phosphorus-containing exhaust emissions are environmentally acceptable. A well-characterized axisymmetric straight-tube opposed jet burner (OJB) tool is used to evaluate H3PO4 addition effects on the air velocity extinction limit (flame strength) of a H2 versus air counterflow diffusion flame. Addition of nitric oxide (NO), also believed to promote catalytic H-atom recombination, was evaluated for comparison. Two to five mass percent H3PO4 in the H2 jet increased flame strength 4.2%, whereas airside addition decreased it 1%. Adding 5% NO to the H2 caused a 2% decrease. Products of H-atom attack on H3PO4 produced an intense green chemiluminescence near the stagnation point. The resultant exothermic production of phosphorus oxides and acids, with accelerated H-atom recombination, released sufficient heat near the stagnation point to increase flame strength. In conclusion, the addition of H3PO4 vapor (or more reactive P sources) to hydrogen in scramjet engine tests may positively affect flameholding stability in the combustor and thrust production during supersonic expansion -- a possible dual benefit with system design / performance implications. Finally, a preliminary assessment of possible environmental effects indicates that scramjet exhaust emissions should consist of phosphoric acid aerosol, with gradual conversion to phosphate aerosol. This is compared to various natural abundances and sources.

Pellett, Gerald↗

Chemical evolution. XL - Clay-mediated oxidation of diaminomaleonitrile

The inhibition of the oligomerization of HCN by montmorillonite clays is shown to be caused by oxidation of diaminomaleonitrile (DAMN) by ferric ion in the clay lattice, with ferrous ion and oxalic acid the reaction products. It is demonstrated that diiminosuccinonitrile is the initial reaction product and is rapidly hydrolized to oxalic acid and HCN. The same oxidative transformations are effected by ferric ion bound to Dowex 50, ferric ion in solution, and Ni(NH3)6(2+). The rate of reaction of DAMN indicates no catalytic role for the clay in the oxidation of DAMN, and little reaction of the latter was observed with montmorillonite in which the bulk of the iron was in the divalent state. The possible significance of these redox reactions to chemical evolution is discussed.

Ferris, J. P.↗

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

Huang, C. J.↗

Pretreatment of Platinum/Tin Oxide-Catalyst

Addition of CO to He pretreatment doubles catalytic activity. In sealed, high-energy, pulsed CO2 laser, CO and O2 form as decomposition products of CO2 in laser discharge zone. Products must be recombined, because oxygen concentration of more than few tenths of percent causes rapid deterioration of power, ending in unstable operation. Promising low-temperature catalyst for combining CO and O2 is platinum on tin oxide. New development increases activity of catalyst so less needed for recombination process.

Hess, Robert V.↗

The interaction of small particles and thin films of metals with gases. I - A brief review of the early stages of oxide formation

Existing work on gas-solid reactions making use of thin film technologies is reviewed. The discussion concentrates on two major areas of gas-metal interactions: chemisorption and the early stages of oxidation of metals (characterized by a non-volatile reaction product) and catalytic surface reactions (featuring volatile reaction products). A brief survey of oxide formation on metals is presented. Here it is of importance to distinguish between reactions on continuous thin film substrates and reactions on particulate deposits. Small particle-gas interactions also affect the nucleation, growth and sintering processes of thin films. It is shown that various combinations of UHV and high resolution electron microscopy techniques, which include in situ experimentation, can provide the appropriate tools for studying angstrom particle chemistry.

Poppa, H.↗

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.↗

Multiphase combustion experimentation in microgravity

This paper examines the need for and implementation of microgravity combustion studies of two phase media. Experimental and analytical aspects of several heterogeneous kinetic systems are discussed. These include: flame propagation and extinction for quiescent clouds of uniformly premixed fuel particulates in an oxidizing atmosphere; autoignition of clouds of uniformly premixed fuel particulates in a quiescent oxidizing atmosphere; and the roles of catalytically significant surfaces in gaseous autoignition processes.

Berlad, A. L.↗

Causes and effects of a hole

Preliminary results from the U.S. National Ozone Expedition (NOZE) to Antarctica are reviewed. The NOZE ozonesonde measurements showed significant vertical structure in the hole, with 80 percent depletion in some of the 1 km layers but only 20 percent in adjacent layers. The depletion was confined to the 12-20 km region, beginning first at higher altitude and progressing downward. This is strong evidence against the theory that the ozone hole is due to solar activity producing odd nitrogen at high altitudes which is transported downwards, leading to enhanced odd-nitrogen catalytic cycles that destroy ozone. Nitrous oxide data show unusually low concentrations within the polar vortex, which is evidence against the theory that the hole is caused by a purely dynamical mechanism in which rising air motions within the polar vortex lead to reduced column densities of ozone. It is tentatively concluded that a chemical mechanism involving man-made chlorofluorocarbons is the likely cause of ozone depletion in the hole.

Margitan, J. J.↗

Computer simulation of water reclamation processors

The development of detailed simulation models of water reclamation processors based on the ASPEN PLUS simulation program is discussed. Individual models have been developed for vapor compression distillation, vapor phase catalytic ammonia removal, and supercritical water oxidation. These models are used for predicting the process behavior. Particular attention is given to methodology which is used to complete this work, and the insights which are gained by this type of model development.

Fisher, John W.↗

Simulation of ablation in Earth atmospheric entry

The process of ablation for Earth atmospheric entry is simulated using a computational approach that allows thermo-chemical nonequilibrium of the flow field and ablation gases. The heat pulse into the heat shield is modeled. The flowfield and graphite heat shield are coupled through surface mass and energy balances. The surface thermochemistry involves the oxidation of graphite and allows for catalytic recombination of diatomic oxygen. Steady-state simulations are performed on a one meter nose radius sphere at an altitude of 65/km and at freestream velocities of 8 km/s and 10 km/s. A transient simulation is performed at 65 km altitude and a freestream velocity of 10 km/s.

Keenan, James A.↗

A survey and analysis of experimental hydrogen sensors

In order to ascertain the applicability of hydrogen sensors to aerospace applications, a survey was conducted of promising experimental point-contact hydrogen sensors and their operation was analyzed. The techniques discussed are metal-oxide-semiconductor or MOS based sensors, catalytic resistor sensors, acoustic wave detectors, and pyroelectric detectors. All of these sensors depend on the interaction of hydrogen with Pd or a Pd-alloy. It is concluded that no single technique will meet the needs of aerospace applications but a combination of approaches is necessary. The most promising combination is an MOS based sensor with a catalytic resistor.

Hunter, Gary W.↗

Estimating the NO(x) produced by lightning from GOME and NLDN data: A case study in the Gulf of Mexico

Nitrogen oxides (NO(x)=NO+NO2) play an important role in tropospheric chemistry, in particular in catalytic ozone production. Lightning provides a natural source of nitrogen oxides, dominating the production in the tropical upper troposphere, with strong impact on tropospheric ozone and the atmosphere s oxidizing capacity. Recent estimates of lightning produced NO(x) (LNO(x)) are of the order of 5 Tg [N] per year with still high uncertainties in the range of one order of magnitude. The Global Ozone Monitoring Experiment (GOME) on board the ESA-satellite ERS-2 allows the retrieval of tropospheric column densities of NO2 on a global scale. Here we present the GOME NO2 measurement directly over a large convective system over the Gulf of Mexico. Simultaneously, cloud-to-ground (CG) flashes are counted by the U.S. National Lightning Detection Network (NLDN(TradeMark)), and extrapolated to include intracloud (IC)+CG flashes based on a climatological IC:CG ratio derived from NASA s space-based lightning sensors. A series of 14 GOME pixels shows largely enhanced column densities over thick and high clouds, coinciding with strong lightning activity. The enhancements can not be explained by transport of anthropogenic NO(x) and must be due to fresh production of LNO(x). A quantitative analysis, accounting in particular for the visibility of LNO, from satellite, yields a LNO, production of 90 (32-240) moles of NO(x), or 1.3 (0.4-3.4) kg [N], per flash. If simply extrapolated, this corresponds to a global LNO(x) production of 1.7 (0.6-4.7) Tg [N]/yr.

Beirle, S.↗

Catalytic-Metal/PdO(sub x)/SiC Schottky-Diode Gas Sensors

Miniaturized hydrogen- and hydrocarbon-gas sensors, heretofore often consisting of Schottky diodes based on catalytic metal in contact with SiC, can be improved by incorporating palladium oxide (PdOx, where 0 less than or equal to x less than or equal to 1) between the catalytic metal and the SiC. In prior such sensors in which the catalytic metal was the alloy PdCr, diffusion and the consequent formation of oxides and silicides of Pd and Cr during operation at high temperature were observed to cause loss of sensitivity. However, it was also observed that any PdOx layers that formed and remained at PdCr/SiC interfaces acted as barriers to diffusion, preventing further deterioration by preventing the subsequent formation of metal silicides. In the present improvement, the lesson learned from these observations is applied by placing PdOx at the catalytic metal/SiC interfaces in a controlled and uniform manner to form stable diffusion barriers that prevent formation of metal silicides. A major advantage of PdOx over other candidate diffusion-barrier materials is that PdOx is a highly stable oxide that can be incorporated into gas sensor structures by use of deposition techniques that are standard in the semiconductor industry. The PdOx layer can be used in a gas sensor structure for improved sensor stability, while maintaining sensitivity. For example, in proof-of-concept experiments, Pt/PdOx/SiC Schottky-diode gas sensors were fabricated and tested. The fabrication process included controlled sputter deposition of PdOx to a thickness of 50 Angstroms on a 400-m-thick SiC substrate, followed by deposition of Pt to a thickness of 450 Angstroms on the PdOx. The SiC substrate (400 microns in thickness) was patterned with photoresist and a Schottky-diode photomask. A lift-off process completed the definition of the Schottky-diode pattern. The sensors were tested by measuring changes in forward currents at a bias potential of 1 V during exposure to H2 in N2 at temperatures ranging from 450 to 600 C for more than 750 hours. The sensors were found to be stable after a break-in time of nearly 200 hours. The sensors exhibited high sensitivity: sensor currents changed by factors ranging from 300 to 800 when the gas was changed from pure N2 to 0.5 percent H2 in N2.

Hunter, Gary W.↗

Chlorine oxide in the stratospheric ozone layer Ground-based detection and measurement

Stratospheric chlorine oxide, a significant intermediate product in the catalytic destruction of ozone by atomic chlorine, has been detected and measured by a ground-based 204 GHz, millimeter-wave receiver. Data taken at latitude 42 deg N on 17 days between January 10 and February 18, 1980 yield an average chlorine oxide column density of approximately 1.05 x 10 to the 14th/sq cm or approximately 2/3 that of the average of eight in situ balloon flight measurements (excluding the anomalously high data of July 14, 1977) made over the past four years at 32 deg N. Less chlorine oxide below 35 km and a larger vertical gradient than predicted by theoretical models of the stratospheric ozone layer are found.

Parrish, A.↗