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At least 19 records

Studies of thermochemical water-splitting cycles

Higher temperatures and more isothermal heat profiles of solar heat sources are developed. The metal oxide metal sulfate class of cycles were suited for solar heat sources. Electrochemical oxidation of SO2 and thermochemical reactions are presented. Electrolytic oxidation of sulfur dioxide in dilute sulfuric acid solutions were appropriate for metal oxide metal sulfate cycles. The cell voltage at workable current densities required for the oxidation of SO2 was critical to the efficient operation of any metal oxide metal sulfate cycle. A sulfur dioxide depolarized electrolysis cell for the splitting of water via optimization of the anode reaction is discussed. Sulfuric acid concentrations of 30 to 35 weight percent are preferred. Platinized platinum or smooth platinum gave the best anode kinetics at a given potential of the five materials examined.

Remick, R. J.↗

Molecular orbital studies in oxidation: Sulfate formation and metal-metal oxide adhesion

The chemical mechanisms for sulfate formation from sodium chloride and sulfur trioxide, which is a product of jet fuel combustion was determined. Molten sodium sulfate leads to hot corrosion of the protective oxide layers on turbine blades. How yttrium dopants in nidkel-aluminum alloys used in turbine blades reduce the spalling rate of protective alumina films and enhance their adhesion was also determined. Two other fulfate mechanisms were deduced and structure of carbon monoxide on a clean chronium and clean platinum-titanium alloys surfaces was determined. All studies were by use of the atom superposition and electron delocalization molecular orbital (ASED-MO) theory. Seven studies were completed. Their titles and abstracts are given.

Anderson, A. B.↗

A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

Schreiber, J. D.↗

Geochemical Constraints on the Oxidation States of the Europan Ocean and Mantle

We present observational, meteoritic, and physical-chemical arguments for an oxidized Fe-metal free mantle and an oxidized sulfate-carbonate rich ocean on Europa. The ocean should be out of equilibrium even with oxidized igneous rocks at the oceanic floor. Additional information is contained in the original extended abstract.

Zolotov, M. Yu.↗

Ceramic oxide reactions with V2O5 and SO3

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Jones, R. L.↗

Mineralogy of Meteorite Groups

Approximately 275 mineral species have been identified in meteorites, reflecting diverse redox environments, and, in some cases, unusual nebular formation conditions. Anhydrous ordinary, carbonaceous and R chondrites contain major olivine, pyroxene and plagioclase; major opaque phases include metallic Fe-Ni, troilite and chromite. Primitive achondrites are mineralogically similar. The highly reduced enstatite chondrites and achondrites contain major enstatite, plagioclase, free silica and kamacite as well as nitrides, a silicide and Ca-, Mg-, Mn-, Na-, Cr-, K- and Ti-rich sulfides. Aqueously altered carbonaceous chondrites contain major amounts of hydrous phyllosilicates, complex organic compounds, magnetite, various sulfates and sulfides, and carbonates. In addition to kamacite and taenite, iron meteorites contain carbides, elemental C, nitrides, phosphates, phosphides, chromite and sulfides. Silicate inclusions in IAB/IIICD and lIE iron meteorites consist of mafic silicates, plagioclase and various sulfides, oxides and phosphates. Eucrites, howardites and diogenites have basaltic to orthopyroxenitic compositions and consist of major pyroxene and calcic plagioclase and several accessory oxides. Ureilttes .are made up mainly of calcic, chromian olivine and low-Ca clinopyroxene embedded in a carbonaceous matrix; accessory phases include the C polymorphs graphite, diamond, lonsdaleite and chaoite as well as metallic Fe-Ni, troilite and halides. Angrites are achondrites rich in fassaitic pyroxene (i.e. , AI-Ti diopside); minor olivine with included magnesian kirschsteinite is also present. Martian meteorites comprise basalts, Iherzolites, a dunite and an orthopyroxenite. Major phases include various pyroxenes and olivine; minor to accessory phases include various sulfides, magnetite, chromite and Ca-phosphates. Lunar meteorites comprise mare basalts with major augite and calcic plagioclase and anorthositic breccias with major calcic plagioclase. Several meteoritic phases were formed by shock metamorphism. Martensite (a2-fe,Ni) has a distorted body-centered-cubic structure and formed by a shear transformation from taenite during shock reheating and rapid cooling. The C polymorphs diamond, lonsdaleite and chaoite formed by shock from graphite. Suessite formed in the North Haig ureilite by reduction of Fe and Si (possibly from olivine) via reaction with carbonaceous matrix material. Ringwoodite, the spinel form of (Mg,Fe)2Si04, and majorite, a polymorph of (Mg,Fe)Si03 with the garnet structure, formed inside shock veins in highly shocked ordinary chondrites. Secondary minerals in meteorite finds that formed during terrestrial weathering include oxides and hy-. droxides formed directly from metallic Fe-Ni by oxidation, phosphates formed by the alteration of schreibersite, and sulfates formed by alteration of troilite.

Rubin, Alan E.↗

Chemical processes involved in the initiation of hot corrosion of B-1900 and NASA-TRW VIA

Sodium sulfate induced hot corrosion of B-1900 and NASA-TRW VIA at 900 C was studied with special emphasis on the chemical reactions occurring during and immediately after the induction period. Thermogravimetric tests were run for set periods of time after which the samples were washed with water and water soluable metal salts and/or residual sulfates were analyzed chemically. Element distributions within the oxide layer were obtained from electron microprobe X-ray micrographs. A third set of samples were subjected to surface analysis by X-ray photoelectron spectroscopy. Evolution of SO2 was monitored throughout many of the hot corrosion tests. Results are interpreted in terms of acid-base fluxing mechanisms.

Fryburg, G. C.↗

A high pressure modulated molecular beam mass spectrometric sampling system

The current state of understanding of free-jet high pressure sampling is critically reviewed and modifications of certain theoretical and empirical considerations are presented. A high pressure, free-jet expansion, modulated molecular beam, mass spectrometric sampling apparatus was constructed and this apparatus is described in detail. Experimental studies have demonstrated that the apparatus can be used to sample high temperature systems at pressures up to one atmosphere. Condensible high temperature gaseous species have been routinely sampled and the mass spectrometric detector has provided direct identification of sampled species. System sensitivity is better than one tenth of a part per million. Experimental results obtained with argon and nitrogen beams are presented and compared to theoretical predictions. These results and the respective comparison are taken to indicate acceptable performance of the sampling apparatus. Results are also given for two groups of experiments related to hot corrosion studies. The formation of gaseous sodium sulfate in doped methane-oxygen flames was characterized and the oxidative vaporization of metals was studied in an atmospheric pressure flowing gas system to which gaseous salt partial pressures were added.

Stearns, C. A.↗

Iron and manganese in anaerobic respiration: environmental significance, physiology, and regulation

Dissimilatory iron and/or manganese reduction is known to occur in several organisms, including anaerobic sulfur-reducing organisms such as Geobacter metallireducens or Desulfuromonas acetoxidans, and facultative aerobes such as Shewanella putrefaciens. These bacteria couple both carbon oxidation and growth to the reduction of these metals, and inhibitor and competition experiments suggest that Mn(IV) and Fe(III) are efficient electron acceptors similar to nitrate in redox abilities and capable of out-competing electron acceptors of lower potential, such as sulfate (sulfate reduction) or CO2 (methanogenesis). Field studies of iron and/or manganese reduction suggest that organisms with such metabolic abilities play important roles in coupling the oxidation of organic carbon to metal reduction under anaerobic conditions. Because both iron and manganese oxides are solids or colloids, they tend to settle downward in aquatic environments, providing a physical mechanism for the movement of oxidizing potential into anoxic zones. The resulting biogeochemical metal cycles have a strong impact on many other elements including carbon, sulfur, phosphorous, and trace metals.

Review, Academic↗

NASA thermal barrier coatings: Summary and update

A durable, two-layer, plasma-sprayed coating consisting of a ceramic layer over a metallic layer was developed that has the potential of insulating hot engine parts and thereby reducing metal temperatures and coolant flow requirements and/or permitting use of less costly and complex cooling configurations and materials. The results are summarized of analytical and experimental investigations of the coatings on flat metal specimens, turbine vanes and blades, and combustor liners. Discussed are results of investigations to determine coating adherence and durability, coating thermal, strength and fatigue properties, and chemical reactions of the coating with oxides and sulfates. Also presented are the effect of the coating on aerodynamic performance of a turbine vane, measured vane and combustor liner temperatures with and without the coating, and predicted turbine metal temperatures and coolant flow reductions potentially possible with the coating. Included also are summaries of some current research related to the coating and potential applications for the coating.

Stepka, F. S.↗

NASA thermal barrier coatings - Summary and update

The work conducted at the NASA Lewis Research Center to evolve and evaluate a thermal-barrier coating system will be discussed. A durable, two-layer, plasma-sprayed coating consisting of a ceramic layer over a metallic layer was developed that has the potential of insulating hot engine parts and thereby reducing metal temperatures and coolant flow requirements and/or permitting use of less costly and complex cooling configurations and materials. The paper summarizes the results of analytical and experimental investigations of the coatings on flat metal specimens, turbine vanes and blades, and combustor liners. Discussed are results of investigations to determine coating adherence and durability, coating thermal, strength and fatigue properties, and chemical reactions of the coating with oxides and sulfates. Also presented are the effect of the coating on aerodynamic performance of a turbine vane, measured vane and combustor liner temperatures with and without the coating, and predicted turbine metal temperatures and coolant flow reductions potentially possible with the coating. Included also are summaries of some current research related to the coating and potential applications for the coating.

Stepka, F. S.↗

Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

Huang, Cunping↗

Oxidation and corrosion behavior of modified-composition, low-chromium 304 stainless steel alloys

The effects of substituting less strategic elements than Cr on the oxidation and corrosion resistance of AISI 304 stainless steel were investigated. Cyclic oxidation resistance was evaluated at 870 C. Corrosion resistance was determined by exposure of specimens to a boiling copper-rich solution of copper sulfate and sulfuric acid. Alloy substitutes for Cr included Al, Mn, Mo, Si, Ti, V, Y, and misch metal. A level of about 12% Cr was the minimum amount of Cr required for adequate oxidation and corrosion resistance in the modified composition 304 stainless steels. This represents a Cr saving of at least 33%. Two alloys containing 12% Cr and 2% Al plus 2% Mo and 12% Cr plus 2.65% Si were identified as most promising for more detailed evaluation.

Stephens, J. R.↗

Substitution for chromium in 304 stainless steel

An investigation was conducted to determine the effects of substituting less strategic elements for Cr on oxidation and corrosion resistance of AISI 304 stainless steel. Cyclic oxidation resistance was evaluated at 870 C. Corrosion resistance was determined by exposure of specimens to a boiling copper-rich solution of copper sulfate and sulfuric acid. Alloy substitutes for Cr included Al, Mn, Mo, Si, Ti, V, Y, and misch metal. A level of about 12% Cr was the minimum amount of Cr required for adequate oxidation and corrosion resistance in the modified composition 304 stainless steels. This represents a Cr saving of 33 percent. Two alloys containing 12% Cr plus 2% Al plus 2% Mo and 12% Cr plus 2.65% Si were identified which exhibited oxidation and corrosion resistance comparable to AISI 304 stainless steel.

Stephens, J. R.↗

Chemical mechanisms and reaction rates for the initiation of hot corrosion of IN-738

Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions: Cr2O3 + 2 Na2SO4(1) + 3/2 O2 yields 2 Na2CrO4(1) + 2 SO3(g)n TiO2 + Na2SO4(1) yields Na2O(TiO2)n + SO3(g)n TiO2 + Na2CrO4(1) yields Na2O(TiO2)n + CrO3(g).

Fryburg, G. C.↗

Chemical reactions involved in the initiation of hot corrosion of IN-738

Sodium-sulfate-induced hot corrosion of preoxidized IN-738 was studied at 975 C with special emphasis placed on the processes occurring during the long induction period. Thermogravimetric tests were run for predetermined periods of time, and then one set of specimens was washed with water. Chemical analysis of the wash solutions yielded information about water soluble metal salts and residual sulfate. A second set of samples was cross sectioned dry and polished in a nonaqueous medium. Element distributions within the oxide scale were obtained from electron microprobe X-ray micrographs. Evolution of SO was monitored throughout the thermogravimetric tests. Kinetic rate studies were performed for several pertinent processes; appropriate rate constants were obtained from the following chemical reactions; Cr203 + 2 Na2S04(1) + 3/2 02 yields 2 Na2Cr04(1) + 2 S03(g)n TiO2 + Na2S04(1) yields Na20(T102)n + 503(g)n T102 + Na2Cro4(1) yields Na2(T102)n + Cr03(g).

Fryburg, G. C.↗

Investigation into the role of sodium chloride deposited on oxide and metal substrates in the initiation of hot corrosion

Sodium chloride is deposited on the surface of alumina substrates and exposed to air containing 1% SO2 at temperatures between 500 C and 700 C. In all cases the sodium chloride was converted to sodium sulfate. The volatilization of sodium chloride from the original salt particles was responsible for the development of a uniform coating of sodium sulfate on the alumina substrate. At temperatures above 625 C, a liquid NaCl-Na2SO4 autectic was formed on the substrate. The mechanisms for these reactions are given. One of the main roles of NaCl in low temperature hot corrosion lies in enabling a corrosive liquid to form.

Birks, N.↗

Turbine Airfoil Deposition Models

Gas turbine failures associated with sea-salt ingestion and sulfur-containing fuel impurities have directed attention to alkali sulfate deposition and the associated hot corrosion of gas turbine (GT) blades under some GT operating conditions. These salt deposits form thin, molten films which undermine the protective metal oxide coating normally found on GT blades. The prediction of molten salt deposition, flow and oxide dissolution, and their effects on the lifetime of turbine blades are examined. Goals include rationalizing and helping to predict corrosion patterns on operational GT rotor blades and stators, and ultimately providing some of the tools required to design laboratory simulators and future corrosion-resistant high-performance engines. Necessary background developments are reviewed first, and then recent results and tentative conclusions are presented along with a brief account of the present research plans.

Rosner, D. E.↗