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At least 19 records

MoO3 Cathodes for High-Temperature Lithium Thin-Film Cells

MoO3 has shown promise as a cathode material that can extend the upper limit of operating temperature of rechargeable lithium thin-film electrochemical cells. Cells of this type are undergoing development for use as energy sources in cellular telephones, wireless medical sensors, and other, similarly sized portable electronic products. The LiCoO2 and LiMn2O4 cathodes heretofore used in these cells exhibit outstanding cycle lives (of the order of hundreds of thousands of cycles) at room temperature, but operation at higher temperatures reduces their cycle lives substantially: for example, at a temperature of 150 C, cells containing LiCoO2 cathodes lose half their capacities in 100 charge/discharge cycles. The superiority of MoO3 as a cathode material was demonstrated in experiments on lithium thin-film cells fabricated on glass slides. Each cell included a layer of Ti (for adhesion to the glass slide), a patterned layer of Pt that served as a cathode current collector, a cathode layer of MoO3, a solid electrolyte layer of Li3.3 PO3.8 N0.22 ("LiPON"), and an anode layer of Li. All the layers were deposited by magnetron sputtering except for the Li layer, which was deposited by thermal evaporation. These cells, along with similar ones containing LiCoO2 cathodes, were subjected to several tests, including measurements of specific capacity in charge/discharge cycling at a temperature of 150 C. The results of these measurements, plotted in the figure, showed that whereas specific capacity of the cells containing LiCoO2 cathodes faded to about half its initial value after only 100 cycles, the specific capacity of the cells containing the MoO3 cathodes faded only slightly during the first few hundred cycles and thereafter not only recovered to its initial value but continued to increase up to at least 5,500 cycles.

West, William↗

Mechanism of corrosion of Ni base superalloys by molten Na2MoO4 at elevated temperatures

The corrosion of nickel base superalloy, U-700, by molten Na2MoO4 was studied in the temperature range of 750 deg to 950 deg C. After an induction period, the rate of corrosion is linear and catastrophic corrosion is observed. It is shown that the induction period is associated with the attainment of a minimum MoO3 activity in the melt, which corresponds to the equilibrium MoO3 activity for the reaction, 2MoO3(l) + Mo = 3MoO2(s). A mechanism is proposed to describe the catastrophic nature of corrosion, which involves transport of Ni++ through the melt resulting in formulation of NiO at the melt gas interface and basic fluxing of Cr2O3. The effect of the amount of Na2MoO4 on the corrosion kinetics was also studied. It is found that evaporation and the thermodynamic calculations for the Na2MoO4 - MoO3 system the activity of MoO3 is reduced considerably when dissolved in Na2MoO4, which causes a sharp decrease in the rate of evaporation of MoO3 from a Na2MoO4 - MoO3 melt.

Misra, A. K.↗

Studies on the hot corrosion of a nickel-base superalloy, Udimet 700

The hot corrosion of a nickel-base superalloy, Udimet 700, was studied in the temperature range of 884 to 965 C and with different amounts of Na2SO4. Two different modes of degradation were identified: (1) formation of Na2MoO4 - MoO3 melt and fluxing by this melt, and (2) formation of large interconnected sulfides. The dissolution of Cr2O3, TiO2 in the Na2SO4 melt does not play a significant role in the overall corrosion process. The conditions for the formation of massive interconnected sulfides were identified and a mechanism of degradation due to sulfide formation is described. The formation of Ns2MoO4 - MoO3 melt requires an induction period and various physiochemical processes during the induction period were identified. The factors affecting the length of the induction period were also examined. The melt penetration through the oxide appears to be the prime mode of degradation whether the degradation is due to the formation of sulfides or the formation of the Na2MoO4 - MoO3 melt.

Misra, A. K.↗

Studies on the hot corrosion of a nickel-base superalloy, Udimet 700

The hot corrosion of a nickel-base superalloy, Udimet 700, was studied in the temperture range of 884 to 965 C and with different amounts of Na2SO4. Two different modes of degradation were identified: (1) formation of Na2MoO4-MoO3 melt and fluxing by this melt, and (2) formation of large interconnected sulfides. The dissolution of Cr2O3, TiO2 in the Na2SO4 melt does not play a significnt role in the overall corrosion process. The conditions for the formation of massive interconnected sulfides were identified and a mechanism of degradation due to sulfide formation is described. The formation of Na2MoO4-MoO3 melt requires an induction period and various physiochemical processes during the induction period were identified. The factors affecting the length of the induction period were also examined. The melt penetration through the oxide appears to be the prime mode of degradation whether the degradation is due to the formation of sulfides or the formation of the Na2MoO4-MoO3 melt.

Misra, A. K.↗

Mechanism of Na2SO4-induced corrosion of molybdenum containing nickel-base superalloys at high temperatures. I - Corrosion in atmospheres containing O2 only. II - Corrosion in O2 + SO2 atmospheres

Kinetics of the Na2SO4-induced corrosion of the molybdenum-containing nickel-base superalloys, B-1900 and Udimet 700, coated with Na2MoO4, has been studied in oxygen atmosphere at temperatures ranging from 750 to 950 C. Because the gas turbine atmosphere always contains some SO2 and SO3, the effect of atmospheric SO2 content on corrosion of Udimet-700 has also been studied. It was found that in the O2 atmosphere the melt in the catastrophic corrosion phase consists of Na2MoO4 plus MoO3, with the onset of the catastrophic corrosion coinciding with the appearance of MoO3. In the presence of low levels of atmospheric SO2 (below 0.24 percent), the melt during catastrophic corrosion contains, in addition to Na2MoO4 and MoO3, some quantities of Na2SO4. At the levels of SO2 above 1 percent, no catastrophic corrosion was observed. At these SO2 levels, internal sulfidation appears to be the primary mode of degradation.

Misra, A. K.↗

A New Method of Metallization for Silicon Solar Cells

The determination of the firing cycle in a horizontal tube furnace for MoO3: Sn ink composition applied by silk screening process on P or N structured solar cells is presented. In comparison with the strip heater used to determine the reaction mechanism, the reduction of MoO3 in the tube furnace progresses at a much faster rate and the Sn:Mo alloy forms at a much lower temperature. The device characteristics determined by the V-I curve showed a high resistance (approx. 10 Ohms) at peak temperatures between 600 C and 800 C. The high series resistance is attributed to the lack of formation of MoSi2 within the used temperature range.

Macha, M.↗

Molybdenum-tin as a solar cell metallization system

The operations of solar cell manufacture are briefly examined. The formation of reliable, ohmic, low-loss, and low-cost metal contacts on solar cells is a critical process step in cell manufacturing. In a commonly used process, low-cost metallization is achieved by screen printing a metal powder-glass frit ink on the surface of the Si surface and the conductive metal powder. A technique utilizing a molybdenum-tin alloy for the metal contacts appears to lower the cost of materials and to reduce process complexity. The ink used in this system is formulated from MoO3 with Sn powder and a trace amount of titanium resonate. Resistive losses of the resulting contacts are low because the ink contains no frit. The MoO3 is finally melted and reduced in forming gas (N2+H2) to Mo metal. The resulting Mo is highly reactive which facilitates the Mo-Si bonding.

Boyd, D. W.↗

Garnet melt viscosity, surface tension and drainage

Good surface morphology and layer uniformity of LPE-grown Bi YIG films are favored by fast melt removal after growth. Three flux modifying oxides: MoO3, V2O3, and WO3 are compared with respect to their effect on viscosity, surface tension and melt drainage. All three oxides increased the viscosities of Bi-garnet melts, but the viscosities and drainage times of V2O3 and MoO3 modified melts were smaller than those of WO3 modified melts. The liquid-gas surface tension was found to be temperature independent. The drainage process was strongly temperature dependent, 40 to 60 kcal/mol, whereas the viscosities of melts had activation energies of 11 to 16 kcal/mol. Contact angles of 16 + or - 2 deg were measured on frozen melt drops.

Luther, L. C.↗

Hot corrosion studies of four nickel-base superalloys: B-1900, NASA-TRW VIA, 713C and IN738

The susceptibility to hot corrosion of four nickel base superalloys has been studied at 900 deg and 1000 deg C in one atmosphere of slowly flowing oxygen. Hot corrosion was induced by coating the samples with known doses of NaSO4 and oxidizing the coated samples isothermally on a sensitive microbalance. In general, the order of susceptibility found was: B-1900 is greater than 713C is greater than NASA-TRW VIA and is greater than IN738. This order corresponds to the order of decreasing molybdenum content of the alloys. Chemical evidence for B-1900 indicates that hot corrosion is instigated by acid fluxing of the protective Al2O3 coating by MoO3.

Fryburg, G. C.↗

Hot corrosion studies of four nickel-base superalloys - B-1900, NASA-TRW VIA, 713C and IN738

The susceptibility to hot corrosion of four nickel-base superalloys has been studied at 900 and 1000 C in one atmosphere of slowly flowing oxygen. Hot corrosion was induced by coating the samples with known doses of Na2SO4 and oxidizing the coated samples isothermally on a sensitive microbalance. In order of decending susceptibility to hot corrosion, these alloys were ranked: B-1900, 713C, NASA-TRW VIA, IN738. This order corresponds to the order of decreasing molybdenum content of the alloys. Chemical evidence for B-1900 indicates that hot corrosion is instigated by acid fluxing of the protective Al2O3 coating by MoO3.

Fryburg, G. C.↗

Lubrication and failure mechanisms of molybdenum disulfide films. 2: Effect of substrate roughness

An optical microscope was used to study the lubrication and failure mechanisms of rubbed MoS2 films applied to three substrate surface finishes; polished, sanded, and sandblasted as a function of sliding distance. The lubrication mechanism was the plastic flow of thin films of MoS2 between flat plateaus on the rider and on the metallic substrate. If the substrate was rough, flat plateaus were created during run-in and the MoS2 flowed across them. Wear life was extended by increasing surface roughness since valleys in the roughened substrate served as reservoirs for MoS2 and as deposit sites for wear debris. In moist air the failure mechanism was the transformation of metallic colored MoS2 films to a black, powdery material that was found by X-ray diffraction to be alpha iron, MoO3, and possibly FeMoO3. In dry argon the failure mechanism was the gradual depletion of MoS2 from the contact region by transverse flow, and the wear debris on the track at failure was alpha iron, residual MoS2, and possibly FeS.

Fusaro, R. L.↗

A new method of metallization for silicon solar cells

The new metallization process based on Mo-Sn system was studied. The reaction mechanism of MoO3 and its mixture with Sn was examined. The basic ink composition was modified in order to obtain a low ohmic contact to the cell. The electrical characteristics of the cells were comparable with the existing metallization processes. However, in comparison with the standard processes using silver as the contacting metal, the saving obtained by the use of the new process was substantial.

Macha, M.↗

Effect of Substrate Surface Finish on the Lubrication and Failure Mechanisms of Molybdenum Disulfide Films

An optical microscope was used to study the lubrication and failure mechanisms of rubbed (burnished) MoS2 films applied to three substrate surface finishes - polished, sanded, and sandblasted - as a function of sliding distance. The lubrication mechanism was the plastic flow of thin films of MoS2 between flat plateaus on the rider and on the metallic substrate. If the substrates were rough, flat plateaus were created during 'run in' and the MoS2 flowed across them. Wear life was extended by increasing surface roughness since valleys in the roughened substrate served as reservoirs for MoS2 and a deposit site for wear debris. In moist air, the failure mechanism was the transformation of metallic colored MoS2 films to a black, powdery material that was found by X ray diffraction to consist primarily of alpha iron and MoO3 powders. In dry argon, the failure mechanism was the gradual depletion of the MoS2 film from the contact region by transverse flow. Analysis of the wear debris on the wear track at failure showed it consisted mainly of alpha iron and some residual MoS2. No molybdenum oxides were found.

Fusaro, R. L.↗

Effect of substrate surface finish on the lubrication and failure mechanisms of molybdenum disulfide films

An optical microscope was used to study the lubrication and failure mechanisms of rubbed (burnished) MoS2 films applied to three substrate surface finishes - polished, sanded, and sandblasted - as a function of sliding distance. The lubrication mechanism was the plastic flow of thin films of MoS2 between flat plateaus on the rider and on the metallic substrate. If the substrate was rough, flat plateaus were created during 'run-in' and the MoS2 flowed across them. Wear life was extended by increasing surface roughness since valleys in the roughened substrate served as reservoirs for MoS2 and a deposit site for wear debris. In moist air, the failure mechanism was the transformation of metallic-colored MoS2 films to a black, powdery material that was found by X-ray diffraction to consist primarily of alpha-iron and MoO3 powders. In dry argon, the failure mechanism was the gradual depletion of the MoS2 film from the contact region by transverse flow. Analysis of the wear debris on the wear track at failure showed it consisted mainly of alpha-iron and some residual MoS2. No molybdenum oxides were found.

Fusaro, R. L.↗

Mechanism of hot corrosion of IN-738

The Na2SO4 - induced hot corrosion of IN-738 in the temperature range 900 C to 1000 C is characterized by an initiation stage during which the corrosion rate is slow followed by a propagation stage during which the corrosion rate is markedly accelerated. In the second stage, corrosion is accelerated due essentially to a sulfidation/oxidation mechanism; in the third stage, the rate becomes catastrophic due to acid fluxing induced by an accumulation of refractory metal oxides (particularly MoO3) in the Na2SO4. The sequential stages in the corrosion process are described and a mechanism proposed. The influence of alloy microstructure on the corrosion mechanism is also discussed.

Meier, G. H.↗

Role of molybdenum in the Na sub 2SO sub 4 induced corrosion of superalloys at high temperatures

Sodium sulfate induced corrosion of a molybdenum containing nickel-base superalloy, Udimet 700, was studied in laboratory furnace tests and in a high velocity (Mach 0.3) burner rig. The effect of SO2 content in the atmosphere on the corrosion behavior in the laboratory furnace tests was determined. Catastrophic corrosion occurs only when the melt contains MoO3 in addition to Na2SO4 and Na2MoO4. The conditions under which catastrophic corrosion occurs are identified and a mechanism is described to explain the catastrophic corrosion.

Misra, A. K.↗

Role of molybdenum in the Na2SO4 induced corrosion of superalloys at high temperature

Sodium sulfate induced corrosion of a molybdenum containing nickel-base superalloy, Udimet 700, was studied in laboratory furnace test and in a high velocity (Mach 0.3) burner rig. Tlhe effect of SO2 content in the atmosphere on the corrosion behavior in the laboratory furnace tests was determined. catastrophic corrosion occursonly when the melt contains MoO3 in addition to Na2SO4 and Na2MoO4. The conditions under which catastrophic corrosion occurs are identified and a mechanism is described to explain the catastrophic corrosion.

Misra, A. K.↗

MoS2 interactions with 1.5 eV atomic oxygen

Exposures of MoS2 to 1.5-eV atomic oxygen in an anhydrous environment reveal that the degree of oxidation is essentially independent of crystallite orientation, and that the surface-adsorbed reaction products are MoO3 and MoO2. A mixture of oxides and sulfide exists over a depth of about 90 A, and this layer has a low diffusion rate for oxygen. It is concluded that a protective oxide layer forms on MoS2 on exposure to the atomic-oxygen-rich environment of LEO.

Martin, J. A.↗