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At least 55 records · Page 3

Oxidation in oxygen at 900 deg and 1000 deg C of four nickel-base cast superalloys: NASA-TRW VIA, B-1900, alloy 713C, and IN-738

The oxidation at 900 and 1,000 C of four nickel-base superalloys in 1 atmosphere of slowly flowing oxygen was investigated. Thermogravimetric rate data were obtained for periods to 100 hours. The morphology and composition of the oxide scales formed after 100 hours were studied by optical microscopy, X-ray diffraction, electron microprobe, scanning electron microscopy, and X-ray photoelectron spectroscopy (ESCA). Alloys B-1900 and VIA were found to be primarily alumina formers, though probably 25 percent of their surface was covered by CR2O3-containing oxides at 900 C. Alloys 713C and IN-738 were primarily chromia formers, though the surface of 713C at 1,000 C was covered with NiO, and the surface of IN-738 at both temperatures was covered with a thin layer of TiO2.

Fryburg, G. C.↗

Effect of magnetic field on reduction of nickel oxide

Results of observations recorded during constant temperature reduction of NiO, a paramagnetic substance, to Ni, a ferromagnetic element, are presented. The application of a large magnetic field (4,200 oersted) does not result in an acceleration of the reduction rate. To explain earlier observations that 500- and 1,400-oersted magnetic fields increase the reduction rate of iron ore which contains hematite (Fe2O3), Peters (1973) had suggested that thermodynamics theory could predict the acceleration in reaction rate when product and reactant species differ widely in their magnetic properties.

Rowe, M. W.↗

The effect of temperature and pressure on the distribution of iron group elements between metal and olivine phases in the process of differentiation of protoplanetary material

The distribution patterns of Ni, Co, Mn, and Cr were studied in olivines of various origins: from meteorites (chondrites, achondrites, pallasites), which are likely analogs of the protoplanetary material, to peridotite inclusions in kimberlite pipes, which are analogs of mantle material. According to X-ray microanalysis data, nickel is concentrated in peridotite olivines, while manganese is concentrated in meteoritic olivines. The maximum chromium content was found in ureilites, which were formed under reducing conditions. Experiments at pressures of 20 to 70 kbar and temperatures of 1100 to 2000 C have shown that in a mixture of olivine and Ni metal or NiO, nickel enters the silicate phase, displacing Fe into the metallic phase. Equilibrium temperatures were estimated from the Fe, Ni distribution coefficients between the metal and olivine: 1500 K for pallasites, 1600 K for olivine-bronzite H6 chondrites, 1200 K for olivine-hypersthene L6, 900 K for LL6, and 1900 K for ureilites (at P = 1 atm). The equilibrium conditions of peridotites are close to T = 1800 K and P over 100 kbar. It is concluded that there is a sharp difference between the conditions of differentiation of the protoplanetary material at the time meteorites were formed and the conditions of differentiation of the planets into concentric layers.

Vinogradov, A. P.↗

Reactions of yttria-stabilized zirconia with oxides and sulfates of various elements

The reactions between partially stabilized zirconia, containing 8 weight-percent yttria, and oxides and sulfates of various elements were studied at 1200, 1300, and 1400 C for times to 800, 400, and 200 hours, respectively. These oxides and sulfates represent impurities and additives potentially present in gas turbine fuels or impurities in the turbine combustion air as well as the elements of the substrate alloys in contact with zirconia. Based on the results, these compounds can be classified in four groups: (1) compounds which did not react with zirconia (Na2SO4, K2SO4, Cr2O3, Al2O3 and NiO); (2) compounds that reached completely with both zirconia phases (CaO, BaO, and BaSO4); (3) compounds that reacted preferentially with monoclinic zirconia (Na2O, K2O, CoO, Fe2O3, MgO, SiO2, and ZnO); and (4) compounds that reacted preferentially with cubic zirconia (V2O5, P2O5).

Zaplatynsky, I.↗

Characteristics of integrated MOM junctions at dc and at optical frequencies

A new metal-oxide-metal device (Ni-NiO-Ni, Edge MOM) which is stable, reproducibly fabricated, and with a 10 to the -10th sq cm tunneling area is presented. Performing detection experiments, the device's nonlinear I-V characteristic is shown to be invariant at audio frequencies, 10.6, 3.39, and 0.6328 microns. Similar devices with 10 to the -8th sq cm tunneling areas perform as well as the Edge MOM's in the visible and the near-infrared range, but deteriorate in performance at the 10-micron range. A dominant competing effect is a thermal-induced signal, which increases with frequency and temperature. Coupling mechanisms at the various regimes are investigated. The device can serve as a broad-band detector and mixer, and might in the future be a basic element of broad-band amplifiers and oscillators.

Heiblum, M.↗

Partitioning of Ni/2+/ between basaltic and synthetic melts and olivines An experimental study

Olivine/liquid distribution coefficients for Ni in basaltic and simple synthetic melts are found in the 1400-1070 C temperature range. The results suggest that: (1) the Ni distribution coefficients and NiO activity coefficients are strongly temperature dependent, (2) the Ni distribution coefficients are functions of melt composition and structure at a constant temperature although the dependence is small for most basaltic magmas, (3) differences in melt composition do not significantly influence generally 'basaltic' melts, (4) the Ni distribution coefficients may be used as geothermometers to predict the olivine crystallization temperatures of basaltic magmas to within plus or minus 50 C, (5) the Ni distribution coefficients are greater than one at all natural magmatic temperatures, and (6) the Ni distribution coefficients do not significantly vary as functions of the Ni content of the melt to at least one mole percent.

Leeman, W. P.↗

Minor elements in lunar olivine as a petrologic indicator

Accurate electron microprobe analyses (approximately 50 ppm) were made for Al, Ca, Ti, Cr, Mn, and Ni in Mg-rich olivines which may derive from early lunar crust or deeper environments. Low-Ca contents consistently occur only in olivines from dunitic and troctolitic breccia: spinel troctolite and other rock types have high-Ca olivines suggesting derivation by near-surface processes. Rock 15445 has olivine with distinctly low CaO (approximately 0.01 wt.%). Chromium ranges to higher values (max.0.2 oxide wt.%) than for terrestrial harzburgites and lherzolites but is similar to the range in terrestrial komatiites. Divalent chromium may be indicated over trivalent Cr because olivines lack sufficient other elements for charge balance of the latter. NiO values in lunar specimens range from 0.00 to 0.07 wt.% and a weak anticorrelation with Cr2O3 suggests an oxidation state effect. Al2O3 values are mostly below 0.04-wt.% and show no obvious correlation with fragment type. TiO2 values lie below 0.13-wt.% and seem to correlate best with crystallization rate and plagioclase content of the host rock. High values of Al2O3 and TiO2 reported by other workers have not been confirmed, and are probably wrong.

Steele, I. M.↗

Corrosion resistance of sodium sulfate coated cobalt-chromium-aluminum alloys at 900 C, 1000 C, and 1100 C

The corrosion of sodium sulfate coated cobalt alloys was measured and the results compared to the cyclic oxidation of alloys with the same composition, and to the hot corrosion of compositionally equivalent nickel-base alloys. Cobalt alloys with sufficient aluminum content to form aluminum containing scales corrode less than their nickel-base counterparts. The cobalt alloys with lower aluminum levels form CoO scales and corrode more than their nickel-base counterparts which form NiO scales.

Santoro, G. J.↗

Characterization of the physico-chemical properties of polymeric materials for aerospace flight

Factors contributing to the final failure of Ni-Cd batteries are listed. A differential thermal analyzer was used to study several positive and negative battery electrodes. The negative plates show a very large peak (endotherm) between 245 C and 250C. The second endotherm occurs at 300C indicating the decomposition of Cd(OH)2. In positive plates, a first weak endotherm occurs at 100C, which indicates loss of H2O from Ni(OH)2(H2O)n molecules. A second large endotherm occurs in the range of 290C to 300C, indicating the decomposition of Ni(OH2) to NiO and H2O. Atomic absorption spectroscopy was used to determine nickel, cobalt, cadmium, and potassium content in battery electrolytes and electrodes. Results are presented in tables.

Rock, M.↗

The oxidation behavior of a model molybdenum/tungsten-containing alloy in air alone and in air with trace levels of NaCl(g)

Thermogravimetric, metallographic, and X-ray studies of a model alloy, Ni-(17 a/o)Al-(10 a/o)Mo+W, oxidized in dry air at 600-1200 C and in air with 10 ppm NaCl gas at 900 C, are reported. The alloy was melted under Ar and pretreated in flowing H2 for 24 h at 1300 C. Polished 1.3 x 1.3 x 0.2-cm specimens were washed and degreased prior to oxidation in a quartz tube within a furnace for up to 120 hr. The oxidation activation energy of the alloy is determined to be about 30 kcal/mole. The specimens oxidized at 900 C and hotter exhibited oxidized and nitrided phases covered by complex NiMoO4, NiWO4, and NiAl2O4 scales and a porous, nonprotective outer layer of NiO. The oxidation behavior is found to be determined by the formation and growth of the scale, especially the (Mo,W)O2 component. Al2O3 scale layers were not formed, and further runs with pure O2 or Ar-(20 percent)O2 ruled out an explanation of this phenomenon based on aluminum nitride formation. The oxidation was accelerated by the addition of NaCl gas, a finding attributed to the reaction of NaCl with external locally protective Al2O3 scales and with the internal(Mo, W)O2 layers.

Smeggil, J. G.↗

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.↗

Adsorption of O2, SO2, and SO3 on nickel oxide. Mechanism for sulfate formation

Calculations based on the atom superposition and electron delocalization molecular orbital (ASED-MO) technique suggest that O2 will adsorb perferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom is a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the perferred orientation in which the SO3 plane is parallel to the surface. On activation, SO3 adsorbed to an O2(-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Possibilities for alternative mechanisms which require the formation of Ni3(+) or O2(-) are discussed. NiSO4 thus formed leads to the corrosion of Ni at high temperatures in the SO2+O2/SO3 The SO2+O2/SO3 atmosphere, as discussed in the experimental literature.

Mehandru, S. P.↗

The effect of variations of cobalt content on the cyclic oxidation resistance of selected Ni-base superalloys

Cobalt levels were systematically varied in the Ni-base turbine alloys U-700 (cast), U-700m(PM/HIP), Waspaloy, Mar-M-247, In-738, Nimonic-115, U-720, and SX-R-150. The cobalt levels ranged from 0 wt % to the nominal commercial content in each alloy. The alloys were tested in cyclic oxidation in static air at 1000, 1100 and 1150 C for 500, 200 and 100 hr respectively. An oxidation attack parameter, Ka derived from the specific weight change versus time data was used to evaluate the oxidation behavior of the alloys along with X-ray diffraction analysis of the surface oxides. The alloys tend to form either Cr2O3/chromite spinel or Al2O3/aluminate spinel depending on the CR/Al ratio in the alloys. Alloys with a ratio of 3.5 or higher tend to favor the Cr oxides while those under 3.0 form mostly Al oxides. In general the Al2O3/aluminate spinel forming alloys have the better oxidation resistance. Increased cobalt content lowers the scaling resistance of the higher Cr alloys while a 5.0 wt % Co content is optimum for the Al controlling alloys. The refractory metals, particularly Ta, appear beneficial to both types of oxides perhaps due to the formation of the omni-present trirutile Ni(Ta,Cb,Mo,W)2O6. Both scales break down as increasing amounts of NiO is formed.

Barrett, C. A.↗

Adsorption of O2, SO2, and SO3, on nickel oxide - Mechanism for sulfate formation

Calculations based on the atom superposition and electron delocalization molecular orbital technique suggest that O2 will adsorb preferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom in a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the preferred orientation in which the SO3 plane is parallel to the surface. The calculations suggest that the strength of adsorption varies as O2 greater than SO2 greater than SO3. On activation, SO3 adsorbed to an O(2-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Alternative mechanisms which require the formation of Ni(3+) or O(-) are discussed. NiSO4 thus formed may play a passivating role for the corrosion of Ni at low temperatures in the SO2 + O2 + SO3 atmospheres and an active role at high temperatures, as discussed in the experimental literature.

Mehandru, S. P.↗

Hydrazine reduction of transition metal oxides - In situ characterization using X-ray photoelectron spectroscopy

The transition metal oxides (TMOs) V2O5, FeO3, Co3O4, NiO, CuO, and ZnO were exposed to hydrazine at various pressures. The metallic surfaces were surveyed by in situ X-ray photoelectron spectroscopy to determine the irrelative rate of reduction by hydrazine. The most easily reducible oxide, CuO, could be reduced to the metallic state at room temperature and 10 to the -6th torr. The reaction is first order with respect to CuO, with an activation energy of about 35 kJ/mol. Two types of adsorption were seen to occur at 295 K: (1) a reversible component in which the measured N:Cu ratio increased to 0.60 at hydrazine pressures up to 0.5 torr, and (2) an irreversible component, with a N:Cu ratio of 0.28, which could not be removed by extended vacuum pumping. The results of this study are useful for the identification of TMO's that can be used as solid neatallizers of hydrazine spills, and for the preparation of metal surfaces for electroplating and evaporative thin-film coating.

Littrell, D. M.↗

Degradation mechanisms in thermal barrier coatings

The degradation mechanism in thermal barrier coating systems subjected to prolonged heating in air as well as to thermal cycling was studied. Bond coat oxidation was found to be the most important reason for degradation. The oxidation produced NiO as well as Al?O? in one set of samples, but the variation in initial coating structure made it difficult to resolve systematic differences between isothermally heated and thermally cycled samples. However, the contribution to degradation from changes in substrate composition seemed less in the cycled sample.

Shinde, S. L.↗

Degradation mechanisms in thermal-barrier coatings

The degradation mechanism in a thermal barrier-coating system subjected to prolonged heating in air as well as to thermal cycling was studied. Bond-coat oxidation was found to be the most important reason for degradation. The oxidation produced NiO as well as Al2O3 in one set of samples, but the variation in initial coating structure made it difficult to resolve systematic differences between isothermally heated and thermally cycled samples. However, the contribution to degradation from changes in substrate composition seemed less in the cycled sample.

Shinde, S. L.↗

Corrosion of metals and alloys in sulfate melts at 750 C

The corrosion of Ni, Co, Ni-10Cr, Co-21Cr, and IN738 was studied at 750 C in the presence of molten sulfate mixtures (Na2SO4-Li2SO4 and Na2SO4-CoSO4) and in an atmosphere consisting of O2 + 0.12 percent SO2-SO3. The corrosion was observed to be similar for both Na2SO4-Li2SO4 and Na2SO4-CoSO4 melts. The corrosion of Ni and Co took place by the formation of a mixed oxide plus sulfide scale, very similar to the corrosion in SO2 or SO3 alone. The initial stage for the corrosion of Ni-10Cr involved the formation of a thick NiO + Ni3S2 duplex scale, and Cr sulfide was formed during the later stages. A pitting type of morphology was observed for both Co-21Cr and IN738. The pit was Cr sulfide at the beginning, and subsequently the sulfides oxidized to Cr2O3. A base-metal oxide layer was present above the pit, and this was observed to be formed very early in the corrosion process. A mechanism is proposed to explain this. In general, the formation of sulfides appears to be the primary mode of degradation in mixed sulfide melts.

Misra, A. K.↗