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  • 1
    ISSN: 1573-4889
    Keywords: Ni-Si alloys ; internal oxidation ; silica ; transition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation of Ni-2.05Si and Ni-4.45Si was studied in oxygen over the range of 600°–1000°C for 18 hr. The oxidation kinetics did not follow a parabolic rate law, bur rather a power law of the form (Δw)n=kt was followed. The value of n ranged from 2.7 to 4.9 for Ni-2.05Si and from 3.0 to 6.4 for Ni-4.45Si. The low-silicon alloy exhibited extensive internal oxidation, whereas the higher-silicon alloy did not internally oxidize. In general, NiO containing little or no silicon formed as an exterior layer on both alloys. The internal oxidation zone in Ni-2.05Si was highly irregular in thickness, and in some areas there was no internal oxidation. The higher-silicon alloy formed a continuous layer of a silicon-rich oxide. X-ray diffraction did not detect silica (amorphous), and no evidence of Ni2SiO4 was observed, although EDAX analysis suggests that small amounts of the silicate might have formed. Theaverage thickness of the internal oxidation zone was found to agree well with calculated values based on oxygen solubility and diffusivity data. No enrichment of silicon occurred in the internal oxidation zone. Calculated values, 0.033 and 0.038 (depending on the model used), of the mole fraction of silicon required for the transition from internal oxidation to continuous silica film formation agreed well with experimental data obtained in both this study and with others reported in the literature.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 1 (1969), S. 1-2 
    ISSN: 1573-4889
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 10 (1976), S. 227-238 
    ISSN: 1573-4889
    Keywords: desorption of oxygen ; transmission electron microscopy ; in situ oxidation studies ; oxidation of thin films ; nucleation of oxides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Partly oxidized copper films were annealed in a controlled vacuum of 10−7 Pa at a temperature of 450° C. The changes discussed below were observed in situ with a specially designed high-resolution transmission electron microscope. The thin, (100)-oriented, single-crystal films of copper had been oxidized immediately prior to the annealing studies at the same temperature and at an oxygen partial pressure of 7×10 −1 Pa, until the desired fraction of the copper film was converted to oxide. It was observed that the oxide disappeared during annealing as long as some copper was left unoxidized. The disappearance of the oxide is explained as being due to dissociation of the oxide at the oxide-metal interface followed by diffusion of oxygen into the metal and desorption of oxygen from the surface of the unoxidized copper. The rate of disappearance of the oxide was found to be proportional to the surface area of unoxidized copper, i.e., the desorption was found to be the rate — limiting step. In the case of heavily oxidized films (〉50%), holes were observed to develop in the oxide near the oxide-metal interface after an annealing period of 2–3 hr. Upon resumption of the oxidation, these holes first disappeared, and the normal oxidation behavior was then resumed. The formation of holes may be explained by vacancy clustering. When completely oxidized films were annealed, recrystallization of the oxide was observed.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 22 (1984), S. 45-57 
    ISSN: 1573-4889
    Keywords: Ni-Cr-Mo alloys ; sulfidation ; scale structures ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The effect of molybdenum additions 5, 10, 15, and 20 wt. %, on the sulfidation behavior of Ni-20Cr, and the effect of chromium additions, 5, 10, 15, and 20 wt.%, on the sulfidation of Ni-20Mo were studied in pure sulfur vapor at 700°C. In general, the alloys followed a linear or near-linear rate law, the sulfidation rate of Ni-20Mo being slightly less than that of Ni-20Cr. The alloys having the lowest ternary addition, e.g., Ni-Cr-5Mo and Ni-20Mo-5Cr. exhibited the most rapid reaction rates. The highest alloying additions of 20 wt.% had no appreciable benefit on reaction rates. Scale structures were complex but generally consisted of several layers. The outer layer was always NiS1.03, although both binaries formed Ni3S2 within the NiS1.03. An inner layer of Cr3S4 existed in which there was considerable dissolved molybdenum. A thin, intermediate layer of Cr2S3 generally formed between the Cr3S4 and the outer nickel sulfide. An innermost layer of MoS2 formed on all alloys containing more than 10 wt. % Mo, and a second phase of Mo2S3 formed within the MoS2 on Ni-20Mo. Although the scales changed with alloy composition, no significant changes in reaction rate were observed. Notable differences in both scale structure and reaction kinetics between this study and previous studies were apparent. The differences and possible reaction mechanisms are discussed.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 29 (1988), S. 271-287 
    ISSN: 1573-4889
    Keywords: Cr-Mn stainless steel ; spinels ; oxidation stability diagrams
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior in air of Fe-19.6Cr-15.1Mn was studied from 700 to 1000°C. Pseudoparabolic kinetics were followed, giving an activation energy of 80 kcal/mole. The scale structure varied with temperature, although spinel formation occurred at all temperatures. At both 700 and 800°C, a thin outer layer of γ-Mn2O3 formed. The inner layer at 700°C was (Fe,Cr,Mn)3O4, but at 800°C there was an intermediate layer of Fe2O3 and an inner layer of Cr2O3 + (Fe, Cr,Mn)3O4. Oxidation at 900°C produced an outer layer of Fe3O4 and an inner layer of Cr2O3+(Fe,Cr,Mn)3O4. Oxidation at 1000°C caused some internal oxidation of chromium. In addition, a thin layer of Cr2O3 formed in some regions with an intermediate layer of Fe3O4 and an outer layer of (Fe,Mn)3O4. A comparison of rates for Fe3O4 formation during oxidation of FeO as well as for the oxidation of various stainless steels, which form spinels, gave good agreement and strongly suggests that spinel growth was rate controlling. The oxidation rate of this alloy (high-Cr) was compared with that of an alloy previously studied, Fe-9.5Cr-17.8Mn (low-Cr) and was less by about a factor of 12 at 1000°C and by about a factor of 100 at 800°C. The marked differences can be ascribed to the destabilization of wustite by the higher chromium alloy. No wustite formation occurred in the high-Cr alloy, whereas, extensive wustite formed in the low-Cr alloy. Scale structures are explained by the use of calculated stability diagrams. The mechanism of oxidation is discussed and compared with that of the low-Cr alloy.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 29 (1988), S. 307-325 
    ISSN: 1573-4889
    Keywords: Preoxidation ; sulfidation ; coal char ; chromia films ; alumina films
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Preoxidation of several chromia-forming and of several alumina-forming alloys at temperatures ranging from 982 to 1260°C in either water-saturated argon or in air was performed prior to corrosion in coal char. Chromia films offered no protection to subsequent sulfidation in char. The chromia films were adherent but permitted rapid inward penetration of sulfur and outward penetration of cations to form extensive sulfides. Alumina films offered protection for much longer times than did chromia films, but localized cracking and/or spalling of the alumina permitted rapid attack at the exposed areas. The addition of yttrium as either a metallic element or as an oxide dispersion improved the mechanical stability of the films and prolonged the period of protectiveness. Alumina films would provide an excellent protective barrier, if thick crack-free films could be grown at reasonable temperatures. The low growth rates at very high temperatures and the susceptibility of alumina films to crack and spall during thermal cycling suggest that preoxidation will not offer adequate corrosion resistance for alloys exposed to char in goal gasifiers.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 25 (1986), S. 1-28 
    ISSN: 1573-4889
    Keywords: sulfidation ; yttrium ; duplex-sulfide scales ; lamellar sulfides ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The sulfidation of Ni-10Cr-5Al, Ni-20Cr-5Al, and Ni-50Cr-5Al, and of the same alloys containing 1% Y, was studied in 0.1 atm sulfur vapor at 700°C. The sulfidation process followed linear kinetics for all the alloys except Ni-50Cr-5Al-1Y, and possibly Ni-50Cr-5Al, which followed the parabolic law. The reaction rates decreased with increasing chromium content in alloys without yttrium, and the addition of yttrium reduced the rates by at least a factor of two for the alloys containing 10 and 20% Cr and by an order of magnitude for Ni-50Cr-5Al. Alloys containing 10 and 20% Cr (with and without yttrium) formed duplex scales consisting of an outer layer of NiS1.03 and an inner lamellar layer of a very fine mixture of Cr2S3 and A12O3 in a matrix of NiS1.03. The two alloys containing 50% Cr formed only a compact layer of Cr2S3, which was brittle and spalled during cooling. The lamellae in the duplex scales were parallel to the specimen surface and bent around corners. The lamellae were thicker than those on Ni-Al binary alloys. The lamellae were also thicker in scales on the 20% Cr alloy than on the 10% Cr alloy. The presence of yttrium refined the lamellae and increased the lamellae density near the scale/metal interface in the 10% alloy, but in the 20% Cr alloy the lammellae were thicker and more closely spaced. Platinum markers were found in the inner portion of the exterior NiS1.03 layer close to the lamellar zone. A counter-current diffusion mechanism is proposed involving outward cation diffusion and inward sulfur diffusion, although diffusion was not rate controlling for alloys containing 10 and 20% Cr. Auger analysis of scales formed on Ni-50Cr-1Y showed an even distribution of yttrium throughout the layer of Cr2S3, suggesting that some yttrium dissolved in the sulfide. The reduced sulfidation rate of samples containing yttrium is explained by the possible dissolution of yttrium as a donor. The presence of Y4+ would then decrease the concentration of interstitial chromium ions in the N-type layer of Cr2S3, which would decrease the reaction rate.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 25 (1986), S. 235-268 
    ISSN: 1573-4889
    Keywords: oxidation ; Mn2O3 ; spinels ; manganowustite ; mechanisms ; fusion reactors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation in air of an austenitic Fe-Mn-Cr steel containing 17.8 Mn, 9.5 Cr, 1.0 Ni, 0.27 C, and 0.03 N was studied over the range 700–1000°C. Oxidation of surface-abraded samples at “low” temperatures, 700–750°C, resulted in only Mn 2O3 containing dissolved chromium, except at corners, where large nodules containing spinel and manganowustite formed. The Mn2O3 layer grew into the substrate forming a globular-type film. This growth mode was the result of slow interdiffusion in the alloy after the cold-worked surface layer had been recrystallized and/or consumed, as evidenced by the formation of a ferrite layer subjacent to the scale and by the instability of the planar interface. No internal oxidation was observed beneath the Mn2O3 film at either 700 or 750°C. Samples oxidized in the“high-temperature” region, 800–1000°C, exhibited vastly different behavior, forming thick stratified scales at long times (24 hr), the scales consisting of a very thin outer layer of Mn2O3 (with appreciable iron in solution), Fe-Mn spinel beneath the outer layer, and a thick inner layer of manganowustite and a chromium-containing spinel. No chromium was found in the outer two layers. A thin layer of nearly pure Fe2O3 formed between Mn2O3 and the outer spinel. Quasiparabolic kinetics were observed. The high-temperature rates were about 103 to 104 times greater than at low temperatures at the “transition” temperature. The rapid rates at high temperatures were attributed to manganowustite growth. However, oxidation of an electropolished sample at 750°C, from which the superficial cold-worked layer had been removed, formed scales similar to those observed at high temperatures at comparable rates. A difference by a factor of over 104 existed between the oxidation rate of the electropolished sample and the surface-abraded sample at 750°C. The much slower oxidation rate of the latter is attributed to greatly enchanced manganese diffusion through the high dislocation-density, cold-worked layer. Short-time tests at 800°C revealed an incubation period during which a thin protective layer of Mn2O3 formed. The incubation period corresponded to the recrystallization time of the cold-worked layer. Subsequently, nodular growth occurred which was associated with internal oxidation. The nodules, consisting of spinel and manganowustite, eventually linked up to form a thick, stratified scale. Comparison of the scale structures with calculated phase diagrams of composition versus oxygen activity (at constant temperature), showed that the protective films formed at low temperatures were due to kinetics factors, involving enhanced manganese diffusion through the cold-worked layer, rather than to thermodynamics. A model for the breakdown of protective films is proposed which involves internal oxidation.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 33 (1990), S. 103-133 
    ISSN: 1573-4889
    Keywords: Ni-Mo alloys ; ternary additions ; sulfidation ; MoS2, intercalation ; Al0.55Mo2S4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Five ternary additions, Cr, Ti, Mn, V, and Al were studied at equi-atomicpercent levels (17 a/o) for their effect on the sulfidation behavior of Ni-19a/o Mo (28–30 w/o) over the range of 600–800°C in 0.01 atm S2. Al was by far the most effective addition. A linear decrease in log kp vs. Al content was observed up to 7.5w/o Al, beyond which no further change was observed. All alloys followed the parabolic rate law. Arrhenius plots gave activation energies of 36.9–41.2 Kcal/mol for alloys containing Ti, Cr, Mn, and V, whereas the activation energies for Al-containing alloys were 47.2 Kcal/mol, indicating that a different diffusion process was involved. Complex scales were formed on all alloys, consisting of an outer layer of Nis1+x and complex inner layers which depended upon alloy composition. Two alloys, those with Cr and Mn, formed intermediate layers of Cr2S3 and MnS, respectively, but these layers had little effect on the kinetics. MoS2 was a constituent of the inner scales except for the alloys with Al. A ternary sulfide, Al0.55Mo2S4 and Al2S3 were observed. The presence of the mixed sulfide was always associated with the low sulfidation rates. The formation of MoS2 on alloys results in a different, less-protective behavior than for MoS2 formed on pure Mo. This effect is due to the intercalation of Ni into MoS2 in octahedral positions between the weakly bonded layers of covalently bonded sheets of trigonal prisms. The size of Al+3 is too small to be intercalated, and thus MoS2 is destabilized by Al.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1573-4889
    Keywords: sulfidation ; Ni-Mo-Al alloys ; Ni-Al alloys ; Al0.55Mo2S4 ; Al2S3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The sulfidation behavior of five Ni-Mo-Al ternary alloys and two Ni-Al binary alloys was studied over the temperature range 600–800°C in sulfur vapor of 10−2 atm. The effect of sulfur pressure was also investigated at $$P_{S_2 } = 10^{ - 2} $$ and10−4 atm. using two Ni-Mo-Al alloys. The sulfidation of all Ni-Mo-Al andNi-Al alloys followed the parabolic rate law. The sulfidation rate decreasedwith increasing Al content for a given Mo content for Ni-Mo-Al alloys. Twobinary alloys, Ni-13.5Al and Ni-31Al, sulfidized at comparable rates toNi-30Mo-7.5Al, which has excellent sulfidation resistance. The activationenergies for ternary alloys range from 44.8–50.8 kcal/mol, whereas those forNi-13.5Al and Ni-31Al are 41.5 and 39.1 kcal/mol, respectively. Complexscales formed on all Ni-Mo-Al alloys, consisting of an outer layer of nickelsulfide and an inner layer of MoS2, A12S3, and Al0.55Mo2S4. Sulfide scalesformed on Ni-Al alloys were bilayered, consisting of an outer layer of nickelsulfide and an inner layer of A12S3. The low sulfidation rate of the ternaryalloys was attributed to the combined presence of both A12S3 and Al0.55Mo2S4.The sulfidation kinetics of two Ni-Mo-Al alloys are independent of sulfurpressure, suggesting that the growth of the inner layer was the dominant process.
    Type of Medium: Electronic Resource
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