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  • 1
    ISSN: 1573-4889
    Keywords: Chromium carbides ; Cr23C6 ; Cr3C2 ; Cr7C3 ; sulfidation kinetics ; sulfide scales
    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 chromium carbide, Cr23C6, was investigated in H2S-H2 gas mixtures over a sulfur partial pressure range of 103.5−10−6 Pa at 1073 K using thermogravimetry, optical and scanning electron microscopy, X-ray diffraction analysis, and electron-probe microanalysis. The kinetics were rapid for short time periods and followed a linear rate law at low sulfur pressures, whereas sulfidation tends to obey a parabolic rate law at high pressures. Sulfidation rates decreased with increasing carbon content in the carbide. Surface morphologies could be divided into three groups: (I) at high sulfur pressures, petal-like. crystals (Cr2S3); (II) at intermediate pressures, a twinlike structure (Cr3S4); (III) and at low pressures, a flat surface with numerous hexagonal pits (Cr1−xS). The scale consisted of two distinct layers: an external scale with a single or multilayer structure and an inner scale with a mixture of Cr1−xS, Cr3C2, and Cr7C3. These higher carbides, Cr3C2 and Cr7C3, may be formed by the sulfidation-carburization of Cr23C6. Pt-marker experiments indicated that the external scale grew by chromium diffusion and that sulfur migration played an important role in the growth of the inner scale.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-4889
    Keywords: Chromium ; sulfidation kinetics ; chromium sulfides ; multilayer structure ; H2S-H2 gas mixtures
    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 chromium was investigated over a temperature range of 973–1173 K in H2S-H2 gas mixtures of 104–10−6 Pa sulfur partial pressures using thermogravimetry, X-ray diffractometry, optical and scanning electron microscopy, and electron-probe microanalysis. Sulfidation kinetics are rapid for short periods and obey a linear rate law at low sulfur pressures, whereas at high sulfur pressures sulfidation tends to be parabolic. The surface morphologies can be divided into four types: at high sulfur pressures a petal-like crystal of Cr2S3(rho. and tri.) (type 1), at intermediate sulfur pressures a twinlike structure of Cr3S4 (type 2), at low sulfur pressures a flat surface with numerous hexagonal pits of Cr1−xS (type 3), and a fine twinlike structure of ordered Cr1−xS (type 4). At 973 K, the sulfur pressure ranges are type 1 at $$p_{S_2 } $$ 〉 10−4, type 2 at $$p_{S_2 } = 10^{ - 5} $$ , and type 3 at $$p_{S_2 }〈 10^{ - 6} Pa$$ . The critical sulfur pressure where type 2 was formed, 10−5 Pa at 973 K, shifts toward higherressures at higher temperatures and becomes 10−3 Pa at 1073 K and 10−1 Pa at 1173K. Type 4 is observed at 1173K and 10−6 Pa sulfur pressure. Thesulfide scale is composed of two distinct layers: an external layer, which is dense with a fine columnar structure, and an inner layer, which is porous with a layered structure of sulfides and voids. The external scale is composed offour layers at high sulfur pressures: at the scale-gas interface Cr2S3(rho.), next Cr2S3(tri.), third Cr3S4, and innermost Cr1−xS. With decreasing sulfur pressures,the number of layers in the external scale was reduced. Pt markers were positioned between the external and inner scales.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Oxidation of metals 27 (1987), S. 267-282 
    ISSN: 1573-4889
    Keywords: Co-Mn alloys ; high-temperature oxidation ; multilayer structures ; cation concentration profiles
    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 of Co alloys containing up to 23.0 % Mn was investigated at temperatures of 1273–1473 K in an oxygen pressure range of 10–105 Pa using thermogravimetry, electron-probe microanalysis, and optical microscopy. Oxidation followed a parabolic rate law, except in the early reaction stage. For the growth of the (Co, Mn)O scale, parabolic rate constants increased with increasing manganese content, whereas with further additions of manganese the rate constants decreased due to an intermediate layer of (Co, Mn)3O4. This critical manganese content increased with increasing temperature. The scale structures were classified into three groups: group I, a single-layer scale; group II, an inner-outer double layer; and group III, an inner-intermediate-outer triple layer. The inner layer consisted of (Co, Mn)O; the outer layer was a mixture of (Co, Mn)O and (Co, Mn)3O4; the intermediate layer was composed of (Co, Mn)3O4. Cation concentration profiles were measured across the external scales with single- or multilayer structures. Diffusional analysis indicated that manganese moved 1.25 times faster than did cobalt in the (Co, Mn)O scale. Activation energies for oxidation are 118–126 kJ/moles for groups I and II, and for the alloys in group III they are 290–367 kJ/moles. Parabolic rate constants and scale structures are discussed on the basis of the Co-Mn-O phase diagram.
    Type of Medium: Electronic Resource
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