The corrosion of Fe-Mo alloys in H2/H2O/H2S atmospheres

The corrosion of Fe-Mo alloys containing up to 40 wt.% Mo was studied over the temperature range 600–980C in a H₂/H₂O/H₂S mixture having a sulfur pressure of 10^–5 atm. and an oxygen pressure of 10^–20 atm. at 850C. All alloys were two-phase, consisting of an Fe-rich solid solution and an intermetallic compound, Fe₃Mo₂. The scales formed on Fe-Mo alloys were bilayered, consisting of an outer layer of iron sulfide (FeS) and of a complex inner layer whose composition and microstructure were a function of the reaction temperature and of the Mo content of the alloys. No oxides formed under any conditions. The corrosion kinetics followed the parabolic rate law at all temperatures. The addition of Mo caused only a slight decrease of the corrosion rate. Platinum markers were always located at the interface between the inner and outer scales, indicating that outer scale growth was primarily due to outward diffusion of iron, while the inner scale growth had a contribution from inward diffusion of sulfur.     

X-ray topographic study of β-NiAl upon growth of an α-Al2O3 film

The Berg-Barrett X-ray topographic method was employed as a microstructural technique to seek correlations of the metal substructure to the morphological features of -Al₂O₃ films grown on -NiAl. An analysis of diffraction micrographs using {112} and {002} reflections from individual grains in -NiAl revealed its subgrain structure to a depth of 30 . The dimensions of these subgrains were directly related to the density of oxide ridges in the -Al₂O₃ films and to the dimensions and shapes of cavities at the NiAl-Al₂O₃ interface.     

High-temperature sulfidation of Fe-30Mo alloys containing ternary additions of Al

Fe-30Mo alloys containing up to 9.1 wt% Al were sulfidized at 0.01 atm sulfur vapor over the temperature range of 700–900°C. The sulfidation kinetics followed the parabolic rate law for all alloys at all temperatures. For alloys containing small and intermediate amounts of Al (<4.8 wt.%), a duplex sulfide scale formed. The outer layers of the scales were found to be relatively compact FeS in all cases; whereas the inner layers were composed of the layered compound MoS ₂ (intercalated with iron), the Chevrel compound Fe _x Mo ₆ S ₈,a spinel double sulfide Al _x Mo ₂ S ₄,depending on the Al content of the alloy and the sulfidation temperature. Extremely thin scales were found on the alloys with higher Al contents. Accordingly, extremely slow sulfidation rates were observed—even slower than the sulfidation rate of pure Mo. The transition of the sulfidation kinetics from a high-rate active mode to a low-rate passive mode requires both a critical Al content in the alloy and a critical Mo content. Because of the two-phase nature of the alloys, the latter requirement implies a critical volume fraction of the intermetallic second-phase in the alloy, which has been known as the multiphase effect. Interestingly, the multiphase effect in these alloys was also a function of the Al content in the alloys.     

The corrosion behavior of Ni-Mo alloys in a H2/H2O/H2S gas mixture

The corrosion behavior of Ni-Mo alloys containing up to 40 wt.% Mo was studied over the temperature range of 550–800C in a mixed gas of H₂/H₂O/ H₂S. The scales formed on all alloys contained only sulfides and were doublelayered. The outer scale was single-phase Ni₃S₂. Depending on the alloy composition and reaction conditions, the inner scale was: (1) a mixture of MoS₂ plus Ni₃S₂ with/without Ni, (2) MoS₂, or (3) MoS₂ plus intermetallic particles and/or double sulfide Ni_2.5Mo₆S_6.7. Neither internal oxidation nor internal sulfidation were observed at lower temperatures. Internal sulfidation was however observed at higher temperature when the scale apparently melted. The parabolic law was generally obeyed for the most concentrated alloys. For the two more-dilute alloys the kinetics were mostly linear. A decrease in the corrosion rate occurred with increasing Mo content of the alloy and may be attributed to the presence of increasing volume fractions of MoS₂ and/or of a double Ni-Mo sulfide in the inner region of the scale. For the two most concentrated alloys this may also be due to the presence of a number of particles of the unsulfidized intermetallic compound, which is Ni₃Mo for Ni-30Mo, but NiMo for Ni-40Mo.     

Effect of cold work on the oxidation resistance of2\tfrac{1}{4} Cr-1 Mo steel

The effect of cold work on the oxidation rate of 21/4 Cr-1 Mo steel in pure oxygen at 1 atm pressure at temperatures ranging from 400 to 950C has been studied for short exposure periods (max. 4 hr). The specimens had been cold worked up to 90% by cold rolling. The results indicate negligible effect of cold work on the oxidation kinetics up to 700C, beyond which there is general reduction in oxidation. The effect was pronounced at 900C. The increased resistance to oxidation has been attributed to the faster diffusion of chromium in the cold-worked material compared to the annealed one, leading to the formation of a chromium-rich spinel which helps in slowing down the oxidation of the alloy. The findings have been corroborated by the examination of all samples oxidized at 900C by optical, EPMA, SEM, and EDAX analyses.     

Kinetics and mechanisms of the oxidation of cobalt at 600–800°C

Two-phase layered scales comprising CoO and Co ₃O₄ formed on cobalt during oxidation at 600°, 700°, and 800°C and at oxygen partial pressures in the range 0.001–1 atm. The kinetics, which were obtained by thermogravimetric analysis, obeyed a parabolic rate law after an initial, non-parabolic stage of oxidation. The monoxide consisted of relatively large grains (10 ) and the spinel comprised small grains (3 ) for all conditions of oxidation. Grain boundary diffusion of cations played a significant role in the growth of the spinel layer. Thermogravimetric data and the steady-state ratio of the oxide layer thicknesses were employed to calculate the rates of thickening of the individual oxide layers and the rate of oxidation of CoO to Co₃O₄.     

On the nature of “easy paths” for the diffusion of oxygen in thermal oxide films on aluminum

Thermal oxide films grown on electropolished aluminum specimens have been investigated by transmission electron microscopy of stripped oxide films and ultramicrotomed sections. Particular attention has been focused on the nucleation sites -Al ₂ O ₃ crystals and the relationship of such sites to surface features on the electropolished aluminum surface. It is evident that easy paths for the diffusion of oxygen, or the nucleation sites of -Al ₂ O ₃ crystals, are not distributed randomly over the electropolished aluminum surface, but form preferentially in the amorphous oxide layer grown over preexisting metal ridges. Thus, the diffusion of molecular oxygen through cracks in the amorphous oxide layer represents the most realistic and acceptable basis for explaining the local growth of the -Al ₂ O ₃ crystals in thermal oxide films on aluminum, although the cracks have not yet been observed directly.Present address: Alcan International, Ltd., Banbury Laboratories, Banbury, Oxford, OX16 7SP, United Kingdom.     

The effect of various oxide dispersions on the phase composition and morphology of Al2O3 scales grown on β-NiAl

A series of oxide-dispersed-NiAl alloys were oxidized in order to explore the effect of various cation dopants on the - phase transformation in the Al₂O₃ scale and the effect of phase composition on the scale microstructure. Larger ions such as Y, Zr, La, and Hf appeared to slow the- to-Al₂O₃ phase transformation, while a smaller ion, Ti, appeared to accelerate the transformation.     

Defect structure and chemical diffusion in nickel sulfide β-Ni3S2

The chemical composition, defect structure, and diffusion in nickel sulfide -Ni₃S₂ have been investigated in H₂S-H₂ mixtures containing between 1 and 65% H₂S between 560 and 700°C. Gravimetric, density, and X-ray studies were carried out. In the thermodynamically stable compound the ratio of Ni/S varied between 1.3 and 1.75. The X-ray examination showed a step change in the lattice parameter at the Ni/S ratio 1.4. A linear dependence of the density values (between 5.5 and 6.2 g/cm³) on the composition was observed. On the basis of the chemical composition and density measurements the number of nickel and sulfur atoms in 1 cm³ were determined. It has been shown that the Ni₃S₂ phase is defected in both anion and cation sublattices and that its chemical formula may be described as follows: Ni_3±yS_2x, where y 2x. It has been found that in the mixture containing 10% H₂S the process of defect formation is determined by their diffusion in the sulfide. The temperature dependence of the diffusion coefficient is described by the equation D = 13.15 exp(-30,000/RT) cm²/sec. No dependence of D on the sulfur partial pressure was observed, but this may be due to the relatively large uncertainties in the measurement of the diffusion coefficients.     

The effect of Mo on the high-temperature sulfidation of Ni

The sulfidation behavior of Ni-Mo alloys containing up to 40 wt.% Mo was studied at =0.01 atm. over the temperature range of 550–800°C. The alloys included two solid solutions (Ni-10Mo and Ni-20Mo), the single-phase intermetallic compound Ni₄Mo(Ni-29Mo), and two alloys which were two-phase, Ni-30Mo and Ni-40Mo (Ni₄Mo+Ni₃Mo). The sulfidation of all alloys followed the parabolic rate law. The rate of sulfidation decreased with increasing amounts of Mo. Activation energies for sulfidation gave values of 39.1±1.0 kcal/mol. The sulfide scales were bilayered, consisting of an outer layer nickel sulfide (NiS_1+x and Ni₃S₂) and an inner, complex layer of MoS₂ plus intermetallic particles. The rate-controlling step of the sulfidation for the alloys was inward sulfur diffusion and/or outward nickel diffusion through the inner MoS₂ layer. Neither selective sulfidation nor internal sulfidation were observed. No significant difference in the sulfidation kinetics, sulfide structure, and scale constitution could be noted between single-phase alloys and two-phase alloys. The location of the markers was the interface between the inner and outer layers, indicating that the inner layer formed by inward diffusion of sulfur, and the outer layer grew by outward nickel diffusion. The inability to form a continuous protective molybdenum sulfide layer is discussed in terms of the structure of MoS₂ and changes caused by intercalation of Ni into the layered crystal structure. The decrease in sulfidation rate with increasing Mo was attributed to increasing amounts of the intermetallic compound. The increasing volume fraction of particles decreased the available diffusion area in the inner layer and provided a blocking effect.     

The high-temperature corrosion behavior of Nb-Al alloys in a H2/H2S/H2O gas mixture

The corrosion behavior of pure Nb and three Nb Al alloys containing 12.5, 25, and 75 at.% Al was studied over the temperature range of 800–1000°C in a H₂/H₂S/H₂O gas mixture. Except for the Nb-12.5Al alloy consisting of a two phase structure of -Nb and Nb₃Al, other alloys studied were single phase. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants increased with increasing temperature, but fluctuated with increasing Al content. The Nb-75Al alloy exhibited the best corrosion resistance among all alloys studied, whose corrosion rates are 1.6–2.2 orders of magnitude lower than those of pure-Nb (depending on temperature). An exclusive NbO₂ layer was formed on pure Nb, while heterophasic scales were observed on Nb-Al alloys whose compositions and amounts strongly depended on Al content and temperature. The scales formed on Nb-12.5Al consisted of mostly NbO₂ and minor amounts of Nb₂O₅, NbS2, and -Al₂O₃, while the scales formed on Nb-25Al consisted of mostly Nb₂O₅ and some -Al₂O₃. The scales formed on Nb-75Al consisted of mostly -Al₂O₃ and Nb₃S₄ atT 900°C, and mostly -Al₂O₃ , Nb₃S₄ and some AlNbO₄ at 1000°C. The formation of -Al₂O₃ and Nb₃S₄ resulted in a significant reduction of the corrosion rates.     

Improvement in the Oxidation Resistance of an Al-Deposited Fe–Cr–Al Foil by Preoxidation

The oxidation kinetics of conventional Fe–20Cr–5Al (in mass %) foil, Al-deposited foil and Al-deposited and preoxidized foil was studied at 1373 K in air. All the foils were 50-m thick and contained minor additions of rare-earth elements. The oxide scales were observed with SEM and TEM combined with EDS and were characterized with X-ray diffractometry and electron diffraction. The deposition of Al onto the foil from the vapor phase improves oxidation resistance. The details regarding this matter were reported elsewhere. The combination of the Al deposition and the subsequent preoxidation at 1173 K for 90 ks in air further increases the oxidation resistance, i.e., the smallest parabolic rate constant among the three kinds of foils, and excellent scale adherence. Preoxidation enhances the growth of -Al₂O₃, which transforms to -Al₂O₃ during subsequent oxidation. However, such -Al₂O₃ grains are much larger than those formed on the conventional foil of similar chemical composition. Small closed voids and small spinel-type, oxide particles appear in -Al₂O₃ grains with the progress of oxidation. The former is explained in terms of the volume decrease accompanying the phase transformation and the latter by the low solubility of Fe in -Al₂O₃.     

High-resolution SIMS and analytical TEM evaluation of alumina scales onβ-NiAl containing Zr or Y

High-resolution SIMS and TEM have been used to evaluate growth processes and interfacial segregation occurring in -Al₂O₃ scales grown at 1200°C on -NiAl containing zirconium or yttrium.¹⁸O/SIMS shows that the extent of aluminum diffusion occurring during -Al₂O₃ growth is reduced by the presence of these alloying elements, which are seen by SIMS imaging as oxide particles within the scale. STEM/EDS of the same oxide scales show that zirconium and yttrium also segregated to the oxide-alloy interface to the extent, respectively, of 0.15 and 0.07 of a monolayer and to oxide grain boundaries (0.2 monolayer). The complementary information provided by SIMS, TEM, and STEM provides a better understanding of the role of reactive elements in modifying scale-growth processes.     

The formation of α-Al2O3 scales at 1500°C

The growth of Al₂O₃ scales on -NiAl was studied at 1500°C. Oxidation rates, diffusion mechanisms, and microstructures were examined in order to achieve a complete understanding of the scale development. Variation of the Al content within the phase field had little effect on the oxidation behavior. Ionimplanted yttrium (2×10¹⁶/cm²) was observed to provide a short-term improvement in scale adhesion but little long-term effect. When doped with Y or Zr, the first 1 m of -Al₂O₃ was observed to grow mainly by an inward oxygen growth mechanism. At longer times when the implant was ineffective, microstructural observations indicate a mixed-growth mode.     

Effect of a marker material on the oxidation of nickel in sulfur dioxide

A marker study of nickel oxidation in SO₂ at 600°C has proved that after the reaction metallic markers (Au, Pt, W) are covered with a sulfide rim. This effect is not observed on quartz markers. The metallic markers make the intermediate NiO layer adjacent to them increase, whereas the quartz marker makes this layer disappear.     

Oxidation ofγ′-Ni3Al andγ′-Ni3Al(Si) intermetallic compounds at low-oxygen pressures

The oxidation behavior of -Ni₃Al and -Ni₃Al(Si) (Ni₇₅Al₂₀Si₅) intermetallic compounds was studied at 1073 K and oxygen partial pressures of 59×10^–6 atm, 1.2×10^–14 atm, and 1.2×10^–19 atm by means of a manometric apparatus, and Rhines packs of NiO/Ni and FeO/Fe, respectively. Oxidation kinetics were determined either by recording weight gains or by measuring the internal-oxidation-zone depths. The structures and morphologies of oxides were also studied. Relatively low oxidation rates occurred for both compounds when oxidized in the manometric apparatus, while fast internal oxidation was observed for both compounds in the NiO/Ni pack. The fastest oxidation occurred in the -Ni₃Al compound in the FeO/Fe pack. A healing Al₂O₃ layer was formed on the surface of -Ni₃Al(Si) compound in the FeO/Fe pack, indicating a synergistic effect between the solute elements in the compound at the oxygen pressures corresponding to the dissociation of FeO. The oxidation rate was found to depend on the volume expansion associated with solute-atom oxidation.     

Protection of Sintered Steels against Corrosion in Neutral Media with an N-M-1 Inhibitor

The effect of an N-M-1 inhibitor (a salt of cyclohexylamine and C₁₀ to C₁₆ aliphatic acids) on the corrosion of sintered powder steels 13 and 141 (with the 14 to 17% porosity) in distilled or tap water at 20 to 80°C, as well as in 0.05 M Na₂SO₄ solution, is studied by gravimetric and electrochemical methods. The protective concentration of the inhibitor is lower in distilled, than in tap water or sodium sulfate solution. The protective action decreased with an increase in temperature. In tap water or sodium sulfate solution, the corrosion-inhibiting effect is weaker for 13 than for 141.     

18O/SIMS characterization of the growth mechanism of doped and undoped α-Al2O3

Sequential oxidation experiments at 1200°C and 1500°C using¹⁶O and >95%¹⁸O-enriched environments were conducted on undoped and Y- and Zr-doped -NiAl and FeCrAl alloys. After oxidation, samples were analyzed by SIMS sputter depth profiling. At 1200°C, a clear pattern was established where the undoped -Al₂O₃ was found to grow by the simultaneous transport of both Al and O. Zr-doped -Al₂O₃ was found to grow mainly by the inward transport of oxygen. The profiles in all cases indicate O diffusion primarily by shortcircuit pathways. Results at 1500°C (only on -NiAl) indicated a similar behavior but were less conclusive. Y and Zr were found to segregate to the oxide grain boundaries at 1200°C and 1500°C. The segregation of these dopants is believed to impede the cation transport in the -Al₂O₃ scale and thereby change the oxidation mechanism.     

Effect of lamellar structure parameters on the properties of titanium alloy VT3-1

Conclusion An increase in the ultimate breaking strength, stress-rupture strength, and fatigue limit of alloy VT3-1 with a lamellar structure may be achieved as a result of refining any parameter of the structure, particularly -phase platelet thickness, and increasing the volume fraction of secondary -phase. An increase in ductility characteristics, toughness, and creep resistance may be provided by increasing the dimensions of -colonies and primary -phase particles (up to 2.5–3.5 m) and reducing the volume fraction and dispersivity of secondary -phase lamellar precipitates. Coarsening of -grains leads to an increase in a_c, k_Q, and refinement leads to an increase in and a_n.Qualitative dependences for mechanical properties of alloy VT3-1 on lamellar structure parameters made it possible to isolate those structural parameters which have the most marked effect on properties.The properties of alloys with a finely lamellar structure (d25 m, b_{I, II}<2 m) are most sensitive to structure. In this case a change in -colony size by 10 m and -platelet thickness by 1 m affects the properties 3–20 times more strongly than a change in -grain size by 100 m. The effect of finely dispersed secondary -phase precipitates is greater, the coarser the primary -phase structure. Refinement of primary -phase structure with an increase in secondary phase platelet thickness to 1 m or more reduces the sensitivity of alloy mechanical properties to the effect of secondary -phase.With coarsening of the intragranular structure (d>25 m, b_{I, II}2 m) the effect of structural parameters d and b on properties is markedly weakened: on strength properties (_f, ₁₀₀ ⁴⁵⁰ ) by a factor of 100, on ductility (, ), by a factor of 10 to 20, and on impact strength and fracture toughness (a_n, a_c, K_Q) by a factor of five.The qualitative relationships obtained between structure and mechanical properties of alloy VT3-1 are fundamental for controlling the structure of semifinished titanium alloy products.Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 7, pp. 52–55, July, 1986.     

Phase and structural transformations in deformation and heat treatment of 08Kh15N5D2T steel tubing

Conclusion Annealing in the intercritical area of the -transformation or hardening from a continuous furnace with subsequent tempering in the -transformation range included in the production plan for cold-rolled 08Kh15N5D2T tubing do not restore the original workability of the steel since the residual austenite is stabilized toward the -transformation in deformation. Annealing at 650°C does not lead to complete recrystallization and detexturing of the metal. To obtain this it is recommended that rapid electric heating for hardening with subsequent tempering be introduced into the production plan for rolling of tubing.Ural Polytechnic Institute. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 8, pp. 7–11, August, 1990.