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.     

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

The corrosion behavior of two Ni-Al alloys and four Ni-Nb-Al alloys was studied over the temperature range of 600° C to 1000° C in a mixed-gas of H₂/H₂O/H₂S. The parabolic law was generally followed, although linear kinetics were also observed. Multiple-stage kinetics were observed for the Ni-Al alloys. Generally, the scales formed on Ni-13.5Al and Ni-Nb-Al alloys were multilayered, with an outer layer of nickel sulfide with or without pure Ni particles and a complex inner scale. The outer scale became porous and discontinuous with increasing temperature. Very thin scales formed on Ni-31Al. The reduction in corrosion rate with increasing Al content is ascribed to the formation of Al₂O₃ and Al₂S₃ in the scale. Platinum markers were found at the interface between the outer and inner scales.     

The high-temperature corrosion behavior of Fe-Mo-Al alloys in H2/H2O/H2S mixed-gas environments

The corrosion behavior of 11 Fe-Mo-Al ternary alloys was studied over the temperature range 700–980°C in H₂/H₂O/H₂S mixed-gas environments. With the exception of Fe-10Mo-7Al, for which breakaway kinetics were observed at higher temperatures, all alloys followed the parabolic rate law, despite two-stage kinetics which were observed in some cases. A kinetics inversion was observed for alloys containing 7 wt.% Al between 700–800°C. The corrosion rates of Fe-20Mo and Fe-30Mo were found to be reduced by five orders of magnitude at all temperatures by the addition of 9.1 or higher wt.% aluminum. The scales formed on low-Al alloys (5 wt.% Al) were duplex, consisting of an outer layer of iron sulfide (with some dissolved Al) and a complex inner of Al_0.55Mo₂S₄, FeMo₂S₄, Fe_1.25Mo₆S_7.7, FeS, and uncorroded FeAl and Fe₃Mo₂. Platinum markers were always located at the interface between the inner and outer scales for the low-Al alloys, indicating that outer-scale growth was due mainly to outward diffusion of cations (Fe and Al), while the inner scale was formed primarily by the inward flux of sulfur anions. Alloys having intermediate Al contents (7 wt.%) formed scales that consisted of FeS and Al₂O₃. The amount of Al₂O₃ increased with increasing reaction temperature. The high-Al-content alloys (9.1 and 10 wt.%) formed only Al₂O₃ which was responsible for the reduction of the corrosion rates.     

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.     

The corrosion behavior of Fe-Nb-Al alloys in H2/H2O/H2S atmospheres

The corrosion behavior of eight Fe-Nb-Al ternary alloys was studied over the temperature range 700–980°C in H₂/H₂O/H₂S atmospheres. The corrosion kinetics followed the parabolic rate law for all alloys at all temperatures. The corrosion rates were reduced with increasing Nb content for Fe-x Nb -3Al alloys, the most pronounced reduction occurred as the Nb content increased from 30 to 40 wt.%. The corrosion rate of Fe-30Nb decreased by six orders of magnitude at 700°C and by five orders of magnitude at 800°C or above by the addition of 10 wt.% aluminum. The scales formed on low-Al alloys (3 wt.% Al) were duplex, consisting of an outer layer of iron sulfide (with Al dissolved near the outer-/inner-layer interface) and an inner complex layer of Fe_xNb₂S₄(FeNb₂S₄ or FeNb₃S₆), FeS, Nb₃S₄ (only detected for Nb contents of 30 wt.% or higher) and uncorroded Fe₂Nb. No oxides were detected on the low-Al alloys after corrosion at any temperature. Platinum markers were found to be located at the interface between the inner and outer scales for the low-Al alloys, suggesting that the outer scale grew by the outward transport of cations (Fe and Al) and the inner scale grew by the inward transport of sulfur. The scales formed on high-Al alloys (5 wt.% Al) were complex, consisting primarily of Nb₃S₄, Al₂O₃ and (Fe, Al)_xNb₂S₄, and minor amounts of (Fe, Al)S and uncorroded intermetallics (FeAl and Fe₂Nb). The formation of Nb₃S₄ and Al₂O₃ blocked the transport of iron through the inner scale, resulting in the significant reduction of the corrosion rates.     

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.     

The corrosion behavior of Ni-Nb alloys in a mixed gas of H2-H2O-H2S

The corrosion behavior of Ni-Nb alloys containing up to 40 wt.% Nb was studied over the temperature range of 550–800°C in a mixed H₂/H₂O/H₂S gas. The scales formed on all alloys were multilayered. The outer scale was single-phase Ni₃S₂, while the structure and constitution of the inner scale depended on alloy composition and reaction conditions. Internal oxidation has been found in Ni-20Nb and Ni-30Nb, external oxidation has been observed on Ni-34Nb. Platinum markers were located at the interface between the outer scale and inner scale. The decrease in corrosion rate with increasing Nb content may be attributed to the presence of increasing amounts of Ni-Nb double sulfides as well as to the presence of Nb₂O₅ in the inner region of the scale.     

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

The corrosion of Fe-Nb alloys containing up to 40 wt.% Nb has been studied over the temperature range 600–980°C in a mixed gas of constant composition having sulfur and oxygen pressures ranging from 10^–8 to 10^–4 atm. and from 10^–27 to 10^–18 atm., respectively. All alloys were two-phase, consisting of an Fe-rich solid solution and an intermetallic compound, Fe₂Nb. The scales formed on the Fe-Nb alloys were duplex, consisting of an outer layer of iron sulfide (FeS) and an inner complex layer of Fe_xNbS₂(FeNb₂S₄ or FeNb₃S₆), FeS and unreacted Fe₂Nb. No oxides were detected at any temperature. The addition of Nb reduced the corrosion rate. The corrosion kinetics of Fe-Nb alloys followed the parabolic rate law, regardless of alloy composition and temperature. Platinum markers, attached to the original alloy surfaces, were always located at the interface between the inner and outer scales.     

Effect of some ternary additions on the sulfidation of Ni-Mo alloys

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 k_p 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 Nis_1+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, Al_0.55Mo₂S₄ 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.     

High-temperature corrosion of Co-15Mo alloys containing ternary additions of Al in mixed-gas environments

The corrosion behavior of Co-15 at.% Mo alloys containing up to 20at.% Al in gaseous H ₂ -H ₂ O-H ₂ S mixtures was studied over the temperature range of 600–900°C. The corrosion kinetics of all alloys followed the parabolic rate law over the temperature range of interest. Corrosion resistance increased with increasing aluminum content. Complex scales formed on the alloys, consisting of an outer layer of cobalt sulfide and a heterophasic inner layer. Al ₂ O ₃ formed only at high temperatures in alloys having aluminum additions of 15at.% or more. The absence of Al ₂ O ₃ in some cases is due to the small volume fraction of the intermetallic phase CoAl in the alloys and the nature of the slow growth rate of Al ₂ O ₃.Improvement in corrosion resistance is attributed to the presence of a ternary sulfide, Al _0.55 Mo ₂ S ₄,and Al ₂ O ₃ in the inner layer.     

Effect of Al on high-temperature corrosion of Co-15a/oNb alloys in H2-H2O-H2S environments

Co–15 at.% Nb alloys containing up to 15 at.% Al were corroded in gaseous H₂–H₂O–H₂S mixtures over the temperature range of 600–900°C. The corrosion kinetics followed the parabolic rate law at all temperatures. Corrosion resistance improved with increasing Al content except at 900°C. Duplex scales formed on alloys consisting of an outer layer of cobalt sulfide and a heterophasic inner layer. A small amount of Al₂O₃ was found only on Co–15Nb–15Al. Contrary to what formed in Co–Nb binary alloys, neither NbS₂ nor NbO₂ were found in the inner layer of all alloys, but Nb₃S₄ did form. The absence of NbS₂ and NbO₂ is due to the formation of stable Al₂O₃ and Al₂S₃ that effectively blocked the inward diffusion of oxygen and sulfur, respectively, and to the reduction of activity of Nb by Al additions in the alloys. Intercalation of ions in the empty hexagonal channels of Nb₃S₄ is associated with the blockage of the transport of cobalt. An unknown phase (possibly Al_0.5NbS₂) was detected. Alloys corroded at 900°C were abnormally fast and formed a scale containing CoNb₃S₆ and Co. Pt markers were found at the interface between the inner and outer layers.     

The corrosion behavior of Co-Mo alloys in H2-H2O-H2S environments

The corrosion behavior of Co alloyed with up to 40 wt.% Mo alloys was studied in H₂-H₂O-H₂S gas mixtures over the temperature range between 600C and 900C. The parabolic rate constants for corrosion decreased with increasing amounts of Mo. The compositions of all gas atmospheres fall in the sulfide(s stability region of the ternary M-O-S phase diagrams at all temperatures investigated. All the corrosion scales were composed of sulfides, while no oxide was detected. The sulfide scales formed were duplex at all temperatures except at 900C. The outer layer consisted primarily of cobalt sulfide, while the inner layer was complex and heterophasic, the phases formed being highly composition dependent. MoS₂ predominated in the inner layer for all alloys. However, a metallic Mo layer was formed in the innermost layer of Co-40 Mo. Activation energies were different for all alloys, increasing with increasing Mo content. Identical kinetics were observed for Co-30Mo corroded at 700–800C. A Chevrel-phase Co_1.62Mo₆S₈ was present in scales formed on the samples exhibiting the temperature-independent kinetics. A possible model in which Co_1.62Mo₆S₈ forms preferentially in H₂-containing mixed gas is suggested. Alloys corroded at 900C formed a lamellar-structure scale which contained Co and CoMo₂S₄ layers perpendicular to the alloy surface. A eutectoid decomposition of an unknown Co-Mo sulfide may be responsible for the presence of the lamellar structure.     

The effect of Al2O3 addition on the milling behavior of NiAl powder

The milling behavior of nickel aluminide, NiAl, powder in the presence of a fine Al ₂ O ₃ powder was investigated in the present study. The milling was carried out in an attrition mill. The size and shape of NiAl particles were not changed after milling while only NiAl powder was milled. When fine Al ₂ O ₃ powder was added to the NiAl powder, the Al ₂ O ₃ particles attached to the surface of NiAl particles during milling. As a consequence, the size of NiAl particles was reduced after milling. The shape of NiAl particles also changed. The presence of fine Al ₂ O ₂ particles enhanced the milling efficiency. The Al ₂ O ₃ particles on the surface of NiAl powder can be removed by washing repeatedly in an ultrasonic bath.     

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.     

Influence of a mixed Al2O3+Cr2O3 superficial coating on the non-isothermal oxidation behavior of Fe and Fe-Cr alloys

The non-isothermal oxidation behavior of electrolytic-grade iron and Fe-Cr alloys in dry air has been studied using linear heating rates of 6 K/min, 10 K/ min, and 15 K/min up to a final temperature of 1273–1473 K. Some of the iron and iron-chromium alloy samples were given a surface treatment by dipping them in an aqueous solution containing both Cr and Al ions before their oxidation studies. This pretreatment has resulted in improved oxidation resistance and scale adherence as depicted by no scale rupture even after a second thermal cycle. Mass changes were recorded gravimetrically, and scales have been characterized by SEM, EPMA, and x-ray diffraction analyses.     

Effect of Al2O3 reinforcement and precipitates on corrosion behaviour of 2618 and 6061 aluminium MMCs

ABSTRACT

The corrosion resistance features of two different Metal Matrix Composites based on 6061 and 2618 aluminium alloys reinforced by 20% Al₂O₃ particles by stir casting process, were studied in 3.5% NaCl and compared. The composites and their respective base alloys were characterised in terms of microstructure by optical and scanning electron microscopy and in terms of corrosion resistance by polarisation curves and electrochemical impedance. Results show how the presence of Al₂O₃ has different effects depending on matrix composition. In 6061 MMC, Al₂O₃ promotes the formation of Mg₂Si which has a cathodic behaviour altering the pitting susceptibility of the composite. In 2618 MMC, the high content of Cu induces a strong uniform attack. The subsequent increase in the Open Circuit Potential caused a pitting attack.     

Sulfidation kinetics and mechanism of some Ni-Mo-Al and Ni-Al alloys over the temperature range 600–800°C

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 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 Al_0.55Mo₂S₄. 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 Al_0.55Mo₂S₄.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.     

The sulfidation behavior of Co-Mo alloys containing various ternary additions

The sulfidation behavior of Co-Mo-X alloys, where X is Al, Cr, Mn, or Ti, has been studied over the temperature range 600 or 700°C to 900°C in 10^–2 atm. sulfur vapor to determine the effectiveness of the various ternary elements at reducing the sulfidation rate relative to Co-Mo alloys. For comparative purposes, each ternary alloy contained a constant atomic proportion (i.e., 55Co, 20Mo, and 25X). All of the alloys were multiphase, and sulfidized to form complex, multilayered scales. The scales usually consisted of an outer layer of cobalt sulfide, an intermediate layer that contained primarily the ternaryelement sulfide, and an inner layer which was heterophasic. Usually, each phase within the multiphase alloy sulfidized independently of one another. In the region of the alloy/scale interface there was often a narrow band of fine porosity (transitional band) together with fine precipitates that separated the inner sulfide from the base alloy. It was found that Al and Cr improved the sulfidation resistance of the Co-Mo binary alloy, whereas Mn had the opposite effect. The Ti-containing alloy underwent a mixed sulfidation/oxidation process, so that its kinetics were inapplicable. Aluminum was found to exert the most beneficial effect. The sulfidation behavior of Co-Mo-Al alloys containing a range of Al concentrations was studied at both 700 and 900°C. It was found that for Al to be effective, a sufficient amount of the spinel, Al_0.55Mo₂S₄, had to form within the inner portion of the scale.     

Effects of Mo and Al Additions on the Sulfidation Behavior of 310 Stainless Steel

The high-temperature sulfidation behavior of 310stainless steel (310SS) with Mo and Al additions (up to10 at.%) was studied over the temperature range700-900°C in pure-sulfur vapor over the range of 10^-3 to 10^-1 atm. Thecorrosion kinetics followed the parabolic rate law inall cases and the sulfidation rates increased withincreasing temperature and sulfur pressure. Thesulfidation rates decreased with increasing Mo and Al contents and it wasfound that the addition of 10 at.% Mo resulted in themost pronounced reduction among the alloys studied. Thescales formed on 310SS with Mo additions were complex, consisting of an outer layer of ironsulfide (with dissolved Cr), (Fe,Ni)₉S₈, andCr₂S₃/Cr₃S₄(with dissolved Fe), and an inner heterophasic layer ofFe_1-xS,Cr₂S₃/Cr₃S₄,NiCr₂S₄,Fe_1.25Mo₆S_7.7, FeMo₂S₄, andMoS₂. The scales formed on 310SS with Mo andAl additions had a similar mixture as above, except thatAl_0.55Mo₂S₄ was alsoobserved in the inner layer. The formation ofMoS₂ andAl_0.55Mo₂S₄ partly blocked the transport of cations throughthe inner scale, resulting in the reduction of thesulfidation rates compared to 310SS.     

The effect of an Al2O3 dispersion on the adhesion of Al2O3 scales on aluminized Co-10% Cr alloys

The beneficial effect of dispersions of reactive-metal oxide particles on the adhesion of Cr₂O₃ and Al₂O₃ scales formed on heat-resisting alloys is wellknown. It has been shown that an Al₂O₃ dispersion in an alloy can improve the adhesion of a Cr₂O₃ scale, and it is of particular interest in assessing the various theoretical proposals for the effect to determine whether such a dispersion can affect the adhesion of an Al₂O₃ scale. In this investigation, a Co–10% Cr–1 % Al alloy was first internally oxidized to form an Al₂O₃ dispersion. This alloy was then aluminized so that on subsequent oxidation an Al₂O₃ scale developed. It was shown that the dispersion did indeed improve the scale adhesion. The implications of this result are discussed.