The problem of sulfur in high-temperature corrosion

The role of defect and transport properties of transition metal sulfides on the kinetics and mechanism of high-temperature sulfide corrosion of metals and alloys is discussed. It has been shown, that due to the very high concentration of defects in common metal sulfides, not only pure metals but also conventional high-temperature alloys (chromia and alumina formers) undergo very rapid degradation in highly sulfidizing environments. Refractory metals, on the other hand, are highly resistant to sulfide corrosion, their sulfidation rates being comparable with the oxidation rate of chromium. Pioneering work of Douglasset al. has shown that alloying of common metals by niobium or molybdenum, and in particular combined alloying by molybdenumand aluminum, dramatically decreases the sulfidation rate. A novel Fe–30Mo–9Al alloy has been proved to be highly resistant to sulfide corrosion, its sulfidation rate being comparable with that of pure molybdenum. Even better resistance to highly-sulfidizing environments show new amorphous Al–Mo and Al–Mo–Si alloys, these materials also being simultaneously oxidation resistant. Thus, new prospects have been created for the development of a new generation of coating materials, resistant to multicomponent sulfidizing-oxidizing atmospheres, often encountered in many branches of modern technology.     

INFLUENCE OF Y,Ce AND La ON HIGH TEMPERATURE SULFIDATION OF Fe-25Cr-40Ni SUPERALLOY

The effects of Y,Ce and La on the sulfidation of alloy Fe-25Cr-40Ni have been investigated.The sulfidation rate of the alloys with RE more than 0.1 wt-% is lower than that of the basealloy.The addition of Y is more effective than La and Ce in lowering the sulfidation rate.Based on the analyses of the structure and composition of the sulfide seales,the sulfidationmechanism of the alloys with RE has been proposed.     

Kinetics and mechanism of high-temperature sulfur corrosion of Fe-Cr-Al alloys

The influence of aluminium on the kinetics and mechanism of high-temperature sulfidation of Fe-Cr alloys containing 20 at.% chromium has been investigated. It has been found that the addition of aluminum greatly improves the scaling resistance of Fe-Cr alloys against attack by sulfur vapors at high temperatures.     

INFLUENCE OF Y,Ce AND La ON HIGH TEMPERATURE SULFIDATION OF Fe-25Cr-40Ni SUPERALLOY

研究了稀土元素Y,Ce和La对Fe-25Cr-40Ni合金高温硫化的影响。当合金中稀土含量为0.1wt-％时,合金的硫化速度明显降低。Y对降低合金硫化速度的影响大于Ce和La。加入Y的合金硫化时,在硫化内层优先形成带有保护性的较致密的硫化铬,它的晶粒较细,与基体很好粘着。在硫化层结构和成分分析的基础上提出了合金加入稀土元素后的硫化机理。     

Impact of Iron-Sulfide Deposits on Oxidized Austenitic Steels as Simulation of Corrosion and Fireside-Tube Wastage in Coal Combustion

The sulfidation effect of molten iron sulfides was studied on oxidized austenitic steels as a simulation of furnace-wall corrosion in PC combustion environments. The test coupons were oxidized to produce an external oxide scale and pyrite was placed on the oxide and thermally treated in an inert atmosphere to decompose the pyrite into pyrrhotite. DSC-TGA and XRD indicated that FeS interacts with the Fe₂O₃ oxide layer, even at 700°C if the contact is good, changing the oxidation state of iron and the physical structure. On the other hand, the interaction of FeS with Cr₂O₃ between 1100 to 800°C, 24 hr in the inert atmosphere, consisted of the formation of a chromium sulfide layer beneath the oxide scale. SEM-EDX showed that the diffusion of sulfur in the steel matrix can be 30 m deep, indicated by small particles of chromium sulfide. It is demonstrated that iron sulfide deposits could be responsible for sulfidation of the alloys.     

The attack of Co-Cr alloys by Ar-SO2 atmospheres

Cobalt alloys containing up to 25% chromium have been exposed to Ar-10% SO₂ atmospheres at temperatures between 600 and 1000° C. The results show that, although an increase in chromium content leads to a reduction in the reaction rate, even to negligible rates in the cases of the higher chromium contents, all of the alloys are eventually subjected to rapid attack at more or less longer times, depending on the chromium content. The mechanism of the reaction appears to involve the formation of a more or less protective oxide layer which is eventually penetrated by sulfur. The sulfur forms chromium sulfides at the metal-scale interface, removing the chromium from solution and causing an expansion that cracks the protective scale, allowing both the ingress of gas and the formation of rapidly growing cobalt compounds. The process occurs rapidly with Co-5% Cr alloys, whereas, only the initial sulfur penetration is observed with Co-25% Cr alloys during the time scale of the investigation. The penetration of sulfur is thought to occur as a molecular gas species permeating through the scale down physical defects.     

Effect of yttrium on the sulfidation behavior of Ni-Cr-Al alloys at 700°C

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 NiS_1.03 and an inner lamellar layer of a very fine mixture of Cr₂S₃ and A1₂O₃ in a matrix of NiS_1.03. 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 NiS_1.03 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.     

Sulfidation properties of austenitic Fe-Mn and Fe-Mn-Al alloys under low sulfur vapor pressure (8 Pa) in the temperature range 873–1173 K

The sulfidation properties of austenitic Fe-Mn and Fe-Mn-Al alloys containing small amounts of carbon have been characterized with respect to the sulfidation kinetics, scale morphological development, structures, and composition of the sulfide phases. The alloys contained 21–40 wt. % Mn and 2.5–8 wt.% Al. The sulfide phase was monosulfide of manganese and iron containing the other metallic elements in solid solution. Two regimes of sulfidation categorized by slow and fast reaction rates were exhibited by all alloys when sulfidized in sulfur vapor at = 8 Pa and over the temperature range 873–1173 K. In the slow regime, a compact duplex -Mn(Fe)S/Fe(Mn)S scale evolved by a classical parabolic law associated with metal diffusion in scale. A porous microcrystalline mixed scale of the above sulfides evolved in the regime of rapid sulfidation by quasilinear kinetics associated with sulfur ingress through the porous scale.     

Kinetics and mechanism of the sulfidation of Fe-Mo alloys

Iron-molybdenum alloys containing up to 40 wt.% molybdenum were exposed to sulfur vapor at a partial pressure of 0.01 atm at temperatures of 600–900°C. Sulfidation kinetics were measured over periods of up to 8 hr using a quartz-spring thermogravimetric method. The sulfidation kinetics of all alloys studied obeyed the parabolic rate law. The sulfidation rate of iron was found to be reduced by factors of 60 at 900°C and 120 at 600°C by the addition of 40 wt.% molybdenum. Duplex sulfide scales formed on all alloys at all temperatures, the scales consisting of an inner layer of mostly MoS₂ and an outer layer of FeS. Platinum markers were located at the interface between the outer and inner scales, showing that outward iron diffusion and inward sulfur diffusion through the inner layer occurred. The improved sulfidation resistance was attributed to the formation of the MoS₂, which acted as a partially protective barrier to the diffusion of the reacting species. Sulfidation activation energies were found to range from 24.3 to 28.5 kcal mole for the alloys compared to 20.6 kcal/mole, for pure iron. The rate-controlling step was outward iron diffusion through the outer iron sulfide layer.     

Sulfidation behavior of Ni-Cr-Mo alloys at 700°C

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 NiS_1.03, although both binaries formed Ni₃S₂ within the NiS_1.03. 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.     

EVOLUTION OF SULFIDE SCALES ON Fe-Mo ALLOYS DURING SULFIDATION

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Effect of 1 wt.% yttrium addition on high-temperature sulfidation behavior of Fe-15Cr-4Al alloy

High-temperature sulfidation studies have been carried out on Fe-15Cr-4Al with and without 1% Y in the temperature range 700–1000°C in an H ₂-H₂ S environment over the sulfur pressure range of 10 ^–9–10^–3 atm. Two-layered and three-layered sulfide scales were observed in both alloys at low and high sulfur pressures, respectively. The pegging phenomenon, similar to that occurring in high-temperature oxidation, across the innermost layer and substrate was observed in the case of the yttrium-containing alloy. Yttrium was found to be associated with aluminum and chromium sulfides. The role of yttrium was more evident at low than at high sulfur pressures and was found to reduce the parabolic rate constants by a factor of about one-half to one-seventh, respectively.     

On the high-temperature corrosion of Fe-Cr alloys in sulfur vapor

The mechanism of sulfidation of Fe-Cr alloys ranging from 8 to 97 wt.% chromium was determined from studies of scale structures, surface morphologies of scale, and reaction kinetics. Although the kinetics of sulfidation were quite similar to those previously determined by Mrowec et al., the structures in the present work were different, being triplex in nature. The growth mechanism of each layer was determined, and the overall sulfidation behavior was compared to the oxidation behavior. Many similarities between the two corrosion processes were observed.     

Sulfidation of iron at high temperatures and diffusion kinetics in ferrous sulfide

The kinetics and mechanism of iron sulfidation have been studied as a function of temperature (950–1200 K) and sulfur pressure (10^–3-0.065 atm). It has been stated that a compact Fe_1–yS scale on iron grows according to the parabolic rate law as a result of outward lattice diffusion of metal ions through cation vacancies. The activation energy of sulfidation increases with sulfur pressure and the 1/n exponent increases with temperature. This nontypical dependence of iron sulfidation kinetics on temperature and pressure results from the analogous effect of both these parameters on defect concentration in ferrous sulfide. The chemical diffusion coefficients,D_FeS, and diffusion coefficients of defects, D_d, in ferrous sulfide have been calculated on the basis of parabolic rate contacts of iron sulfidation and deviations from stoichiometry in ferrous sulfide. It has been shown thatD_FeS is practically independent of cation vacancy concentration whereas the diffusion coefficient of defects depends strongly on that parameter. A comparison of self-diffusion coefficients of iron in Fe_1–yS calculated from the kinetics of iron sulfidation to those obtained from radioisotopic studies indicates that within the range studied of temperatures and sulfur vapor pressures the outward diffusion of iron across the scale occurs preferentially along the c axis of columnar ferrous sulfide crystals.     

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.     

Effect of Al on the high-temperature sulfidation of Fe-30Nb

Fe-30Nb-Al alloys containing up to 9.1 wt.% Al were sulfidized at 0.01 atm sulfur vapor over the temperature range of 600–900°C. The sulfidation kinetics followed the parabolic rate law for all the alloys at all temperatures. The parabolic rate constants decreased with increasing Al content. Extremely slow sulfidation rates, even slower than that of pure Nb at low temperatures, were observed for alloys containing high Al (>4.8 wt.%). Duplex sulfide scales formed on alloys containing small amounts of Al. The outer layers were compact FeS, while the inner layers were a double sulfide, Fe _xNb₂S₄,containing partially sulfidized intermetallic islands. Very thin scales formed on the alloys containing high Al, but the nature of the scales is unknown. The intercalation of Al into the Nb-sulfides and the associated charge transfer induced a blockage of the transport of iron through the sulfide as well as a greater incorporation of Nb into the scale.     

PROTECTION AND DAMAGE OF PREFORMED OXIDE SCALES OF Fe-25Cr-5Al AND-10Al ALLOYS DURING THEIR SUBSEQUENT SULFIDATION

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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.     

Sulfidation-oxidation of advanced metallic materials in simulated low-Btu coal-gasifier environments

The corrosion behavior of structural alloys in complex multicomponent gas environments is of considerable interest for their effective utilization in coal conversion schemes. Little understanding of the degradation mechanisms of advanced high-temperature alloys in conditions typical of low-Btu coal gasifiers presently exists. Analysis of scale and subscale characteristics of several alloy types after exposure to the aggressive simulated low-Btu gasifier environments yielded a reaction model for these sulfidation-oxidation conditions. Initial competition between reactive metal oxide and base metal sulfide nuclei is followed by base metal sulfide overgrowth, chromium sulfide formation at the scale-metal interface, dissociation near voids in the subscale, and internal chromium sulfide precipitation. Additions of aluminum, titanium, and an oxide dispersion improve the sulfidation resistance by increasing the number of oxide nucleation sites and their growth kinetics on the surface in the crucial competition stage. Thermogravimetric tests carried out in three mechanistic regimes agreed with these hypotheses.     

The corrosion of some superalloys in contact with coal chars in coal gasifier atmospheres

Six alloys, 310 stainless steel, Hastelloy X, Inconel 671, Incoloy 800, Haynes 188, and FeCrAlY (GE1541 and MA956), were corroded in two chars at 1600° and 1800°F. The chars, FMC and Husky, contained 2.7% and 0.9% sulfur, respectively. Various parameters were investigated, including char size, cover gas, char quantity, char replenishment period, gas composition, and the use of coatings. The corrosion process was strictly sulfidation when the char was replenished every 24 hr or less. The kinetics of reaction were nearly linear with time. The reaction resulted in thick external sulfide scales with extensive internal sulfidation in the substrate. The kinetics and reactionproduct morphologies suggested that diffusion through the sulfide scale played a minor role, and that an interfacial reaction was the rate-controlling step, A mathematical model was developed which supported this hypothesis.The reaction rates showed a relatively minor role on alloy composition, depending upon whether the alloys were tested singularly or in combination with others. Inconel 671, the best alloy in CGA environments, consistently corroded the most rapidly of the chromia-former types regardless of char sulfur content or of the temperature. Type 310 stainless was marginally better than Inconel 671. Incoloy 800 was intermediate, whereas, Haynes 188 and Hastelloy X exhibited the best corrosion resistance. The FeCrAlY alloys reacted very rapidly in the absence of preoxidation treatments. All alloys corroded in char at least 1000 times more rapidly than in the CGA (MPCITTRI) environment. None of the alloys will be acceptable for use in contact with char unless coatings are applied.