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.     

Role of Al2O3 layer in oxidation resistance of Cu-Al dilute alloys pre-annealed in H2 atmospheres

Copper was alloyed with small amounts of Al (0.2, 0.5, 1.0 and 2.0 mass%) to improve the oxidation resistance. Copper (6 N) and the Cu-Al alloys were oxidized at 773-1173 K in 0.1 MPa oxygen atmosphere after hydrogen annealing at 873 K. Continuous very thin Al₂O₃ layers were formed on the surface of all Cu-Al dilute alloys during the hydrogen annealing. Oxidation resistance of Cu-Al alloys was improved especially for Cu-2.0Al at 773-973 K, while it decreases on increasing the oxidation temperature. Cu-Al alloys followed the parabolic rate law at 1173 K, but most of other cases do not at and below 1073 K. Oxidation resistance for Cu-Al alloys was found relevant to the maintenance of the thin Al₂O₃ layer at the Cu₂O/Cu-Al alloy interface.     

Sulfidation behavior of a binary Fe-Mn alloy

An Fe-27 w/o (weight %) Mn alloy was sulfidized at temperatures of 973, 1073, and 1173 K inflowing H₂/H₂S/N₂ atmospheres corresponding to equilibrium sulfur pressures of 8 Pa. Steady-state parabolic kinetics were always observed after an initial period during which the instantaneous parabolic rate constant increased with time. Product scales were compact and consisted of a layer of Fe(Mn)_1–x S over an inner layer of -Mn(Fe)S. Preoxidation led to a diminution in the subsequent sulfidation rate. Conflicts between differing reports in the literature of the kinetics of this reaction are resolved, and it is concluded that the protective effect expected of an -MnS layer is in fact possible.     

Sulfidation properties of Fe-6.1 at.% Mo alloy at 973–1273 K

Sulfidation of an Fe-6.1 at% Mo alloy was investigated in H₂S-H₂ atmospheres, 10^?4 ? P_s2 ? 10²Pa, at 973-1273 K. The reaction kinetics are parabolic except at 1273 K as liquid sulfide formation leads to catastrophic corrosion. This solid-liquid transformation between Fe₂Mo₂S₄ and Mo₂S₃ occurs at 1214 ± 9 K. At 1073 K and P_s2 = 10^?4Pa, growth of a duplex Mo₂S₃/FeMo₂S₄ scale offers high resistance to sulfidation. At 973, 1073 and 1173 K, 10^?2 ? P_s2 ? 10²Pa, parabolic sulfidation kinetics of the same magnitude as for pure iron describe growth of a duplex scale composed of an inner (FeMo₂S₄ + Mo₂S₃) layer and at an outer FeS layer. Marker measurements indicated that growth of the inner two-phase layer was supported by inward migration of sulfur and that growth of the outer FeS layer resulted from outward migration of iron.     

Sulfidation behavior of an aluminum-manganese steel

An alloy steel containing 4.5 weight percent (w/o) manganese, 8.8 w/o aluminum, and 0.36 w/o carbon was sulfidized at temperatures of 973, 1073, and 1173 K in flowing H₂/H₂S gas mixtures corresponding to sulfur partial pressures in the range 10^–8-10^–4 atm. Slow parabolic weight uptake kinetics were observed at T=973 K whenP _{s 2}10^-7 atm and at T =1073 K when PS ₂=10^-7 atm. Under these conditions, a thin external scale rich in -MnS was formed. At higher values of PS ₂ at these temperatures, and at all values of PS ₂ [(Fe, Mn)S plus (Fe, Mn)Al₂S₄] porous layer, which grew by inward sulfur transport, and an outer region of FeS, which grew by outward diffusion of iron.     

Sulfidation of manganese in sulfur vapor at low pressure and temperatures between 873 and 1273 K

An investigation was carried out on the sulfidation kinetics of manganese plates by thermogravimetry in pure sulfur vapor at low pressures, 4.5×10^–5< p_S2 (atm)<7.2×10^–4, at temperatures between 973 and 1173 K. The reaction kinetics were parabolic and the sulfidation rate constant at 1073 K was proportional to where n = 6.4±0.8. The activation energy for the sulfidation reaction at atm was 25,000±3000 cal·mol^–1. The -MnS developed a preferred orientation texture, and grain growth was observed even though the metal exhibited no preferred orientation.     

High-temperature corrosion of titanium-, niobium-, and manganese-rich Fe-25Cr alloys in H2-H2O-H2S gas mixtures

The simultaneous sulfidation and oxidation of Fe-25Cr, Fe-25Cr-4.3Ti, Fe-25Cr-7.5Nb, and Fe-25Cr-9.0 Mn alloys were studied at 1023, 1123, and 1223 K, respectively, in H₂-H₂O -H₂S gas mixtures. The influences of titanium, niobium, and manganese on the transition from protective oxide formation to the formation of sulfide-rich corrosion products of Fe-25Cr alloys have been investigated. It has been found that additions of titanium and niobium can improve the scaling resistance of Fe-25Cr alloys against sulfidation in H₂ -H₂O -H₂S gas mixtures at high temperatures. However, the addition of manganese does not increase the resistance to sulfidation of Fe-25Cr alloy. The oxide Cr₂Ti₂O₇, which can suppress sulfide formation, formed on the Fe-25Cr-4.3Ti alloy. The addition of manganese to Fe-25Cr does not form more stable and protective oxides than Cr₂O₃ which formed on Fe-25Cr. Thermodynamic stability diagrams are used to explain the experimental results.     

Sulfidation mechanism of an Fe-26.6 at.% Cr alloy at temperatures 973–1173 K in H2S-H2 atmospheres at sulfur pressures 104–10−6 Pa

An investigation has been carried out to establish the sulfidation mechanism of an Fe-26.6 at. % Cr alloy at 973, 1073, and 1173 K in H₂S-H₂ atmospheres at sulfur pressures 10⁴ .     

High-temperature sulfidation of Fe-Mn-Cr alloys

Alloys of composition (in weight percent) Fe-10Mn-10Cr, Fe-10Mn-25Cr, and Fe-25Mn-10Cr were reacted at temperatures of 973 and 1073 K with flowing hydrogen-hydrogen sulfide mixtures corresponding to equilibrium sulfur partial pressures of 10^?3 and 8 Pa. Sulfide-scale-growth kinetics and morphologies were compared with those found on pure iron and on the binary alloys Fe-25Cr and Fe-25Mn. All alloys reacted according to parabolic kinetics after an initial period of slow approach to this steady state. Of the materials examined, the binary Fe-25Mn showed the slowest sulfidation rates, except at 973 K and a sulfur pressure of 8 Pa, where Fe-10Mn-25Cr had the best performance. Ternary alloys provided improved performance only when a scale layer of Cr₃S₄ was formed, an event dependent on temperature and sulfur activity. Multilayered scales were always formed on the ternary alloys, and the role of these layers in controlling sulfidation rates is discussed.     

Sulfidation processing and Cr addition to improve oxidation resistance of TiAl intermetallics in air at 1173 K

High temperature oxidation properties of TiAl- (1,2,4 and 10) Cr and 40Ti-56Al–4Cr alloys, which were sulfidized at 1173 K for 86.4 ks at 1.3 Pa sulfur partial pressure in a H₂–H₂S gas mixture, were investigated at 1173 K in air for up to 2.7 Ms. The sulfidation processing formed a (Cr,Ti)Al₂ layer between a TiAl₃ (TiAl₂ included) layer and a Ti-rich sulfide scale by selective sulfidation of Ti. Oxidation of the sulfidation-processed alloys was examined for up to 2.7 Ms in air under isothermal and room temperature to 1173 K heat cycle conditions. In both oxidation experiments the sulfidation processed TiAl–10Cr alloy showed very good oxidation resistance up to 2.7 Ms, due to the formation of a continuous Ti(CrAl)₂ Laves layer, which was changed from (Cr,Ti)Al₂ and has a composition of 28.7Cr–36.2Al–35.1Ti, between the layers of protective Al₂O₃ (TiO₂ included) and TiAl₂, which was changed from TiAl₃. The sulfidation processed TiAl, TiAl–4Cr, and 40Ti–56Al–4Cr alloys showed better oxidation resistance than conventional TiAl based alloys, but displayed localized oxidation. The Ti(Cr,Al)₂ Laves on the sulfidation processed TiAl–4Cr alloy was discontinuous, leading to a localized oxidation after long oxidation. The sulfidation processed 40Ti–56Al–4Cr alloy oxidized faster than the sulfidation processed TiAl–10Cr alloy due to the formation of an Al₂O₃ and TiO₂ mixture, although the TiAl₂ layer remains. It was concluded that the Ti(Cr,Al)₂ Laves layer between the oxide scale and alloy substrate caused the good oxidation resistance.     

Corrosion resistance of dilute CuMg alloys at elevated temperature

In comparison with CuAl (Al: 0.2 and 0.5 wt.%) alloys, corrosion resistance (CR) of CuMg (Mg: 0.12 and 0.34 wt.%) alloys was studied at 673-1173 K in atmospheric O₂. All the samples were pre-annealed at 873 K in atmospheric H₂. The CR of CuMg alloys at 673-973 K is improved in contrast to a pure Cu but much poorer than that of CuAl alloys, while the improvement can hardly be observed for CuMg alloys at and above 1073 K, which is similar to CuAl alloys. The poorer CR of CuMg alloys compared with that of CuAl alloys at 673-973 K is largely attributed to the incorporation of Cu in the MgO surface layer and the low Pilling-Bedworth ratio of CuMg-O system smaller than unity, and the vanishing of CR for CuMg alloys at and above 1073 K is ascribed to the instability of the MgO layer at the Cu₂O/CuMg interface.     

Sulfidation kinetics and scale structures of chromium at temperatures of 973–1173 K and 104–10−6 Pa sulfur pressures

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 Cr_1–xS (type 3), and a fine twinlike structure of ordered Cr_1–xS (type 4). At 973 K, the sulfur pressure ranges are type 1 at > 10^–4, type 2 at , and type 3 at . 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 Cr_1–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.Emeritus Professor.     

High-Temperature Corrosion Resistance of Al–Re and Re Coatings

The oxidation behavior in air at 1473 K, and sulfidation behavior in a H2S–H2 gas mixture with a sulfur partial pressure of 10^–2 Pa at 973 K of Al–Re coated CMSX-4 were studied. Investigation on the sulfidation behavior of the Re-coated CMSX-4 was carried out in a H2S–H2 gas mixture with a sulfur partial pressure of 10^–2 Pa at 973 K. The experimental results show that a Re-rich alloy layer was formed between an -Al₂O₃ layer and the inner concentration zone of Ta and Ti for the CMSX-4 single crystal alloy with an Al–Re coating after oxidation. The Re-rich alloy layer containing Cr, W, Ni, Co, and Mo effectively inhibited the outward diffusion of alloying elements and the inward diffusion of Al. The Al/Re-coated CMSX-4 single crystal alloy had excellent sulfidation resistance; the Re-rich alloy layer, containing W, Ti, Ta, and Mo, which formed during the sulfidation process and located between the alumina scale and the CMSX-4 base alloy, plays a role in inhibiting the outward diffusion of alloying elements. The sulfidation resistance of CMSX-4 single-crystal alloy is greatly improved by a Re coating on the CMSX-4 alloy surface; this is attributed to a Re–Cr–W alloy layer that retarded the outward diffusion of cations and the oxide layer containing Ta, Ti, and Al, which inhibited the inward penetration of sulfur.     

Sulfidation properties of Fe-Al alloys at 1173 K in H2S-H2 atmospheres

The sulfidation kinetics and morphological development of reaction products are reported for Fe-9 and 18 at.% Al alloys exposed at 1173 K to H₂S-H₂ atmospheres at sulfur pressures in the range 10^–1–10³ Pa. The Fe-9 Al alloy sulfidized parabolically at Pa giving rise to a duplex scale composed of an outer Al-doped FeS layer and an inner FeS + FeAl₂S₄ lamellar layer and to an internal sulfidation zone containing Al₂S₃ precipitates. The Fe-18 Al alloy which was sulfidized at .     

The influence of aluminum on the transition from oxide to sulfide of aluminum-rich Fe-25Cr alloys with low-oxygen and high sulphur pressures

The simultaneous oxidation and sulfidation of Fe-25Cr, Fe-25Cr-5Al and Fe-25Cr-10Al alloys were studied at 1023, 1123, and 1223 K in H₂-H₂O-H₂S gas mixtures. Fe-25Cr and aluminum-rich alloys with 0–10 wt.% Al show, in H₂H₂O-H₂S gas mixtures at high temperatures, a transition from protective oxide-scale formation to the formation of a sulfide-rich corrosion product. The kinetics boundary, which indicates the transition from oxide formation with slow weight gains to sulfide formation with rapid weight gains, has been found in these three alloys. The critical oxygen partial pressures to stabilize oxide formation at the constant-sulfur partial pressures of aluminum-rich Fe-25Cr alloys were systematically below those of Fe-25Cr alloy. When the oxygen partial pressure is much higher than the critical one, the oxide scale formed on the Fe-25Cr alloy was mainly Cr₂O₃ with a small amount of FeCr₂O₄; on the other hand, the oxide scale formed on the aluminum-rich Fe-25Cr alloys was mainly Fe(Cr,Al)₂O₄ with a small amount of Al₂O₃ and Cr₂O₃. The thermodynamic stability diagrams for (Fe, Cr, Al) -S-O systems were constructed, and the experimental results which show the existence of Fe(Cr, Al)₂O₄ in the simultaneous sulfidation and oxidation of aluminum-rich Fe-25Cr alloys are explained by these diagrams. The reaction kinetics were measured by a stainless-steel spring balance, and the reaction products were characterized by x-ray diffraction, Auger spectroscopy, and scanning electron microscopy. The reaction rate usually decreased with an increase of the oxygen partial pressure at a constant sulfur partial pressure. The existence of aluminum plays an important role to suppress the sulfidation of Fe-25Cr alloys.     

Oxidation behavior of sulfidation processed TiAl–2 at.%X (X=Si,Mn, Ni,Ge, Y,Zr, La,and Ta) alloys at 1173 K in air

The oxidation behavior of sulfidation processed TiAl–2 at.%X (X=Si, Mn, Ni, Ge, Y, Zr, La, and Ta) alloys was investigated at 1173 K in air for up to 630 ks under a heat-cycle condition between 1173 K and room temperature. During the sulfidation processing the TiAl–2 at.%Ta alloy formed Ta-aluminides on the TiAl₃ layer, while the alloys containing Mn, Ni, Y, and Zr formed a TiAl₃ (TiAl₂ included) layer including a small amount of the third element, like the TiAl binary alloy. The cross-sectional microstructure of the TiAl–2 at.%Ta alloy shows the sequence: oxide scale/TiAlTa/TiAl₂/alloy substrate; and the cross sections of the alloys containing Mn, Ni, Y, and Zr are: oxide scale/Ti₃Al/alloy substrate. The TiAl–2 at.%Ta alloy showed some scale exfoliation at the initial stage of oxidation, but very little exfoliation after long oxidation times, whereas alloys containing other third elements such as Si and Ge showed little exfoliation at the first several cycles and then tended to exfoliate significantly, resulting in very rapid oxidation. The TiAlTa/TiAl₂ layers formed by the reaction between the Ta-aluminide and TiAl₃ improve the oxidation properties of the TiAl–2 at.%Ta alloy.     

Sulfidation properties of an Fe-23.4Cr-18.6Al alloy at temperatures 1073 and 1173 K in H2S-H2 atmospheres of sulfur at pressures 104-10−5 Pa

An investigation is reported on the sulfidation properties of an Fe-23.4Cr-18.6Al(at.%) alloy at 1073 and 1173 K in H₂S-H₂ atmospheres, 10⁴ > P_{S 2} 10⁵Pa. The sulfidation kinetics exhibited an early transient period before onset of parabolic kinetics. Values of the parabolic sulfidation rate constants increased by as much as 10⁵ from their smallest values at low sulfur pressures, P_{S 2} 10^–4 Pa, to maximum values at sulfur pressures P_{S 2} 10² Pa. Multilayered scales were formed, the number and types of layers dependent on sulfur pressure. A fully developed scale at sulfur pressures P_{S 2} > 10^–3 Pa.     

Effect of H2S on High Temperature Corrosion of Fe–Ni–Cr Alloys in Carburizing/Oxidizing Environments

This investigation involves the corrosion behavior of two Fe–Ni–Cr alloys containing different Si content at 1050?°C in carburizing-oxidizing environments (typical of ethylene pyrolysis) with varied concentration of H₂S. High-Si containing alloy could form thinner but less uniform oxide scale than low-Si alloy after pre-oxidation due to the barrier effect of continuous SiO₂ at interface of scale/substrate. Pre-oxidized alloy showed a better resistance to carburization/sulfidation attacks than the bare alloy in absence of pre-oxidation. It was found that carburization and sulfidation of the Fe–Ni–Cr alloys could be prevented in the environment with a ratio of $ P_{{{\text{H}}_{ 2} {\text{S}}}} /P_{{{\text{H}}_{ 2} }} $ at 1.7?×?10^?5. When the sulfur partial pressure was lower than this value, oxides were found to be converted to porous and non-protective carbides. When the sulfur potentials were increased, manganese or chromium sulfide on outer layer and internal sulfide stringers mixed with silicon oxide in substrate could be formed. Under high sulfur partial pressures, spallation of outer sulfide or oxide scale was observed on high-Si alloy due to less stability of oxide layer formed at surface which was converted to sulfide faster than on low-Si alloy.     

Sulfidation properties of an Fe-26.6 at.% Cr alloy at temperatures of 973–1173 K in H2S-H2 atmospheres at sulfur Pressures 104–10−6 Pa

An investigation is reported on the sulfidation properties of an Fe-26.6 at. % Cr alloy at 973, 1073, and 1173 K in H₂S-H₂ atmospheres at sulfur pressures 10⁴ 10^–6 Pa. The sulfidation kinetics when plotted according to a parabolic relationship usually exhibited an early slow transient period before onset of parabolic kinetics. Scales contained up to three layers. A triplex (CrFe)S_x/(CrFe)₃S₄/-(FeCr)S_x scale was formed at high sulfur pressures (range I), a single-phase (FeCr)S_x or a duplex (CrFe)S_x/(FeCr)S scale at intermediate sulfur pressures (range II), and a single-phase (CrFe)S_x scale at low sulfur pressures (range III). These pressure ranges at 973 K were: range I = 10^–2Pa, 10^–2 > (range II) 10^–5 Pa, and range III .     

The influence of sulfur pressure on Sulfidation behaviour of NiCoCrAl(Y) alloys at high temperature

Sulfidation of alloy having nominal composition Ni-23Co-19Cr-12Al (wt%) with and without the addition of 0.6% yttrium was studied at temperatures 1073–1273 K in sulfur vapor at atmospheric pressure and in H₂/H₂S gas mixtures at sulfur pressure of 10^?3 and 10^?1.5 Pa. Sulfidation runs were followed thermogravimetrically. Phase and chemical composition of sulfide scales and scale morphologies were determined by means of XRD, EDX, EPM and SEM analyses. After certain initial period sulfidation of both materials followed approximately a parabolic rate law. The estimated sulfidation rates for each alloy increased with sulfur pressure and temperature. The sulfide scales on both materials showed complex microstructures and compositions, depending on sulfidation conditions, with several sulfide and sulfospinel phases present, such as (Ni,Co)S, (Ni,Co)₃S₄, (Ni,Co)Cr₂S₄, (Cr,Ni,Co)Al₂S₄ or (Cr,Ni,Co)S and (Cr,Ni,Co)₃S₄. There was no evidence of yttrium segregation either to the grain boundary regions in the scale or to the alloy/scale interface. Yttrium dissolved in the sulfide phases and accelerated the sulfidation process. This behaviour was ascribed to the doping effect.