High temperature corrosion of Fe-Cr-Mn-alloys in H2-H2S and H2-H2O-H2S gas mixtures

The sulfidation of Fe-20% Cr-30% Mn, Fe-25%Cr-20%Mn and Fe-25% Cr was studied at 700°C in H₂-H₂S and the oxidation and sulfidation in H₂-H₂O-H₂S after preoxidation in H₂-H₂O. The sulfidation rate is strongly increased for the Mn-containing alloys, layers of (Mn,Cr)S and (Mn,Fe)Cr₂S₄ are formed. Also the oxidation rate is enhanced compared to Fe-25% Cr by formation of MnCr₂O₄ instead of Cr₂O₃. The sulfidation after preoxidation leads to internal and external sulfidation of the Mn-containing alloys. With increasing oxygen pressure p(O₂) = 10^?26…10^?22 atm. of the H₂-H₂O-H₂S mixtures the sulfidation is suppressed, for the higher oxygen pressure 10^?23 and 10^?22 atm. fast oxidation prevails under formation of MnCr₂O₄. Manganese cannot increase the sulfidation resistance of alloys, in spite of the stability and low degree of disorder of its sulfide, since the mixed sulfide (Mn,Cr)S is formed which has a high degree of disorder, high diffusivities and high growth rate according to the doping effect of trivalent Cr³⁺.     

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.     

Diffusion of cations in chromia layers grown on iron-base alloys

Diffusion of the cations Cr, Fe, Mn, and Ni in Cr₂O₃ has been investigated at 1173 K. The diffusion measurements were performed on chromia layers grown on the model alloys Fe-20Cr and Fe-20Cr-12Ni in order to consider effects of small amounts of dissolved alien cations in Cr₂O₃. The samples were diffusion annealed in H₂-H₂O at an oxygen partial pressure close to the Cr₂O₃/Cr equilibrium. For all tracers the lattice-diffusion coefficients are 3–5 orders of magnitude smaller than the grain-boundary diffusion coefficients. The lattice diffusivity of Mn is about two orders of magnitude greater than the other lattice-diffusion coefficients, especially in Cr₂O₃ grown on Fe-20Cr-12Ni. The values of the diffusion coefficients for Cr, Fe, and Ni are in the same range. Diffusion of the tracers in Cr₂O₃ grown on different alloys did not show significant differences with the exception of Mn.     

Transition from oxidation to sulfidation of Fe-Cr alloys in gases with low oxygen and high sulfur pressures

Fe-Cr alloys with 17–30% Cr show in H₂-H₂O-H₂S mixtures at 1273 and 1073 K a transition from protective oxide scale formation to rapid sulfidation. The critical oxygen pressure to stabilize the oxide formation increases with increasing sulfur pressure of the gas and decreasing Cr content of the alloy. Cr₂O₃ with traces of Fe₂O₃ is formed under these conditions. Below the critical oxygen pressure, a primarily formed Cr₂O₃ film becomes overgrown by (Fe, Cr)S. The kinetic boundary of oxidation-sulfidation, which lies in the stability field (Fe, Cr)S + spinel Fe_1+xCr_2–xO₄ of the Fe-Cr-O-S phase diagram, is explained with the help of the Fe-Cr-O-S phase diagram and the assumption that Fe diffuses faster through the (Cr, Fe)₂O₃ solid solution than does Cr.     

Sulfidation behavior of Fe-25Cr-20Ni-1.5Al2O3 in simulated coal combustion/gasification environments

The effect of minor addition of -Al₂O₃ dispersoids on the sulfidation behavior of Fe-25Cr-20Ni was investigated over a range of pO₂, 1.13×10^–20 to 1.18×10 ****^–22 atm. at constant pS₂=1.22×10^–8 atm. Fe-25Cr-20Ni and Fe-25Cr-20Ni 1.5 Al₂O₃ with and without preformed oxide scales were exposed to bioxidant gas mixtures H₂/H₂O/H₂S/Ar at 700° C. Both isothermal and cyclic exposures were included. Scales were characterized by a combination of several surface analytical tools. A remarkable improvement in sulfidation resistance is observed in Fe-25Cr-20Ni-1.5Al₂O₃ under the conditions investigated here. This is attributed to the ability of the alloy to form and maintain a predominantly Cr₂O₃ scale with reduced Fe-diffusion and content. Possible scientific reasons for such improvement are discussed. The base alloy, Fe-25Cr-20Ni, fails to develop and retain such a Cr₂O₃ scale and undergoes sulfidation within a few minutes of exposure. The scale breakdown process by sulfidation is explained qualitatively. Experimental evidence suggests that sulfur in the environment enhances Fe-diffusion and content in the scale.     

The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.     

Oxidation at defects in scales on iron-chromium alloys

A prior investigation on the lateral spreading of oxide into defects in Wustite scales on iron was extended to study the same phenomena in Fe-Cr alloys. Included were two Fe-Cr-Mo alloys and an Fe-25Cr-6Al alloy. Three types of experiments were conducted to study flaws introduced to simulate damage to protective oxide layers caused by particle erosion. It was found that outer scales of Wustite on the Cr-Mo alloys spread into flaws in much the same way as Wustite on unalloyed iron. However, inner scales of (Fe,Cr)₃O₄ on the Cr-Mo alloys and the scale formed on the Fe-25Cr-6Al alloy had only a slight tendency to spread into flaws. These results are consistent with the known higher diffusion coefficients and higher defect concentrations in Wustite than in other oxide phases.     

The influence of alloying elements on the chlorine-induced high temperature corrosion of Fe-Cr alloys in oxidizing atmospheres

The effect of the alloying elements Al, Cr, Mn, Mo, Si and Ti on the corrosion behaviour of ferritic Fe-15Cr model alloys was studied in a N₂/He-5 vol.% O₂ gas mixture with and without additions of 500–1500 vppm HCl at 600°C. The main corrosion mechanism is “active oxidation”, characterized by the formation of volatile metal chlorides at the metal/oxide interface. Volatilization and subsequent conversion of the chlorides into oxides results in the formation of porous and poorly adherent oxide scales. Large mass gains were observed for Fe-15Cr, Fe-35Cr and Fe-15Cr with additions of 5 wt.% Ti, 10 wt.% Mn or 10 wt.% Mo. The specific morphology of the corrosion products depends strongly on the alloying elements. For the Fe-Cr alloys, a model for the formation of the scales, which are characterized by alternating dense and porous layers, is presented. The addition of 5 wt.% Si or Al to Fe-15Cr leads to much better corrosion resistance by the formation of protective Cr₂O₃/Al₂O₃-layers, however in the case of Al addition the behaviour depends strongly on the experimental conditions, as surface treatment and flow velocity. In Fe-15Cr-10Mo preferential removal of the more reactive metals Fe and Cr was observed resulting in a Mo-enriched porous metal zone underneath the metal-oxide interface. The effect of carbon on the corrosion behaviour was examined by addition of 0.3–0.8 wt.% C to the model alloys. Cr-rich M₂₃C₆-carbides were attacked preferentially while Mo-rich M₆C-carbides are very stable relative to the matrix and the attack occurs in regions surrounding the carbides.     

Effects of nitrogen on the passivity of Fe-20Cr alloy

Influences of nitrogen on the passivity of Fe-20Cr-(0, 1.1)N alloys were examined by in situ electrochemical techniques. Nitrogen was incorporated in the form of (Fe, Cr)-nitrides in the passive film, and Cr was enriched in the film of the alloy with nitrogen. Photocurrent analysis demonstrated that the structure of passive film formed on Fe-20Cr-1.1N alloy is Cr-substituted γ-Fe₂O₃ with (Fe, Cr)-nitrides. Mott-Schottky analysis revealed that the film formed on Fe-20Cr-1.1N contained higher Cr⁶⁺ and lower Cr³⁺ vacancy concentrations compared with that on Fe-20Cr alloy. All of these results were associated with the enhanced protectiveness of the film on Fe-20Cr-1.1N.     

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.     

The influence of manganese on the High-temperature oxidation of iron-chromium alloys

An investigation has been undertaken into the oxidation behaviour of manganese-containing Fe-28% Cr alloys in oxygen at 800° and 1000°C. The presence of the tertiary element has a detrimental effect on the oxidation resistance, resulting in enhanced scale-growth rates during isothermal exposure and increased incidences of scale failure at temperature. This is largely due to relatively rapid rates of diffusion of manganese across the Cr₂O₃ scale and formation of MnCr₂O₄ spinel on its outer surface. The scale on Fe-28% Cr-1% Mn consists of a layer of Cr₂O₃, containing a small concentration of manganese, with an outer layer of the spinel oxide. During the early stages, an inner layer of the spinel also develops, but, eventually, this almost completely disappears as the manganese diffuses into the outer scale. A similar scale forms on Fe-26% Cr-5% Mn, but the higher manganese concentration enables a significant amount of this element to be retained in the inner regions. The overall growth rate of the scale is significantly faster than on Fe-28% Cr or the 1% Mn-containing alloy.     

The effect of preoxidation on the sulfidation of Ni-20Cr (2–5)Al Alloys

Ni-20Cr alloys with 2, 3.5, and 5 wt.% Al have been preoxidized up to 100 hr at 1000°C in dry H₂, in H₂/23% H₂O and in air and subsequently exposed to an H₂/5% H₂S atmosphere at 750° C. During the preoxidation treatment different types of oxide scales were formed which affect the sulfidation protection in different ways. Optimum results were obtained for alloys with 3.5 and 5 wt.% Al after 20 hr exposure to dry H₂ at 1000°C. A thin Al₂O₃ scale is formed which decreases the sulfur attack by more than one order of magnitude. Preoxidation conditions for Ni-20Cr-2Al alloys in H₂ and for Ni-20Cr-2Al and Ni-20Cr-3.5Al in H₂/H₂O were observed to be less effective. No improvement was found for preoxidation in air or for Ni-20Cr-5Al alloys preoxidized in H₂/H₂O.     

XPS and AES studies of the high temperature corrosion mechanism of Fe-30Cr alloy

Fe-30Cr alloy specimens were pre-oxidized at two different oxygen partial pressures (10^?16 and 10^?19 atm) at 900°C and subsequently exposed to environments containing both oxygen and sulfur. The sulfur and oxygen partial pressures were maintained such that Cr₂O₃ was the stable phase. The Cr₂O₃ scales formed during pre-oxidation became rapidly unstable when exposed to an environment whose composition approached the chromium sulfide-chromium oxide phase boundary; but when exposed to a higher oxygen partial pressure with the same sulfur partial pressure, the preformed scales remained intact. For elucidating the sulfidation mechanisms, the reaction products on the surface were analyzed at different stages of sulfidation by X-ray photo-electron spectroscopy and Auger electron spectroscopy. Correlation of the reaction mechanisms with thermodynamic and transport parameters are discussed.     

The corrosion of ferritic stainless steels and high-purity Fe-Cr alloys in basaltic lava and simulated magmatic gas

Three ferritic stainless steels, types 410, 430, and 446, containing 12, 17, and 26% Cr, respectively, and two high-purity binary alloys, Fe-19Cr and Fe-24Cr, were subjected to molten tholeiitic basaltic lava with a cover gas simulating magmatic gas at 1150°C for periods up to 400 hr. The oxygen and sulfur partial pressures were 9.8×10^?10 and 7.0×10^?3, respectively. All alloys formed Cr₂O₃ scales. Internal sulfidation occurred in the commercial alloys resulting in the formation of chromium and manganese sulfides. Internal oxidation of silicon also occurred. The extent of internal sulfidation decreased with increasing chromium content. There was a “critical” chromium content between 12 and 17%, above which internal sulfidation did not occur in 96 hr. However, the “critical” chromium level increased with exposure time to nearly 26% for 400 hr. Little internal sulfidation was observed in the high-purity alloys. The different behavior between the commercial and high-purity alloys may be attributed to (i) the formation of more perfect scales on the latter, which inhibited the inward migration of sulfur, and (ii) changes in the sulfur activity gradient across the scale caused by the presence of silicon and manganese.     

Oxidation of Fe-8Cr-14Ni-Al-Si-Mn from 700 to 1000°C

This paper reports an investigation into reducing the Cr concentration in commercial-grade stainless steels while maintaining oxidation protection at elevated temperatures. Aluminum and Si were added as partial substitute alloy elements to enhance the reduced operation protection resulting from Cr concentration reduced by approximately 50 pct of that found in stainless steels. The goal of this study was to determine the oxidation mechanism of such an Fe, Al-Si alloy: Fe-8Cr-14Ni-1Al-3.5Si-1Mn. During the initial oxidation period the protection resulted from a thin film of Al₂O₃ over an Fe and Cr spinel. Long-term oxidation protection resulted from the gradual formation of a Cr sesquioxide (Cr₂O₂) inner oxide layer. Eventually an outer oxide layer formed that was a mixed composition spinel of Cr and Mn (MnO · Cr₂O₃). The Al₂O₃, which was part of the original protective layer flaked off early in the oxide testing, and the aluminum oxide that formed later appeared as an internal oxide precipitate.     

Penetration of sulfur through preformed protective oxide scales

Thermodynamic assessment of sulfur penetration through otherwise protective scales such as Cr₂O₃, Al₂O₃ has been carried out for Co-Cr- and Co-Cr-Al-base alloys. Limiting conditions for sulfide formation following gas molecular transport and solution-diffusion transport have been established and the results partially confirmed by experiments carried out on Co-10Cr, Co-25Cr, and Co-10Cr-5Al alloys in sulfurous atmospheres. The results show that molecular transport of sulfurous gas species through the growing oxide scale definitely occurs. It was not possible to confirm or disprove the solutiondiffusion mechanism.     

Oxidation behavior of Ni-Cr-1ThO2 alloys at 1000 and 1200°C

The oxidation behavior of Ni-13.5-33.7Cr-1ThO₂ alloys in flowing oxygen at 150 Torr was investigated in the temperature range 1000–1200°C. Gravimetric measurements of the oxidation kinetics have been combined with microstructural studies of the reacted samples in order to evaluate the reaction mechanisms. The oxide products formed on the alloys were a function of Cr content, sample surface preparation, reaction time, and temperature. The presence of ThO₂ appears to produce two effects during alloy oxidation. First, enhanced Cr diffusion to the alloy surface results in rapid formation of a Cr₂O₃ subscale beneath NiO on Ni-13.5Cr-1ThO₂ and selective oxidation of Cr for Ni-22.6Cr-1ThO₂. Second, the mechanism of formation of Cr₂O₃ is apparently different from that for simple Ni-Cr alloys, resulting in about an order of magnitude reduction in the Cr₂O₃ growth rate. The oxidationvaporization of Cr₂O₃ to CrO₃ becomes rate controlling for the higher Cr alloys after only a few hours of exposure at 1200°C.     

High temperature oxidation of Fe-Al and Fe-Cr-Al alloys: The role of Cr as a chemically active element

Good high-temperature corrosion resistance of Fe-Al alloys in oxidizing environments is due to the α-Al₂O₃ film which is formed on the surface provided temperature is above 900 °C and the Al-content of the alloy exceeds the critical value. Ab initio calculations combined with experiments on Fe-13Al, Fe-18Al, Fe-23Al and Fe-10Cr-10Al alloys show that the beneficial effect of Cr on the oxidation resistance is significantly related to bulk effects. The comparison of experimental and calculated results indicates a clear correlation between the Fe-Cr chemical potential difference and the formation of the protective oxide scales.     

High temperature corrosion of pure Fe, Cr and Fe-Cr binary alloys in O2 containing trace KCl vapour at 750 °C

Pure Fe, Cr and Fe-Cr binary alloys were corroded in O₂ containing 298 ppm KCl vapour at 750 °C. The corrosion kinetics were determined, and the microstructure and the composition of oxide scales were examined. During corrosion process, KCl vapour reacted with the formed oxide scales and generated Cl₂ gas. As Cl₂ gas introduced the active oxidation, a multilayer oxide scales consisted of an outmost Fe₂O₃ layer and an inner Cr₂O₃ layer formed on the Fe-Cr alloys with lower Cr concentration. In the case of Fe-60Cr or Fe-80Cr alloys, monolayer Cr₂O₃ formed as the healing oxidation process. However, multilayer Cr₂O₃ formed on pure Cr.     

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.