Corrosion Behavior of Y–Al Alloys in a H2/H2S/H2O Gas Mixture at 800–950°C

The corrosion behavior of pure Y and two Y–Al alloys containing 5 and 10 wt.% Al was studied over the temperature range 800–950°C in a H₂/H₂S/H₂O gas mixture. Both alloys had the two-phase structure of Y+Y₂Al. With the exception of Y–10Al, for which a kinetics inversion was observed between 800°C and higher temperatures (T 850°C), the parabolic rate constants generally increased with increasing temperature, but decreased with increasing Al content. The scales formed on pure Y and the Y–Al alloys were single but heterophasic, consisting of mostly Y₂O₃ and minor Y₂O₂S. XRD results showed no evidence of Al₂O₃ and pure sulfides. The formation of Y₂O₃ and Y₂O₂S on Y–10Al at 800°C resulted in a subsurface phase transformation from Y+Y₂Al to YAl₂ and broke the structural integrity of the scale, being responsible for the fast corrosion rate.     

The Corrosion of Titanium Aluminides in H2/H2S/H2O Atmospheres at 800–1000°C

The corrosion behavior of three Ti–Al intermetallics containing 20, 30, and 40 wt.% Al was studied over the temperature range 800–1000°C in a H₂/H₂S/H₂O gas mixture. Ti–20Al and Ti–40Al alloys had the single-phase structure of Ti₃Al and TiAl, respectively, while Ti–30Al was a two-phase mixture of Ti₃Al+TiAl. 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 decreased with increasing Al content. The Ti–40Al alloy exhibited the best corrosion resistance among all alloys studied. The scales formed on Ti–Al intermetallics were heterophasic and duplex, consisting of an outer-scale layer of pure -TiO₂ and an inner layer of -TiO₂ with minor amounts of -Al₂O₃ and Ti_l-xS. The amount of -Al₂O₃, which increased with increasing Al content, is responsible for the reduction of the corrosion rates as compared with those of pure Ti oxides.     

Corrosion of Binary Fe–Si Alloys in Reducing Oxidizing and Sulfidizing–Oxidizing Atmospheres at 700 °C

The corrosion behavior of three Fe–Si alloys containing approximately 5, 9 and 13 at.% Si was studied at 700 °C in an H₂–CO₂ gas mixture providing 10^?20 atm O₂ as well as in an H₂–H₂S–CO₂ gas mixture providing the same oxygen pressure coupled to an S₂ pressure of 10^?8 atm. All the alloys followed complex kinetics which were mostly linear for Fe–5Si, but showed one or two parabolic stages for the other two alloys. Simple oxidation produced essentially two-layered scales in which Si was confined to the alloy consumption zone in the form of silicon oxide and iron-silicon double oxide. Corrosion in the oxidizing–sulfidizing gas mixture produced scales composed of a thick external zone of pure FeS followed by an internal region containing complex mixtures of FeS with Si and Fe oxides. Internal oxidation of silicon was only observed for the oxidation of Fe–5Si in both environments. The extent of corrosion decreased in both gas mixtures with an increase in the Si content of the alloys. Finally, the addition of sulfur produced a significant increase of the overall mass gains for each alloy.     

The corrosion behavior of Fe-Al alloys in H2/H2S/H2O atmospheres at 700–900°C

The corrosion behavior of five Fe-Al binary alloys containing up to 40 at. % Al was studied over the temperature range of 700–900°C in a H₂/H₂S/H₂O mixture with varying sulfur partial pressures of 10^–7–10^–5 atm. and oxygen partial pressures of 10^–24–10^–2° atm. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants decreased with increasing Al content. The scales formed on Fe-5 and –10 at.% Al were duplex, consisting of an outer layer of iron sulfide (FeS or Fe_1–xS) and an inner complex scale of FeAl₂S₄ and FeS. Alloys having intermediate Al contents (Fe-18 and –28 at.% Al) formed scales that consisted of mostly iron sulfide and Al₂O₃ as well as minor a amount of FeAl₂S₄. The amount of Al₂O₃ increased with increasing Al content. The Fe 40 at.% Al formed only Al₂O₃ at 700°C, while most Al₂O₃ and some FeS were detected at T800°C. The formation of Al₂O₃ was responsible for the reduction of the corrosion rates.     

The Effect of Doping on the Corrosion Behavior of Quasi-Crystalline Alloys in the Al–Cu–Fe–Cr System

The electrochemical behavior of five alloys of variable compositions in the Al₆₅Cu₂₅Fe_10–хCr _х system in dependence on the number of QC phases in acidic and alkaline media has been investigated by the potentiodynamic method. It has been established that the samples’ corrosion stabilities increase along with the increase of the solution pH. Higher stability was manifested by alloys with a predominant quasi-crystalline (dexagonal and icosahedral) structural component.     

Corrosion of low carbon steel weldments at 600–800 °C in N2/H2S/H2O gases

A low carbon steel was arc-welded, and corroded at 600, 700 and 800 °C for up to 20 h in 1 atm of either N₂/H₂S-mixed gases or N₂/H₂S/H₂O-mixed gases to characterize the effects of H₂S and H₂O gases on the high-temperature corrosion of welded joints. Corrosion proceeded fast and almost linearly. It increased with the increases in the corrosion temperature and with the addition of H₂S and H₂O. H₂S formed FeS, while H₂O formed iron oxides such as Fe₃O₄. Hydrogen and sulfur that were released from H₂S and H₂O made the scales fragile and nonadherent. Weld metals corroded faster than base metals because the former had coarser grains than the latter.     

The Corrosion Behavior of Carbon Steel in Sulfide Aqueous Media at 30°C

In this paper, we studied the effect of sulfide ions on the corrosion behavior of carbon steel to simulate the geological disposal of high-level radioactive waste. In geological storage conditions, sulfidogenic environment was sustained by sulfate-reducing bacteria. Corrosion tests were conducted in systems in a controlled atmosphere of 5% H₂/N₂. Batch experiments were conducted at 30°C for 1 month with steel coupons immersed in Na₂S solutions. The structural characterization of the corrosion products was investigated by scanning electron microscope/energy dispersive x-ray spectroscopy, confocal micro-Raman spectrometry, and x-ray diffraction. In the absence of sulfide ion, a magnetite (Fe₃O₄) corrosion product layer was formed on steel surface while in the presence of sulfide ions we observed the formation of a poorly crystallized irons sulfide at low-sulfide concentration (1 mg/L) and a solid adherent pyrrhotite layer at higher sulfide concentration (5-15 mg/L). The strong drop in steel corrosion rate with sulfide concentration was revealed and related to the formation of well-crystallized pyrrhotite.     

The Sulfidation of Two-Phase Fe-Cu Alloys in H2-H2S Mixtures at 500-700°C

The sulfidation behavior of three two-phaseFe-Cu alloys containing 25, 50, and 75 wt.% copper hasbeen investigated in H₂-H₂Smixtures at 500-700^°C under gas-phase sulfur pressures, which is significantly abovethose for the dissociation of both FeS andCu₂S. In all cases, the three alloyssulfidized more slowly than both pure metals under thesame conditions. At all temperatures, Fe-25Cu showed the slowestgrowth rates, whereas Fe-50Cu sulfidized more rapidlythan the other two alloys. However, the kinetics curvesfor the three alloys tended to overlap, particularly at the higher temperatures. The scales werecomplex and contained an outer layer composed of amixture of two different Cu-Fe double sulfides,Cu₅FeS₄ and CuFeS₂,plus an inner zone containing a mixture of metalliciron with the double sulfideCu₅FeS₄formed by completesulfidation of the copper-rich phase and partialsulfidation of the iron-rich phase. This region also contained large voids,possibly because of outward diffusion of metal cations,whereas the iron-rich islands were mainly unattacked.The depth of internal attack increased with increasing temperature and/or iron content. Finally,particles of almost pure copper metal, probably formedduring cooling from the reaction temperature, werepresent at the scale-subscale interface, as inclusions in the scale and as whiskers protruding out ofthe external scale surface.     

Effect of Cyclic Reaction on Corrosion Behavior of Chromium-Containing Alloys in CO2 Gas at 650 °C

Oxidation of Metals - In this work, seven commercial alloys (602CA, 310SS, 253MA, F321, F316L, 800H and 304SS) were investigated in Ar–20% CO2 gas at 650 °C under a cyclic...     

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.     

The Corrosion of Co-15 wt.% Y at 600-800°C in Sulfidizing-Oxidizing Atmospheres

The corrosion of Co-15 wt.% Y has been studiedat 600-800°C inH₂-H₂S-CO₂ mixturesproviding a sulfur pressure of 10^-8 atm at600-800°C and of 10^-7 atm at 800°Cand an oxygen pressure of 10^-24 atm at 600°C and of10^-20 atm at 700-800°C. The corrosionrates in such sulfidizing-oxidizing atmospheres werecompared with those of pure cobalt and yttrium. Theaddition of yttrium to cobalt is only slightly beneficial, sincefor a yttrium content of 15 wt.% the corrosion rate isreduced quite significantly with respect to pure cobaltat 800°C under 10^-7 atm S₂,only to a limited extent at 600°C, and even slightlyincreased at 700°C. Moreover, the alloy corrodesconsiderably more rapidly than pure yttrium at800°C, when the latter behaves protectively. At 600 and 700°C, yttrium exhibitedbreakaway behavior, while the alloy corroded morerapidly than yttrium at short times, but more slowly atlong times. Under all conditions, except at 800°Cunder 10^-8 atm S₂, the alloy formsan external layer of cobalt sulfide overlying anintermediate region of very complex compositioncontaining a mixture of the compounds of the two metalsand an innermost region of internal attack containing compoundsof yttrium with both oxygen and sulfur. Thus, cobalt canstill diffuse through the intermediate region to formthe outer cobalt-sulfide layer at nonnegligible rates. The scaling behavior of the Co-15% Yalloy is discussed by taking into account the limitedsolubility of yttrium in cobalt as well as the presenceof an intermetallic Co-Y compound in thealloy.     

Sulfidation Behavior of Inconel 738 Superalloy at 500–900°C

The high-temperature sulfidation behavior of the cast nickel-base superalloy Inconel 738 (IN-738) was studied over the temperature range 500–900°C in pure sulfur vapor over the range 10²–10⁴ Pa. The sulfidation kinetics followed the parabolic rate law in all cases. The sulfidation rates increased with increasing temperature and sulfur pressure. The scales formed were bilayered and temperature-dependent. At T700°C, the outer scale consisted of mostly NiS (with dissolved Co) and minor (CoS₂ and NiCo₂S₄, while the inner layer was a heterophasic mixture of NiS, NiCo₂S₄, and minor amounts of Al₂S₃ and chromium sulfide (Cr₂S₃/Cr₃S₄). At T750°C, the outer scale consisted of mostly Ni₃S₂ (with dissolved Co) and minor amounts of Co₃S₄ and Cr₂S₃/Cr₃S₄, while the inner layer was a complex, heterophasic mixture of Ni₃S₂, Cr₂S₃/Cr₃S₄, CoCr₂S₄, and minor Al₂S₃. Platinum markers were found to be located at the interface between the inner and outer scales, suggesting that the outer scale grew by the outward transport of cations and the inner scale grew by the inward transport of sulfur. The formation of Al₂S₃ and Cr₂S₃/Cr₃S₄ partly blocked the transport of cations through the inner scale and consequently reduced the sulfidation rates as compared to pure nickel.     

Oxidation of Fe–Si,Fe–Al and Fe–Si–Al alloys in CO2–H2O gas at 800 °C

Binary Fe–(1, 2, 3)Si and Fe–(2, 4, 6)Al, and ternary Fe–(2, 3)Si–(4, 6)Al alloys (all in wt%) were oxidised in Ar–20% CO₂, with and without H₂O, at 800 °C. All binary alloys except Fe–6Al, in all gases, formed a thin outer layer of Fe₃O₄, an intermediate Fe₃O₄ + FeO layer, an inner FeO + Fe₂SiO₄ (or FeAl₂O₄) layer and internally precipitated SiO₂ (or FeAl₂O₄). Ternary alloys and Fe–6Al developed a protective Al₂O₃ layer beneath Fe₂O₃ in Ar–20% CO₂. Water vapour affected ternary alloy oxidation only slightly, but Fe–6Al oxidized internally in high H₂O-content gas, and its scale was non-protective.     

The Oxidation of Two Ternary Ni–Cu–5 at.%Al Alloys in 1 atm of Pure O2 at 800–900°C

The oxidation of a Ni-rich and a Cu-rich single-phase ternary alloy containing about 5at.% aluminum has been studied at 800 and 900°C under 1atm O₂. The behavior of the Ni-rich alloy is similar to that of a binary Ni–Al alloy with a similar Al content at both temperatures, with formation of an external NiO layer coupled to the internal oxidation of aluminum. The Cu-rich ternary alloy shows a larger tendency to form protective alumina scales, even though its behavior is borderline between protective and non-protective. In fact, at 800°C, after an initial stage of fast reaction during which all the alloy components are oxidized, this alloy is able to develop a continuous layer of alumina at the base of the scale which prevents the internal oxidation of aluminum. On the contrary, at 900°C the innermost alumina layer undergoes repeated rupturing followed by healing, so that internal oxidation of Al is only partly eliminated. As a result, the corrosion kinetics of the Cu-rich ternary alloy at 900°C are much faster than at 800°C and very similar to those of pure copper and of Al-dilute binary Cu–Al alloys. Possible reasons for the larger tendency of the Cu-rich alloy to form external alumina scales than the Ni-rich alloy are examined.     

High-Temperature Corrosion of Aluminized and Chromized Fe–25.8 %Cr–19.5 %Ni Alloys in N2/H2S/H2O-Mixed Gases

Alloys of Fe–25.8 %Cr–19.5 %Ni (SUS310 stainless steel) were either chromized or aluminized via pack cementation, and corroded at 800 °C for 100 h in 1 atm of (0.9448 atm of N₂ + 0.031 atm of H₂O + 0.0242 atm of H₂S)-mixed gases. The chromized layer consisted primarily of Cr_1.36Fe_0.52 and some Cr₂₃C₆. Its corrosion resulted in the formation of Cr₂S₃ and some FeS and Fe₅Ni₄S₈. The aluminized coating consisted primarily of FeAl. Its corrosion resulted in the formation of α-Al₂O₃, Al₂S₃, and Cr₂S₃. Aluminizing was more effective than chromizing in increasing the corrosion resistance of the substrate, due mainly to the formation of α-Al₂O₃.     

Oxidation Behavior of Ni-3, 6 wt% Al Alloys at 800 °C in Atmospheres Containing Water Vapor

The oxidation behavior of Ni, Ni–3Al, and Ni–6Al alloys at 800 °C in air + H₂O was investigated. The oxidation kinetics of Ni and the alloys in air + H₂O were very similar, but the mass gains of Ni and each alloy were smaller in air + H₂O than in air. Oxidation products formed on Ni-3 and 6Al alloys consisted of an outer NiO scale and internal Al₂O₃ precipitates. The growth rates of both NiO and the internal oxidation zone were much smaller in air + H₂O. The NiO scale formed in air + H₂O was duplex in structure with outer porous and inner dense layers. The outer porous layer consisted of fine powder-like NiO particles. A thicker metallic Ni(Al) layer formed at the NiO/alloy interface in air + H₂O, caused by extrusion of Ni from the substrate due to volume changes accompanying the internal oxide formation. Formation of the metallic Ni layer appeared to be the reason for the similarity between the oxidation kinetics of both Ni and the alloys in air + H₂O.     

Sulfidation of Three Two-Phase Cu-Cr Alloys in H2-H2S Mixtures at 400-600°C

The sulfidation of three Cu-Cr alloys withnominal Cr contents of 25, 50, and 75 wt.% and of thetwo pure metals has been studied at 400-600°C inH₂-H₂S mixtures under sulfurpressures of 10^-12 atm at 400 and 500°C and 10^-10 atm at 500and 600°C, slightly above the Cu-Cu₂Sequilibrium. All the alloys were two-phase, containinga mixture of the solid solution of chromium in copperwith nearly pure chromium. The corrosion rates of the three materialsunder the same conditions were similar and intermediatebetween those of the two pure metals and increased withtemperature and sulfur pressure. The scales had a complex composition, often containing anexternal Cu₂S layer, which becamediscontinuous or even disappeared, in some cases,followed by an intermediate layer of the double Cu-Crsulfide CuCrS₂ and an innermost complex layer, which generallyconsisted of a mixture of the double Cu-Cr sulfideCuCr₂S₄ with the chromium sulfideCrS and also commonly contained unsul fidized chromiummetal particles. No chromium depletion was developed in the alloys beneaththe corrosion-affected region. Moreover, no internalsulfidation of chromium was observed in the alloyrichest in copper and no exclusive external sulfidation of chromium in those richest in chromium, inspite of the large difference in the thermodynamicstabilities of the sulfides of the two pure metals.These peculiar scale features are interpreted by taking into account the special two-phase nature ofthese alloys.     

The oxidation of Iron-Chromium-Manganese alloys at 900°C

The oxidation of nine ternary iron-chromium-manganese alloys was studied at 900°C in an oxygen partial pressure of 26.7 kPa. The manganese concentration was set at 2, 6, and 10 wt. %, and chromium at 5, 12, and 20 wt. %. The scales formed on the low-chromium alloys consisted of (Mn,Fe)₂O₃, -Fe₂O₃, and Fe₃O₄. These alloys all exhibited internal oxidation and scale detachment upon cooling. The scales formed on the higher-chromium alloys were complicated by nodule formation. Initially, these scales had an outer layer of MnCr₂O₄ with Cr₂O₃ underneath, adjacent to the alloy. With the passage of time, however, nodules formed, and the overall reaction rate increased. This tendency was more marked at higher manganese contents. Although these alloys contained a high chromium content, the product chromia scale usually contained manganese. It was concluded that the presence of manganese in iron-chromium alloys had an adverse effect on the oxidation resistance over a wide range of chromium levels.     

Hot Corrosion Behavior of Some Superalloys in a Simulated Incinerator Environment at 900 °C

Incinerators are being used to burn solid waste of all types. This burning of waste creates a very aggressive environment at extremely high temperature. This environment attacks the various components of the incinerators. Some studies have been reported regarding behavior of steels in simulated incinerator environment at 550 °C. In present work superalloys Superco 605, Superni 600, and Superni 718 have been subjected to cyclic oxidation in 40 wt.% K₂SO₄ + 40 wt.% Na₂SO₄ + 10 wt.% KCl + 10 wt.% NaCl environment at 900 °C under cyclic condition. Weight change measurements have been done and weight change has been plotted against the numbers of cycles. The oxide scales formed on the surface of the corroded superalloys have been characterize by FESEM, EDS, XRD, cross-sectional analysis, and x-ray mapping. The nickel-based superalloys Superni 600 and Superni 718 indicated better resistance to corrosion in the above environment whereas Superco 605 lead to massive weight gain.     

Corrosion Behavior of Ψ and β Quasicrystalline Al–Cu–Fe Alloy

Two nanostructured Al–Cu–Fe alloys, Al64Cu24Fe12 and Al62.5Cu25.2Fe12.3, have been studied. Icosahedral quasicrystalline(w) Al64Cu24Fe12 and crystalline cubic(b) Al62.5Cu25.2Fe12.3cylindrical ingots were first produced using normal casting techniques. High-energy mechanical milling was then conducted to obtain w icosahedral and b intermetallic nanostructured powders. Electrochemical impedance spectroscopy, linear polarization resistance, and potentiodynamic polarization were used to investigate the electrochemical corrosion characteristics of the powders in solutions with different p H values. Current density(icorr), polarization resistance(Rp), and impedance modulus(|Z|) were determined. The results showed that regardless of p H value, increasing the solution temperature enhanced the corrosion resistance of the both phases. However, the electrochemical behavior of the w phase indicated that its stability depends on the submerged exposure time in neutral and alkaline environments. This behavior was related to the type of corrosion products present on the surfaces of the particles along with the diffusion and charge-transfer mechanisms of the corrosion process.