High-temperature corrosion in mixed gas environments

Scaling reactions between pure metals and multiple oxidant gases are reviewed briefly. It is recognized that elemental oxidant activities are usually so low that the actual reactant species are heteronuclear molecules such as SO₂, CO₂, etc. The formation of duplex, sulfide-oxide scales on iron and manganese, even when sulfide is unstable with respect to oxide, is attributed to direct reaction with SO₂. The persistence of the metastable sulfide is due to its preservation by the rapidly growing scale. The reaction of pure chromium with a number of mixed gases is also discussed. The continued formation of carbides and nitrides beneath an external Cr₂O₃ scale layer indicates that the latter material is permeable to gas species. Interaction among different gas species is observed, and is attributed to selective adsorption on internal surfaces within the chromium oxide. New work on the reaction of alloys with mixed gases is reported. Several austenitic heat-resistant alloys were exposed at 1000°C to gases containing one, two or all of the oxidants carbon, sulfur and oxygen. Gases containing two or more oxidants produced multiple zones of internal precipitation. The precipitates were chromium-rich oxides, sulfides and carbides arranged in order of thermodynamic stability: oxides beneath the external scale, carbides deepest within the alloys and sulfides in an intermediate zone overlapping the oxide zone. Each precipitate zone widened according to parabolic kinetics. This finding confirms the as yet untested prediction made by J. L. Meijering in 1971. However, the rate at which a particular zone grows changes according to presence of other oxidants. Interactions between the oxidants can be large and reaction rates are currently not predictable.     

An analysis of the internal oxidation of binary M-Nb alloys under low oxygen pressures at 600–800°C

The corrosion of M–Nb alloys based on iron, cobalt, and nickel and containing 15 and 30 wt% Nb has been studied at 600–800°C under low oxygen pressures (10^–24 atm at 600°C and 10^–20 atm at 700–800°C). Except for the Co–Nb and Ni–Nb alloys corroded at 800°C, which formed external scales of niobium oxides, corrosion under low O₂ pressures produced an internal oxidation of niobium. This attack was much faster than expected on the basis of the classical theory. Furthermore, the distribution of the internal oxide in the alloys containing two metal phases was very close to that of the Nb-rich phase in the original alloys. These kinetic, microstructural, and thermodynamic aspects are examined by taking into account the effects of the limited solubility of niobium in the various base metals and of the two-phase nature of the alloys.     

General and localized corrosion of magnesium alloys: A critical review

Magnesium (Mg) alloys as well as experimental alloys are emerging as light structural materials for current, new, and innovative applications. This paper describes the influence of the alloying elements and the different casting processes on the microstructure and performance of these alloys and corrosion. It gives a comprehensible approach for the resistance of these alloys to general, localized and metallurgically influenced corrosion, which are the main challenges for their use. Exposure to humid air with ∼65% relative humidity during 4 days gives 100–150 nm thickness. The film is amorphous and has an oxidation rate less than 0.01 μm/y. The pH values between 8.5 and 11.5 correspond to a relatively protective oxide or hydroxide film; however above 11.5 a passive stable layer is observed. The poor corrosion resistance of many Mg alloys can be due to the internal galvanic corrosion caused by second phases or impurities. Agitation or any other means of destroying or preventing the formation of a protective film leads to increasing corrosion kinetics. The pH changes during pitting corrosion can come from two different reduction reactions: reduction of dissolved oxygen (O) and that of hydrogen (H) ions. Filiform corrosion was observed in the uncoated AZ31, while general corrosion mainly occurred in some deposition coated alloys. Crevice corrosion can probably be initiated due to the hydrolysis reaction. Exfoliation can be considered as a type of intergranular attack, and this is observed in unalloyed Mg above a critical chloride concentration.     

The Internal Oxidation of Ternary Alloys I: The Single Oxidation of the Most-Reactive Component Under Low Oxidant Pressures

The internal oxidation of the most-reactive component C of ternary A–B–C alloys by a single oxidant is examined assuming a gas-phase oxidant pressure below the stability of the oxides of the other two components. The precipitation of the most-stable oxide leaves behind a matrix composed of a binary alloy of the two less-reactive components, whose composition affects the solubility and diffusivity of the oxidant within the region of internal oxidation, with an effect on the reaction kinetics. Approximate relations between these properties are proposed and used to predict the kinetics of internal oxidation of C under the assumption of parabolic rate law. The results obtained for the ternary alloys are compared with the behavior of binary A–C and B–C alloys with the same C content. A new important factor in establishing the difference between the internal oxidation in ternary A–B–C alloys and in binary A–C and B–C alloys under a fixed gas-phase oxygen pressure and C content is the ratio between the concentrations of A and B in the bulk ternary alloy.     

Corrosion of iron-, nickel-, and cobalt-base alloys in atmospheres containing carbon and oxygen

The corrosion of iron-, nickel-, and cobalt-base alloys has been studied in atmospheres containing carbon and oxygen in the temperature range 894–1366 K. It was observed that preformed Cr₂O₃ films are not effective barriers to carbon transport in atmospheres in which the oxide is not stable but that stable, growing Cr₂O₃ films are excellent barriers to carbon penetration. The presence of Fe-containing oxides on Fe-Ni-Cr and Fe-Cr alloys cause the scales to be permeable to carbon. This phenomenon was found to be sensitive to alloy surface preparation. Carbon transport through oxide scales may occur by two mechanisms: diffusion or molecular transport through physical defects. The present work has evidence of the latter but cannot rule out the former in cases where the carbon activity is sufficiently large. In gases containing CO and CO₂ in which Cr carbide is stable Cr₂O₃ was found to form at the carbide-alloy interface by oxygen transport through the carbide. In A-CH₄ Fe-Ni-Cr were found to undergo graphitization attack. The results were consistent with the formation and subsequent decomposition of metastable carbides, as proposed by Hochmann.     

Influence of solid-state CaS-CaO-CaSO4 deposits on corrosion of high-temperature alloys in simulated FBC environments

This study addresses questions concerning the likelihood of sulfidation attack of heat-exchanger alloys beneath deposits of sulfur-sorbent material in fluidized-bed combustors. Alloy specimens were exposed at 900°C in calcium sulfate-calcium oxide and calcium sulfide-calcium oxide mixtures, in environments in which the oxygen partial pressures were fixed at values corresponding to the equilibrium values for each solids mixture, using controlled ratios of CO and CO₂. The only source of sulfur in these systems was the calcium sulfate or sulfide. Sulfidation attack of nickel-base alloys occurred in both mixtures, the calcium sulfide-calcium oxide mixture being the more aggressive. Iron-base alloys were less susceptible to attack, although susceptibility increased with increasing nickel content. FeCrAlY-type alloys were resistant to attack. Comparison with corrosion behavior under conditions in which the oxygen and sulfur partial pressures were the same as those used here, but in which the sulfur source was in the gas phase, indicates that the form of the sulfidation attack is similar but that its progress is much slower under solid deposits.     

低氧压下三元合金最活泼组元单一内氧化的理论分析

对含单一氧化剂的气氛中氧分压低于A与B两组元氧化物分解压的情况，三元A-B-C合金系中最活泼组元C内氧化过程进行了理论分析.由于最活泼组元C内氧化生成氧化物的沉淀析出，令内氧化带的基体变成富集A、B两组元的合金.该合金的组成将影响氧在其 中的溶解度和扩散，进而影响内氧化反应动力学过程.对于内氧化遵循抛物线律的情况，我们提出了描述这种影响的一个近似关系式，并据此预测组元C的内氧化动力学.同时，对三元合金的预测结果与含有等量组元C的多种二元A-C 和 B-C合金的氧化行为进行了比较，提出并定义了“三元合金中A与B的浓度比” 的新参数.对于任何给定氧压和组元C含量的情况，借助该参数可以方便地界定三元A-B-C与二元A-C或B-C合金的内氧化行为间的差别.  〖HT5”H〗中图分类号：〖HT5”SS〗〓〓     

The oxidation of two Fe−Nb alloys under low oxygen pressures at 600–800°C

The oxidation of two Fe–Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800°C under low oxygen pressures, similar to those prevailing in environments of the coal-gasification type. The reaction produced only an internal oxidation of niobium to form two niobium oxides (NbO₂ and Nb₂O₅) and in some cases a double Fe–Nb oxide. The kinetics of this reaction were very slow at 600°C but rather fast at 700 and 800°C. A peculiar feature of the internal oxidation of these alloys is that the distribution of the internal oxides follows closely that of the Nb-rich phase in the original two-phase alloys. This behavior, as well as the lack of formation of external scales of niobium oxides, is mainly a result of the limited solubility of niobium in iron and of the consequent presence of two metal phases in the alloys.     

MnFeNiCuPt and MnFeNiCuCo high-entropy alloys designed based on L10 structure in Pettifor map for binary compounds

Quinary exact equi-atomic MnFeNiCuPt and MnFeNiCuCo alloys were investigated to examine their formation of high-entropy alloys (HEAs) by focusing on an L1₀ structure from Pettifor map for binary compounds with 1:1 stoichiometry. The MnFeNiCuPt alloy was practically selected through computer-assisted alloy design under conditions of ≤ 20 at% noble metals, and the condition that the L1₀ structure appears as frequently as possible in the constituent binary equi-atomic compositions comprised of 78 elements. MnFeNiCuCo was selected by substituting Pt with Co from the MnFeNiCuPt alloy as the second candidate. X-ray diffraction and observations by scanning electron microscopy (by energy dispersive spectroscopy for composition analysis) revealed that as-prepared MnFeNiCuPt and MnFeNiCuCo alloys were formed into HEAs with dual fcc structures containing dendrites of ∼10 μm in width. The MnFeNiCuPt and MnFeNiCuCo alloys annealed at 1373 K for 43.2 ks and subsequently quenched in water formed single fcc phases and dual fcc phases, respectively. The annealed MnFeNiCuPt and MnFeNiCuCo alloys were subsequently cooled in a furnace and formed single L1₂ ordered phases and dual fcc phases, respectively. These phases, experimentally observed in the annealed samples, could be partially explained by thermodynamic calculations using Thermo-Calc with SSOL4 and SSOL5 databases for solid solutions. The MnFeNiCuPt and MnFeNiCuCo alloys exhibit soft magnetism with saturation magnetization of 0.23 and 0.43 T, respectively, with coercivity values of ∼1 kA m⁻¹. An alloy design for HEAs based on digitalized crystallographic data of these samples could lead to the discovery of new HEAs.     

Progress in the design of sulphidation-resistant alloys

The interaction of metallic materials with sulphur and sulphur-bearing gases at elevated temperatures leading to the formation of sulphide corrosion products, sulphidation, is generally an extremely rapid process, much more so than oxidation. Conveniently-developed high-temperature alloys with adequate oxidation performance generally have poor resistance to sulphidation and the design of alloys or coatings to withstand such aggressive environments represents a major technological challenge. The principles underlying the development of sulphidation resistance in alloys via selective attack of specific alloying additions to promote the formation of barrier layer protective sulphides are reviewed. The actual limited efficiency of additions of elements such as Cr and Al to Fe, Ni or Co is illustrated. The prospects in the use of other Group IV-VI semi-refractory and refractory addition elements are discussed and the greatly enhanced performance of various experimental alloys containing these metals is illustrated and interpreted. Future research areas are indicated.     

Der Angriff von Metallen durch Gase 50 Jahre Grundlagenforschung Rückblick und Ausblick

The attack of metals by gases — fifty years' fundamental research — retrospective and perspectives Citing more than 100 references the author points out the development since the establishment of Tammann's oxidation formula in 1920. In this context the author deals with the reactions and processes making the reaction follow a parabolic law, e.g. diffusion processes, ion and electron migration, reaction rates as functions of pressure, successive formation of various corrosion products. These statements are explained using examples such as reactions with pure metals and with alloys. In this context due attention is given to the case of the simultaneous action of several oxidizing agents.     

LAVES PHASE ALLOYS FOR HIGH TEMPERATURE APPLICATIONS

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A laboratory study of the corrosion behaviour of Alloys exposed in a non-equilibrated coal gasification atmosphere at 600°C

The ability of alloys to resist corrosion during exposure to high temperature process atmospheres is one of the primary factors governing their selection in the manufacture of components such as heat exchangers in coal conversion plant. In particular, sulphidation attack in the low oxygen-containing environments often encountered in such plant can pose significant problems. Many laboratory studies have been carried out over the years in gases simulating those found in coal gasifiers but these experiments have almost always utilised equilibrated gas mixtures in which the activities of the principal reactants, S, O and C were known and controlled. In many industrial situations, however, the combustion gases are quenched from very high temperatures, e.g. 1200–1400°C before coming in contact with the much cooler heat exchanger tube surfaces and therefore chemical equilibration between the gaseous constituents does not have time to occur. This paper presents results from a study concerned with the corrosion behaviour of candidate heat exchanger alloys exposed to a CO-rich, non-equilibrated gas mixture of the type found in a dryfeed entrained slagging gasifier. Data on three selected alloys, i. e. HR 3C (a chromia-former), MA 956 (an alumina-former) and HR 160 (a silica-former) exposed at 600°C are reported. The kinetics and mechanisms of corrosive degradation are described for test durations of up to 2000 hours. Significant differences in corrosion rate and in the depths of metal loss exhibited by these alloys were observed. Alloy HR 160, containing approximately 2.75% Si, exhibited the best corrosion resistance.     

Corrosion of some pure metals in basaltic lava and simulated magmatic gas at 1150°C

The extraction of thermal energy from subterranean magma can be achieved by the use of a suitable heat exchanger extending into the molten rock. Although the engineering feasibility of this scheme has not been proven, engineering data, including materials compatibility information, will be required ultimately. The work summarized in this paper was designed to provide an understanding of the reaction mechanisms and modes of degradation of various metals so that the best generic types of alloys can be selected for structural components and instrumentation. Fifteen pure metals were studied. These included base metals such as iron, nickel, and cobalt; some precious metals: platinum, rhodium, and palladium (possible thermocouple or lead-wire materials); refractory metals: tungsten, molybdenum, tantalum, niobium, vanadium, and rhenium; plus other high melting metals such as titanium and zirconium. Samples were exposed to basaltic lava at 1150°C for periods of 24 and 96 hr. A cover gas was used to produce oxygen and sulfur fugacities corresponding to those of the gases dissolved in basaltic melts. The corrosion behavior can be classified into five categories: (A) no attack (Pt and Re); (B) slight oxidation (Cr and Mo); (C) heavy oxidation (W, Ta, Nb); (D) sulfidation (Fe, Ni, Co, Pd, Rh); and (E) reaction with lava constituents (V, Ti, Zr). Group (A) metals were inert for all practical purposes. Group (B) metals formed thin adherent oxides initially, under which sulfides eventually formed in the substrate. Attack was minimal. Group (C) metals exhibited extensive oxide formation and virtually no sulfidation. Some reaction between the base-metal oxides and those in the lava took place. Group (D) metals all formed liquid sulfides which penetrated the substrate grain boundaries. All of these metals except cobalt were completely degraded. Cobalt was only partially penetrated by the liquid sulfide formed. Group (E) metals formed silicates, oxides, mixed oxides, and dissolved oxygen in the metal which completely embrittled the metal substrate. A small amount of sulfidation occurred, but sulfidation played virtually no role in the corrosion of these metals. Extensive analyses of the reaction products by scanning electron microscopy, X-ray energy dispersive analysis, electron microprobe analysis, and metallography are presented for each metal. The products formed are discussed with reference to thermodynamic stability diagrams, and the reaction path concept is used to explain some of the corrosion product morphologies.This work supported by the United States Department of Energy under Contract AT(29-1)-789.on leave at Sandia Laboratories, Albuquerque, New Mexico.     

The Corrosion of metals in an oxidizing-chloridizing environment at high temperature

An investigation has been undertaken into the behaviour of metals which form the basis of high-temperature alloys in an argon ?5.5% oxygen ?0.96% hydrogen chloride ?0.86% sulphur dioxide gas mixture at 900°C. The intention has been to ascertain the reaction products, with particular emphasis on the formation of volatile species which can cause considerable degradation of commercial alloys in this environment. From consideration of the thermodynamics of the gas system, the potentials of the reactive species can be determined and correlated with the possible reaction products. In this gas mixture, the oxides of nickel, iron, cobalt, chromium, molybdenum and tungsten are the stable phases with respect to the corresponding metals. Indeed, on exposure of the metals to the environment, the appropriate oxide scales are developed. However, the reactions are complicated by formation of volatile corrosion products, particularly for nickel, cobalt and molybdenum. Although a Cr₂O₃ scale is established on chromium, there is evidence for penetration of chlorine-containing species to the scale/alloy interface. The oxide scale on tungsten is not very protective and thickens rapidly while that on molybdenum is volatile, resulting in rapid consumption of the specimen.     

Effect of NaCl vapor on the oxidation of Ni-Cr alloys

Ni-Cr alloys are known for their resistance to high temperature oxidation. The kinetics of scale formation and the nature of the scale in these alloys are affected by NaCl liquid or vapor. There have been a few investigations dealing with the influence of NaCl on long-time exposure. But the nature of reaction at short times can provide information on the initiation of such attack. In this investigation, Ni-Cr alloys with Cr varying from 0 to 25 wt% were exposed to NaCl vapor at 850°C for a few minutes. The surface chemistry of these alloys along with the unattached ones was analyzed by Auger electron spectroscopy. The nature of scale and the distribution of chlorine was found to vary with the Cr content in the alloys, which has a direct bearing on the rate of oxidation of these alloys in NaCl vapor.     

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.     

The Internal Oxidation of Ternary Alloys. V: The Transition from Internal to External Oxidation of the Most-Reactive Component under Low Oxidant Pressures

This paper examines the conditions for the transition from internal to external oxidation of the most-reactive component C of ternary A–B–C alloys by a single oxidant under gas-phase oxidant activities below the stability of the oxide of the two most-reactive components using Wagners criterion. For this, approximate relations between the solubility and diffusivity of oxygen and the composition of the binary A–B alloy matrix in the zone of internal oxidation, already developed previously, are used. The critical C content needed for the transition in ternary alloys is calculated as a function of the many parameters involved. At variance with the behavior of binary alloys, for ternary alloys this critical C content depends also on the ratio between the concentrations of A and B in the bulk alloy. The results calculated for ternary alloys are compared with those obtained for binary A–C and B–C alloys under the same values of all the relevant parameters. Finally, complete oxidation maps for ternary alloys under low oxidant pressures,including the condition for the stability of external scales of the C oxide, are also presented.     

The oxidation of Fe?Nb alloys in 1 atm of pure oxygen at 600–800°C

The corrosion of two Fe-Nb alloys containing 15 and 30 wt% Nb has been studied at 600–800°C under 1 atm of pure oxygen. The reaction followed the parabolic rate law to a reasonable approximation with rate constants much lower than for the oxidation of pure iron under the same conditions. Internal oxidation and depletion of niobium in the alloy have never been observed. The external scales were composed of a matrix of Fe₂O₃ containing a dispersion of double Fe-Nb oxide, while FeO and Fe₃O₄ were not observed. The oxidation behavior of these alloys is interpreted with reference to an approximate phase diagram of the ternary system Fe? Nb? O, taking into account the effects of the low solubility of niobium in the base metals and of the presence of two metal phases in the alloy.     

Factors affecting the high-temperature oxidation behavior of some dilute nickel- and cobalt-base alloys

Oxidation of nickel- and cobalt-base alloys, containing small additions of a higher valent second metal, in oxygen or air at high temperatures results in the formation of relatively complicated scale morphologies which change subtly with increasing additions of the second element and its characteristics. The various factors that can influence the oxidation behavior of such alloys are assessed and correlated with the oxidation kinetics and scale morphology types. For very dilute alloys the increase in oxidation rate compared with that of the corresponding pure metal (nickel or cobalt) is largely due to doping of the external oxides. However, once the solubility limit of the second metal in this oxide is exceeded, additional increases in second metal content of the alloy can either increase further or decrease the oxidation rate. The exact behavior depends on the relative interplay of factors such as internal oxide formation and coalescence, blocking effects of incorporated internal oxide or pores in the scale, short-circuit paths through the scale, doping, and the relative diffusion rates of the two metals in the scale. Probable rate-determining steps for oxidation of different alloy composition ranges are proposed.