High-temperature corrosion observed in austenitic coils and tubes in a direct reduction process

The subject of this study is related to the performance of austenitic steel coils and tubes, in a range of temperatures between 425 and 870°C for the transport of reducing gas, in an installation involving the direct reduction of iron-ore by reforming natural gas. Evidence is presented that metal dusting is not the only unique high-temperature corrosion mechanism that caused catastrophic failures of austenitic 304 (UNS S304 00) coils and HK-40 (UNS J94204) tubes. Sensitization as well as stress corrosion cracking occurred in 304 stainless steel coils and metal dusting took place in HK-40 tubes, a high resistance alloy. The role of continuous injection of H₂S into the process is suggested to avoid the high resistance metal dusting corrosion mechanism found in this kind of installation.     

On the mechanism of catastrophic carburization: ‘metal dusting’

Metal dusting is a disintegration of metals and alloys into small metal particles and carbon (graphite) occurring at carbon activities of a_C > 1 in a range of intermediate temperatures 400–800°C. The phenomenon was simulated in CO---H₂---H₂O atmospheres at 650°C. For iron and low alloy steels a mechanism was confirmed in which the unstable carbide M₃C is an intermediate, which decomposes according to M₃C = 3M + C, the metal particles serving as catalysts for further coke deposition. According to thermodynamic considerations this mechanism might be suppressed by alloying with Ni or Mn. Exposures with Fe---Ni alloys, however, showed that at high Ni contents another mechanism applies, the disintegration of a supersaturated solid solution. Also Fe---Mn alloys were susceptible to metal dusting after Mn depletion of the surface-near region by selective Mn oxidation; similar behaviour is to be expected for Fe---Cr alloys after selective Cr-oxide or Cr-carbide formation. Thus, in principle no alloys are resistant against metal dusting if no protective oxide layer is formed.     

Recent advances in understanding metal dusting: A review

Recent experimental investigations have widened the understanding of metal dusting significantly. Microscopic observations have been used to dissect dusting mechanisms. Iron dusts by growing a cementite surface scale, which catalyses graphite nucleation and growth. The resulting volume expansion leads to cementite disintegration. Cementite formation on iron can be suppressed by alloying with germanium. Nonetheless, dusting occurs via the direct growth of graphite into the metal, producing nanoparticles of ferrite. This process is faster, because carbon diffusion is more rapid in α‐Fe than in Fe₃C. Austenitic materials cannot form cementite, and dust via formation of graphite at external surfaces and interior grain boundaries. The coke deposit consists of carbon nanotubes with austenite particles at their tips, or graphite particles encapsulating austenite. TEM studies demonstrate the inward growth of graphite within the metal interior. It is therefore concluded that the dusting mechanism of austenitic materials like high alloy Cr–Ni steels and Ni base materials is one of graphite nucleation and growth within the near surface metal. In all alloys examined, both ferritic and austenitic, the principal mass transfer process is inward diffusion of carbon. Alloying iron with nickel leads to a transformation from one mechanism with carbide formation to the other without. Copper alloying in nickel and high nickel content stainless steels strongly suppresses graphite nucleation, as does also an intermetallic Ni–Sn phase, thereby reducing greatly the overall dusting rate. A surface layer of intermetallic Ni–Sn Fe‐base materials facilitates the formation of a Fe₃SnC surface scale which also prevents coking and metal dusting. Current understanding of the roles of temperature, gas composition and surface oxides on dusting rates are summarised. Finally, protection against metal dusting by coatings is discussed in terms of their effects on catalysis of carbon deposition, and on protective oxide formation.     

Metal Dusting of Alumina-Forming Creep-Resistant Austenitic Stainless Steels

Three developmental alumina-forming austenitic stainless steels were exposed to metal dusting conditions at 650?°C in a gas of 50%CO–49%H₂–1%H₂O (a _C: 36.7 and $ p_{{{\text{O}}_{2} }} $ : 2.83?×?10^?26?atm) under thermal cycling conditions. Metal wastage measurement showed initially slow kinetics followed by a fast weight loss. This observation is attributed to the formation of protective chromia/alumina oxide scales in the early stage of the reaction, followed by local oxide failure/spallation during cyclic reaction. Metal dusting initiated from these local defects, and pitting-type attack was observed after 131 cycles of reaction. After 352 cycles, severe dusting had developed, forming heavy and distinctive “tentacles” of superficial coke. This carbon deposit was composed of fine carbon filaments. Examination by TEM of the coke-metal reaction front showed direct surface metal disintegration, indicating that the dusting follows the classical mechanism for austenitic materials. Etching with aqua regia revealed a carburised zone formed in the alloy underneath the coke layer. Analysis by TEM of this zone revealed the formation of ultra-fine, needle-shaped chromium carbide precipitates within a chromium depleted austenite matrix.     

Metal dusting

Metal dusting is a catastrophic carburization of steels which leads to disintegration of the material to a mixture of powdery carbon and metal particles leaving pits and grooves. The phenomenon was simulated by carburization of low-and high-alloy steels in CO-H₂-H₂O mixtures at carbon activities > 1 in the temperature range 600–700°C. The occurance of an unstable carbide M₃C (M=Fe, Ni), as an intermediate in metal dusting, was proven—the reaction sequence involves over saturation of the metal matrix with carbon, M₃C formation at the surface, subsequent decomposition of the M₃C layer M₃C3 M+ C, leading to carbon with interspersed metal particles which act as catalysts for additional carbon deposition from the gas atmosphere. With increasing Ni content in Fe-Ni alloys, typical metal dusting is suppressed, but another mode of deterioration was observed, involving graphite growth on the grain boundaries. The high-alloy, chromia-forming alloys showed metal dusting only when chromia formation was suppressed by electropolishing the materials.     

Metal dusting of Fe3Al and (Fe,Ni)3Al

Metal dusting is a deterioration of metallic materials in strongly carburizing atmospheres under disintegration into a dust of carbon and fine metal particles (coke). The intermetallic compound Fe₃Al is also very susceptible to metal dusting and disintegrates under formation of vast amounts of coke. The mechanism corresponds to the metal dusting of iron and steels, Fe₃C is formed as an intermediate and the Al is oxidized. With increasing Cr-addition and with increasing Ni-content in alloys (Fe,Ni)₃Al-Cr the materials become more resistant, Ni₃Al is not attacked by metal dusting.     

Role of alloying elements in steels on metal dusting

Metal dusting of Fe-Ni-Cr alloys has been observed in industrial processes in strongly carburizing atmospheres at temperatures from 450°C to 800°C. At temperatures below 650°C the alloys are generally not able to form dense, well adherent oxide layers in spite of relatively high Cr-contents, therefore, metal dusting can take place. Already a lot of experimental work has been done to elucidate the mechanism and to compare the resistance against metal dusting for high alloy steels [1]. The intention of this study was to obtain additional information concerning the role of alloying elements and the effects of carbide precipitates in austenitic high alloy steels such as Alloy 800. The susceptibility to metal dusting was determined by measuring the metal loss under metal dusting conditions of Fe-20%Cr-32%Ni alloys modified with additions of different carbide formers (W, Mo, Nb) or oxide formers (Si, Al). The samples were exposed at 600°C in a CO-H₂-H₂O-gas mixture for repeated periods up to 500 – 1500 h. The attack by the oxidizing and carburizing atmosphere leads to the precipitation of internal carbides and metal dusting and more or less to formation of an oxide layer. In comparison to the undoped material, the addition of carbide formers retards the initiation of metal dusting attack. The additions of Si and Al seem to prevent metal dusting under the given laboratory conditions. When carbides are present at the metal surface, they affect the initial oxide growth and have a negative effect on the protectivity of scales. Very striking is the effect of Ce, this rare earth element is generally known to favour Cr-oxide formation and to improve the adherence of the oxide layer [2], but in the case of metal dusting it clearly enhances metal dusting and metal wastage.     

Effect of H2S on metal dusting of iron

A review is given on the effect of H₂S on metal dusting of iron which has been studied by gas carburisation in CO‐H₂‐H₂O‐H₂S and CH₄‐H₂‐H₂S mixtures at 500 and 700°C. The presence of H₂S in carburising gas atmospheres leads to sulphur adsorption on the iron surface, which retards carbon transfer. Segregation experiments and surface analyses have shown that sulphur segregates (and thus adsorbs) on cementite surfaces as well as on iron surfaces. The adsorbed sulphur also suppresses graphite nucleation and thus can stop the reaction sequence of metal dusting. Experiments by thermogravimetric analysis (TGA) have shown that the extent of retardation of metal dusting depends on temperature, carbon activity and H₂S content. The higher the carbon activity, the higher is the H₂S content required for suppression of metal dusting. At carbon activities a_C > a_C(Fe/Fe₃C) the metastable iron carbide, cementite (Fe₃C), occurs as an intermediate phase during metal dusting. Carburisation experiments in CO‐H₂‐H₂O‐H₂S mixtures at 500°C and X‐ray diffraction analysis (XRD) of carburised samples have revealed that at very high carbon activities a second iron carbide, Hägg carbide (Fe₅C₂), forms on the cementite surface. Microstructural investigations have shown that both metastable carbides decompose during metal dusting. Metal dusting experiments on iron at 700°C have been performed in CH₄‐H₂‐H₂S gas mixtures. By adding 15 ppm H₂S to the CH₄‐H₂ atmosphere the onset of metal dusting can be retarded for more than 350 hours. By means of Auger electron spectroscopy (AES), scanning electron microscopy (SEM) and energy dispersive X‐ray analysis (EDX) it was shown that coke contains graphite, cementite and iron particles with adsorbed sulphur.     

Metal dusting

This introductory review paper summarizes shortly the research on metal dusting, conducted in the MPI for Iron Research during the last dozen years. Metal dusting is a disintegration of metals and alloys to a dust of graphite and metal particles, occurring in carburizing atmospheres at a_C > 1 and caused by the tendency to graphite formation. The cause of destruction is inward growth of graphite planes into the metal phase, or in the case of iron and low alloy steels into cementite formed as an intermediate. The kinetics of metal dusting on iron and steels was elucidated concerning dependencies on time, temperature and partial pressures. High alloy steels and Ni‐base alloys are attacked through defects in the oxide scale which leads to pitting and outgrowth of coke protrusions, after initial internal formation of stable carbides M₂₃C₆, M₇C₃ and MC. A dense oxide layer prevents metal dusting, but formation of a protective Cr‐rich scale must be favored by a fine‐grain microstructure and/or surface deformation, providing fast diffusion paths for Cr. Additional protection is possible by sulfur from the atmosphere, since sulfur adsorbs on metal surfaces and suppresses carburization. Sulfur also interrupts the metal dusting mechanism on iron and steels, causing slow cementite growth. Under conditions where no sulfur addition is possible, the use of high Cr Nickelbase‐alloys is recommended, they are largely protected by an oxide scale and if metal dusting takes place, its rate is much slower than on steels.     

Coking by metal dusting of steels

In process industries coking is an annoying phenomenon, the carbon deposition causes decrease of heat transfer and hinders gas flow. Coking in a process may indicate metal dusting, i.e. the disintegration of metals and alloys in carbonaceous atmospheres under formation of graphite and fine metal particles. The metal particles act as catalysts for vast coke formation. The thermodynamics, mechanisms and kinetics of metal dusting have been studied on iron and steels in synthesis respectively reduction gas CO-H₂- H₂O, here the aspects are presented of coking due to metal dusting. From the interplay of the metal disintegration and carbon deposition rather complex coupled kinetics are resulting, even different in a low temperature range where the decomposition of the intermediate cementite is rate determining and in a higher temperature range where the carbon transfer from the atmosphere is rate controlling. Coking by metal dusting can be suppressed in the same way as metal dusting, by sulfur addition to the atmosphere and/or by a stable dense protective oxide layer.     

Surface analytical studies of metal dusting of iron in CH4‐H2‐H2S mixtures

The metastable iron carbide, cementite (Fe₃C), occurs as an intermediate phase during the high temperature corrosion process called “metal dusting”. The kinetics and thermodynamics of metal dusting of iron have been studied by Grabke et al. [1–5] using CO‐H₂‐H₂O and CH₄‐H₂ gas mixtures. H₂S additions to carburising atmospheres impede the carbon transfer and retard the onset of metal dusting [6–14], thus allowing to study the early stages of the process. In this work the metal dusting process was studied in CH₄‐H₂‐H₂S atmospheres at 700 °C. Segregation experiments and surface analyses showed that S segregates on iron surfaces as well as on cementite surfaces. By means of Auger electron spectroscopy (AES), scanning Auger electron microscopy (SAM) and energy dispersive X‐ray analysis (EDX) it was shown that coke contains graphite, cementite and iron particles with adsorbed sulphur.     

不锈钢电化学着黑色工艺与成膜机理研究

采用电化学着色法对不锈钢着黑色进行了研究,讨论了钝化处理、着色液组成等因素对着色的影响,测定了着色膜的耐磨性和耐蚀性,并根据着色膜的组成、微观结构分析了成膜机理.结果表明:钝化和封闭处理能明显提高着色膜的耐磨性和抗色变性;电化学分析表明在1 mol/L H2SO4溶液、3.5%NaC l溶液和10%NaOH溶液中,着色膜腐蚀电位比不锈钢基体分别正移1130、565和790 mV,且腐蚀电流密度都比相应介质中的小;扫描电镜和能谱结果显示膜层为封闭块状结构,着色膜主要成分是Fe、Cr、Mn等元素,封闭处理能明显减少其裂纹数目.该成膜反应机理为:1)不锈钢基体的溶解形成大量的M e2+;2)金属/溶液界面上的M e2+与Cr3+水解形成合金氧化膜沉积在基体表面上;3)电化学致密过程中4H2MoO4+2SO42-+4H+2(MoO)2SO4+6H2O+6[O]和M e+[O]=M eO反应是着色膜致密的主要原因.     

Metal dusting on an alumina forming Ni-base alloy

A high-performance commercial alumina-forming Ni-base alloy was studied after a 2 years field exposure at 540 °C in a methanol plant with a gas composition of 10-20%CO and 20-40%H₂O, with some CO₂ and the remainder H₂. The same material was also used in laboratory studies performed at 650 °C using a gas mixture with higher CO and lower H₂O content; 50%CO + 3%H₂O + 47H₂ (carbon activity a_c = 39). Post-exposure metallographic examinations together with thermodynamic calculations were used to identify and describe the metal dusting processes.A growth mechanism for metal dusting in nickel base alloys, which is independent of metal bulk diffusion, is identified. The process involves a separation of the carbon-saturated metal into a network of discontinuous precipitated carbides and a depleted Ni-austenite matrix followed by selective oxidation of the carbide network. The corrosion product consists of Cr-depleted Ni-particles, Cr-rich oxides and free carbon. The estimated metal dusting corrosion rate in the field exposure was 20-25 μm/year, based on metallography and it was correlated to a theoretical model based on boundary diffusion processes.     

Metal dusting resistance of high chromium alloys

Samples of 5 high Cr‐alloys were discontinuously exposed for 10,000 hours under severe metal dusting conditions, i. e. in flowing 49%CO‐49%H₂‐2%H₂O at 650°C. After each of the 11 exposure periods the mass change was determined and any coke removed and weighed. Metallographic cross sections were prepared after about 4,000 h and 10,000 h. The high Cr‐alloys: 1. PM 2000 (Fe‐19%Cr‐5.5%Al‐0.5%Ti‐0.5%Y₂O₃), 2. Cr‐44%Fe‐5%Al‐0.4%Ti‐0.5%Y₂O₃, 3. Cr‐50%Ni, 4. Cr‐5%Fe‐1%Y₂O₃ and 5. porous chromium showed no or only minute metal dusting attack. Compared to the attack on reference samples of Alloy 601 (Ni‐23%Cr‐14%Fe‐1.4%Al), the metal dusting symptoms were negligible on the 5 high Cr‐alloys, minor coking and pitting and no internal carburization was observed. Because of the high Cr‐content, carbon solution and ingress should be minute, and in addition are inhibited by the formation of a chromia scale, as confirmed for four of the Cr‐rich alloys, and formation of an alumina scale on PM 2000. These alloys could be used for parts exposed to severe metal dusting conditions, and in fact, 50Cr‐50Ni has been applied successfully under such conditions.     

Improving metal dusting resistance of. transition‐metals and Ni‐Cu alloys

The present study focuses on a new technique for the prevention of metal dusting in carbonaceous gas environments at intermediate temperature. Preliminary laboratory metal dusting test was conducted for transition‐metals and Ni‐x%Cu binary alloys in a simulated 60%CO‐26%H₂‐11.5%CO₂‐2.5%H₂O (in vol.%) gas mixture at 650°C for 100 h. The metal dusting caused no coke deposition on transition‐metals of Cu, Ag, and Pt, while those of Fe, Co, and Ni have a large amount of coke and lost mass. Whether or not coking behavior of Ni‐Cu binary alloys formed any oxide scales in the simulated gas environment depended on the Cu content. Specimens containing low Cu were entirely covered with coke and showed rough metal surfaces due to the degradation of metal. Alloys of 20% and more Cu, on the contrary, had no coke deposition and smooth metal surfaces, suggesting alloys with an adequate Cu do not react with CO in the gas mixture without an oxide scale barrier. Based on these results, we conclude that Cu does not protect by formation of the oxide scale but has a “Surfactant‐Mediated Suppression” against metal dusting. This effect can be explained in terms of atomistic interaction of CO with transition‐metal surfaces by electronic structure analyses. The concept can be also useful for the practical material design of Ni‐Cr base alloy with excellent metal dusting resistance.     

Metal dusting of high temperature alloys

Metal dusting, i.e. disintegration into fine metal particles and carbon, was induced on a selection of chromia forming high temperature alloys in a flowing CO-H₂-H₂O atmosphere in exposures at 650°C, 600°C, 500°, and 450°C. The materials were pretreated by annealing in H₂ at 1000°C and electropolishing, this leads to large grain size and low surface deformation, both is disadvantageous for formation of a Cr₂O₃ scale. The resistance to metal dusting is only dependent on the ability to form a protective Cr₂O₃ scale, thus the high Cr ferritic steels proved to be very resistant, the ferritic steels with 12–13% Cr were less resistant. Due to the lower Cr diffusivity in the austenitic steels, these were very susceptible, especially two alloys with about 30% Ni (Alloy 800, AC 66). The appearance of metal dusting was somewhat different for Ni-base materials but they were also attacked under pitting. The metal dusting is preceded in all cases by internal carburization whereby the chromium is tied up, afterwards the remaining Fe or Fe-Ni matrix can react to the instable intermediate carbide M₃C which decomposes to metal particles and carbon, in case of Ni-base materials a supersaturated solid solution of carbon is the intermediate.     

Alloying with copper to reduce metal dusting of nickel

Copper is thought to be noncatalytic to carbon deposition from gas atmospheres, and owing to its extremely low solubility for carbon, inert to the metal dusting reaction. Thus, the addition of copper to nickel, which forms a near perfect solid solution, may be able to suppress or greatly retard the metal dusting of the alloy, without the need for a protective oxide scale on the surface. The dusting behaviour of Ni‐Cu alloys containing up to 50 wt% Cu, along with pure Cu, was investigated in a 68%CO‐31%H₂‐1%H₂O gas mixture (a_C: 19) at 680°C for up to 150 h. Surface analysis showed that two types of carbon deposits, graphite particle clusters and filaments, were observed on pure Ni and Ni‐Cu alloys with Cu contents of up to 5 wt%. Alloys with more than 10 wt% Cu showed very little coking, forming filaments only. SEM and TEM analyses revealed metal particles encapsulated by graphite shells within the graphite particle clusters, and metal particles at filament tips or embedded along their lengths. A kinetic investigation showed that alloy dusting rates decreased significantly with increasing copper levels up to 10 wt%. At copper concentrations of more than 20 wt%, the rate of metal dusting was negligible. Although pure copper is not catalytic to carbon formation, scattered carbon nanotubes were observed on its surface. The effect of copper on alloy dusting rates is attributed to a dilution effect.     

Microprocesses of coke formation in metal dusting

The microprocess of coke formation during metal dusting on iron in a carburizing atmosphere with medium and extremely high carbon activities as well as the influence of sulphur have been studied down to the nanometer scale using high resolution electron microscopy (HREM) and analytical electron microscopic techniques (AEM). While for medium carbon activities the metal dusting proceeds via a formation, disintegration and further decomposition of a metastable carbide Fe₃C into Fe and C, the additional formation of the carbide Fe₅C₂ and the stabilization of carbides in the coke region have been observed for extremely high carbon activities. If sulphur is present in the atmosphere metal dusting takes place solely in the S-free surface areas. Furthermore, sulphur deposited from the atmosphere will suppress the nucleation of graphite in the coke. In addition, the results reveal that, irrespective of the degree of the carbon activity, there is a fundamental initial reaction micromechanism of metal dusting characterized by a vertically oriented deposition of graphite lattice planes with respect to the original surface of the substrate and with free ends affecting the decomposition of the carbides and thus forming a coke of carbon and iron, or of carbide particles, depending on the carbon activity.     

Effect of Pressure on Metal Dusting Initiation on Alloy 800H and Alloy 600 in CO-rich Syngas

The effect of pressure on metal dusting initiation was studied by exposing conventional alloys 600 and 800H in CO-rich syngas atmosphere (H₂, CO, CO₂, CH₄, H₂O) at ambient and 18 bar total system pressure and 620 °C for 250 h. It was verified that, at constant temperature, increasing the total system pressure increases both oxygen partial pressure (pO₂) and carbon activity (a _C), simultaneously. Both samples exposed at ambient pressure showed very thin oxide scale formation and no sign of metal dusting. By contrast, samples exposed in the high-pressure experiment showed severe mass loss by metal dusting attack. Iron- and chromium-rich oxides and carbides were found as corrosion products. The distinct pressure-dependent behavior was discussed by considering both thermodynamic and kinetic aspects with respect to the protective oxide formation and pit initiation.