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

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.     

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.     

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.     

Iron layer formation during cementite decomposition in carburising atmospheres

In the following report cementite (Fe₃C) formation and subsequent decomposition is investigated on pure iron samples at 700 °C in CO-H₂-H₂O gas mixtures. The carbon activities of the atmospheres are a_C=15.9 and 20, values higher than the value of the equilibrium α-Fe+Fe₃C. During the carburisation process cementite forms at the surface. Graphite deposition at the surface initiates cementite decomposition. An iron layer of 1-3 μm thickness forms between cementite and graphite as a result of cementite decomposition. In previous studies of metal dusting on iron it was found that at lower temperatures T?650°C the decomposition product iron is found in the coke as small particles.     

Coking by metal dusting of nickel-base alloys

Metal dusting of nickel and Ni-base alloys occurs by inward and internal growth of graphite in the metal phase, leading to extrusion and ejection of metal particles, which catalyze carbon deposition, i.e. coking. Compared to metal dusting of iron and steels which occurs via intermediate carbide formation and leads to much finer metal particles, coking on the Ni-base alloys is much less. This is caused by the larger size and smaller amount of metal particles formed by metal dusting and also by the clearly smaller rates of metal wastage on Ni-base alloys.     

Metal dusting and coking of alloy 803

Investigation was made by SEM examination on metal dusting and coking behaviours of alloy 803 in a flowing gas mixture of H₂-CO-H₂O. It was found that an oxide scale arisen on the sample surface at the beginning of exposure. Metal dusting started when graphite deposition occurred earlier at the local defects in the oxide scale than the defects were repaired by enough supply of chromium from the interior of alloy matrix. Coke consisted of graphite filaments and metallic particles produced by disintegrating of alloy matrix, and grew up from the defects in the oxide scale with pit left in the sample surface. Increasing chromium content, doping a small amount of silicon and reducing grain size to create fast diffusion paths for chromium and silicon to alloy surface, all promote the formation of a dense oxide scale and favor early self-repairing of the defects in the oxide scale before occurrence of graphite deposition. The resistance of an alloy to metal dusting can be improved generally by means of these methods.     

Investigation of Metal-Dusting Mechanism in Fe-Base Alloys Using Raman Spectroscopy,X-Ray Diffraction,and Electron Microscopy

The metal-dusting phenomenon, which is a metal loss process that occurs in hot reactive gases, was investigated in iron and certain iron-base alloys by Raman scattering, X-ray diffraction (XRD), and scanning-electron microscopy (SEM). Coke from metal dusting exhibits six Raman bands at 1330(D band), 1580(G band), 1617, 2685, 3920, and 3235 cm^-1. The bandwidths and the relative intensities of the 1330 and 1580 cm^-1 bands are related to the crystallinity and defect structure of the coke. Both Raman and XRD analyses suggest that the metal-dusting process influences the catalytic crystallization of carbon. A new mechanism of metal dusting is, therefore, proposed, based on the premise that coke cannot crystallize well by deposition from carburizing gases at low temperature without catalytic activation because of its strong C–C bonds and high melting temperature. Cementite or iron participates in the coke-crystallizing process in a manner that tends to improve the crystallinity of the coke. At the same time, fine iron or cementite particles are liberated from the pure metal or alloys.     

Metal dusting of nickel-base alloys

Metal dusting, the disintegration of metallic materials into fine metal particles and graphite was studied on nickel, Fe Ni alloys and commercial Ni-base alloys in CO H₂ H₂O mixtures at temperatures between 450–750°C. At carbon activities a_c > 1 all metals can be destroyed into which carbon ingress is possible, high nickel alloys directly by graphite growth into and in the material, steels via the intermediate formation of instable carbide M₃C. Protection is possible only by preventing carbon ingress. Chromium oxide formation is the best way of protection which is favoured by a high chromium concentration of the alloy and by a surface treatment which generates fast diffusion paths for the supply of chromium to the surface. The metal dusting behaviour of Alloy 600 is described in detail. A ranking of the metal dusting resistance of different commercial nickel-base alloys was obtained by exposures at 650°C and 750°C.     

Initiation and growth of iron metal dusting in CO-H2-H2O gas mixtures

The initiation and growth of iron metal dusting in CO-H₂-H₂O gas mixtures at 700 °C were investigated by surface observations of very early stages of the reaction. At first, iron was supersaturated with dissolved carbon and its surface became facetted. The nucleation of graphite and cementite depended on the surface crystallographic orientation. A fine grain structure at ground surfaces and a high carbon activity accelerated cementite nucleation. Further carburisation resulted in the formation of particulate areas mixed with deposited graphite, which accelerated the spallation of cementite and the protrusion of round particles. In some areas, large graphite mounds and bulk graphite were formed on the surface. Filamentous carbon was found in particulate areas and surrounding the graphite mounds. Based on these observations, a possible process of iron metal dusting was discussed.     

Effect of gas composition on cementite decomposition and coke formation on iron

Cementite decomposition and coke formation in the metal dusting process of iron were investigated at 700 °C in CO-H₂-H₂O gas mixtures. The presence of graphite deposited on the surface initiates the decomposition of cementite into iron and graphite. The morphology of the reaction products varies with gas composition. For CO concentrations less than 5 vol%, particles of iron or even closed iron layers have been observed at the cementite/graphite interface. With increasing CO content the amount of iron in the interface decreases. At CO concentrations higher than 30 vol%, iron could not be detected at the interface by optical microscopy. Thermo-gravimetric analysis shows that the rate of carbon take-up increases with increasing CO concentration reaching a maximum at about 60-75 vol%.The morphologies of graphite in the coke layer can be identified as three types: porous graphite clusters with embedded iron-containing particles, compact bulk graphite with a uniform thickness and a columnar layered structure, and filamentous carbon with iron-containing phases at the tip or along its length. For gas mixtures with low CO concentrations, e.g. 5 vol%, porous graphite clusters are the main form of carbon although filamentous carbon can be seen at the early stage of reaction. With increasing CO concentrations to, e.g. 30 vol%, a compact bulk graphite is formed on the top of the surface. Under this compact graphite, there is an inner layer of graphite which is the combination of porous graphite clusters and filaments. These two layers of graphite are clearly distinguishable when CO content reaches more than 75 vol%. In this case, the main form of graphite in the inner layer is filamentous carbon. The compact graphite layer suffers a serious deformation and forms many cracks because of the growth of catalytic filamentous carbon underneath. These filaments grow outside from compact graphite crevices and finally cover the whole surface. The higher the CO content in the gas, the more the tendency of filamentous carbon formation. The interplay between morphologies of carbon formation and metal dusting has been discussed.     

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.     

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.     

Microprocesses of metal dusting on iron‐nickel alloys and their dependence on the alloy composition

Metal dusting of iron proceeds via the formation and disintegration of the metastable carbide Fe₃C, and the resulting fine Fe particles in the coke further catalyse carbon deposition. By contrast, nickel disintegrates directly, and larger grains are released. As revealed by TEM and AEM techniques, in both cases the disintegration proceeds by inward growth of thin graphite filaments, the atomic basal planes of which being oriented perpendicular to the surface thus effecting a high reactivity at the growth front. Consequently, successive alloying of iron with nickel should lead to a change over from one disintegration mechanism to the other, and, in fact, we could evidence that the carbide formation takes place only up to a nickel content of about 5 wt.%. Already at a Ni concentration of 10 wt.% a direct disintegration of the metal proceeds, as it is typical for pure nickel. Furthermore, in all investigated Ni‐Fe alloys a surface‐near enrichment of Ni was observed which indicates a selective corrosion of Fe, decreasing with increasing Ni content of the basic alloy.     

Micromechanisms of metal dusting on Fe-base and Ni-base alloys

Phenomena of metal dusting on iron and nickel (and their alloys) were studied by characterizing both microstructure and nanochemistry of the reaction zones using TEM and AEM techniques. While in case of iron a metastable carbide (cementite) is formed nickel directly disintegrates. In the chromium-rich steel HK40 and the chromium-rich Ni-base alloy Inconel 600 some microstructural chromium dependent features were observed with protective effects against metal dusting. Independent of these differences, in all groups of materials a fundamental common starting mechanism on the atomic scale could be deduced, which first of all comprises the arrangement of basal graphite lattice planes perpendicularly oriented to the carbide (or metal) surface acting as active sites in the disintegration process.     

Thermodynamics,mechanisms and kinetics of metal dusting

A survey is given on recent research on “metal dusting” i.e. a catastrophic carburization or rather graphitization of metals and alloys occuring in carbonaceous atmospheres at carbon activities a_C>1. The thermodynamics are explained, the mechanisms for iron, low and high alloy steels, nickel and Ni-base alloys are described and the kinetics derived for iron and low alloy steels. Protection against metal dusting is possible by the presence of sulfur in the atmosphere, since adsorbed sulfur retards carbon transfer and hems graphite nucleation. Also dense oxide layers are protective, the preconditions for the formation of Cr-rich protectivee layers on steels and Ni-base alloys are shortly presenteed.     

α‐Fe layer formation during metal dusting of iron in CO‐H2‐H2O gas mixtures

The formation of an α‐Fe layer between cementite and graphite was observed and investigated during metal dusting of iron in CO‐H₂‐H₂O gas mixtures at both 600°C and 700°C. The condition to form this phenomenon is determined by the gas composition which depends on temperature. The iron layer formation was observed for CO content less than 1 % at 600°C and less than 5 % at 700°C. With increasing CO contents, no α‐Fe layer was detected at the cementite/graphite interface by optical microscopy. In this case cementite directly contacts with the coke layer. The morphologies of the coke formed in the gas mixtures with low CO contents were also analysed. Three morphologies of graphite have been identified with 1 % CO at 600°C: filamentous carbon, bulk dense graphite with columnar structure, and graphite particle clusters with many fine iron containing particles embedded inside. At 700°C with 5 % CO the coke mainly consists of graphite particle clusters with some filamentous carbon at the early stage of reaction. Coke analysis by X‐ray diffraction shows that both α‐Fe and Fe₃C are present in the coke. The mechanism of α‐Fe accumulation between cementite and graphite is discussed in this paper.     

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.     

Filamentous carbon formation caused by catalytic metal particles from iron oxide

The thermodynamic equilibrium between metallic iron, iron oxides, iron carbides and an hydrocarbon/hydrogen mixture was calculated at 600°C. On the basis of the metastable Fe‐C‐O phase diagram, both metallic iron and iron oxides can be directly converted into carbides in reducing and carburizing atmosphere. Thermogravimetric (ATG) measurements have been performed in iC₄H₁₀‐H₂‐Ar atmosphere at 600°C on reduced and pre‐oxidised iron samples. The kinetic of coke formation was studied on both surface states by sequential exposure experiments. The initial stages of the transformation were characterised by scanning electron microscopy (SEM) observations and X‐ray diffraction (XRD) analysis. On a reduced surface, the results are consistent with the mechanism currently proposed to explain catalytic coke formation. Cementite (Fe₃C) is formed on the iron surface after carbon supersaturation (a_c > 1). The graphite deposition on its surface (a_c = 1) induces its decomposition. Iron atoms from cementite diffuse through the graphite and agglomerate to small particles that act as catalysts for further carbon deposition. A new mechanism of catalytic particle formation is proposed when an oxide scale initially covers the iron surface. In the carburizing and reducing atmosphere, magnetite (Fe₃O₄) can be directly converted into cementite (Fe₃C). XPS analysis confirm that, in this process, metallic iron is not an intermediary specie of the oxide/carbide reaction. At the same time, graphite deposition occurs at the metal/oxide interface through the cracks present in the oxide scale. Iron carbide in contact with graphite is partially decomposed and acts as catalyst for graphitic filaments growth.