Metal Dusting-Mechanisms and Preventions

Metal dusting attacks iron, low and high alloy steels and nickel-or cobalt-base alloys by disintegrating bulk metals and alloys into metal particles in a coke deposit. It occurs in strongly carburising gas atmospheres (carbon activity aC>1) at elevated temperatures (400℃～1000℃). This phenomenon has been studied for decades, but the detailed mechanism is still not well understood. Current methods of protection against metal dusting are either directed to the process conditions-temperature and gas composition-or to the development of a dense adherent oxide layer on the surface of the alloy by selective oxidation. However, metal dusting still occurs by carbon dissolving in the base metal via defects in the oxide scale. The research work at UNSW is aimed at determining the detailed mechanism of metal dusting of both ferritic and austenitic alloys, in particular the microprocesses of graphite deposition, nanoparticle formation and underlying metal destruction. This work was carried out using surface observation, cross-section analysis by focused ion beam and electron microscopic examination of coke deposits at different stages of the reaction. It was found that surface orientation affected carbon deposition and metal dusting at the initial stage of the reaction. Metal dusting occurred only when graphite grew into the metal interior where the volume expansion is responsible for metal disintegration and dusting. It was also found that the metal dusting process could be significantly changed by alterations in alloy chemistry. Germanium was found to affect the iron dusting process by destabilising Fe<,3>C but increasing the rate of carbon deposition and dusting, which questions the role of cementite in ferritic alloy dusting. Whilst adding copper to iron did not change the carburisation kinetics, cementite formation and coke morphology, copper alloying reduced nickel and nickel-base alloy dusting rates significantly. Application of these fundamental results to the dusting behaviour of engineering alloys is discussed.     

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.     

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.     

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.     

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.     

Coking and Dusting of Fe–Ni Alloys in CO–H2–H2O Gas Mixtures

Metal dusting of Fe–Ni alloys was investigated in a CO–H₂–H₂O–Ar gas corresponding to a _C = 19.6 at 650 °C. Thermogravimetric analysis showed that increasing the nickel content in the alloy decreased the initial rate of carbon uptake. A uniform Fe₃C scale formed on pure iron, a layer with mixed structures of Fe₃C, γ and α-Fe developed on ferritic Fe–5Ni, and small amounts of Fe₃C developed at the surface of an austenite layer grown on two-phase (α + γ) Fe–10Ni. At nickel levels above 10%, no carbide appeared. These observations are shown to be broadly consistent with local equilibrium according to the Fe–Ni–C phase diagram. However, the failure of higher nickel austenitic alloys to form the (Fe,Ni)₃C expected at high carbon activities indicates a barrier to nucleation and growth of this phase. Graphite deposition was catalysed by (Fe,Ni)₃C on ferritics and by the metal itself on austenitics. The rates of carbon deposition on Fe–60Ni corresponded to the existence of three parallel and independent paths: the synthesis gas, the Boudouard and the carbon methanation reactions.     

Orientation dependence of metal dusting nanoprocesses on nickel single crystals

Nanoprocesses of metal dusting have been studied on nickel single crystal surfaces by TEM and AEM techniques. The samples had been exposed to strongly carburizing conditions (a_C > 1) for 4 h at 650°C. On Ni(111) and Ni(110) epitaxial growth of graphite was observed, graphite layers with their basal planes had grown parallel to the surface and there was no indication of metal dusting attack. In contrast, on Ni(100) metal dusting had started by inward growth of graphite lattice planes oriented more or less vertically to the surface.     

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.     

Influence of H2S on metal dusting

Presence of H₂S in a carburizing atmosphere causes S-adsorption which retards carbon transfer and deposition and can suppress metal dusting of iron and steels. In the latter process cementite Fe₃C is an intermediate, graphite deposition would initiate its decomposition but graphite nucleation is prevented by adsorbed sulfur. Thus continued Fe₃C growth can be observed in the presence of H₂S. Thermogravimetric studies in CO-H₂-H₂O-H₂S mixtures have been conducted at 500°C at various carbon activities a_C and H₂S/H₂-ratios. With increasing a_C higher H₂S/H₂-ratios are needed to suppress metal dusting, with increasing H₂S/H₂-ratio the kinetics of Fe₃C growth change from diffusion controlled parabolic kinetics to linear carbon transfer controlled kinetics. At very high a_C≥1000 besides Fe₃C also the Hägg carbide Fe₅C2 was observed as an outer layer on the cementite.     

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.     

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

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.     

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.     

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.     

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.     

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.     

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.     

Effects of molybdenum additions on the structure, depth, and austenite grain size of the case of carburized 0.13% carbon steels

Carbon (0.13%) steel samples containing about 0.48% molybdenum (Mo) singly and in combination with nickel (Ni) were carburized in a natural Titas gas atmosphere at a temperature of 1223 K (950 °C) and at a pressure of about 0.10 MPa (15 psia) for time periods ranging from 1–4 h followed by slow cooling in the furnace. Their microstructure was studied by optical microscopy. The austenite grain size of the case and the case depths were determined. It was found that Mo and Ni alone and in combination decrease the thickness of the cementite network near the surface of the carburized case of the steels. However, Ni is found to be more effective than Mo in decreasing the thickness of cementite network. Both Mo and Ni enhance the formation of Widmanstätten cementite plates at the grain boundary and within the grains near the surface of the carburized steels. However, Ni alone is more effective than Mo in the formation of Widmanstätten cementite plates. In the presence of Ni, Mo is much more effective in the formation of Widmanstätten cementite plates than Mo in absence of Ni. It was also revealed that both Mo and Ni increased the case depth. Ni is more effective than Mo in increasing the case depth. The combined effect of Mo and Ni is much greater than that of either Mo or Ni alone in increasing case depth. Mo as Mo carbide (Mo₂C) particles refined the austenite grain size of the carburized case. Ni in solution was not found to have any effect in restricting grain growth of austenite, but the presence of Ni enhances the austenite grain size refining effect of Mo in the carburized case.