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.     

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 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.     

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.     

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.     

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.     

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.     

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.     

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.     

镍基高温合金的灰化破坏

结合SEM、TEM分析,研究了GH600镍基高温合金和一种表面可形成致密氧化膜的镍基高温合金在CO+H2合成气氛中的金属灰化行为。结果表明,氧化膜破坏是合金灰化的开始,焦碳石墨丝的形成与灰化蚀坑的产生是相互促进的。合金表面破坏的氧化膜得到及时修复即可抑制合金的灰化。     

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.     

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.     

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

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 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.     

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.     

金属材料在高温碳气氛中的结焦与渗碳行为

叙述了碳气氛温度、金属材料种类及表面状态、构成碳源的气体种类、比例及流速等因素对金属材料结焦行为的影响，介绍了催化结焦的引发机理及其应用．然后以FeCrNi合金为例，分别介绍了内部渗碳和金属粉化这两种渗碳行为，并叙述了温度、碳气氛、合金材料晶体结构及成分构成的影响．最后分析了结焦和渗碳的关系，并介绍了添加结焦抑制剂、调整金属材料结构及成分构成、表面涂层化3种防护对策。     

Effect of copper on metal dusting of austenitic stainless steels

Three steels, 304SS, 310SS and 800H, were alloyed with 5%, 10%, and 20% (by weight) copper, and then exposed to 68%CO-31%H₂-1%H₂O gas at 680 °C (a_C = 19 and p_O2=5.4×10^-25 atm) under thermal cycling conditions. Kinetic measurements showed that copper-free alloys all dusted, with 304SS experiencing the greatest metal wastage. Copper additions did not have any effect on metal wastage of 304SS, but reduced the attack on 310SS and 800H markedly at levels of 5% and 10%. However, increasing the copper content to 20% produced large copper-rich precipitates which accelerated dusting by promoting internal graphitisation.Dusting was associated with surface coking. When pitting occurred, on copper-free alloys and on copper containing 304SS, large coke structures grew above the pits. Internal grain boundary carburisation always took place, and intragranular carbides also precipitated when dusting occurred. A lamellar surface layer of internally precipitated spinel and austenite also developed in association with dusting. The copper effect is discussed in terms of its alloy solubility and its known beneficial effect in Ni-Cu binaries.     

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.     

K-GTAW process: A new welding technology combining quality and productivity

Summary

Inconel 706 Ni-base superalloy has been developed on the basis of Inconel 718 to confer the economic advantage of Ni content saving. The modified alloy has much the same high strength, high ductility and high-temperature oxidation resistance as Inconel 718, while having a slightly higher hot-cracking susceptibility. The hot-cracking susceptibility of Inconel 706, however, has not yet been investigated in any great detail.

The trans-varestraint test was conducted to determine the solidification cracking susceptibility of Inconel 706 depending on the base metal Ni content. Three types of Ni-base alloys with an Ni content of 44, 55, and 65mass%Ni were used.

The fracture surfaces of the trans-varestraint test specimens show the typical dendrite structure. Quantitative analysis of the cracks reveals that the solidification crack length and the temperature range in which hot-cracking occurs (brittle temperature range (BTR)) decreases with an increasing Ni content. Calculation of the liquidus and solidus temperatures of the alloys by thermocalc data also shows that the solidification temperature range decreases with an increasing Ni content.

Based on these results, it is concluded that improvement of the solidification cracking susceptibility with an increasing Ni content is due to a decrease in the solidification temperature range of the alloys.