Coke formation during metal dusting of iron in CO‐H2‐H2O gas with high CO content

Iron carburisation and coke formation during metal dusting of iron have been investigated in the gas mixture of 75%CO‐24.8%H₂‐0.2%H₂O at 600°C and 700°C. In all cases, cementite is formed at the surface, together with a coke layer on the top. In the coke layer, two morphologies of graphite are identified: compact bulk graphite with a uniform thickness and a columnar structure, and filamentous carbon with iron‐containing phases at the tip or along its length. The examination of coke formation in different stages of reaction at 700°C reveals that the coke contains two layers. The inner layer is composed of filaments, while the outer layer consists of the compact columnar graphite. After 2 h reaction the top compact graphite layer has suffered a serious deformation and has formed fractures because of the growth of catalytic filamentous carbon underneath. These filaments grow outside from these fractures and finally cover the whole surface after 4 h reaction. At 600°C, however, the coke contains a thick bulk graphite layer and non‐uniformly distributed filaments on the top. The bulk graphite layer is composed of many graphite columns which are loosely piled and are vertical to the surface. Each graphite column consists of many fine graphite fibres in parallel with the columnar axis. Filaments grow outside preferably from the gaps among these graphite columns and along the grinding scratches. TEM analysis of the coke detects very convoluted filaments with iron‐containing particles at the tip or along their length. XRD and TEM analyses show that these particles are Fe₃C rather than metallic iron.     

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.     

Study of the metal dusting behaviour of high‐temperature alloys

The corrosion phenomenon named metal dusting has been observed in many high‐temperature industrial plants. An experimental research programme is being carried out into the degradation resistance of wrought and cast commercial and development high‐temperature alloys in H₂/CO gas mixtures at temperatures of 550°C to 750°C. Emphasis is placed on very high carbon activities, consistent with the next generation of steam‐reforming and similar plants that are susceptible to metal dusting. The overall programme is concerned with the mechanisms of initiation and propagation of dusting and the sensitivity to damage of the more resistant alloys, as a function of environmental parameters. Initial tests have been carried out on a number of commercial alloys: Alloy 600, 693, 602CA, 601, 603 XL, 671, 617, 690 (wrought), and H46M (cast). The specimens were exposed to a gas mixture of high carbon activity at 650°C for a total of 1000 hours. Many of the alloys showed at least the initial stages of metal dusting. Preliminary analysis using electron microscopy revealed that initiation of metal dusting is influenced by microstructure, stress state and composition. In some cases, attack was enhanced at stress points, such as corners and edges. Sample holders were found to influence strongly the length of the initiation period for the onset of the corrosion phenomenon. The reaction layers in the alloy beneath areas of damage were analysed by EDX and EPMA. Mechanical characterisation of such areas has been carried out using nanoindentation methods. These early results are discussed in terms of the effectiveness of oxide scales in inhibiting the onset of damage and presence of impurities in the ceramic holder in initiating the onset of damage.     

Effect of pre‐oxidation on coke formation and metal dusting of electroplated Ni3Al–CeO2‐based coatings in CO–H2–H2O

Pre‐oxidation was introduced to improve the resistance of electroplated pure, 5 µm CeO₂‐dispersed, and 9–15 nm CeO₂‐dispersed Ni₃Al coatings to coke formation and metal dusting in 24.4%CO–73.3%H₂–2.3%H₂O at 650 °C. Coke formation and metal dusting of pre‐oxidized Ni₃Al‐based coatings were retarded up to 200 h owing to a thin Al₂O₃ scale induced during pre‐oxidation. The long‐term effectiveness of pre‐oxidation nonetheless depended on the integrity of Al₂O₃ scale. The pure Ni₃Al coating suffered severe spallation after pre‐oxidation and thereby showed the worst long‐term resistance. Two pre‐treated 9–15 nm CeO₂‐dispersed Ni₃Al coatings exhibited the best long‐term resistance to carbon attack because nano‐CeO₂ particles maintained a full coverage of Al₂O₃ scale on the coatings. Two 5 µm CeO₂‐dispersed Ni₃Al coatings showed significant spallation after pre‐oxidation because of an overdoping effect and experienced coke formation and metal dusting during long‐term exposure.     

Occurrence of metal dusting – referring to failure cases

Twelve years of research on metal dusting at the Max‐Planck‐Institut for Iron Research have led to comprehensive knowledge on the mechanisms and kinetics of metal dusting and on ways and means for prevention of this corrosion phenomenon, – this knowledge is shortly summarized in this paper. Inspite of this state of understanding, the present opinion in industry is that metal dusting is mysterious and not predictable and cannot be controlled. This paper is intended to show that the occurrence of metal dusting and its reasons can be well understood, by describing and explaining five failure cases.     

Kinetics and mechanisms of nickel metal dusting I. Kinetics and morphology

The kinetics of nickel metal dusting were investigated at different gas compositions at 680 °C. The carbon uptake rate on nickel exposed to supersaturated H₂/CO/H₂O gas mixtures (nominal a_C = 19) increased as p_CO increased from 0.31 to 0.68 atm, but decreased with further increase in p_CO. This behaviour was ascribed to the existence of parallel, independent reaction paths, and the rate was well described by

     

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.     

Effect of experimental conditions on the metal dusting phenomenon in several commercial nickel‐base alloys

The corrosion phenomenon, metal dusting, has been observed in many high‐temperature industrial plants, such as ammonia, syngas and steam‐reforming industries. An experimental research programme has been carried out into the degradation resistance of wrought and cast commercial high‐temperature nickel‐base alloys in H₂/CO gas mixtures at 650 °C. The results in this paper are focused on the effect of the experimental set‐up on the response of the alloy during exposure to the gas mixture; in particular, the specimen holders had an important role on the onset of carbon transfer from the gas to the alloy surfaces. Specimens of most alloys exposed to the gas mixture while suspended from quartz hangers were shown to have good resistance to the environment for periods up to 5000 h. On the other hand, specimens of these alloys, exposed while located in porous refractory ceramic holders, gained large amounts of coke and underwent severe damage. A series of short tests were carried out in order to ascertain the main factors influencing the alloy reactivities in the experimental rig. The presence of specimens of a less‐resistant alloy and slight variations in gas composition (with the addition of CO₂) were observed to have a marked impact on the alloy reactivities. Factors such as catalysts, contaminants and gas composition were considered and are discussed.     

钛基非晶态钎料钎焊高强石墨与铜的界面特征

石墨在核工业中得到广泛应用,铜与其连接起到加强散热的作用,二者间的连接问题成为必须要解决的技术关键.采用非晶态TiZrNiCu钎料箔真空钎焊紫铜与普通高强石墨,研究了工艺参数对接头界面组织的影响.结果表明,接头室温剪切和拉伸时均断于石墨母材侧,经接头微观组织分析,认为高强度的结合界面是由于钎料与石墨反应生成了TiC薄层,钎缝主要是以固溶体为基,由金属间化合物相间其中的组织结构形成的.     

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.     

Corrosion resistance of Ni‐50Cr HVOF coatings on 310S alloy substrates in a metal dusting atmosphere

Metal dusting attack has been examined after three 168 h cycles on two Ni‐50Cr coatings with different microstructures deposited on 310S alloy substrates by the high velocity oxy‐fuel (HVOF) thermal‐spray process. Metal dusting in uncoated 310S alloy specimens was found to be still in the initiation stage after 504 h of exposure in the 50H₂:50CO gas environment at 620 °C. Dense Ni‐50Cr coatings offered suitable resistance to metal dusting. Metal dusting was observed in the 310S substrates adjacent to pores at the interface between the substrate and a porous Ni‐50Cr coating. The porosity present in the as‐deposited coatings was shown to introduce a large variability into coating performance. Carbon formed by decomposition of the gaseous species accumulated in the surface pores and resulted in the dislodgement of surface splats due to stresses generated by the volume changes. When the corrosive gas atmosphere was able to penetrate through the interconnected pores and reach the coating–substrate interface, the 310S substrate was carburized, metal dusting attack occurred, and the resulting formation of coke in the pores led to local failure of the coating.     

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.     

The influence of surface condition on the metal dusting behavior of cast and wrought chromia forming alloys

The current work investigated the impact of surface condition on the metal dusting behavior of chromia forming alloys. Five commercial alloys were included in the study, wrought 800H, 353MA, and cast G4859, G4852 Micro, and ET45 Micro, these alloys have a chromium and nickel content in the range of 20–35 wt% and 32–45 wt%, respectively. The wrought alloys were tested in a pickled state and the cast alloys with a machined surface, all the alloys were tested using a laboratory ground surface condition for comparison. The exposures were performed using a gas with a composition of 44 vol% CO, 52 vol% H₂, 2 vol% CO₂, and 2 vol% H₂O at a temperature of 600 °C and a pressure of 5.5 bar. The samples were periodically characterized by measuring the mass loss, pit density, pit size, and pit depth. The results show that the pickled surfaces were sensitive toward metal dusting attack while the machined and the ground surfaces had better resistance. This shows that the surface pre‐treatment plays a crucial role.     

焊接残余应力对接头尘化腐蚀影响的有限元模拟

金属尘化腐蚀是发生在含碳气氛中的一种高温腐蚀现象,碳在金属基体中的扩散是其过程的第一步.文中开发了碳扩散的耦合计算程序,进行了加热炉炉管焊态和工况温度状态下焊接残余应力对碳扩散影响的数值模拟,并与无应力状态下的碳扩散情况进行了比较.结果表明,在热影响区附近焊接残余应力梯度最大,对碳扩散的影响也最大,并且形成一个碳浓度峰值,在峰值两侧则会形成相应的碳浓度低谷,这是碳向高应力梯度区扩散所致.经过升温至工况温度后,残余应力得到松弛,对碳扩散的影响有所降低,可以延缓炉管的损坏时间.但由于残余应力的影响仍然存在,因此在炉管检修期间要注意焊接接头附近的尘化腐蚀情况.     

Improvement of thermal and mechanical properties of graphite/copper composites through interfacial modification

Unidirectionally reinforced graphite/copper composites have been fabricated using a pressure infiltration casting procedure. T300 and T650 graphite fibers have been used to reinforce copper and copperchromium alloys. The effects of the chromium level in the copper matrix on the tensile strength, stiffness, and thermal expansion behavior of the composites have been evaluated through tensile and three-point bend testing, and thermal cycling. At the 0.5 wt% alloying level, chromium increases the stiffness and optimizes the thermal expansion behavior of graphite/copper composites. The longitudinal tensile strengths of these composites are above 1606 MPa, whereas the transverse tensile strengths are lower than 40 MPa due to incomplete infiltration during processing. Scanning electron microscopy analyses reveal that the unalloyed copper matrix composites experienced extensive fiber/matrix debonding under tensile loading. The addition of chromium to the copper increases the level of matrix bonding to the graphite fibers, as evidenced by observations of fractured tensile specimens. Auger electron spectroscopy analyses indicate that a chromium carbide phase present at the interface is responsible for the improved bonding.     

钢管表面铜金属污染的危害性分析

天然气输气管线钢管的母材在现场检测时发现硬度不合格现象,通过宏观观察、电镜扫描、金相分析及微观硬度测试等多种检测方法确定钢管表面有铜金属污染存在.铜金属污染实质上属于异金属夹杂,产生的原因是冶炼操作不当,合金料未完全熔化或浇注系统中掉入异金属.该异金属夹杂物由于与基体的组织、性能均不同,与基体组织有明显的界限,会割裂基...     

Numerical simulation of copper based filler metal droplets spreading under arc brazing

1 INTRODUCTION Arc brazing technology is a newly developed joining technology .For its advantages ,it has been used more and more frequently in automobile industry and other wiring equipments . And this technology is considered to have a big foreground in practical joining applications . But up to now, the studies of this technology are restrained in practical production applications[1 3]and experi- mental analyses[4 ,5]; and few researchers have studied the spreading of liquid droplets ,…     

化学镀镍作为钢酸性镀铜前处理工艺的应用研究

为了防止钢表面酸性电镀铜出现置换铜,采取在电镀铜前增加化学镀镍工序,研究了化学镀镍工艺对酸性电镀铜的影响。结果表明,化学镀镍时间超过6 min时(镍层厚度>2.5～3μm),工件在酸性镀铜液中浸泡10 min,无置换铜出现。化学镀镍层对后续的酸性镀铜层的表面形貌和附着力均无明显影响,表明化学镀镍可作为钢酸性镀铜的底层。     

Metal dusting behaviour of welded Ni‐base alloys with different surface finish

Welded Ni‐base alloys and Alloy 800 were exposed under metal dusting conditions at 600°C and 650°C for up to 6000 hours. Alloy 800 was attacked very strongly already in the first days and Alloy 600 also rather soon and widespread, on both materials attack started mainly in the heat affected zone. Several surface states of Alloy 600: brushed, ground, sand‐blasted and pickled were tried only grinding caused a modest delay and decrease of metal dusting attack. Generally the attack was less widespread but deeper at 650°C than at 600°C, also for Alloy 601 and 602. The latter alloys show minor, mainly local attack, but especially the welds are affected. TIG welding led to better resistance than hand‐welding.