Prevention of metal dusting on Ni-based alloys by MCrAlY coatings

The flame tubes from the domestic heating devices made of different Ni-based alloys (alloy 601/NiCr23Fe and even alloy 602/NiCr25FeAlY) showed after a short operation time severe attack by metal dusting. This phenomenon occurred only during combustion of the fuel oil with a new chemical composition. The german market offers such fuel oils with a reduced sulphur content due to more severe environment regulations. Sulphur is able to stabilize the cementite suppressing or retarding the appearance of metal dusting. Metallographical studies revealed that under this operation conditions the oxide scale on the Ni-based alloy forms only partially.In order to prevent the appearance of metal dusting, the flame tubes were coated by a high performance layer (MCrAlY-alloy) which shows a good stability under these corrosive conditions. Uncoated and MCrAlY-coated samples made of alloy 601 and alloy 602 were used for metal-dusting experiments. The specimens were tested using a computer-controlled special equipment which was developed and built in order to simulate the parameters in a flame tube of an oil heating device.Metallographical investigations of the tested samples revealed that the oxide scale present on the uncoated based alloy was formed only partially, whereas in the case of the MCrAlY coatings the oxide scale has an uniform distribution and a good stability due to the presence of the β-NiAl phase which is considered the Al-reservoir for its formation.     

Cementite decomposition and coke gasification in He and H2-He gas mixtures

Cementite decomposition and coke gasification were investigated by first carburisation of iron samples at 700 °C in a 50%CO-49.81%H₂-0.19%H₂O gas mixture for 4 h and then further treatment in He and He-H₂ gas at the same temperature for different time periods. After carburisation cementite is formed at the iron surface covered by a coke layer. Scanning electron microscopy (SEM) shows carbon filaments and columnar layered bulk graphite in the carbon deposits. X-ray diffraction (XRD) and transmission electron microscopy (TEM) reveal only cementite as the iron-containing phase in the coke. Cementite in the iron specimen and cementite in the coke show a different decomposition behaviour during treatment in He and He-H₂ gases. In the iron specimen cementite decomposition proceeds fast and is comparable in both He and He-H₂ gases. However, cementite in the coke is much more stable than that at the sample surface especially in the case of only He gas. By using thermogravimetric analysis (TGA) no gasification is detected in He gas but very significant gasification in He-H₂ gas mixture until all the coke is removed. By adding some H₂O into the He-H₂ gas the gasification process is accelerated.     

An investigation on oxidation/carburisation of 9Cr-1Mo steel heat exchanger tube in an AGR environment

Abstract

9Cr–1Mo steels have been used extensively in the power generation industry. In this study, a wide range of experimental samples exposed at different times and temperatures in a CO₂ environment were analysed to look at the development of the metal and oxides over time. The main objective of this work was to obtain a better understanding of the carburisation and oxidation behaviour of 9Cr 1Mo steels as a function of temperature/time, with special attention paid to the transition from protective to breakaway oxidation. In addition, experiments were also carried out to investigate any links between oxidation transition and carburisation behaviour of these materials.     

Carbon deposition on iron surfaces in CO–CO2 atmosphere

Thermodynamic calculations and thermogravimetric (TG) analysis were performed in order to understand the mechanism of carbon deposition on the surfaces of iron particles during the reduction of iron ore in a CO–CO₂ atmosphere. The results of the thermodynamic equilibrium phase analysis indicate that the phases of the carbon deposition process can be predicted on the basis of the carbon potential, reaction temperature and gas pressure. The optimal thermodynamic conditions for carburisation are a low temperature (T?<?T_m) and a high carbon potential (α_c>1). TG analysis is performed in a gas mixture of 65 vol.-% CO and 35 vol.-% CO₂ at 650, 706 and 750°C. Cementite (Fe₃C) is generated as an intermediate product, which acts as a catalyst for carbon deposition. Carbon deposition is inhibited at high temperatures (T>791°C) owing to the high stability of Fe₃C. When the reaction temperature is higher than the thermodynamic limit for the formation of Fe₃C, carbon deposition cannot occur. A mechanism for carbon deposition is proposed based on the experimental results.     

Tribocorrosion behaviour of low temperature plasma carburised 316L stainless steel in 0.5 M NaCl solution

Experiments have been carried out to study the tribocorrosion behaviour of low temperature plasma carburised 316L stainless steel under unidirectional sliding in 0.5 M NaCl solution, using a pin-on-disk tribometer integrated with a potentiostat for electrochemical control. It is found that the carburised layer exhibits much better resistance to material removal than the untreated specimen, particularly at anodic potentials. No corrosion pits are observed inside the wear track on the carburised specimen at anodic potentials as high as 750 mV (SCE). The results are discussed in terms of the relative contribution of wear and corrosion to overall material removal by tribocorrosion.     

High temperature corrosion of cast heat resisting steels in CO + CO2 gas mixtures

Two commercial variants of the cast heat resistant grade HP40Nb (Fe-25Cr-35Ni, Nb modified) were exposed to CO/CO₂ gases at 982 and 1080 °C in order to simulate exposure to the carbon and oxygen potentials realised in steam reformers under normal and overheated conditions. Both alloys developed external chromium-rich oxide scales, intradendritic silica precipitates and interdendritic oxide protrusions where primary, interdendritic carbides were oxidised in situ. Surprisingly, the lower silicon content alloy developed a more continuous internal silica layer, thereby slowing external scaling. Intradendritic oxidation was fast in both alloys, and is attributed to interfacial oxygen diffusion. Both alloys underwent rapid internal carburisation, indicating that their oxide scales failed to prevent carbon access to the underlying alloys under these reaction conditions.     

Metal dusting of binary iron aluminium alloys at 600 °C

In this work experiments on metal dusting of binary iron aluminium alloys with 15, 26 and 40 at.% Al were performed in strongly carburising CO‐H₂‐H₂O gas mixtures at 600 °C. The mass gain kinetics was measured using thermogravimetric analysis (TGA). The carburised samples were characterised by means of light optical microscopy (LOM), scanning electron microscopy (SEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). It was found that the mass gain kinetics depends on the CO content of the gas mixtures and on the Al content of the alloys. With decreasing carbon activity the carburisation reaction kinetics decreases and the onset of metal dusting is retarded for increasing time periods. With increasing Al content of the alloys the carburisation reaction is slower and metal dusting sets on at later times. The samples were not pre‐treated for the formation of a protective oxide scale. By X‐ray Photoelectron Spectroscopy (XPS) analyses of the carburised iron aluminium samples it was found that the formation of Al₂O₃ layers has taken place in the CO‐H₂‐H₂O gas atmospheres. Needle‐ or plate‐like κ‐phase (Fe₃AlC_x) precipitates close to the surface of the carburised Fe‐15Al sample were detected by means of XRD and LOM. The coke on top of the carburised samples mainly consists of filamentous carbon with metal particles at their tips.     

Non-steady state carburisation of martensitic 9–12%Cr steels in CO2 rich gases at 550 °C

Two martensitic steels were reacted with Ar–50%CO₂ at 550 °C for exposure times up to 150 h. Microstructural analyses and glow discharge optical emission spectroscopy revealed that internal carburisation of both steels beneath external oxide scales occurred, in spite of the very low equilibrium carbon activity of the atmosphere. The carbon concentration at the metal–scale interface increased throughout the reaction and the carbon uptake varied approximately linear with time. A model is proposed to describe the non steady-state carburisation kinetics whereby the usual diffusion equation describing carbon movement into the alloy is modified to account for loss of carbon as precipitated carbides.     

Effects of cobalt additions on WC grain growth

Abstract

Inhomogeneity in the particle size of the tungsten carbide raw material can result in abnormal WC grain growth in WC–Co cemented carbides. For the preparation of ultrafine tungsten carbide powders and ultrafine cemented carbides, abnormal WC grain growth is the most troublesome issue. This paper deals with the effects of cobalt additions on WC grain growth during the carburisation process of nano- and coarse tungsten powders and the sintering process of ultrafine tungsten carbide powders. For the preparation of tungsten carbide powders, it was shown that through the incorporation of 0·035 wt-%Co into W+C mixtures, a dramatic change in WC grain morphology took place for coarse tungsten raw material, while for nanotungsten raw material, a pronounced WC grain growth took place. Plate-like truncated trigonal and hexagonal WC grains were formed during the carburisation process of coarse tungsten raw material containing 0·035 wt-%Co. For the sintering of ultrafine tungsten carbide powders containing 0·3 wt-%Co, an anisotropic and abnormal WC grain growth took place. The mechanisms for WC grain growth were discussed, and suggestions were made for the quality improvement of nano- and ultrafine tungsten carbide powders and ultrafine cemented carbides.     

Effect of surface nanocrystallisation on the microstructure and wear resistance of vacuum carburised alloy

In this work, a nanocrystallisation surface layer with an average grain size of 29?nm was fabricated on the 12Cr2Ni4A steel by the supersonic fine particles bombarding (SFPB). The vacuum carburising process was carried out on the original and the SFPB pre-treatment samples. X-ray diffraction, scanning electron microscopy and hardness tester were employed to study the phase constituents, grain size, hardness and residual stress of the two carburised samples. Experimental results showed that compared to the coarse-grain carburised layer (without SFPB), the carburised layer with SFPB pre-treatment has smaller martensite and carbide, and its thickness, hardness, compressive residual stress and wear resistance have been significantly improved. The dominant wear mechanisms of the two carburised samples were both abrasive wear and fatigue wear.