Long-Term Oxidation of Candidate Cast Iron and Stainless Steel Exhaust System Alloys from 650 to 800 °C in Air with Water Vapor

The oxidation behavior of candidate cast irons and cast stainless steels for diesel exhaust systems was studied for 5,000 h at 650–800 °C in air with 10 % H₂O. At 650 °C, Ni-resist D5S exhibited moderately better oxidation resistance than did the SiMo cast iron. However, the D5S suffered from oxide scale spallation at 700 °C, whereas the oxide scales formed on SiMo cast iron remained relatively adherent from 700 to 800 °C. The oxidation of the cast chromia-forming austenitics trended with the level of Cr and Ni additions, with small mass losses consistent with Cr oxy-hydroxide volatilization for the higher 25Cr/20–35Ni HK and HP type alloys, and transition to rapid Fe-base oxide formation and scale spallation in the lower 19Cr/12Ni CF8C plus alloy. In contrast, small positive mass changes consistent with protective alumina scale formation were observed for the cast AFA alloy under all conditions studied. Implications of these findings for exhaust system components are discussed.     

The oxidation of 18/8 type stainless steel in high pressure CO2/2% CO

The oxidation of a variety of 18/8 stainless steels in high pressure CO₂/2% CO has been followed in the temperature range 550–650°C using intermittent weight gain measurement metallography, fractography and scanning electron microscopy. Duplex scales formed at an early stage of oxidation. The weight gain curves were analysed in terms of a two stage process, the initial stage exponentially approaching a slower secondary stage. The primary rate of duplex scale formation did not show the usual temperature dependence. Rather a maximum in the rate was observed at ～600°C. Secondary rates were well established at 650°C and 550°C the secondary rate at 550°C, however, being higher than that at 650°C. Various spinels occurred and the results are explained in terms of the rate controlling process being cation diffusion through different inner spinels.     

Development of novel diffusion coatings for 9–12 % Cr ferritic‐martensitic steels

Eventhough 9–12% Cr steels are mechanically designed for power plant applications up to 650 °C, their effective use is limited by the corrosion resistance at this temperature. Therefore, the present paper addresses the development of diffusion coatings on 9% Cr ferritic‐martensitic steels. The difficulty of coating these materials with conventional diffusion processes arises from the temperature limit above which the conversion of the martensite is accelerated and the mechanical properties would be deteriorated. Aluminide coatings consisting of Fe₂Al₅ or FeAl phases were thus developed for deposition temperatures between 650 and 715 °C by the conventional pack cementation technique. As the addition of boron was expected to improve the oxidation properties of the coating, the influence of B on the aluminide coating was investigated. The precedent diffusion of Cr as an interdiffusion barrier before switching to the Al diffusion step was also investigated. As a further technique, the fluidised bed chemical vapour deposition (FBCVD) method allowed the development of Fe₂Al₅ coatings at 550 °C. Furthermore, Si or codiffusion Al‐Si coatings were developed at temperatures as low as 550 °C.     

Comparison between field and laboratory steam oxidation testing on aluminide coatings on P92

Steam oxidation has become an important issue for steam power plants as operating temperatures increase from the current 550 to 600–650 °C. For the last 10 years several groups have been carrying out steam oxidation testing of both uncoated substrates and coatings in the laboratory. On the other hand, field testing results are very scarce. In this paper, a comparison of laboratory steam oxidation testing with field test results carried out by Alstom at the Kraftwerk Westfalen power station located in Hamm, Germany will be presented. Both slurry deposited aluminide coatings and uncoated P92 steel have been included in the study. Under steam (atmospheric pressure) and isothermal conditions in the laboratory at 650 °C, spallation of oxides formed on ferritic steels occurs after significantly longer time when compared to exposure to real operating conditions. Oxide spallation results in serious damage in steam power plants by obstructing heat exchanger tubes, erosion of valves and turbine blades, etc. Moreover, the thickness of the oxide scales formed under field testing conditions is significantly higher after similar exposure. On the other hand, aluminide coated P92, which exhibit thickness through cracks, have shown to be stable in the laboratory for up to 60 000 h at 650 °C under steam, without evidence of crack propagation. However, field test results indicate that some degree of crack propagation occurs but without causing substrate attack up to 21 700 h of exposure. Moreover, the aluminium oxide observed in both laboratory and field tested specimens is different.     

The erosion‐corrosion resistance of uncoated and aluminized 12% chromium ferritic steels under fluidized‐bed conditions at elevated temperature

In this paper, some results from a study of the erosion‐corrosion resistance of uncoated and aluminized 12% chromium steel in a fluidized‐bed rig are reported. The aims of the research are to establish and compare the erosion‐corrosion resistance of these materials for possible applications as heat exchangers in future power plants, and to obtain an increased understanding on their behaviour and mutual superiority in a range of conditions. Damage to the uncoated 12% chromium steel occurs by an oxidation‐affected erosion process under all the studied conditions, with spallation of scale being the primary mechanism of material wastage. At a temperature of 550°C, the uncoated steel follows the typical angle‐dependence of a brittle material, while, at temperatures above 550°C, it follows an angle‐dependence that is more typical of a ductile material. This change in the angle‐dependence with temperature is related to characteristics, i.e. uniformity, adhesion and density, of the formed oxide scales. The rate of material wastage increases with increase in speed and temperature, due to the development of thicker, more uniform and more dense oxide scales, that promote more severe scale spallation. The erosion‐corrosion behaviour of the aluminized 12% chromium steel changes in the temperature range from 600°C to 650°C. This is due to a shift from a brittle‐like to a ductile‐like angle‐dependence and to a more rapid oxide scale build‐up at temperatures above 600°C. At an impact angle of 30° and at 550°C and 600°C, the prevailing erosion‐corrosion process for the aluminized steel is oxidation‐affected erosion. At 650°C and 700°C for an impact angle of 90°, the primary erosion‐corrosion mode is essentially erosion‐enhanced oxidation. The results of the study have also demonstrated that the Al₅Fe₂ coating deposited by pack aluminization offers enhanced protection against erosion‐corrosion at shallow impact angles at 550°C and 600°C and at steeper impact angles at 700°C.     

The duplex oxidation of vacuum annealed 316 stainless steel in CO2/CO gas mixtures between 500 and 700°C

The duplex oxidation of vacuum annealed 316 stainless steel has been studied at 650°C (923 K) and 700°C (973 K) in CO₂/CO gas mixtures of varying oxygen potential covering the range of Fe₃O₄ stability at these temperatures. The weight gain curves obtained were interpreted in terms of the usual 2-stage process of duplex scaling on 18/8 type stainless steels. The primary rate at 650° C showed an approximate dependence on the oxygen partial pressure of the oxidising gas of K_p π P_o2^11.15. At 700°C however the primary rate appeared nominally independent of oxygen partial pressure. Primary duplex oxidation rate constants were also measured at constant P_o2 over the temperature range 500–700°C (773–973 K). An Arrhenius relationship was found between the primary rate and temperature with an associated activation energy of 40 ± 6 K cal mol^?1 (167 ± 25 kJ mol^?1). In general there was no obvious correlation between the composition of the inner spinel and primary rate with the exception that low oxidation rate constants in both the primary and the secondary or healing stage were associated with spinels containing less than 10 wt. % Ni and more than 35 wt. % Cr, the nickel content appearing the more significant.     

High-Temperature Corrosion Behaviour of Aluminized-Coated and Uncoated Alloy 718 Under Cyclic Oxidation and Corrosion in NaCl Vapour at 750 °C

To evaluate the suitability of HR3C and 22Cr–25Ni–2.5Al AFA steels as the heat-resistant alloys, the oxidation behavior of them was investigated in air at 700, 800, 900 and 1000 °C. The evolution of oxide layer on the surface and subsurface was investigated using a combination of compositional/elemental (SEM, EDS) and structural (XRD, GDOES) techniques. A dense and continuous Cr₂O₃ healing layer on the HR3C was formed at the temperature of 700 or 800 °C, but the Cr₂O₃ oxide film on HR3C was unstable and partly converted into a less protective MnCr₂O₄ with the increase in temperature to 900 or 1000 °C. The composition and structure of oxide film of 22Cr–25Ni–2.5Al AFA steels are significantly different to the HR3C alloys. The outer layer oxides transformed from Cr₂O₃ to Al-containing oxides, leading to a better oxidation resistance at 700 or 800 °C compared to HR3C. Further, the oxide films consist of internal Al₂O₃ and AlN underneath the outer loose layer after 22Cr–25Ni–2.5Al AFA oxidized at 900 or 1000 °C. It can be proved that the internal oxidation and nitrogen would make 22Cr–25Ni–2.5Al AFA steels have worse oxidation resistance than HR3C alloys at 900 or 1000 °C.     

Kinetic Features of Iron Oxidation in Liquid Lead Saturated with Oxygen Below and Above the Chaudron Point (570 °C)

The oxidation kinetics of Armco–Fe in stagnant lead melts saturated with oxygen at 550 and 650 °C was investigated and the peculiarities of structure, phase and elemental composition of scales were determined. At 550 °C oxidation follows a parabolic law up to 1,500 h and then (1,500–2,000 h) oxidation accelerated. At 650 °C during 100 h the scale grew rapidly according to a quadratic time dependence. Then (100–500 h) the oxidation rate decreased sharply. From 500–1,000 h oxidation accelerated. The scales formed at 550 and 650 °C consisted of Fe₃O₄ and FeO/Fe₃O₄, respectively. The scales had a duplex structure. The outer-oxide layer grew from the initial solid metal–liquid metal interface towards the melt while the inner layer grew towards the iron substrate. The defectiveness of scale altered with time. The possible reaction mechanisms in the Fe–Pb[O] system are discussed.     

Anomalous temperature dependence of oxidation kinetics during steam oxidation of ferritic steels in the temperature range 550-650 °C

The oxidation behavior of a number of selected ferritic steels in a simulated steam environment at temperatures between 550 and 650 °C was studied. In the prevailing test gas, some of the studied 9-12% Cr steels tended to exhibit an anomalous temperature dependence of the oxidation behavior. This means, that the oxidation rates do not steadily increase with increasing temperature. At higher temperatures, some of the studied steels tend to form a very thin and protective oxide scale whereas at lower temperature rapidly growing, less-protective oxides are being developed. The anomalous temperature dependence is related to differences in chromium distribution in the inner part of the oxide scale. The effect is observed for steels with intermediate-Cr contents (∼10-12%) whereas steels with either lower or higher Cr contents exhibit an increasing oxidation rate with increasing temperature.     

High temperature air oxidation behaviour of “poor man” high manganese-aluminum steels

The behaviour of austenitic high manganese (19.8%–32.5%)aluminum (7.1%–10.2%) steels in high temperature air has been examined. Tests have been carried out in the 600–900°C temperature range for durations up to 200 h. The steels form a high manganese scale at high oxidation rates; aluminum does not contribute to the formation of this scale. Only a 1.5% silicon bearing steel shows a good oxidation resistance up to 700°C, the oxidation rate being lower because as shown by XPS analyses a silicon-containing scale is formed. The oxidation resistance of these steels is always lower than that of conventional grades of austenitic stainless steels.     

Materials for ultrasupercritical coal power plants—Boiler materials: Part 1

The efficiency of conventional boiler/steam turbine fossil power plants is a strong function of the steam temperature and pressure. Research to increase both has been pursued worldwide, since the energy crisis in the 1970s. The need to reduce CO₂ emission has recently provided an additional incentive to increase efficiency. Thus, steam temperatures of the most efficient fossil power plants are now in the 600 °C (1112 °F) range, which represents an increase of about 60 °C (108 °F) in 30 years. It is expected that steam temperatures will rise another 50 to 100 °C (90 to 180 °F) in the next 30 years. The main enabling technology is the development of stronger high-temperature materials, capable of operating under high stresses at ever-increasing temperatures. Recently, the EPRI performed a state-of-the-art review of materials technology for advanced boiler/steam turbine power plants (ultrasupercritical power plants). The results of the review show that with respect to boilers, high-strength ferritic 9–12Cr steels for use in thick section components are now commercially available for temperatures up to 620 °C (1150 °F). Initial data on two experimental 12Cr ferritic steels indicate that they may be capable of long-term service up to 650 °C (1112 °F), but more data are required to confirm this. For higher temperatures, austenitic steels and Ni-based alloys are needed. Advanced austenitic stainless steels for use as super and reheater tubing are available for service temperatures up to 650 °C (1112 °F) and possibly 700 °C (1292 °F). Ni-based superalloys would be needed for higher temperatures. None of these steels have been approved by the ASME Boiler Code Group so far. Higher-strength materials are needed for upper water walls of boilers with steam pressure above 24 MPa (3400 psi). A high-strength 2-1/2%Cr steel recently ASME code approved as T-23 is the preferred candidate material for this application. Field trials are in progress. This paper will present the results of the EPRI review in detail, relating to boiler material. Results relating to turbine materials are presented in a companion paper as Part 2.     

Prediction of Oxide Phases Formed upon Internal Oxidation of Advanced High-Strength Steels

The effect of Cr on the oxidation of Fe–Mn-based steels during isothermal annealing at different dew points was investigated. The Fe–Mn–Cr–(Si) phase diagrams for oxidizing environments were computed to predict the oxide phases. Various Fe–Mn steels with different concentrations of Cr and Si were annealed at 950 °C in a gas mixture of Ar or N₂ with 5 vol% H₂ and dew points ranging from ? 45 to 10 °C. The identified oxide species after annealing match with those predicted based on the phase diagrams. (Mn,Fe)O is the only oxide phase formed during annealing of Fe–Mn binary steel alloys. Adding Cr leads to the formation of (Mn,Cr,Fe)₃O₄ spinel. The dissociation oxygen partial pressure of (Mn,Cr,Fe)₃O₄ in the Fe–Mn–Cr steels is lower than that of (Mn,Fe)O. The Si in the steels results in the formation (Mn,Fe)₂SiO₄, and increasing the Si concentration suppresses the formation of (Mn,Cr,Fe)₃O₄ and (Mn,Fe)O during annealing.     

Performance of Al‐rich oxidation resistant coatings for Fe‐base alloys

The oxidation resistance of Al‐rich coatings made by chemical vapor deposition and pack cementation was examined on representative ferritic‐martensitic (FM, e.g. Grade 91, Fe‐9Cr‐1Mo) and austenitic steel substrates at 650°‐800 °C. To evaluate the potential benefits and problems with these alumina‐forming coatings, oxidation exposures were conducted in a humid air environment where the uncoated substrates experience rapid oxidation, similar to steam. Exposure temperatures were increased to accelerate failure by oxidation and interdiffusion of Al into the substrate. The difference in the coefficient of thermal expansion (CTE) between coating and substrate was found to cause cracking and coating failure during rapid thermal cycling on thicker coatings with Fe‐Al intermetallic phases. Therefore, thinner coatings with less Al and a ferritic Fe(Al) structure were evaluated more extensively and tested to failure at 700° and 800 °C on FM steels. The remaining Al content at failure was measured and used to improve a previously developed coating lifetime model. At 700° and 800 °C, thin coated austenitic specimens continue to exhibit protective behavior at more than double the lifetime of a similar coating on FM steel. The longer lifetime was attributed to the ferritic coating‐austenitic substrate phase boundary inhibiting Al interdiffusion.     

Corrosion Inhibition of 304 Stainless Steel by Nano-Sized Ti/Silicone Coatings in an Environment Containing NaCl and Water Vapor at 400–600°C

The corrosion behavior of 304 stainless steel (SS) and its corrosion inhibition by brushing nano-sized Ti/silicone coatings on its surface in an environment containing a solid NaCl deposit and water vapor at 400–600°C was studied. Results indicated that water vapor or NaCl, especially water vapor plus NaCl accelerated the corrosion of the steel markedly. The corrosion scales of the uncoated steel had a duplex structure at 400–500°C and internal oxidation occurred for the uncoated steel at 600°C in an environment containing NaCl and water vapor. The corrosion of the 304SS was inhibited efficiently by the coatings at 400–500°C, and the coated steel suffered corrosion to some extent and most of the coatings were destroyed at 600°C. X-ray diffraction (XRD) indicated that the corrosion products of the uncoated steel were mainly Fe₂O₃, Cr₂O₃, NiO or Na₂CrO₄, and the coatings consisted mainly of TiO₂ and SiO₂ after exposure at 400–500°C. The good corrosion resistance of the nano-sized Ti/silicon coatings was attributed to the formation of SiO₂, and TiO₂ that resulted from the decomposition of the organic components in the coating and fast oxidation of nano-Ti powder respectively during the experiments, TiO₂ mixed together with SiO₂ and formed a new coating on the steel surface that played an important role in the protection of the steel.     

Oxide scale formation and subsurface phase transformations during long‐term steam exposure of the cobalt base alloy 25

High chromium nickel and cobalt base alloys are presently being considered as construction materials for various components in high efficiency steam turbines with envisaged operating temperatures around 700 °C. In the present study, the steam oxidation behavior of the cobalt base alloy 25 in the temperature range 650–800 °C was investigated whereby exposures up to 10 000 were carried out. Post exposure analyses of the oxidation products and alloy microstructures included optical microscopy, scanning and transmission electron microscopy, X‐ray diffraction analysis and secondary neutrals mass spectrometry. The experiments showed in all cases formation of oxide scales mainly consisting of chromia with minor amounts of outer Cr/Mn spinel and internal silica. The oxidation induced chromium depletion resulted in a number of microstructural changes in the subsurface depletion layer. First, the intermetallic phase Co₃W became enriched at the scale alloy interface. Additionally, the chromium rich M₂₃C₆ and the tungsten rich M₆C dissolved in the depletion layer. The mechanisms for occurrence of these effects are discussed on the basis of phase equilibria in the binary Co–W and the ternary Co–Cr–W system.     

Kinetics and Mechanism of the Oxidation of Molybdenum

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MoOs is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo0_{3(vaporizing)}/Mo0_3(surface) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 600°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total Mo0₈ on molybdenum has been evaluated. The suboxide Mo0₂ does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions.     

Corrosion behavior of various steels in the simulated fluidized bed boiler environment

The corrosion behavior of various austenitic stainless steels and high-alloy steels has been studied in simulated fluidized bed boiler environment to develop a new corrosion resistant austenitic stainless steel for the superheater tube. The superheater is usually not installed within the bed position, which is different from the evaporator installed within the bed position. Therefore, the superheater tubes are exposed to an oxidizing environment; but it is also necessary to estimate the corrosion resistance of the steels in a reducing environment. It is already known that the high temperature corrosion behavior in conditions where CaSO₄ is coated on the steels is more important than the erosion of the superheater tubes. The main results in this present study are as follows: The Nb bearing steels and low C steels showed good resistance to high-temperature corrosion in CaSO₄/CaO, e.g. 347, 304L and HR3C. The corrosion rate of all steels used increased with increase in temperature, particularly at temperatures higher than 650°C. Internal penetration was not detected at temperatures lower than 550°C, but it was detected at temperatures higher than 600°C, in particular, higher than 650°C. The corrosion thickness loss was almost the same as the internal penetration depth at 700 and 750°C in the 300 series steels placed in CaSO₄/CaO, including the fine grained 347 steel, while the internal penetration depth was larger than the corrosion thickness loss in high-alloyed materials such as Alloy 800 and 310 steels. At temperatures higher than 800°C, the same result was also obtained for the fine grained 347 steel. The corrosion during exposure to oxidizing or reducing gases without CaSO₄/CaO or CaS was slight, but when the test specimens were placed in CaSO₄/CaO or CaS, the corrosion rate sharply increased, regardless of the atmospheric gas composition. Cr, Si, Mn (less than 5 %), Mo and Nb are beneficial elements while C, Cu and Al are harmful elements. From the above results, the following steel was developed for high temperature corrosion resistance in CaSO₄/CaO: low C-22/25Cr-17/25Ni-3/5Mn-(2Mo)-Nb-0.08/0.2N-Al-(B).     

Oxidation of X20 in Water Vapour: The Effect of Temperature and Oxygen Partial Pressure

The oxidation behaviour of X20 in various mixtures of water, oxygen, and hydrogen was investigated at temperatures between 500 °C and 700 °C (time: 336 h). The samples were characterised using reflected light microscopy and scanning electron microscopy equipped with energy dispersive spectroscopy. Double-layered oxides developed during oxidation under all conditions. The morphology of the oxide layers was strongly influenced by temperature, whereas the influence of the oxidising environment appeared to be less pronounced, as long as it contained water vapour. The inner layer consisted of converted M₂₃C₆ embedded in Fe–Cr spinel after oxidation at 500 and 600 °C, while alternating layers of Cr-rich and Cr-poor oxide were observed after oxidation at 700 °C. An internal oxidation zone developed during oxidation at 500 and 600 °C, with its depth influenced by the oxidising environments. The results are discussed based on the various hypotheses of the accelerating effect of water vapour that have been put forth in the literature.     

TG–mass spectrometry studies in coating design for supercritical steam turbines

Ferritic steels in steam turbines for the power industry operate without coatings in the temperature range of 590–600 °C. For higher operation temperatures the substrate has to be replaced or coated, otherwise the ferritic substrate at a temperature of 650 °C develops thick oxide scales that promote sudden turbine blade failure. The advantage of the use of coatings is that coated ferritic steels are much less expensive than austenitic stainless steels or nickel base superalloys. In order to go forward to coatings design, the Thermo‐Calc code was used as a base for the mass spectrometry (MS)‐data. Thermogravimetry (TG)–MS experiments were conducted in a closed steam loop in order to obtain information about the oxyhydroxides formation as reaction between coatings and steam. From those results the role of the different coating element could be established and optimized for the coating durability. An oxidation mechanism based on the TG–MS results is given.     

Effect of Sulphur on the Oxidation Behaviour of Possible Construction Materials for Heat Exchangers in Oxyfuel Plants in the Temperature Range 550–700 °C

During oxyfuel combustion metallic heat exchangers are subjected to service environments which substantially differ from those prevailing during the conventional air firing process. In the present study the behaviour of three selected construction materials (P92, super S304HCu and alloy 617) during exposure in simulated oxyfuel gas with and without addition of SO₂ at temperatures between 550 and 700 °C has been investigated. The alloy microstructure and the corrosion products formed during exposures up to 1000 h were studied by SEM/EDX and correlated with gravimetric data collected during the discontinuous exposures. It was found that the behaviour of the martensitic steel was hardly affected by the presence of SO₂; however, in the case of the austenitic steel S304HCu the SO₂ suppressed internal oxidation occurring at 650 °C in the SO₂-free gas, thus promoting formation of a protective chromium-rich oxide. In the case of the nickel base alloy 617 the SO₂ addition increased the corrosion rates at 550 and 650 °C due to replacement of the external chromia scale by a multiphase scale with sulphur-containing surface nodules. At 700 °C the alloy formed a chromia base surface scale and SO₂ addition suppressed the formation of volatile Cr species. The results are explained using classical oxidation theory related to conditions for external scale formation in combination with thermodynamic considerations of phase stability as well as relative rates of adsorption of various gas species.