Investigation on steam oxidation behaviour of TP347H FG Part 1: Exposure at 256 bar

The stainless steel TP347H FG is a candidate material for the final stage tubing of superheater and reheater sections of ultra supercritical boilers operated at steam temperatures up to 620°C in the mild corrosion environments of coal‐firing. A series of field tests has been conducted with the aforementioned steel in coal‐fired boilers and this paper focuses on the steam oxidation behaviour for specimens tested at various metal temperatures for exposure times of 7700, 23000 and 30000 hours as investigated by light optical and scanning electron microscopy. The oxide present on the specimens is a duplex oxide, where the outer layer consists of two sub‐layers, an iron oxide layer and an iron‐nickel oxide layer; the inner layer is chromium rich chromium‐iron‐nickel oxide. Microstructure examination showed that for all these samples the varying grain size of subsurface metal affected the oxide thickness, where the larger the metal grain size, the thicker the oxidation scale. This gave the appearance of uneven inner oxides with a varying pit thickness. Comparison of the pit thickness measurement and oxide composition reveals that the oxidation rate is fast during the initial oxidation stage, but the subsequent growth of oxide from further exposure is slower due to the formation of a healing layer consisting of chromium rich oxide near original alloy grain boundaries. At a temperature region above 600°C a thin oxide rich in chromium and manganese is sometimes formed. In addition precipitation of secondary carbides in the bulk metal also occurs at this temperature region.     

Microstructural investigation of the oxide formed on TP 347H FG during long‐term steam oxidation

The long‐term oxidation behaviour of TP347H FG in ultra supercritical steam conditions was assessed by exposing the steel in test superheater loops in a Danish coal‐fired power plant and characterising the oxide layer with reflective light and electron microscopy. Double layered oxide scales formed during steam oxidation. TEM investigations reveal that the inner oxide layer consists of particles of metallic Ni/Fe and Fe? Cr spinel in the interior of the former alloy grains and a compact layer of Fe? Cr spinel and Cr₂O₃ along the former alloy grain boundaries. The morphology suggests that the inner layer grows by internal oxidation of the interior of the alloy grains. The thickness of the inner oxide layer did not change significantly with oxidation time and temperature for exposure times up to 30 000 h. Faster Cr diffusion within the fine‐grained alloy at higher temperatures is held responsible for this observation. This hypothesis is supported by kinetic data. The oxide thickness at low and high temperatures after 58 000 h exposure was higher than expected.     

Surface nanocrystallization of 310s stainless steel and its effect on oxidation behavior

Two techniques, unbalanced magnetron sputter deposition and high-energy short-pulsed plasma discharge, have been used to produce a nanocrystalline surface on AISI 310S stainless steel specimens. The average grain size after surface modification was estimated as ~100 nm by using atomic force microscopy. Cyclic oxidation was performed at 1000°C with treated and untreated 310S stainless steel specimens. The oxide products formed on the specimens consisted of an outer spinel layer that was rich in chromium, iron, manganese, and nickel, and an inner chromium-rich layer. It was found that the concentrations of iron and manganese in the outer layer of treated specimens were higher, and adherence of the scale was better in the treated specimens. The observed oxidation behavior can be explained by the increase of the creep diffusion rate in the fine oxide scale formed on the nanocrystalline surfaces.     

An investigation of thin oxide films thermally grown in situ on Fe24Cr and Fe24Cr11Mo by auger electron spectroscopy and X-ray photoelectron spectroscopy

AES depth profiling and XPS have been used for the characterization of thin oxide layers thermally grown in situ in the UHV-analysis chamber on pure iron, chromium and the alloys Fe24Cr and Fe24Cr11Mo at a temperature of 384°C. The apparent oxide film thickness and the film composition were monitored as a function of oxygen exposure. The oxidation rate of the Fe24Cr alloy was found to lie in between that of pure iron and chromium. The films formed have a duplex structure, the outer part being iron oxide, the inner part mostly chromium oxide. Alloying with molybdenum decreases the rate of oxidation by a mechanism involving the formation of a barrier layer rich in molybdenum at the oxide-metal interface. No molybdenum is found in the outer part of the oxide film.     

Kinetics of oxidation of ferrous alloys by super-heated steam

The kinetics of the oxidation of ferrous alloys in steam (10–60 kPa) at 450–550°C have been studied by measuring both the rate of hydrogen emission and the amount of metal oxidized. Excellent agreement has been found between the amount of metal oxidized calculated from both the total mass of hydrogen produced in the reaction and the thickness of the oxide layer formed; rate constants calculated from the rate of hydrogen emission, the mass of hydrogen produced as the reaction proceeds, and the oxide formed agree within experimental error. The rate of oxidation of a 9%Cr-1%Mo alloy at 501°C was found to be independent of the partial pressure of the steam. For this alloy, the activation energy agreed with literature values obtained at higher temperatures and pressures. The effect of the chromium and silicon content on the oxidation rates is compared. The rate constants are compared with theoretical calculations, assuming that the rate is determined by diffusion of iron in the magnetite lattice. For the 9%Cr-1%Mo alloy, the parabolic rate constant and activation energy are in excellent agreement with values calculated using Wagner's theory. The experimental rate constants are greater for the alloys containing smaller amounts of chromium; diffusion of iron along magnetite grain boundaries may be the dominant mechanism.     

氧化时间及铬含量对Fe-Cr钢高温氧化行为的影响

为了测定不同氧化时间以及铬含量对高温条件下钢材表面氧化铁皮组织和厚度的影响,将Fe-5Cr钢与Fe-10Cr钢在1000 ℃空气条件下氧化60~180 min,采用增重法绘制其氧化动力学曲线,并利用光学显微镜、能谱仪和X射线衍射仪对氧化铁皮的断面形貌和物相进行研究。结果表明,两试验钢氧化初期为“气-固”反应,中后期为“气相-氧化铁皮-固相”反应。两试验钢氧化铁皮结构均由外氧化层、内氧化层和内氧化区域组成。当氧化时间为180 min时,Fe-10Cr钢检测到了内氧化物Cr₂O₃。空气中氧元素向内扩散与基体中铬元素发生反应生成内氧化物Cr₂O₃,再与氧化铁皮层中的FeO发生固相反应生成尖晶石结构产物FeCr₂O₄。随着氧化时间的增加,由于内氧化物Cr₂O₃不断受到内氧化层的包裹而转为外氧化,内外氧化的转变使得基体不断被腐蚀,氧化铁皮厚度不断增加。     

Selective oxidation of FeCr alloys in the 295–450 K temperature range

A series of iron-chromium alloys were oxidized for 10² to 6×10⁴ s in air and in the 295–500 K temperature range. Room-temperature oxidation of iron, chromium, antimony, and copper were also conducted at extended times. Oxidation characteristics such as oxide thickness and composition of the oxide and of the underlying alloy were evaluated from measurements by electron spectroscopy for chemical analysis (ESCA). An initial selective oxidation of chromium with a concomitant chromium depletion in the alloy was found. This initial oxidation step is followed by growth of an outer, iron rich oxide which causes the former chromium depletion to vanish. Apparent activation energies extracted from parabolic oxidation kinetics (295–500 K) of the investigated metals were found to be in the 10–20 kcal/mole range.     

Oxide scale formation on Al containing Ni–Cr‐based high temperature alloys during application as flame tube material in recirculation oil burners

The flame tube is an important functional component of burners using the concept of the flame tube stabilised combustion. Under typical combustion conditions the material of the flame tube is exposed to high temperatures (≥900 °C) and to corrosion attack by the combustion gases. Furthermore as the burners are generally operated intermittently, the material suffers from extreme temperature and atmosphere changes. For flame tubes, a lifetime of approximately 8000 h is desired. Predominantly metallic high temperature materials are used. The scope of the present work was to test—under application conditions and for maximum material temperatures exceeding 900 °C—alternative high temperature alloys for use as tube material. The corrosion resistance of the austenitic Ni–Cr‐based alloys (601, 602 CA, 617 and 693) has been investigated in a burner rig at maximum material temperatures of 950 and 1000 °C and with exposure times from 50 to 3000 h. The chromium content of the alloys was between 20 and 30 wt% and that of aluminium between 1 and 3.4 wt%. Metallographic cross‐sections of samples of the alloys were analysed by electron microprobe yielding information about the microstructure and composition of the oxides in the surface zone and variations during exposure time. This study focuses on the observed specific effects of the alloying element aluminium on the development of the oxide scale and on the lifetime of the alloys. At the alloy surface after 500 h exposure time a chromium oxide scale had formed with aluminium oxides underneath predominantly along grain boundaries. For the alloys with the lower aluminium content, the aluminium oxides built up an open network but not a closed layer. For the alloy with the highest aluminium content (alloy 693) after 50 h two different characteristic microstructures at the surface were found. In one case, the grains at the surface were covered with chromium oxide on top and the remaining grain surface was completely enclosed by aluminium oxides. In the other case, the aluminium oxide formed a thin layer directly below the chromium oxide scale. After 500 h exposure time, a significantly thinner chromium oxide scale and massive internal chromium oxides were observed. Catastrophic corrosion, formation of internal oxides and aluminium nitrides started even after 500 h. It will be demonstrated that the early breakdown of alloy 693 is linked to the aluminium oxides which act as a barrier constricting the diffusion of chromium from the alloy matrix towards the surface. Under the conditions of extreme temperature changes given in the burner the aluminium oxide layer on its part did not provide corrosion protection.     

Oxidation mechanisms of Cr‐containing steels and Ni‐base alloys at high‐temperatures –. Part I: The different role of alloy grain boundaries

It is essential for materials used at high‐temperatures in corrosive atmosphere to maintain their specific properties, such as good creep resistance, long fatigue life and sufficient high‐temperature corrosion resistance. Usually, the corrosion resistance results from the formation of a protective scale with very low porosity, good adherence, high mechanical and thermodynamic stability and slow growth rate. Standard engineering materials in power generation technology are low‐Cr steels. However, steels with higher Cr content, e.g., austenitic steels, or Ni‐base alloys are used for components applied to more severe service conditions, e.g., more aggressive atmospheres and higher temperatures. Three categories of alloys were investigated in this study. These materials were oxidised in laboratory air at temperatures of 550°C in the case of low‐alloy steels, 750°C in the case of an austenitic steel (TP347) and up to 1000°C in the case of the Ni‐base superalloys Inconel 625 Si and Inconel 718. Emphasis was put on the role of grain size on the internal and external oxidation processes. For this purpose various grain sizes were established by means of recrystallization heat treatment. In the case of low‐Cr steels, thermogravimetric measurements revealed a substantially higher mass gain for steels with smaller grain sizes. This observation was attributed to the role of alloy grain boundaries as short‐circuit diffusion paths for inward oxygen transport. For the austenitic steel, the situation is the other way round. The scale formed on specimens with smaller grain size consists mainly of Cr₂O₃ with some FeCr₂O₄ at localized sites, while for specimens with larger grain size a non‐protective Fe oxide scale is formed. This finding supports the idea that substrate grain boundaries accelerate the chromium supply to the oxide/alloy phase interface. Finally, in the Ni‐base superalloys deep intergranular oxidation attack was observed, taking place preferentially along random high‐angle grain boundaries.     

The high temperature oxidation behaviour of austenitic stainless steels

High temperature annealing in a dynamic vacuum has been utilised to induce the growth of duplex oxide over the whole surface of stainless steel specimens. It is found that duplex oxide grows at a rate which does not obey a simple power law. The oxidation kinetics and oxide morphology have also been studied for a series of ternary austenitic alloys which cover a range of composition between 5 and 20% chromium. A model has been developed from the observations to describe the formation of duplex oxide and the subsequent formation of a “healing layer” which virtually causes the oxidation process to stop. This phase tends to form at grain boundaries and a relationship has been derived for the reaction kinetics which relates the reaction rate with grain size of the substrate.     

The effect of yttrium on scale formation and breakdown of Fe-Cr-Al in mixed gas

The effects of 1 wt. % yttrium addition to an iron-base model alloy, Fe-25Cr-6Al, on the scale formation and breakdown mechanisms in a mixed gas at temperatures 500–700°C were studied. In this environment, the equilibrium gas contained sulfur and oxygen at high and low vapor pressures, respectively. During the exposure, the formation of an alumina scale was favored kinetically on the surfaces of the alloys. The oxide scale formed on the base (Y-free) alloy had a fine-grained structure which exhibited excellent sulfidation/oxidation resistance. However, because of severe segregation along the grain-boundaries of the Y-containing alloy, which resulted in second-phase precipitation rich in Fe and Y, the morphology of the surface oxide on this alloy exhibited a distinction along the wide substrate grain boundaries. These Fe- and Y-rich regions served as short circuits for Fe diffusion from the underlying substrate to the scale/gas interface and, eventually, allowed iron sulfide to form on the oxide scale. With a pre-oxidation treatment, the transient stage from oxidation to sulfidation was prolonged; however, the sulfidation process was not eliminated. Based on thermodynamic calculations, the probable phases forming on the alloy surface in the oxidizing/sulfidizing environment were predicted, and a qualitative model for the corrosion mechanisms was proposed.     

3种典型轧辊材料氧化行为的原位观察

轧辊表面氧化膜的形成及剥落对轧辊的消耗及产品质量有显著影响。采用VL2000DX—SVF18SP型超高温激光共聚焦显微镜观察了高铬铸铁、高铬铸钢和高速钢在连续加热及等温过程中其表面氧化膜形成的特征，同时对比研究了这3种材料在循环加热、冷却后的氧化行为。结果表明，高铬铸铁和高铬铸钢开始形成氧化膜的温度较低，约为300 ℃，但氧化膜致密均匀，抑制了高温及等温过程氧化膜的生长；而高速钢氧化膜开始形成温度较高，氧化膜快速形成的温度约为480 ℃，但氧化膜均匀性差，具有较快的生长速率，高速钢的抗氧化性显著低于高铬铸铁和高铬铸钢。     

3种典型轧辊材料氧化行为的原位观察

轧辊表面氧化膜的形成及剥落对轧辊的消耗及产品质量有显著影响。采用VL2000DX-SVF18SP型超高温激光共聚焦显微镜观察了高铬铸铁、高铬铸钢和高速钢在连续加热及等温过程中其表面氧化膜形成的特征，同时对比研究了这3种材料在循环加热、冷却后的氧化行为。结果表明，高铬铸铁和高铬铸钢开始形成氧化膜的温度较低，约为300 ℃，但氧化膜致密均匀，抑制了高温及等温过程氧化膜的生长；而高速钢氧化膜开始形成温度较高，氧化膜快速形成的温度约为480 ℃，但氧化膜均匀性差，具有较快的生长速率，高速钢的抗氧化性显著低于高铬铸铁和高铬铸钢。     

Oxidation of Heat-resistant Alloys

The oxidation performance of three novel, heat-resistant alloys, namely KHR35C HiSi, KHR45A LC, and UCX, was studied at relatively low temperatures (i.e. 650 and 750 °C) for 1,000 h. The study was focused mainly on exploring oxide-layer growth and characterizing the oxide phases in order to prevent or minimizing metal dusting in carbonizing environments. The specimens were examined by visual and metallographic examination, SEM/EDX, XRD, and weight-change measurements. The results have been compared with a previous, short-term study (100 h) in order to understand the influence of exposure time on oxidation. It is concluded that exposing the alloys to air at 650 and 750 °C led to the formation of oxides of chromium, nickel, iron, silicon, and iron-containing spinels. Moreover, increasing the exposure time, temperature or both resulted in further oxide growth, leading to more continuous, adherent, and thicker oxides. The alloys, however, did not form a completely protective scale, especially at 650 °C, even after 1,000 h of exposure.     

A surface study of the oxidation of type 304L stainless steel at 600 K in air

The oxidation of type 304L stainless steel at 600 K in air was studied using a number of surface-analytical techniques, including Auger electron spectroscopy (AES), scanning electron microscopy with energy-dispersive analysis of X-rays (SEM-EDAX), secondary ion mass spectrometry (SIMS), and X-ray photoelectron spectroscopy (XPS). Spectral analysis showed that a duplex oxide was formed, the outer layer of which formed rapidly and was essentially iron (III) oxide. Beneath this was a mixed iron-chromium oxide. SIMS sputter-profile curves showed region of relatively low iron concentration in the oxide film at the metal-oxide interface. This resulted from the rapid diffusion of iron within the oxide film. The oxide grain boundaries were examined using SEMEDAX. Higher chromium and silicon levels were detected in these regions compared with the corresponding grain centers. AES indicated the presence of silicon as SiO₂.     

Oxidation of FeCrAl alloys at 500–900°C in dry O2

This paper reports on the oxidation of a commercial FeCrAl alloy, Kanthal AF, in the temperature range 500–900°C. The samples are exposed isothermally in dry oxygen for up to 72 h using a thermo‐balance. In addition, 168 h exposures are carried out in a tube furnace. The exposed samples are investigated by grazing angle X‐ray diffraction (XRD), scanning electron microscopy/energy dispersive X‐ray analysis (SEM/EDX), and auger electron spectroscopy (AES). The rate of oxidation increases with temperature, the kinetics being parabolic in the range 700–900°C. At all exposure temperatures, most of the sample surface is covered by a thin smooth base oxide. In addition, RE‐rich particles, with a typical size of 1–3 μm form. At 800 and 900°C patches of thick oxide appear, featuring needle‐formed crystallites situated on top of the base oxide. The thick oxide usually forms around Y‐rich oxide particles. The concentration of iron and chromium in the oxide decreases with increasing temperature. XRD proves the formation of α‐Al₂O₃ already at 700°C. The low temperature of formation of α‐Al₂O₃ is attributed to the presence of chromium in the initial oxide. It is proposed that corundum nucleation is facilitated on a surface consisting of the isostructural escolaite, (Cr₂O₃). After exposure at 900°C AES shows large amounts of Mg in the outer part of the oxide, MgAl₂O₄ being detected by XRD together with γ‐ and γ‐Al₂O₃.     

Sulfur segregation during the high-temperature oxidation of chromium

A TEM and STEM examination has been carried out of cross-sectioned specimens of convoluted chromia scale formed by oxidizing chromium at 950° C. Sulfur was detected at the oxide/metal interface and the oxide grain boundaries (apart from low-angle grain boundaries), but not within the oxide grains. These results are consistent with the sulfur effect theory.     

Chromium transport through Cr2O3 scales. II. Changes in scale morphology during high vacuum treatment of oxidized chromium specimens

Chromium specimens oxidized at 1200 and 1300° O to give Cr₂O₃ scales with varying thicknesses have been high vacuum annealed for extended periods at temperature. During the high vacuum anneal chromium is transported through the scale and evaporates from the scale surface. Initially the rate of chromium evaporation decreases with time as a result of recrystallization and densification of the scale. On extended high vacuum treatment the rate of chromium evaporation again increases and major changes in scale morphology takes place. The outer scale surfaces develop hollows in the oxide grains while the grains protrude from the scale at the inner surfaces. The morphological changes are interpreted in terms of differences in diffusion rates along grain boundaries and through the lattice and resultant variations in surface energy along the surfaces.     

Laser surface treatment and its influence on the development of healing Cr2O3 scales on nickel-chromium alloys

The influence of laser surface treatment on the isothermal oxidation of Ni-10%Cr and Ni-15%Cr at 1025°C in oxygen at 1 atm pressure has been studied. Particular emphasis has been placed on the progressive establishment of a Cr₂O₃ healing layer, which is facilitated by rapid-diffusion paths for chromium to the surface from the bulk alloy. For nonlaser treated alloys, such paths are alloy grain boundaries. A partial Cr₂O₃ layer forms initially in localized sites at, and immediately adjacent to, these boundaries and progresses into the alloy grains in a stepwise manner following lateral diffusion of chromium from the grain boundaries, thereby developing a contoured configuration. For Ni-15%Cr, there is sufficient chromium in the bulk alloy grains to sustain the eventual development of a self-healing layer parallel to the surface. For Ni-10%Cr, this is not the case and complete development of the healing layer results entirely from the stepwise progression from the grain boundaries. Establishment of the healing layer on laser-glazed surfaces is facilitated by additional rapid-diffusion paths, particularly retained alloy grain boundaries, retained alloy twins, a laser-induced microstructure and solidification artifacts (such as ripples). The relative importance of these features is discussed in relation to the oxidation behavior.     

Corrosion of 9Cr Steel in CO2 at Intermediate Temperature III: Modelling and Simulation of Void-induced Duplex Oxide Growth

9Cr–1Mo steel forms in CO₂ at 550?°C a duplex oxide layer containing an outer magnetite scale and an inner Fe–Cr rich spinel scale. The inner spinel oxide layer is formed according to a void-induced oxidation mechanism. The kinetics of the total oxide growth is simulated from the proposed oxidation model. It is found that the rate limiting step of the total oxide growth is iron diffusion through high diffusion paths such as oxide grain boundaries in the inner Fe–Cr rich spinel oxide layer. In the proposed oxidation model, a network of nanometric high diffusion paths through the oxide layer allows the very fast supply of CO₂ inside pores formed at the oxide/metal interface. Its existence is demonstrated to be physically realistic and allows explaining several observed physical features evolving in the oxide layer with time.