The Influence of the Rare Earth Element Ce on the High-Temperature Oxidation Kinetics of Low-Cr Steels

The oxidation behavior of steels containing low-Cr concentrations (0.5-2.25 wt.%) has been studied in laboratory air in the temperature range of 400-550 °C. The oxidation rate of the steels was lower than that of pure iron, but higher than that of pure iron when a small amount of rare earth element cerium (0.03 wt.%) is added to the 2.25Cr1Mo steel. The mass change follows a nearly parabolic law for the case of pure iron and the steel without Ce addition, while linear behavior describes the oxygen uptake for the case of the 2.25Cr1Mo+0.03Ce steel. SEM cross-section observations and thermodynamic calculations confirm that there is no wustite (FeO) formation during oxidation of pure iron and low-Cr steels at 550 °C, whereas FeO might be formed in the oxide scale of 2.25Cr1Mo+0.03Ce at the same oxidation conditions (temperature, atmosphere, and exposure time). By investigating the temperature for FeO stability, this study reveals that the temperature for FeO formation on pure iron is 568 °C, for the 2.25Cr1Mo steel 589 °C, and 471 °C for the 2.25Cr1Mo+0.03Ce. This low value for the FeO stability temperature found for the steel 2.25Cr1Mo+0.03Ce steel explains why this steel oxidizes very fast at 550 °C.     

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.     

Effects of Temperature and Straining on the Oxidation Behavior of Electrical Steels

The effect of Si content (in the range of 0.01–1.91 wt%) on scale formation of electrical steels in dry air at temperatures ranging from 850 to 1200 °C was investigated. The effect of applied tensile strain on oxidation behavior was also explored. A thermo-mechanical simulator (Gleeble machine) was employed to conduct the oxidation tests at different load conditions. The experimental results showed that at 1000 °C the oxidation rate decreased with increasing Si content in the steel. The formation of an inner scale, mainly consisting of amorphous silica, was responsible for the improved oxidation resistance. However, a substantial increase in oxidation rate due to the formation of molten eutectic fayalite (Fe₂SiO₄) was observed when the temperature was raised to 1200 °C. Under straining conditions at a very short oxidation time, the inner scale structure was slightly modified though the scale thickness remained almost unchanged for the steel containing 1.91 wt% Si.     

Effect of Shot-peening on the Oxidation Behaviour of Boiler Steels

The presence of short diffusion paths is very important for rapid diffusion processes which are involved in forming protective oxide layers against high temperature corrosion, e.g. on boiler steels. Rapid diffusion paths can be produced by applying cold work such as shot-peening to the surface of the boiler steels prior to oxidation. The effect of shot-peening on oxidation behaviour was tested experimentally on 12 wt% Cr martensitic steel and 18 wt% Cr austenitic steel. Isothermal oxidation tests were performed at 700 and 750 °C. The surface treatment proved to be very effective in improving oxidation protection at 700 °C. Shot-peening the surface prior to the oxidation has an influential effect in changing the diffusion mechanisms of the elements involved in oxidation and changes the oxidation kinetics substantially at the applied conditions in this study.     

Roles of Manganese in the High-temperature Oxidation Resistance of Alumina-forming Austenitic Steels at above 800?°C

A new family of alumina-forming austenitic (AFA) stainless steels is under development for uses in aggressive oxidizing conditions. This paper investigates the effect of manganese additions on the oxidation kinetics and alumina scale formation in two series of AFA steels, i.e., Fe–20Ni–14Cr–2.5Al and Fe–18Cr–25Ni–3Al base. At 800?°C in dry air, the oxidation resistance was moderately degraded with additions of larger than 1 wt% Mn in the AFA steels based on Fe–14Cr–20Ni–2.5Al. At 900?°C in air with 10?% water vapor, however, additions of Mn in these AFA steels based on Fe–18Cr–25Ni–3Al would significantly destabilize the alumina scale formation and degrade the oxidation resistance. Our analysis revealed that additions of Mn stimulated formation of the coarse spinel CrMn_1.5O₄ and Cr₂O₃ oxide and destroyed the continuity of the protective alumina scales, thus worsening the oxidation performance. In addition, it was found that there exists an upper limit for the Mn additions which is decreased with the increase of the service temperatures and presence of aggressive oxidizing agents.     

Effect of Cobalt Content on the Oxidation and Corrosion Behavior of Ni–Fe-Based Superalloy for Ultra-Supercritical Boiler Applications

The oxidation and corrosion behavior of three model alloys with different cobalt contents (6–20 wt%) were investigated in static air and a simulated coal ash/gas environment at 750 °C. The model alloys follow a parabolic law approximately during the oxidation in static air. High cobalt level improves the oxidation resistance, however, without noticeable improvement in coal ash/gas corrosion resistance. The sample with the highest cobalt content grows the thinnest oxide layer and the fewest internal oxidation products in the oxidation test. Cobalt in the model alloys promotes the establishment of a protective chromium oxide scale during the oxidation test, but did not show much difference in restraining the inward diffusion of sulfur by increasing its content. The oxidation and corrosion products formed on the sample surface consist mainly of a protective chromium oxide film. Internal aluminum oxide particles have been found especially along the grain boundaries of the base alloy.     

Effect of Cr Contents and Heat Treating on Reverted Austenite in Maraging Steel Weldments

By conducting flux cored arc welding (FCAW) on maraging steels with Cr contents of 1.4 and 5.2 wt%, this study observed the effects of Cr content and heat treating on reverted austenite formation in welded maraging steel. Aging treatment was carried out at the temperatures of 450, 480 and 530 °C for 3 h in each condition. As the aging temperature increased, reverted austenite was formed along the interdendritic and intercellular grain boundaries, and the proportion of reverted austenite increased with increasing Cr addition. The aging process led to the segregation of Ti and Mo along the interdendritic and intercellular grain boundaries. Some of the welded specimens were subjected to solution heat treatment at 820 and 1250 °C for 1 h after welding, resulting in a decrease in reverted austenite fraction.     

Influence of water vapour on high temperature oxidation of steels used in petroleum refinery heaters

The oxidation behaviours of three different steels used in the construction of petroleum refinery heaters were investigated by thermogravimetric analysis (TGA) technique. C‐5, P‐11 and P‐22 steel samples were tested in two different environments: air and CO₂ + 2H₂O + 7.52N₂, a gas composition which simulates the combustion products of natural gas, at 450 and 500 °C. P‐22 steel had the best oxidation resistance at both temperatures in air. In CO₂ + 2H₂O + 7.52N₂ environment, the oxidations of all the steels were accelerated and C‐5 exhibited better oxidation resistance than P‐22 and P‐11. Analyses of oxidation products by optical microscopy, SEM‐EDX and XRD were carried out to correlate TGA results to oxide composition and morphology. The lower oxidation rate of P‐22 in air was explained with reference to the formation of a protective Cr‐containing oxide layer between the steel and the iron oxide scale. The higher oxidation rates of chromium containing steels in CO₂ + 2H₂O + 7.52N₂ environment were attributed to the depletion of protective Cr‐containing oxide scale, which was deduced from the lower Cr content of this layer than that formed in air oxidation, as a result of probably faster oxidation of Cr even inside the steel. Therefore, the oxidation mechanisms of Fe? Cr alloys with intermediate Cr contents at higher temperatures could also be valid for steels with low chromium contents such as P‐22 (2.25%) even at 450 and 500 °C.     

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.     

Influence of Aluminum and Rhenium on the Isothermal Oxidation Behavior of CoNiCrAlY Alloys

The oxidation behavior of a Co32Ni21Cr8Al0.6Y (wt%) alloy with and without the addition of 3.5 wt% rhenium, 2 wt% aluminum or a combination of the two was investigated at 1000 °C. Results showed that increasing the Al content from 8 to 10 wt% led to an increase of the alloy ??-phase, but did not affect the oxidation behavior. Re addition induced (Cr,Re,Y)-rich phase to precipitate in the alloy, accelerated the ??- to ??-alumina transformation, reduced the oxidation rate and enhanced the rate of alloy Al diffusion. Adding both Al and Re further improved the oxidation behavior by promoting the development of the external alumina scale and suppressing the formation of Ni, Co containing spinel. This alloy also showed the largest reduction of oxidation rate and emerged to be the most beneficial. A continuous Cr?CRe rich layer was observed at the oxide/alloy interface of the Re, Al containing alloy after longer oxidation times, but this layer is not expected to affect the continued growth of the alumina scale.     

In Situ Oxide Growth Characterization of Mn-Containing Ni–25Cr (wt%) Model Alloys at 1050 °C

The oxidation behaviour of four model alloys with the composition Ni–25Cr–xMn (with x = 0, 0.5, 1 and 1.5 wt%) was investigated at 1050 °C in air by thermogravimetry and by in situ observations in an environmental scanning electron microscope (ESEM). The addition of manganese modifies the oxidation rate of Ni–25Cr alloys by (1) increasing the parabolic constant k _p compared to that for Ni–25Cr and (2) lowering the short-time oxidation rate. Regardless of the Mn concentration, in situ ESEM observations indicated the formation of spinel crystallites from the very beginning of the oxidation process. The size of the spinel crystallites was directly linked to the initial Mn concentration. The obtained results suggested that the formation of the spinel layer at the top of the chromia oxide scale rather than at the metal–oxide interface as thermodynamically expected must be attributed to the higher diffusion rate of Mn than Cr both in the lattice and at the grain boundary.     

晶粒尺寸对耐热钢在高温水蒸汽中的氧化行为的影响

从氧化动力学、氧化膜相组成及微观结构方面,研究了晶粒尺寸对18Cr-8Ni耐热钢在700 ℃下的高温水蒸汽中氧化行为的影响。结果表明：晶粒细化提高了耐热钢的抗水蒸汽氧化性能,降低了其氧化增重,推迟了失稳氧化的发生;晶粒细化改变了耐热钢氧化膜的微观结构,减小了“弹坑”区的尺寸且促进了“弹坑”区与合金界面上富Cr氧化物层的形成;晶粒细化对耐热钢抗水蒸汽氧化性能的改善主要归因于其对氧化物的形核和Cr向氧化膜/合金界面扩散的促进作用。     

Increasing the Upper Temperature Oxidation Limit of Alumina Forming Austenitic Stainless Steels in Air with Water Vapor

A family of alumina-forming austenitic (AFA) stainless steels is under development for use in aggressive oxidizing conditions from ~600?C900 °C. These alloys exhibit promising mechanical properties but oxidation resistance in air with water vapor environments is currently limited to ~800 °C due to a transition from external protective alumina scale formation to internal oxidation of aluminum with increasing temperature. The oxidation behavior of a series of AFA alloys was systematically studied as a function of Cr, Si, Al, C, and B additions in an effort to provide a basis to increase the upper-temperature oxidation limit. Oxidation exposures were conducted in air with 10% water vapor environments from 800?C1000 °C, with post oxidation characterization of the 900 °C exposed samples by electron probe microanalysis (EPMA), scanning and transmission electron microscopy, and photo-stimulated luminescence spectroscopy (PSLS). Increased levels of Al, C, and B additions were found to increase the upper-temperature oxidation limit in air with water vapor to between 950 and 1000 °C. These findings are discussed in terms of alloy microstructure and possible gettering of hydrogen from water vapor at second phase carbide and boride precipitates.     

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.     

Oxidation Characteristics of Fe–18Cr–18Mn-Stainless Steel Alloys

Air oxidation studies of Fe–18Cr–18Mn stainless steels were conducted at 525, 625, and 725 °C. Alloys were evaluated with respect to changes in oxidation properties as a result of interstitial additions of nitrogen and carbon and of minor solute additions of silicon, molybdenum, and nickel. Interstitial concentrations possibly had a small, positive effect on oxidation resistance. Minor solute additions significantly improved oxidation resistance but could also reduce interstitial solubility resulting in formation of chromium carbides. Loss of solute chromium resulted in a slight reduction in oxidation protection. Oxidation lasting over 500 h produced a manganese rich, duplex oxide structure: an outer sesquioxide and an inner spinel oxide.     

Grain-Size Effects on the High-Temperature Oxidation of Modified 304 Austenitic Stainless Steel

The high-temperature oxidation behavior of modified 304 austenitic stainless steels in a water vapor atmosphere was investigated. Samples were prepared by various thermo mechanical treatments to result in different grain sizes in the range 8–30 μm. Similar Σ3 grain boundary fraction was achieved to eliminate any grain-boundary characteristics effect. Samples were oxidized in an air furnace at 700 °C with 20 % water vapor atmosphere. On the fine-grained sample, a uniform Cr₂O₃ layer was formed, which increased the overall oxidation resistance. Whereas on the coarse-grained sample, an additional Fe₂O₃ layer formed on the Cr-rich oxide layer, which resulted in a relatively high oxidation rate. In the fine-grained sample, grain boundaries act as rapid diffusion paths for Cr and provided enough Cr to form Cr₂O₃ oxide on the entire sample surface.     

Selective Oxidation of Chromium by O2 Impurities in CO2 During Initial Stages of Oxidation

This study shows that the corrosion behaviour of 12 wt% Cr steel in CO₂ at 550 °C is determined in the first stage of oxidation by reaction with O₂ impurities. Depending on the amount of theses impurities and the thermal ramp rate, selective oxidation of chromium could lead to the formation of a protective chromium-rich oxide. An oxidation model describing qualitatively the nature of the oxide layer formed in the initial period of oxidation is presented. From these observations, surface engineering processes for protecting 9–12 wt% chromium steels from fast corrosion rate have emerged.     

Influence of Minor Alloying Elements on the High Temperature Oxidation Behaviour of a 20 % Cr-25 % Ni-Nb steel

The influence of minor alloying additions of yttrium, silicon and manganese on the oxidation behaviour of a 20% Cr -25% Ni-Nb steel is considered for an environment of carbon dioxide at 800–1100°C. Emphasis is given to the fact that accurate assessments of the effects, based upon comparisons of the behaviour of different steels, frequently require variables such as metallurgical condition and surface finish to be controlled as closely as composition. In particular large grain size is associated with poor oxidation resistance. Yttrium at the level of 0.1–1.3% increases the adherence of the oxide scale over the whole temperature range considered, but only enhances oxidation resistance at 1000–1100°C. It also results in intergranular oxidation at the higher temperatures. Manganese at a concentration of 0.5–1.0% might exert an adverse influence during the early stages of oxidation but has no effect over the long term (i.e. 1000–6000 h). Silicon is considered beneficial at temperatures up to at least 850°C, with there being an optimum concentration in the region of 0.6–0.7%. By a process of deduction it is concluded that the oxidation resistance of the basis steel and its derivatives results primarily from the protection afforded by a thin layer of oxide at the oxide/metal interface. The outer scale affords little or no protection.     

Dependence on the Chromium Content of the High-Temperature Oxidation Behavior of Ta-Rich Nickel-Based Cast Alloys

The high-temperature stability of primary tantalum carbides is a problem of importance for chromium-rich cast alloys, based on cobalt or nickel. The focus of this study was nickel-based alloys, as these alloys are particularly sensitive to a lack of TaC in the as-cast state and by dissolution due to high-temperature exposure. In this work, a possible way for promoting the formation of many TaC precipitates by changing from the usual 30 wt% chromium content was investigated. Five alloys with Cr content varying from 10 to 50 wt% were prepared and then subjected to microstructure characterization and to oxidation tests. In contrast with what was expected, decreasing the Cr content in comparison with the Ni–30Cr–0.4C–6Ta reference alloy did not succeed in obtaining more TaC precipitates, but instead had the opposite effect. Concerning the high-temperature oxidation behavior at 1127 and 1237 °C, loss of resistance was observed only for a Cr content at the lower level of 10 wt%. It was noticed that a subscale CrTaO₄ developed during oxidation and seemed to promote oxide spallation during cooling.     

Preparation of Self-Healing α-Al2O3 Films by Low Temperature Thermal Oxidation

This paper reports a new approach to lowering the temperature necessary for the preparation of α-Al₂O₃. Oxidation of Al–Cr alloys, with Cr contents of 18, 23 and 27 %, was performed at temperatures ranging from 620 to 720 °C in air for 100 h. The resulting oxide films were analyzed by SEM, EDS, XRD and XPS. The results showed that α-Al₂O₃ films were obtained following oxidation of the 18 and 23 wt% Cr alloy samples at 720 °C and that rough surfaces were conducive to the formation of α-Al₂O₃ such that peened surface samples showed significant α-Al₂O₃ growth while polished samples showed no oxide by XRD. A 23 wt% Cr sample with a roughened surface exhibited the formation of α-Al₂O₃ at a temperature of 670 °C. Conversely, only a very thin oxide film was observed on a 27 wt% Cr sample after oxidation at 720 °C.