Electric Current Effects on the Corrosion Behaviour of High Chromium Ferritic Steels

The high-temperature corrosion behaviour of the Cr containing ferritic alloys Crofer 22 APU and Crofer 22 H were investigated for their potential application as interconnects in planar-type solid oxide electrolysis cells (SOECs) operating at 800 °C for syngas production in steam/CO₂ co-electrolysis mode. To simulate the operating conditions for this application, oxidation tests in relevant atmospheres with and without electric current were conducted. The corrosion behaviour was influenced by the electric current resulting in accelerated oxidation on the negative side and suppressed oxidation on the positive side. The scale structure was influenced by a combination of atmosphere and electric current effects. The modified oxidation of the interconnect steels due to the electric current effect could have detrimental impact for the O₂ side and beneficial effect for the CO₂/H₂O side in an SOEC stack operating in co-electrolysis mode.     

The Oxidation of Ferritic Stainless Steels in Simulated Solid-Oxide Fuel-Cell Atmospheres

The cyclic oxidation of a variety of chromia-forming ferritic stainless steels has been studied in the temperature range 700–900°C in atmospheres relevant to solid-oxide fuel-cell operation. The most detrimental environment at 800°C and 900°C was found to be air with 10% water vapor. This resulted in excessive oxide spallation or rapid scale growth. Impurities in the alloys, particularly Al and Si, were found to have a significant effect on the oxidation behavior. Oxide growth was slow at 700°C but the higher-Cr-content alloys were observed to form sigma-phase at this temperature. The sigma phase formation was accelerated by higher silicon contents, and remarkably, by the presence of water vapor in the exposure environment. Alloys containing Mn were observed to form an outer layer of MnCr₂O₄ over the chromia scale. The potential for this overlayer to suppress reactive evaporation of the chromia scales has been analyzed.     

High Temperature Oxidation Behaviour of High Al Content Ferritic and Austenitic Stainless Steels With and Without Rare-Earth Element Addition

The oxidation behaviour of austenitic and ferritic alloys containing 4% Al and rare-earth element addition of (La?+?Ce) has been investigated, and comparisons made to an austenitic alloy with no such addition. The alloys were all found to exhibit good oxidation resistance; although, such resistance was highest when the alloy contained rare-earth elements. The addition led to a reduction in the amount of scale spalling. The scales formed after 10 and 100?h at 1,000?°C were examined using transmission electron microscopy and found to have bi-layered microstructures. The dislocation density and an amount of distortion in the scale were found to differ, depending on the absence or presence of (La?+?Ce) in the metal. It was observed that the outer-to-inner layer thickness ratio changed with time and the rare-earth element addition promoted growth of the inner layer relative to the outer layer. Analysis of the scale compositions demonstrated an apparent synergistic relationship between the effects of the rare-earth element addition and the degree to which iron is incorporated within the scales. The results are discussed in relation to the relative oxidation performance of the austenitic and ferritic alloys.     

Rhenium Oxidation by Steam at High Temperatures

The kinetics of rhenium oxidation were studied under flowing steam+argon mixtures, at atmospheric total pressure and steam partial pressure in the range 24–74 kPa, and at temperatures from 1600°C up to 2200°C. No regime change was observed in the temperature dependence of the oxidation rate, which shows that the same chemical regime extends up to the highest temperature investigated. Moreover, at high temperature, the results showed a dependence of the oxidation rate on the gas velocity and the steam partial pressure, in good agreement with a gas-phase mass-transfer correlation for laminar flow, revealing that, for the conditions used, mass-transport processes in the gas phase also act as a limiting factor. It was assumed that the mass-transport limiting factor is the steam diffusion through a volatile oxides gaseous layer above the rhenium surface. A comparison of these results with rhenium oxidation rates reported for air leads us to propose the dissociative adsorption of the H₂O molecule as the limiting chemical stage of the oxidation process.     

Grain-Size Effects on the High-Temperature Oxidation Behaviour of Chromium Steels

Oxidation of two low-Cr (Cr content 1.5 wt% and 2.25 wt%) and three high-Cr (Cr content 9 wt%, 12 wt% and 18 wt%) boiler steels was investigated at temperatures between 550 °C and 830 °C in laboratory air. Thermogravimetry (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) were applied for evaluation of the oxidation kinetics, oxides phase identification and scale structure analysis. Particular attention was paid to the phenomenon of inward oxidation and its relationship with the Cr content of the steels under investigation. The results showed that the inward oxidation of the Cr steels is governed by grain boundary diffusion. Two different Cr-depending tendencies concerning the effect of alloy grain size on the inward oxidation were observed. For low-Cr steels (less than 2.25 wt% Cr), an increase in the grain size improved the oxidation resistance, while steels with high Cr content (18 wt% Cr) can form a thin and protective chromia scale on the surface more easily at finer grain size. In the latter case an increase in grain size deteriorates the oxidation resistance by the formation of a thicker scale composed of both an outer and an inner Fe-oxide-based layer.     

Effect of Specimen Thickness on the Oxidation Rate of High Chromium Ferritic Steels: The Significance of Intrinsic Alloy Creep Strength

Previous studies revealed that initial sample thickness affects the growth rate of oxide scales formed during 800 or 900 °C air exposure. The effect is partially related to differences in depletion of minor alloying additions such as Mn, Ti, La in thick and thin specimens. However, it has previously been proposed that the specimen thickness dependence is partially governed by differences in creep strength of thick and thin substrates. To investigate this hypothesis, discontinuous air oxidation experiments were carried out with the Laves phase strengthened ferritic steel Crofer 22 H at 800 °C. Comparing the data for solution annealed and pre-aged (500 h, 900 °C) materials it could be shown that intrinsic creep strength of the alloy substantially affects oxidation rates. The observations can qualitatively be explained by assuming the relaxation of oxide growth stresses by plastic deformation of the metallic substrate to be an important parameter affecting the kinetics of oxide scale growth.     

Influence of Nickel on the Oxidation Resistance at High Temperatures of Thin Chromium Coatings

Oxidation of Metals - The oxidation behavior of four valve steels (X33CrNiMn23-8, X50CrMnNiNbN21-9, X53CrMnNiN20-8 and X55CrMnNiN20-8) covered with thin sputter-deposited coatings containing...     

Oxidation Kinetics of AISI 441 Ferritic Stainless Steel at High Temperatures in CO2 Atmosphere

Ferritic stainless steels used as interconnectors in SOFC stacks are subjected to air and fuel atmospheres at 800 °C. The use of hydrogen as fuel gas may be substituted by fermentative biogas consisting of mainly CO₂ and CH₄. In this gas mixture, carbon dioxide leads to steel oxidation whereas methane induces carburization. The objective of this study was to investigate the oxidation kinetics of the AISI 441 ferritic stainless steel under pure CO₂ in order to understand oxidation mechanisms. The results show that the kinetic behaviour is linear at low temperatures (800–900 °C) and initially linear then parabolic at higher temperatures (925–1,000 °C). Oxide scale consisted of major Cr₂O₃-rich oxide, topped with MnCr₂O₄ and a dispersion of TiO₂. The chromium-rich oxide was analysed by using the photoelectrochemical method. It exhibits N-type semi-conductor. Oxidation kinetics is modelled by the mixed surface and oxide-diffusion limited steps.     

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。     

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.     

Oxidation of Rimming Steels in Carbon Dioxide Atmospheres*

Abstract

A study has been made of the kinetics and mechanisms of the oxidation resistance of rimming steels to carbon dioxide atmospheres over long periods of testing. The effects of moisture and carbon monoxide additions to the carbon dioxide, gas pressures up to 600 psig and temperatures from 350 to 550° have been investigated.

It is shown that protective oxide films are usually formed at a gas pressure of one atmosphere, but at high pressures and particularly with moisture and carbon monoxide in the gas, the oxide film may locally break down, giving rise to oxide excrescences which can grow in size and number to cover most or all of the surface of the specimen. The formation of excrescences causes the rate law to change from cubic or parabolic to linear over a transitional period. The reaction rate constants are dependent essentially on the temperature whilst moisture, carbon monoxide and gas pressure are mainly effective in promoting the initiation and development of excrescences.

Possible causes for the formation of excrescences, as well as the mechanism of the linear rate law during the post-breakaway period, are discussed.     

Oxidation Behaviors of Different Grades of Ferritic Heat Resistant Steels in High-Temperature Steam and Flue Gas Environments

For steam tubes used in thermal power plant, the inner and outer walls were operated in high-temperature steam and flue gas environments respectively. In this study, structure, microstructure and chemical composition of oxide films on inner and outer walls of ex-service low Cr ferritic steel G102 tube and ex-service high Cr ferritic steel T91 tube were analyzed. The oxide film was composed of outer oxide layer, inner oxide layer and internal oxidation zone. The outer oxide layer on the original surface of tube had a porous structure containing Fe oxides formed by diffusion and oxidation of Fe. More specially, the outer oxide layer formed in flue gas environment would mix with coal combustion products during the growth process. The inner oxide layer below the original surface of tube was made of Fe-Cr spinel. The internal oxidation zone was believed to be the precursor stage of inner oxide layer. The formation of internal oxidation zone was due to O diffusing along grain boundaries to form oxide. There were Fe-Cr-Si oxides discontinuously distributed along grain boundaries in the internal oxidation zone of G102, while there were Fe-Cr oxides continuously distributed along grain boundaries in that of T91.     

不同表面粗糙度镍铬铝合金的高温氧化行为

采用热重法并结合X射线衍射、扫描电子显微镜、能谱仪等分析手段,研究在1000 ℃条件下Ni-10Cr-5Al (质量分数,%) 合金样品表面粗糙度对其氧化行为的影响。结果表明：经1000 ℃氧化215 h后,不同表面粗糙度的合金其氧化动力学均服从抛物线规律,并存在两个抛物线常数,氧化膜主要由Al₂O₃,NiCr₂O₄和NiAl₂O₄组成。随着表面粗糙度的增加,氧化增重越明显,同时氧化膜脱落越严重、氧化膜金属界面越起伏。其中,表面粗糙度对合金氧化的影响主要是在氧化前期阶段促进生成了尖晶石NiCr₂O₄和NiAl₂O₄氧化物。     

Resistance to Oxidation at Elevated Temperatures of a Number of Alloy Steels

Abstract

A wide range of steels, extending from a plain carbon steel to high chromium-nickel, austenitic types and some nickel-based alloys, have been subjected to a cyclic oxidation test in natural gas combustion products at various temperatures. Resistance to oxidation can be expressed in terms of a breakdown temperature which provides a convenient parameter by means of which the behaviour of steels and alloys may be compared. On this basis, the beneficial effects of additions of chromium of up to 30% are confirmed, as are additions of silicon and/or aluminium to chromium steels. Cobalt, copper, molybdenum, vanadium, tungsten, niobium, titanium and nitrogen have comparatively little effect. Manganese appears to be detrimental when added to chromium steels and carbon can be in some circumstances. Nickel can enhance oxidation resistance in some circumstances but is detrimental in others. The presence of sulphur in free-machining, stainless steels appears to counteract the effect of a higher-thannormal manganese content.     

Oxidation of Inconel 718 in Air at High Temperatures

Experiments were conducted with Inconel 718 at high temperatures to evaluate the rate of oxidation of the material over as wide a temperature range as possible, as well as to determine the high-temperature failure limit of the material. Samples of Inconel 718 were inserted into preheated furnaces at temperatures ranging from 973 to 1620 K and oxidized in air for varying periods of time. After being oxidized in air at a constant temperature for the prescribed time and then being allowed to cool, the samples were reweighed to determine their mass gain due to the uptake of oxygen. From these mass-gain measurements, it was possible to identify three regimes of oxidation for Inconel 718: a low-temperature regime in which the samples behaved as if passivated after an initial period of transient oxidation, an intermediate-temperature regime in which the rate of oxidation was limited by diffusion and exhibited a constant parabolic rate dependence, and a high-temperature regime in which material deformation and damage accompanied an accelerated oxidation rate above the parabolic regime.     

Stress-Strain Behaviors Simulation of High Chromium Steel at Elevated Temperatures

It is important but difficult to study the constitutive equations describing the mechanical properties of steels. In this work, a thermal/mechanical simulator was used in conjunction with the Anand model to obtain the stress-strain curves for a high chromium steel associated with different temperature/strain rate pairs. The finite element software, ANSYS, was used to simulate the stress-strain behavior of a high chromium steel during casting at the strain rates of 1, 0.1, and 0.01 1/s, and to validate the Anand model. The results show that the high-temperature deformation is mainly plastic and the von Mises stresses are small, the stresses introduced at elevated temperatures have little effect on the residual stress fields, and the simulation of the mechanical behavior of steels using an elastic-plastic model at low temperatures during cooling is acceptable.     

Comparative Study of Micro- and Nano-structured Coatings for High-Temperature Oxidation in Steam Atmospheres

For many high-temperature applications, coatings are applied in order to protect structural materials against a wide range of different environments: oxidation, metal dusting, sulphidation, molten salts, steam, etc. The resistance achieved by the use of different kind of coatings, such as functionally graded material coatings, has been optimized with the latest designs. In the case of supercritical steam turbines, many attempts have been made in terms of micro-structural coatings design, mainly based on aluminides, and other diffusion coating systems in order to consider alternatives, nano-structured coatings based on Cr and Al compositions and deposited by a physical vapor deposition technique, were assessed to high-temperature oxidation resistance in steam environments. The oxidation kinetics where analyzed for up to 2,000 h at 650 °C by means of gravimetric measurements. The evaporation behavior was also analyzed by thermogravimetric-mass spectrometry. Excellent results where observed for some of the nano-structured coatings tested. Those results where compared to results obtained for micro-structured coatings. Based on that comparison, it was deduced that the nano-structured coatings have a potential application as protective systems in high-temperature steam environments.     

纳米晶Cu-Si合金的抗氧化性能

采用电弧熔炼和机械合金化方法制备了两种晶粒尺寸差别较大的Cu-Si合金,并采用热重分析方法对其在700℃和800℃、1×105Pa流动O2中氧化24 h的抗高温氧化性能进行了研究。结果表明,不是所有合金氧化动力学都遵循抛物线规律,甚至有些合金的动力学曲线十分不规则。总的来说,机械合金化法制备的合金单位面积氧化增重小于相应的熔炼合金。合金氧化后都未形成连续的SiO2保护膜,而形成了相似的复杂的氧化膜,其中都包含由Cu2O和SiO2组成的富含SiO2的混合氧化物层,它限制了铜和氧的进一步扩散。晶粒尺寸的减小促进了活泼组元Si的扩散,加速了SiO2和富含SiO2的Cu2O+SiO2混合氧化物层的形成,提高了Cu-Si合金的抗高温氧化性能。