Materials Science Forum Vols. 595-598

Abstract: The corrosion resistance of MOCVD Al2O3 coating system was investigated to protect a TA6V Alloy under hot salt corrosion conditions: This coating was corroded with a salt deposit without mechanical loading at 480°C during 100 h. Corrosion products formed in salted areas were studied by Energy Dispersive Spectroscopy (EDS). Although all coated specimens were damaged with corrosion products presence in salted area, Al2O3 coatings showed the lowest salt damage on titanium substrate after a metallographic cross section observation compared to uncoated ones. As well as these interesting experimental results, coated specimens exhibit a good adherence on titanium substrate

Abstract: A family of creep-resistant, Al2O3-forming austenitic (AFA) stainless steels was recently developed. The alloys exhibit excellent oxidation resistance up to ∼800°C, but are susceptible to internal attack of Al at higher temperatures. In the present work, higher levels of Ni, Cr, Al, and Nb additions were found to correlate with improved oxidation behavior at 900°C in air. The alloys generally appeared to be initially capable of external Al2O3 scale formation, with a subsequent transition to internal attack of Al (internal oxidation and internal nitridation) that is dependent on alloy composition. Compositional profiles at the alloy/scale interface suggest that the transition to internal oxidation is preceded by subsurface depletion of Al in the lower-Al compositions. In higher Al-containing compositions, NiAl second-phase precipitates act as an Al reservoir, and Al depletion may not be a key factor. Alloy design directions to increase the upper-temperature limit of protective Al2O3 scale formation in these alloys are discussed.

Abstract: The aim of the present work is to investigate the effect of Lanthanum surface addition on the oxidation behaviour of the AISI 304 stainless steel, in air, at 1000°C. The in situ X-ray diffraction (XRD) analyses on the blank steel reveal that after the first 10h oxidation, a change in the structural composition of the oxide scale occurs. During the first ten hours oxidation an initial growth of chromia and Mn1,5Cr1,5O4 is observed. After 10 h oxidation, chromia is not detected anymore and iron-containing oxides such as hematite (Fe2O3) and iron chromite (FeCr2O4) are observed in the outer part of the scale. With blank AISI 304 specimens, the iron-containing oxides are generally not very protective and show severe spallation during cooling to room temperature due to thermal stresses. They do not allow a good adherence of the corrosion layer under thermal cycling. On the Lanthanum coated AISI 304 Stainless Steel the oxidation rate is 10 times lower. In situ XRD analyses show the absence of iron containing oxides. It reveals the formation of a fine convoluted Cr2O3 layer associated with the formation of the mixed oxides Mn1,5Cr1,5O4 and LaCrO3. LaCrO3 is found to be located at the oxide/steel interface. Our results show that, even though the scale formed under isothermal conditions is not composed of iron containing oxides, Lanthanum sol-gel coating does not prevent spallation during thermal cycling at 1000°C.

Abstract: The SiMo cast iron is a spheroidal graphite cast iron which major alloying elements are silicon and molybdenum. This alloy is currently used in diesel engines as part of exhaust gas system like exhaust manifold or turbocharger housing components. It is then designed to work at high temperature under corrosive atmosphere. However, this alloy presents sometimes unusual high corrosion rates, and it is thus advisable to define the critical conditions leading to this type of problem. In the present study, the SiMo cast iron is tested in complex atmospheres containing N2, O2, SO2, CO2 and H2O in a temperature range lying between 300°C and 600°C. SEM observations and EDX and XRD analyses allow to qualify the nature of the corrosion products. Some thermodynamic calculations complete the experimental results. Three experimental parameters are especially studied in this work: the temperature of the isothermal corrosion tests, the presence of water vapour and the SO2 content in the gas mixture. The main results show that the corrosion products are metallic sulphides, sulfates and oxides. When sulphides and / or sulfates are present, the corrosion scale does not ensure a sufficient protection of the substrate and it is necessary to find conditions where only oxides are present. Such conditions are obtained for the highest temperature used in this study (600°C), or with highly oxidant atmospheres.

Abstract: Due to the reduction of operating temperature from 1000°C to 800°C, chromia forming alloys are the best candidates for interconnects in Solid Oxide Fuel Cells (SOFCs). These interconnects have to be operational in service conditions, at 800°C in air (cathode side) and in humidified hydrogen (anode side). The performance of the interconnect stainless steels is limited by the oxide scale formation (chromia), the low electronic conductivity of this scale and the possible volatility of chromium oxides. In the field of high temperature oxidation of metals, it is well known that the addition of a nanometric layer made of reactive element oxide such as, La2O3, Nd2O3 and Y2O3 by MOCVD (Metal Organic Chemical Vapor Deposition) on alloy surface resulted in an important improvement in the high temperature oxidation resistance. These coatings are made on metallic alloys in order to form perovskite oxides such as LaCrO3, NdCrO3 and YCrO3, which are expected to present a good conductivity at 800°C in air. However, this temperature looks somewhat too low to guarantee the formation of perovskite oxides and thus to improve the oxidation resistance and electrical conductivity. In fact, XRD analyses revealed that for Y2O3 coatings, perovskite oxides were not formed after oxidation in air at 800°C for 100 hours. The goal of this study is to perform pre-oxidation at 1000°C for 2 hours in air under atmospheric pressure on coated Crofer22APU to pre-form perovskite phases. The so-prepared perovskite were tested in a thermobalance in air. Experiments performed in H2/10%H2O under 150 mbar at 800°C validated the coating influence from the anode side as well as the cathode side. The corrosion products were analyzed after 100 hours ageing at 800°C by SEM, EDX, and XRD. ASR (Area Specific Resistance) was measured for the same times and temperature in air.

Abstract: The high temperature corrosion behavior of Fe20Cr6Al-Y,Hf steel was studied in the range of temperature 800-1000oC in H2/H2S atmospheres at pS2=10-2 ,10-3 and 10-4 Pa sulphur vapor pressures. Kinetics depend on the temperature and sulphur vapor pressure. After 24 hours the whole specimen was practically consumed because the samples were 0,06 cm thick. Morphology of the scales have been performed by SEM techniques. Phase and chemical composition have been studied by EDX and XRD techniques. It was found that scale formed on Fe20Cr6Al-Y,Hf alloy was built with porosity sulphides layer. EDX analysis of the scale surface show that the any aluminum, hafnium and yttrium sulfides were found in the formed scale layer, however small amounts of Al2S3 was detected in scale/steel interface. Also internal sulphidation was observed. A phase analysis of the formed scale revealed that it is composed mainly of an FeS, Fe7S8 phases and CrS, Cr5S6. Result were compared with data obtained on the pure Fe and Cr samples.

Abstract: Spherical Al particles sized in the range of 2 to 5 μm were deposited with an organic binder by brushing on the austenitic steel X6 CrNi 18-10 (Alloy 304H). The coated samples were annealed in air at 400°C for 1 h in order to expel the binder. For studying the oxidation behaviour in air, isothermal experiments were performed at 700°C and 900°C with oxidation times of 5 h, 100 h and 1000 h. The oxide formation was studied in situ by high temperature X-ray diffraction (HTXRD) up to 100 h. Field emission scanning electron microscopy (FE-SEM) was applied to investigate the surface and the cross-section of the particle coating. During oxidation, the stable α-Al2O3 was identified in situ by HT-XRD on all studied samples at both temperatures. No meta-stable alumina phases were found. In the initial state, 2 h at 900°C, the Al particles are completely oxidised to hollow alumina spheres, controlled predominantly by the reaction due to the small particle size and relatively high surface portion. Simultaneously, the Alrich diffusion layer is formed in the substrate. On further exposure, a thin protective alumina scale continues growing on the top of the diffusion layer. After exposure to both 700°C and 900°C, a coating structure was encountered, which consists of a quasi-foam top coat from conjoint hollow spherical alumina particles and an Al-rich diffusion layer below. The quasi-foam top coat has the potential to effectuate as thermal barrier by gas phase insulation, while the diffusion layer below serves as protective coating against oxidation. The approach by particle size processing opens a potential for obtaining a complete thermal barrier coating system in one manufacturing step. The coating properties can be adjusted by parameters like selection of source metal/alloy, particle size, substrate, binder and heat treatment.

Abstract: In recent years solid-oxide fuel cell (SOFC) interconnect components have proven to be a key-component accountable for the functionality of high temperature fuel cells. Amongst adequate thermal expansion and high temperature strength, highest oxidation resistance in anode and cathode gases under thermal cycling conditions is required in order to reach long term durability, particularly when using thin film light-weight components with particular focus on automotive applications. In order to match the challenging parameter profile Plansee developed the mechanically alloyed ITM, a ferritic P/M Fe26Cr alloy strengthened with additions of Y2O3 dispersoids, since it has been observed that apart from their HT strengthening effect, which is of specific interest for thin sheets components, finest ODS particles reduce the growth and enhance the adhesion of the forming oxide layers. The latter effect is of particular interest in applications where alloys are exposed to HT cyclic conditions. In this work the nucleation phase of the oxide scale formation on P/M ODS Fe26Cr ITM is compared to that on a reference ingot steel Fe22Cr in typical anode gases containing significant amounts of H2, CO and approximately 3% H2O as well as in laboratory air at 850°C. Thermal cycling oxidation tests following the COTEST standard up to 168h are carried out in both environments. Moreover cyclic oxidation tests are performed in dry anode gas. Detailed studies of oxide scale formation and evolution by means of electron microscopy of cross sections as well as oxide surfaces are undertaken.

Abstract: Effects of atmosphere and specimen geometry on thermal fatigue (TF) crack initiation and propagation in a low Si content hot work tool steel X38CrMoV5-47HRC were investigated. The TF specimen’s geometry enhances the uni-axial TF loading conditions. A high frequency induction heating (3 to 4 MHz) is used. A new TF rig, working under air and/or inert atmosphere with reduced PO2 has been set up. The reduction of PO2 results in localized oxidation sites. Whatever geometry and atmosphere conditions, TF cracks initiate exclusively in the oxide layers. Damage mechanisms are environment dependant. Under laboratory air, parallel macroscopic cracks initiate perpendicular to the hoop stress. Under argon and nitrogen, SEM surface observations show that initiated cracks coalesce by zigzagging along crystallographic paths between non-oxidized zones. In-depth crack propagation mechanism is mainly trans-granular. TF crack initiation life under air and in presence of Fe-Al intermetalllics is decreased in comparison to inert atmosphere.

Abstract: Ternary Mn-Co-Fe metallic thin films were deposited by RF-magnetron co-sputtering on SiO2/Si wafers and on ZMG232L (Hitachi Metals®), a special ferritic stainless steel for Solid Oxide Fuel Cell applications. The deposition was followed by heat treatment in an oxidizing atmosphere in order to convert the metallic thin films to (Mn,Co,Fe)3O4 spinel oxides. Coated and uncoated steel samples were analyzed after 1 h heat treatment in order to confirm the presence of the spinel structure on top of the steel, as well as to investigate and characterize the growth of oxides, namely (Mn,Cr)3O4 and Cr2O3, at the internal steel/coating interface. From Grazing Incidence X-ray Diffraction (GI-XRD) investigations together with Energy Dispersive X-ray analysis – Scanning Electron Microscopy and Time of Flight – Secondary Ions Mass Spectroscopy sputtering depth profiling the presence of well adherent (Mn,Co,Fe)3O4 coatings with approximately 500 nm thickness and a grain size of about 150 nm was confirmed. After the preparation annealing, some samples were heat-treated in simulated cathodic atmospheres at 800 °C for 500 h in order to assess the stability of the coatings. GI-XRD spectra still showed the presence of the protective coatings, however sputtering depth profile analysis indicated the presence of Cr on the surface.