Oxygen Diffusion in Alumina. Application to Synthetic and Thermally Grown Al<sub>2</sub>O<sub>3</sub>

S. Chevalier, B. Lesage, C. Legros, G. Borchardt, G. Strehl, M. Kilo Laboratoire de Recherches sur la Reactivite des Solides, CNRS UMR 5613, Universite de Bourgogne, F-21078 Dijon, France Laboratoire d’Etudes des Materiaux Hors Equilibre, CNRS UMR 8647, Universite Paris XI, F-91405 Orsay, France. Institut fur Metallurgie, TU Clausthal, Robert Koch Strasse 42, D38678 Clausthal-Zellerfeld, Germany. * sebastien.chevalier@u-bourgogne.fr

Scale composition and oxidation mechanism of the Ti–46Al–8Nb alloy in air at 700 and 800 °C

It is known that the oxide scale formed on TiAl alloys is generally composed of a mixture of alumina (Al2O3) and titania (TiO2). The presence of niobium changes the activities of Ti and Al and influences the kinetics of oxidation and oxide layer composition. In this work, the Tie46Ale8Nb alloy was subjected to cyclic oxidation in air at 700 � C (for 2 and 24 h) and 800 � C (for 300 h). Scale composition was analyzed by means of different techniques including X-ray photoelectron spectroscopy, X-ray diffraction and secondary ion mass spectroscopy. The scale consisted of several layers. The outer layer was built of alumina (amorphous or with very fine grains), whereas the inner layer e mainly …

Influence of reactive element oxide coatings on the high temperature cyclic oxidation of chromia-forming steels

Abstract The beneficial effects of reactive element oxide coatings, Y2O3, Nd2O3 and Yb2O3, on the cyclic oxidation behaviour of a Fe–30Cr model alloy, were studied at 950 °C in air under atmospheric pressure. The oxide scale grown on uncoated samples started to spall after 2 cycles, because of its poor adherence. The coated specimens remarkably resisted to the thermal shocks, since no oxide scale spallation or cracks could be observed, even after 1000 h of cycling experiments. The surface oxide scale consisted of facetted oxide grains on the uncoated samples. On the contrary, it exhibited a fine-grained structure on the coated specimens. The reactive element beneficial effect was ascribed t…

High temperature alloy chloridation at 850°C

The resistance of eight alloys against chloridation was tested at 850 °C in Ar/Cl 2 (2.5% Cl 2 ) for 15 min. Pre-oxidation treatments were performed for 1 h and 8 h at 850°C in order to produce a thin, adherent and protective oxide scale able to improve the chloridation behaviour of the tested materials. The chloridised sample morphologies were compared to the morphologies observed on the non pre-oxidised samples. The alloys containing a large amount of iron did not exhibit any chloridation resistance, even after pre-oxidation, and were severely damaged. The nickel based alloys gave interesting results but were also attacked by chloride, probably by the "active oxidation" mechanism. The dur…

Metallic interconnects for solid oxide fuel cell: Effect of water vapour on oxidation resistance of differently coated alloys

International audience; The need of interconnect to separate fuel and oxidant gasses and connect individual cells into electrical series in a SOFC stack appears as one of the most important point in fuel cell technology. Due to their high electrical and thermal conductivities, thermal expansion compatibility with the other cell components and lowcost, ferritic stainless steels (FSS) are nowconsidered to be among the most promising candidate materials as interconnects in SOFC stacks. Despite the formation at 800 ◦C of a protective chromia Cr2O3 scale, it can transform in volatile chromium species, leading to the lost of its protectiveness and then the degradation of the fuel cell. A previous…

Role of Minor Element Addition in the Formation of Thermally Grown Alumina Scales

Hydrothermal ageing of fibre metal laminates made of flax fibres

International audience; In the past two decades, fibre metal laminates (FMLs) have been widely used to manufacture aircraft and aerospace components. FMLs are hybrid composite structures based on thin sheets of metal alloys reinforced by organic matrix composites (Sinmazçelik et al., 2011). When compared to mono-material solutions, FMLs provide added functionalities such as high specific bending strength, fatigue resistance, acoustical absorption, vibration transmissibility and damping characteristics. They overcome most of the limitations of metal and polymeric reinforced composites. The first generation of FMLs was based on thermoset resins. To shorten the process cycle times, lower the p…

OXYDATION D'INTERCONNECTEURS METALLIQUES DE PILE A COMBUSTIBLES DE TYPE SOFC SOUS HYDROGENE ENRICHI EN VAPEUR D'EAU

Les interconnecteurs représentent une pièce maîtresse des piles à combustibles à oxyde solide (Solid Oxide Fuel Cells : SOFCs) car ils sont chargés de collecter et de délivrer le courant produit par la pile. Les matériaux d'interconnecteurs sont à la fois en contact avec l'anode et la cathode et doivent donc être parfaitement stables dans l'air (côté cathodique) et dans l'hydrogène enrichie en vapeur d'eau (côté anodique). Les matériaux métalliques les plus prometteurs sont les chromino-formeurs. Ces alliages sont choisis car, à haute température, ils forment une couche de chromine, Cr2O3, protectrice vis-à-vis des conditions corrosives de fonctionnement de la pile. Cependant, cette couche …

The Role of Zr in the High-Temperature Oxidation of Fe<sub>3</sub>Al

The paper describes an examination of the effect of the addition of zirconium as a third element on the heat-resisting properties and explains the high temperature oxidation mechanism of Fe3Al intermetallic compounds. The Fe3Al and Fe3Al-0,05Zr specimens have been isothermally oxidized in the temperature range of 1173-1473 K in synthetic air for 100 hrs. The formed oxide layer, about 1,5-2 μm thick, was Al2O3. An examination of the cross-sectioned scales by SEM-EDS showed that the alumina layer consisted of a small inner columnar layer and an outer equiaxed grain layer. Additionally, very fine (50-150 nm) oxide grains rich in Zr, further identified as ZrO2, were found across the alumina sca…

Effect of surface finishing on the oxidation behaviour of a ferritic stainless steel

Abstract The corrosion behaviour and the oxidation mechanism of a ferritic stainless steel, K41X (AISI 441), were evaluated at 800 °C in water vapour hydrogen enriched atmosphere. Mirror polished samples were compared to as-rolled K41X material. Two different oxidation behaviours were observed depending on the surface finishing: a protective double (Cr,Mn) 3 O 4 /Cr 2 O 3 scale formed on the polished samples whereas external Fe 3 O 4 and (Cr,Fe) 2 O 3 oxides grew on the raw steel. Moreover, isotopic marker experiments combined with SIMS analyses revealed different growth mechanisms. The influence of surface finishing on the corrosion products and growth mechanisms was apprehended by means o…

Dense Mosi2 produced by reactive flash sintering: Control of Mo/Si agglomerates prepared by high-energy ball milling

The objective of this work is to determine the influence of the agglomeration state of the MA mixture on the microstructure and the chemical composition of SPS end-products. In order to produce MoSi2 with a microstructure and a density perfectly controlled via reactive sintering implying an SHS reaction, the characteristics of Mo/Si mechanically activated (MA) powder mixtures were investigated. Indeed, the MA powders have been characterized in terms of their surface specific area, size, phase composition and microstructure. The high-energy milling allows the formation of agglomerates (0.8 to 800 μm) composed of nanometric crystallites of molybdenum and silicon, as a consequence of a continu…

Reactive Sintering of molybdenum disilicide by Spark Plasma Sintering from mechanically activated powder mixtures: Processing parameters and properties

Abstract Dense molybdenum disilicide with a nano-organized microstructure was synthesized by mechanical activation, by producing nanostructured agglomerates of a 1:2 mixture of Mo and Si, followed by the synthesis/consolidation in one step using SPS technology. In order to synthesize a dense molybdenum disilicide with a perfectly controlled microstructure, an investigation of the influence of Spark Plasma Sintering processing parameters (temperature, heating rate, mechanical pressure and holding time) on the chemical composition and the microstructure characteristics has been performed. The present work shows also that the so-obtained materials present better oxidation resistance in compari…

INTERCONNECTEURS METALLIQUES DE PILES A COMBUSTIBLES DE TYPE SOFC : EFFET DE LA VAPEUR D'EAU SUR LA RESISTANCE A LA CORROSION

Les interconnecteurs représentent une pièce maîtresse des piles à combustibles à oxyde solide (Solid Oxide Fuel Cells : SOFCs) car ils sont chargés de collecter et de délivrer le courant produit par la pile. Les matériaux d'interconnecteurs sont à la fois en contact avec l'anode et la cathode et doivent donc être parfaitement stables dans l'air (côté cathodique) et dans l'hydrogène enrichie en vapeur d'eau (côté anodique). Les matériaux métalliques les plus prometteurs sont les chromino-formeurs. Ces alliages sont choisis car, à haute température, ils forment une couche de chromine, Cr2O3, protectrice vis-à-vis des conditions corrosives de fonctionnement de la pile. Cependant, cette couche …

Inverse growth transport in thermal chromia scales on Fe–15Cr steels in oxygen and in water vapour and its effect on scale adhesion

Chromia scales of near equivalent thickness were thermally grown on Fe–15Cr steels in 16O2 followed by 18O2 and in H216O followed by H218O. SIMS oxygen isotope profiles showed that oxidation in oxygen proceeded by outward chromium transport, whereas oxidation in H2O involved inward transport of hydroxide species. Adhesion measurements using room temperature tensile testing could quantify adhesion energy: 20 J m−2 for O2-grown scales and 80 J m−2 for scales formed in H2O, a result of this mass transport inversion.

High Temperature Corrosion Behaviour of Coated F17Ti Stainless Steel

Nous avons etudie l'effet de revetements de chromine et d'alumine sur le comportement de l'acier inoxydable F17Ti. Les films ont ete formes a la surface de l'alliage par pyrolyse de la vapeur d'un precurseur organometallique (MOCVD). Cette technique permet egalement de preparer des oxydes d'elements de terres rares. Ceci nous a conduit a envisager la formation de couches barrieres dopees par un element actif, soit par depots successifs, soit par codeposition de chromine ou d'alumine et d'un oxyde de terre rare, suivi d'un traitement de recuit d'homogeneisation. Les revetements ainsi obtenus ont ete caracterises par microscopie electronique a balayage, microanalyse X, diffraction des rayons …

High temperature alloy chloridation at 850°C. Part I: Comparison of Ni-based and Fe-based alloy behaviour

Eight alloys were tested under Ar/Cl 2 atmosphere at 850 °C for 15 min and 1 h. Their gross and net weights were evaluated together with the base metal consumption. Macroscopic and microscopic micrographs, associated with chemical analyses and X-ray diffraction gave the composition and microstructure of the corrosion products. Huge differences were observed if one compared the nickel based alloy behaviour to that of the iron based alloy. Molybdenum and tungsten could also play a role, but it was not clearly defined until now. A tentative evaluation of the best candidates will be given, according the experimental conditions of this work and the chosen criteria. A corrosion index was establis…

Crystallization kinetics of amorphous SiC films: Influence of substrate

Abstract The crystallization kinetics of amorphous silicon carbide films was studied by means of X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The films were deposited by radio frequency (r.f.) magnetron sputtering on glassy carbon and single crystalline silicon substrates, respectively. TEM micrographs and XRD patterns show the formation of nano-crystalline β-SiC with crystallite sizes in the order of 50 nm during annealing at temperatures between 1200 and 1600 °C. A modified Johnson–Mehl–Avrami–Kolmogorov (JMAK) formalism was used to describe the isothermal transformation of amorphous SiC into β-SiC as an interface controlled, three-dimensional growth processes fr…

The combined effect of refractory coatings containing reactive elements on high temperature oxidation behavior of chromia-forming alloys

Abstract The high temperature oxidation behaviors of chromia-forming alloys (F17Ti and Fe–30Cr alloys) have been studied at 1273 K under isothermal conditions and at 1223 K under cyclic conditions, in air under the atmospheric pressure. To extend the oxidation lifetime, coatings have been applied onto the alloy surfaces. Al2O3 and Cr2O3 films doped with Sm2O3 or Nd2O3 were prepared via the metal-organic chemical vapor deposition technique. Single Cr2O3, Al2O3, Nd2O3 and codeposited Cr2O3–Nd2O3, Al2O3–Nd2O3, Al2O3–Sm2O3 coatings drastically improved the chromia-forming alloy high temperature oxidation behavior, since they decreased the oxidation rate and enhanced the oxide scale adhesion. Re…

Synthesis and characterisation of pack cemented aluminide coatings on metals

Abstract The exposition of metallic materials to high temperature environments leads to their corrosion because of oxidation or sulphidation. One way to protect such materials is to produce an Al 2 O 3 layer which needs to be continuous enough to limit diffusion of oxygen or metallic elements, and withstand this corrosion. Since a few years, it has been proved that aluminide compounds are one of the most effective materials to achieve this goal. Indeed, they possess sufficient Al and many beneficial mechanical properties when exposed to high temperature conditions to make possible the formation of a protective Al 2 O 3 scale. This study is aimed at the elaboration of iron, nickel and molybd…

Influence of the mode of introduction of a reactive element on the high temperature oxidation behavior of an alumina-forming alloy. Part I: Isothermal oxidation tests

Several routes of yttrium introduction were applied to test the high temperature oxidation performance of a FeCrAl alloy. Isothermal oxidation tests were described in a previous paper (Part I of this paper in this journal, 2004, 55, 352). Cyclic oxidation tests were performed in air under atmospheric pressure on blank specimens, Y 2 O 3 sol-gel coated-, Y 2 O 3 metal-organic chemical vapor deposited (MOCVD)-, yttrium ion implanted-alloys, as well as on a steel containing 0.1 wt.% of yttrium as an alloying element. For the 20 hours cycles, all the samples, except FeCrAl-0.1Y, exhibit weight losses after a few cycles, indicating drastic spallation of the oxide scales. The MOCVD coated specime…

MOCVD deposition of YSZ on stainless steels

Abstract Yttria stabilized zirconia was deposited on stainless steel using the metal–organic chemical vapor deposition (MOCVD) technique, from β-diketonate precursors. The variation of the evaporation temperatures of yttrium and zirconium precursor allowed to control the level of Y within the film. Over the temperature range 125–150 °C, the Y content increased from 2.5 to 17.6 at.%. X-ray diffraction (XRD) analyses evidenced tetragonal phase of zirconia when the Y content was below 8 at.%, and cubic phase for higher concentration. Sputtered neutral mass spectrometry (SNMS) profiles confirmed that the control and stability of Y precursor temperature were of major importance to guarantee the …

Metallic interconnects for solid oxide fuel cell: Performance of reactive element oxide coating during long time exposure

One of challenges in improving the performance and cost-effectiveness of SOFCs (solid oxide fuel cells) is the development of suitable interconnects materials. Chromia-forming alloys and especially ferritic stainless steels, like Crofer22APU, are considered to be among the most promising candidate materials as interconnects in SOFC stacks. However, the performance of chromia-forming materials can be limited by the low electronic conductivity of the oxide scale (high ASR – area specific resistance – value). Such degradation are unacceptable regarding the long-term operation (>40 000 h). A previous study 1 demonstrated that in air, the addition of a nanometric reactive element oxide (La2O3) l…

Coated interconnects development for high temperature water vapour electrolysis: Study in anode atmospher

International audience; High temperature water vapour electrolysis (HTE) is an efficient technology for hydrogen production. In this context, a commercial stainless steel, K41X (AISI 441), was chosen as interconnect. In a previous paper, the high temperature corrosion and the electrical conductivity were evaluated in both anode (O-2-H2O) and cathode (H-2-H2O) atmosphere at 800 degrees C. In O-2-H2O atmosphere, the formation of a thin chromia protective layer was observed. Nevertheless, the ASR parameter measured was higher than the maximum accepted value. These results, in addition with chromium evaporation measurements, proved that the K41X alloy is not suitable for HTE interconnect applic…

Presentation, Calibration and First Experiments Using a New Thermobalance for Experiments in Sulfur Vapor Atmospheres

Investigation of Solid State Diffusion Processes Involved in the Zinc Oxide Sulfidation Reaction

Sulfidation of undoped and aluminum doped zinc oxide materials has been performed by TGA under a H2S atmosphere in order to evaluate the impact of the doping element on sulfidation reaction kinetics and mechanism. The presence of aluminum seems to slow-down the reaction kinetics. This phenomenon might be explained by a modification of the solid state diffusion processes involved in ZnO sulfidation reaction and the related ZnS outward growth, assuming the presence of aluminum atoms inside ZnO and ZnS phases. In order to determine solid state diffusion mechanisms controlling the reaction kinetics, molecular dynamics simulations were performed using a Coulomb-Buckingham potential. Firstly, the…

Numerical Determination of Intrinsic Diffusion Coefficient of Aluminide Coatings on Metals

This paper presents a numerical method to determine the composition dependent diffusivities and to predict the concentration profile during the interdiffusion process. The intrinsic diffusion coefficients in diffusion aluminide coatings (Fe-Al) were determined at 1000oC. The obtained diffusion coefficient for iron in Fe3Al or FeAl is in the range 10-10 to 10-9 cm2.s-1. The aluminum diffusion coefficient varies from 10-11 to 10-7 cm2.s-1 in the same phases.The present approach also permits to model the reactive diffusion in the Fe-Al systems.

MoSi2 Formation Mechanisms during a Spark Plasma Synthesis from Mechanically Activated Powder Mixture

Study of the Growth Mechanism of some Oxide Scales on Alloy 230 in High Temperature Vapor Electrolysis (HTVE) Conditions

Alloy 230 (also named Haynes® 230) was tested as interconnect for production of hydrogen via High Temperature Vapor Electrolysis (HTVE). Samples were oxidized at 800°C in the both atmospheres representative of the HTVE operating conditions: Ar-1%H2-9%H2O (for cathode side) and air (for anode side). The high temperature oxidation behaviour was studied in both atmospheres together with the electrical conductivity of the thermally grown oxide scales. Oxidation kinetics indicated lower oxidation rate in H2/H2O compared to air (kp = 3.8 .10-15 g2.cm-4.s-1 in H2/H2O and kp = 1.6 .10-14 g2.cm-4.s-1 in air). The corrosion products were characterized by scanning electron microscopy associated with X…

The functionalization of nanodiamonds (diamondoids) as a key parameter of their easily controlled self-assembly in micro- and nanocrystals from the vapor phase.

We detail herein readily accessible processes to control previously unobserved robust self-assemblies of nanodiamonds (diamondoids) in micro- and nanocrystals from their mild vapor deposition. The chemical functionalization of uniform and discernible nanodiamonds was found to be a key parameter, and depending on the type of functional group (hydroxy, fluorine, etc.) and its position on the diamondoid, the structure of the discrete deposits can vary dramatically. Thus, well-defined anisotropic structures such as rod, needle, triangle or truncated octahedron shapes can be obtained, and self-assembled edifices of sizes ranging from 20 nm to several hundred micrometers formed with conservation …

Evaluation of a new Cr-free alloy as interconnect material for hydrogen production by high temperature water vapour electrolysis: Study in cathode atmosphere

International audience; For economic and ecological reasons, hydrogen is considered as a major energetic vector for the future. Hydrogen production via high temperature water vapour electrolysis (HTE) is a promising technology. A major technical difficulty related to high temperature water vapour electrolysis is the development of interconnects working efficiently for a long period. Working temperature of 800 degrees C enables the use of metallic materials as interconnects. High temperature corrosion behaviour and electrical conductivity of a new Cr-free Fe-Ni-Co alloy were tested in cathode atmosphere (H-2/H2O) at 800 degrees C. The alloy exhibits a poor oxidation resistance but an excelle…

Effect of coatings on long term behaviour of a commercial stainless steel for solid oxide electrolyser cell interconnect application in H2 /H2O atmosphere

Abstract K41X (AISI 441) stainless steel evidenced a high electrical conductivity after 3000 h ageing in H 2 /H 2 O side when used as interconnect for solid oxide electrolyser cells (SOEC) working at 800 °C. Perovskite (La 1 − x Sr x MnO 3 − δ ) and spinel (Co 3 O 4 ) oxides coatings were applied on the surface of the ferritic steel for ageing at 800 °C for 3000 h. Both coatings improved the behaviour of the steel and give interesting opportunities to use the K41X steel as interconnect for hydrogen production via high temperature steam electrolysis. Co 3 O 4 reduced into Co leading to a very good Area Specific Resistance (ASR) parameter, 0.038 Ω cm 2 . Despite a good ASR (0.06 Ω cm 2 ), La …

Evaluation of Haynes230 for Solid Oxide Fuel Cell Interconnect Application

National audience; Abstract - Interconnects are among the most critical parts for commercialization of SOFCs. They separate the fuel and oxidant gases and provide electric connection between the anode and cathode of adjacent cells. A Ni-based alloy, Haynes230 alloy, was evaluated in this work as a candidate material for SOFC interconnects application. During operation, a scale of chromia forms on Haynes230. Unfortunately, this scale can degrade the fuel cell performances. Thus, protective coatings are required to increase long-term stability. In this study, a nanometric layer made of reactive element oxide (La2O3, Nd2O3 and Y2O3) was applied on alloy surface by MOCVD. Perovskite oxides, suc…

Micro-Raman analysis of the fuel-cladding interface in a high burnup PWR fuel rod

International audience; New insights on the fuel-cladding bonding layer in high burnup nuclear fuel were obtained using micro-Raman spectroscopy. A specimen was specifically prepared from a fuel rod which had been irradiated to an average burnup of 56 GWd.tU-1 in a pressurized water reactor (PWR). Both inner and outer corrosion scale regions were investigated. A 10-15 et956;m thick zirconia bonding layer between fuel and cladding materials which consisted of three distinct regions was observed. Close to the fuel, tetragonal, then monoclinic zirconia was identified as the main phases. Close to the bonding layer-cladding interface, peculiar Raman signals were observed. Similar signals were ob…

Dual atmosphere study of the K41X stainless steel for interconnect application in high temperature water vapour electrolysis

Abstract High temperature water vapour electrolysis (HTE) is one of the most efficient technologies for mass hydrogen production. A major technical difficulty related to high temperature water vapour electrolysis is the development of interconnects working efficiently for a long period. Working temperature of 800 °C enables the use of metallic materials as interconnects. High temperature corrosion behaviour and electrical conductivity of a commercial stainless steel, K41X (AISI 441), were tested in HTE dual atmosphere (95%O 2 -5%H 2 0/10%H 2 -90%H 2 O) at 800 °C. The alloy exhibits a very good oxidation resistance compared to single atmosphere tests. However, a supplied electrical current s…

Mechanisms Involved by Reactive Elements upon High Temperature Chromia Scale Growth

The influence of Y 2 O 3 , Pr 2 O 3 , Nd 2 O 3 , Sm 2 O 3 and Yb 2 O 3 coatings on Fe-30Cr alloy oxidation behaviour was investigated at 1000°C in air under atmospheric pressure. Isothermal exposures indicated that the Y 2 O 3 coating was the most protective after 100 hours. Pr 2 O 3 , Nd 2 O 3 and Sm 2 O 3 coatings were less effective, but the less beneficial effect was observed when Yb 2 O 3 coating was applied onto the Fe-Cr alloy surface. Two-stage oxidation experiments in 16 O 2 and then 18 O 2 were performed to get information about the chromia growth phenomena with and without reactive elements. The 18 O-tracer distribution was determined by secondary ion mass spectrometry (SIMS) and…

Interface reactivity study between La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) cathode material and metallic interconnect for fuel cell

Abstract Interface reactivity between La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) cathode material and metallic interconnect (Crofer22APU) was investigated in laboratory air at 700 °C. Due to the interconnect geometry, two interfaces have been analysed: (i) interconnect rib/cathode interface (physically in contact); (ii) the interface under the channel of interconnect. In both cases, formation of a parasite phase was observed after various ageing treatments (20 h, 100 h and 200 h). However, the growth of the determined SrCrO4 parasite phase depends on interface type and on ageing time. Two different mechanisms have been established in function of interface type: (i) SrCrO4 phase was formed after solid …

Metallic interconnects for SOFC : characterization of their corrosion resistance in hydrogen/water atmosphere and at the operating temperatures of differently coated metallic alloys

International audience; Chromia forming alloys are one of the best candidates for the interconnecting materials in solid oxide fuels cells (SOFC). Recent research has enabled to decrease the operating temperature of the SOFC from 1000 °C to 800 °C. However, low electronic conductivity and high volatility of the chromia scale need to be solved to improve performance of interconnects. In the field of high temperature oxidation of metals, it is well known that the addition of reactive elements into alloys or in thin film coatings, improve the oxidation resistance of alloys at high temperature. The elements of the beginning of the lanthanide group and yttrium are the most efficient. The goal of…

CHAPTER 6 Development of SOFC Interconnect Stainless Steels

The chapter introduces components and working principle of solid oxide fuel cells (SOFCs). It is followed by the explanation on the choices of materials focussing on ferritic stainless steels. The review is further made on the required properties of these steels, i.e. low oxidation rate, low chromium species volatilisation rate, high electrical conductivity and good scale adhesion. For the oxidation aspect, the behaviour of stainless steel interconnect in cathode, anode (hydrogen and biogas), and dual atmospheres are described. Surface modification by pre-oxidation and coatings to improve the oxide electrical conductivity and to reduce chromium species volatilisation is finally reviewed.

On the Effect of Surface Treatment to Improve Oxidation Resistance and Conductivity of Metallic Interconnects for SOFC in Operating Conditions

International audience; 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 Y2O…

Protection of iron-based alloys likely to be exposed to corrosive atmospheres

Summary This study examines the influence of temperature on oxidation kinetics of the alloys Z2CT 17 and Z4CN 18-09. A thin layer of aluminium oxide was laid down on these, using chemical, vapor deposition, in order to give improved protection.

High Temperature Oxidation of TiAl and TiAl8Nb Alloys in Air

Isothermal oxidation of two g-TiAl-based intermetallic alloys: Ti48Al and Ti46Al8Nb alloys was studied in synthetic air at 1073-1223 K for up to 240 hrs. Mass change per unit area for the oxidized samples followed approximately the parabolic rate law. The kp values for the studied temperature interval were in the range from 7.2×10-13 to 1.8×10-11 g2cm-4s-1. The activation energy for oxidation of Ti48Al alloy in air at 1073-1223 K was Ea = 165±12 kJ/mol. Niobium addition to Ti48Al alloy in the amount of 8% increased its oxidation resistance. Structure and chemical composition of the oxidation products, and morphology of the oxidized samples were investigated using XRD, SEM-EDS, and TEM. The …

Développer ses compétences transversales pour réussir ses études en santé

International audience; Cette communication propose une réponse à la question « Quels outils pédagogiques mobiliser, notamment pour l’acquisition des compétences transversales ? ».Nous présentons une expérimentation qui s'est déroulée auprès de 66 étudiants en L2 Sciences pour la Santé à l’Université de Lorraine. La formation d’une semaine, proposée conjointement par les projets IDEFI Remis et TalentCampus en septembre 2017, visait à :- permettre à chacun de découvrir l’importance des compétences transversales ;- travailler son estime de soi ;- développer des compétences de travail en groupe et de communication orale.La L2 Sciences pour la Santé présente la particularité d’accueillir un pub…

NaCl induced corrosion of Ti-6Al-4V alloy at high temperature

International audience; This paper presents a study on the Ti-6Al-4V behaviour in presence of NaCl deposit under dry and moistair environments at 560◦C. The results evidence a detrimental effect of the NaCl deposit with a synergisticeffect in presence of moist air environment. Treatments under dry and moist air with NaCl deposit for600 h, lead respectively to weight gains per unit area 5 and 15 times higher than observed under classicoxidation in dry air. Enhancement of the corrosion phenomenon is attributed to the presence of gaseousmetal chlorides, leading to the establishment of an active corrosion process.

Which tool to distinguish transient alumina from alpha alumina in thermally grown alumina scales?

International audience; Alumina scales constitute excellent protective barriers when they form on alumina-forming steels. If they keep tightly adherent to the underlying substrate, they isolate it from the surrounding aggressive atmosphere at high temperature. The protectiveness of the alumina scale is highly dependant upon its growth mechanism. The nucleation and transformation of transient alumina (mainly g-Al2O3 and y-Al2O3) is known to play an important role on alumina scale formation. It is therefore fundamental to characterise these transient alumina especially during the early stages of the oxidation process. The morphology of the transient alumina was observed by scanning electron m…

Optimisation of metallic interconnects for hydrogen production by high temperature water vapour electrolysis

For economical and environmental reasons, hydrogen is considered as a major energetic vector for the future. Hydrogen production via high temperature water vapour electrolysis (HTE) is a promising technology. A major technical difficulty related to high temperature water vapour electrolysis is the development of interconnects working efficiently for a long period. Working temperature of 800°C enables the use of metallic materials as interconnects. Chromia forming alloys are among the best candidates. The interconnect material chosen in the present study is a ferritic stainless steel with 18% chromium content. High temperature corrosion resistance and electrical conductivity of the alloy was…

Microstructure impact on high temperature corrosion behavior of AISI 316L stainless steel additively manufactured by Selective Laser Melting (AM-SLM)

International audience; Additive Manufacturing by Selective Laser Melting (AM-SLM) is a near-net shape method producing dense and geometrically complex materials from micrometric powders. This process involves complete melting and very high cooling rates who induce a refinement of microstructure, improving the mechanical properties of the material [1,2]. However, the impact of these new microstructures on real functioning properties, like for instance the high temperature durability, needs to be studied. In this purpose, AISI 316L is considered in this work. Samples elaborated by AM-SLM and by conventional metallurgy were oxidized under laboratory air at 900°C for periods up to 3000h. The r…

Diffusion of Oxygen in Thermally Grown Oxide Scales

High temperature reactivity of materials under oxidizing atmospheres is based on the formation of protective oxide scales. The protectiveness is obtained when the thermally grown oxide scales are dense, continuous and adherent to the metallic substrates (even during thermal shocks); as a matter of fact, the growth of the scale has to be governed by diffusion of species across the growing scale. The diffusing species are coming from the substrate (metallic ions) and/or from the oxidizing atmosphere (oxygen ions). The understanding of growth mechanisms can be reached by making two stage oxidation experiments, using oxygen isotopes. The experiment consists in oxidizing first the metallic subst…

High temperature reactivity of nickel aluminide diffusion coatings

Abstract The high-temperature oxidation behaviour of nickel aluminides has been studied at 900 °C in air under atmospheric pressure. Yttria doped and undoped specimens of nickel were aluminised and then oxidised for 100 h under isothermal and cycling conditions. The results showed that when yttria is added by metal-organic chemical vapour deposition technique prior to the aluminisation process, it increased the oxidation rate of aluminised nickel, but improved the oxide scale adherence under cyclic conditions. The effects of yttria on the scale morphology, oxidation behaviour and scale spallation tendency are discussed based on the experimental results, using X-ray diffraction (XRD), scanni…

Interconnecteurs métalliques de piles à combustibles de type SOFC : effet d'un traitement de surface par MOCVD.

Les performances des alliages chromino-formeurs, utilisés comme interconnecteurs de piles à combustibles sont limitées par la formation d'une couche de chromine qui a une conductivité électrique faible et par la volatilisation des oxydes de chrome qui polluent la pile, et par conséquent détériorent son comportement. La réalisation d'une couche nanométrique d'oxydes d'éléments réactifs (La2O3, Y2O3, Nd2O3) par MOCVD permet d'améliorer la résistance à la corrosion à 800°C des alliages chromino-formeurs. Ces revêtements ont été réalisés sur l'alliage Crofer22APU dans le but de former des oxydes de type pérovskite tels que LaCrO3, NdCrO3 et YCrO3 lors de l'oxydation et qui possèdent une meilleu…

Metallic interconnects for SOFC: Characterisation of corrosion resistance and conductivity evaluation at operating temperature of differently coated alloys

Abstract One of challenges in improving the performance and cost-effectiveness of solid oxide fuel cells (SOFCs) is the development of suitable interconnect materials. Recent researches have enabled to decrease the operating temperature of the SOFC from 1000 to 800 °C. Chromia forming alloys are then among the best candidates for interconnects. However, low electronic conductivity and volatility of chromium oxide scale need to be solved to improve interconnect performances. In the field of high temperature oxidation of metals, it is well known that the addition of reactive element into alloys or as thin film coatings, improves their oxidation resistance at high temperature. The elements of …

Elaboration of Nickel Aluminide Diffusion Coatings: Application to Oxidation Resistance

Aluminide diffusion coatings are widely used in aeronautic domain. Nickel based superalloys present good mechanical properties and creep resistance at high temperature but their corrosion resistance is somewhat poor. In order to enhance their lifetime at high temperature, aluminide coatings can be applied on alloy surface. Aluminium present on material surface can form, at high temperature, alumina scale which is a protective oxide scale. In the present study, nickel aluminide coatings were carried out by aluminisation in a single step pack cementation process on nickel based superalloys 600 and AM1. Ni-Al intermetallic was obtained in each case. Oxidation tests were carried out at 900°C in…

Investigation of La2O3 and/or (Co,Mn)3O4 deposits on Crofer22APU for the SOFC interconnect application

International audience; Chromia forming alloys (stainless steels) are among the best candidates for SOFC interconnects. However, problems of decreasing electronic conductivity during high temperature service and volatility of chromium oxide scales need to be solved. Electronically conductive surface coatings, which also reduce oxide scale growth and chromium volatility, are needed to improve stainless steel interconnects. The goal of this study is to investigate combinations of lanthanum oxide (La2O3) and cobalt manganese oxide ((Co,Mn)3O4) coatings on Crofer22APU stainless steel. Thin film coatings of La2O3 (~200 nm) and Co,Mn (1:1) (~2 mm) were deposited via metal organic chemical vapor d…

Effect of Microstructure on the High Temperature Oxidation and Pesting Behaviour of MoSi<sub>2</sub>

Numerical Determination of Intrinsic Diffusion in Fe-Cr-Al Systems

The intrinsic diffusion coefficients in diffusion aluminide coatings based on Fe-30Cr were determined at 1000oC. The diffusion fluxes were given by the Nernst Planck formulae and the Darken method for multicomponent systems was applied. This paper summarizes some numerical results to determine the composition dependent diffusivities in Fe-Cr-Al systems. The method presented in this study to obtain average intrinsic diffusion coefficients is as an alternative to the Dayananda method. Our method based on empirical parameters allowed us to predict the concentration profile during the interdiffusion process.

Spark Plasma Sintering à partir de poudres mécaniquement activées : compréhension des transitions de phase au cours d'un frittage réactif

International audience; À " basse température " (entre 400 et 600 ◦C), l'oxydation de MoSi2 entraîne sa désintégration en poudre (phénomène de " peste "). De récents travaux ont montré que l'utilisation de MoSi2 dense et nano-organisé permettrait de ralentir ce phénomène de " peste ". Le défi de produire des matériaux denses et nano-organisés peut être relevé par le frittage " flash " réactif sous champ électrique à partir des poudres mécaniquement activées (Mechanically-Activated Spark Plasma Sintering, MASPS). Le contrôle de la composition et de la microstructure du composé intermétallique MoSi2 nécessite de déterminer les paramètres du frittage SPS (température, rampe de montée en tempér…

Metal-organic chemical vapor deposition of Cr2O3 and Nd2O3 coatings. Oxide growth kinetics and characterization

Thin oxide films of Cr2O3 and Nd2O3 were prepared, using Metal-Organic Chemical Vapor Deposition (MOCVD) technique, to protect stainless steels against corrosion at high temperature. The conditions of precursor volatilization were studied by thermogravimetry. Deposited film growth kinetics depended on the deposition parameters, particularly substrate temperature, gas flow rate and location of substrate in the coating reactor. The influence of the deposition parameters on the deposition rate and the uniformity of the films is discussed. The oxide films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and atomic force mi…

Opportunity of metallic interconnects for ITSOFC : Reactivity and electrical property.

International audience; Iron-base alloys (Fe-Cr) are proposed hereafter as materials for interconnect of planar-type intermediate temperature solid oxide fuel cell (ITSOFC); they are an alternative solution instead of the use of ceramic interconnects. These steels form an oxide layer (chrornia) which protects the interconnect from the exterior environment, but is an electrical insulator. One solution envisaged in this work is the deposition of a reactive element oxide coating, that slows down the formation of the oxide layer and that increases its electric conductivity. The oxide layer, formed at high temperature on the uncoated alloys, is mainly composed of chromia; it grows in accordance …

Metallic interconnects for SOFC: competitive effect of water vapour and oxygen on the oxidation behaviour of ferritic stainless steel.

Due to their low environmental impact, their high efficiency and their fuel flexibility, Solid Oxide Fuel Cells are studied for many years in order to supply electricity without fossil sources. The need of interconnect to create a stack (providing electrical connection between anode and cathode) and seal every single cell (having to avoid any contact between air and fuel) appears as a crucial point. Ferritic Stainless Steel (FSS) like Crofer22APU are considered as good candidates for interconnects. These chromia forming alloys have to be operational in the service conditions: 800°C in air (cathode side) and in humidified hydrogen (anode side). The performance of the interconnect stainless s…

Metallic interconnects for SOFC: effect of water vapour on oxidation resistance of differently coated alloys.

The need of interconnect to separate fuel and oxidant gasses and connect individual cells into electrical series in a SOFC stack appears as one of the most important point in fuel cell technology. Due to their high electrical and thermal conductivities, thermal expansion compatibility with the other cell components and low cost, Ferritic Stainless Steels (FSS) are now considered to be among the most promising candidate materials as interconnects in SOFC stacks. Despite the formation at 800°C of a protective chromia Cr2O3 scale, it can transform in presence of water vapour in volatile chromium species leading to the lost of its protectiveness and then the degradation of the fuel cell. A prev…

Study of titanium alloy Ti6242S oxidation behaviour in air at 560°C: Effect of oxygen dissolution on lattice parameters

Abstract High temperature oxidation of titanium alloy Ti6242S was studied in air at 560 °C up to 10000 h. Oxidation kinetics obeys a parabolic law (kp = 8.7 × 10−15 g². cm−4.s-1). Oxygen dissolution in the metal was found to represent between 80 and 90% of the total mass gain. Thin oxide scales are mainly composed of TiO2, in top of which some alumina is present. Titanium nitride was detected as a very thin layer at the outer part of the metallic substrate. Underneath, the oxygen dissolution area was found to reach the maximum brittleness after 1000 h of oxidation.

High Temperature Oxidation Behaviour of Aluminide Coatings Obtained by Pack Cementation