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The impact of the microstructure of Fe-16Cr-0.2C on high-temperature oxidation – sulphidation in SO2
(2021)
This study elucidates the impact of the microstructure of Fe-16Cr-0.2C on oxide layer formation at 650 ◦C in Ar-0.5 % SO2. A cold-rolled and two heat-treated states of the alloy were exposed for up to 1000 h. The samples were characterised in detail from microstructural and chemical perspectives using scanning electron microscopy (SEM), X-ray diffraction (XRD) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The microstructural modification of the alloy by heat-treatment was advantageous. It was found that Cr-carbides support chromia formation and reduce sulphidation when their area fraction is low and diameter is small.
High-temperature corrosion is a widespread problem in various industries.
As soon as a hot and reactive gas (CO2, O2, H2O, SO2, NOx, etc.) is in contact with a solid, physico-chemical processes at the surface and interfaces lead to material degradation. The processes are dynamic and controlled by thermodynamic and kinetic boundary conditions. Whether a reaction product is protective or not depends on various factors, such as chemical composition of the solid and the reactive media, surface treatment as well as diffusion and transport paths of cations and anions. Resulting chemical and structural inhomogeneities with the corrosion layers are characterized by off stoichiometry within cationic and anionic sub lattices. The competitive processes can be studied by various techniques of applied crystallography.
This chapter gives an overview on the challenges of chemical-structural Analysis of reaction products by crystallographic methods such as X-ray diffraction and X-ray near-edge structure spectroscopy and scanning electron microscopy electron backscatter diffraction (SEM-EBSD) for corrosion science.
A variety of materials of technological interest change their properties through contact with reactive media. Solid-gas reactions lead to a variety of reaction products on the surfaces and internal interfaces. The observation of nucleation and growth processes in the environment where they occur (in situ) from a chemical-structural perspective is especially challenging for aggressive atmospheres. The talk presents innovative approaches to study corrosion mechanisms using advanced X-ray methods. Using energy dispersive X-ray diffraction and X-ray absorption spectroscopy in different tailor made environmental reaction chambers, valuable insights into high temperature oxidation and sulfidation processes were gained. Fe-based alloys were exposed to hot and reactive atmospheres containing gases like SO2, H2O and O2 at 650°C. During the gas exposure the tailor made reaction chambers were connected to a high energy diffraction end station at the synchrotron. The crystallization and growth of oxide and sulfide reaction products at the alloy surfaces were monitored by collecting full diffraction pattern every minute. Careful examination of shape and intensity of phase-specific reflections enabled to a detailed view on growth kinetics. These studies showed, oxides are the first phases occurring immediately after experimental start. As soon as reactive gas media enter the chamber, the conditions change and different reaction products, such as sulfides start to grow. A comparison of different gas environments applied, illustrated the differences in the type of reaction products. The in situ observation of high temperature material degradation by corrosion made it possible to study the contribution of phases, which are not stable at room temperature. For instance, wuestite (Fe1-xO), was frequently observed at high temperatures in humid gases on Fe with 2 wt.% and 9 wt.% chromium, but not at room temperature. The strength of the occurrence of this phase additionally explains why, despite a higher Cr content, ferritic alloys with 9 wt.% Cr in a challenging atmosphere prevent the intrinsic formation of protective layers. The in situ observations were supplemented by careful considerations of thermodynamic boundary conditions and detailed post characterization by classical metallographic analysis. Additionally, the structure and chemistry of the dominant oxide layers were evaluated using X-ray absorption near edge structure spectroscopy. The talk will give an overview about chances and challenges for studying high temperature corrosion phenomena by advanced X-ray methods.
Ferritic-austenitic chromia-forming alloys are frequently used as boiler tubes and heat exchanger materials for fossil-,biomass, and co-fired power plants. In all applied environments several strongly corrosive gaseous species such as CO2, SO2, SO3, H2O, O2 exist, causing materials degradation by high-temperature corrosion. The elucidation of degradation mechanisms introduced by multiple gases is challenging due to the presence of different oxidizing agents contributing to the competing reactions for oxidation, sulfurization or carburization. The degradation processes can be divided into initial stages, a transitional stage and the further proceeding steady-state oxidation reaction. Especially the long-term steady-state oxidation and further materials’ life-time are strongly dependent on the initial stages. The adsorption and absorption of the reactive species at the alloy surface and the growing oxide in the initial reaction is further influenced by dissociation and re-reactions of the gas phase molecules. To understand these mechanisms from a fundamental point of view in more detail, dedicated experiments and advanced characterization techniques on various length scale need to be applied. Real-time approaches using highly energetic synchrotron X-ray diffraction showed a high potential to enlighten competitively mechanisms by following the corrosion reactions in-situ in the environment they occur. Despite various other thin film characterization techniques, time of flight secondary ion mass spectroscopy (ToF-SIMS) is a powerful tool to visualize light atoms or labeled isotopes enabling the Differentiation between different oxidizing species. It was especially shown to be applicable in challenging atmospheres containing KCl deposits or in CO/CO2/O2 environments. The present study analyses the competing oxidation/sulfidation process in a humid atmosphere on two ferritic alloys with 2 and 9 % in weight chromium by in situ energy dispersive X-ray diffraction (EDXRD) and comparative tube furnace exposure using S16O2 and H2 18O atmosphere.
Surface degradation phenomena of two model equiatomic alloys from the CrMnFeCoNi alloy system were investigated in 2% O2 and 10% H2O (pO2 = 0.02 and 10−7 atm, respectively) at 800 °C for times up to 96 h. The crystallographic structures, morphologies, and chemical compositions of the corrosion layers developing on CrMnFeCoNi and CrCoNi were comparatively analyzed by mass gain analysis, X-ray diffraction, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy and electron backscatter diffraction. The oxidation resistance of CrMnFeCoNi is relatively poor due to the fast growth of porous Mnoxide(s). CrCoNi forms an external chromia layer that is dense and continuous in a dry 2% O2 atmosphere. This layer buckles and spalls off after exposure to 10% H2O atmosphere. Beneath the chromia layer, a Cr-depleted zone forms in the CrCoNi alloy in both environments. As the oxide scale spalls off in the H2O-containing
atmosphere, a secondary chromia layer was observed and correspondingly enlarges the Cr-depleted zone. In contrast, as the chromia layer remains without significant spallation when CrCoNi is exposed to a dry oxidizing atmosphere, the region depleted in Cr is narrower.
The high-entropy alloy (HEA) CrMnFeCoNi and the medium-entropy alloy (MEA) CrCoNi with a face-centered cubic (fcc) structure have excellent mechanical properties and are considered for high-temperature applications. Both materials were exposed under several oxidized atmospheres in a wide temperature range/regime. Mn-oxide (Mn3O4, Mn2O3) was mainly formed on the HEA and Cr2O3 on the MEA. The fast diffusion of manganese prevents the formation of a continuous chromia layer on CrMnFeCoNi in Ar-O2, Ar-H2O and Ar-SO2 at 800°C.
The Cantor alloy and his ternary subsystem CrCoNi were exposed in Ar-O2-H2O-SO2 at 800°C up to 96 h to clarify their oxidation behavior in a mixed atmosphere. The oxidized samples were analyzed by weight measurement, scanning electron microscopy (SEM), and X-ray diffraction analysis (XRD). It was found that mass gain of all samples increased with increasing exposure time. The oxidation rate of the Cantor alloy is significantly higher than that of the ternary alloy system.
Mixed ionic electronic conducting ceramics Nd6-yWO12-d (d is the Oxygen deficiency) provide excellent stability in harsh environments containing strongly reactive gases such as CO2, CO, H2, H2O or H2S. Due to this chemical stability, they are promising and cost-efficient candidate materials for gas separation, catalytic membrane reactors and protonic ceramic fuel cell technologies. As in La6-yWO12-d, the ionic/electronic transport mechanism in Nd6-yWO12-d is expected to be largely controlled by the crystal structure, the conclusive determination of which is still lacking. This work presents a crystallographic study of Nd5.8WO12-d and molybdenum-substituted Nd5.7W0.75Mo0.25O12-d prepared by the citrate complexation route. High-resolution synchrotron and neutron powder diffraction data were used in combined Rietveld refinements to unravel the crystal structure of Nd5.8WO12-d and Nd5.7W0.75Mo0.25O12-d. Both investigated samples crystallize in a defect fluorite crystal structure with space group Fm3m and doubled unit-cell parameter due to cation ordering. Mo replacesWat bothWyckoff sites 4a and 48h and is evenly distributed, in contrast with La6-yWO12-d. X-ray absorption spectroscopy as a function of partial pressure pO2 in the near-edge regions excludes oxidation state changes of Nd (Nd3+) and W(W6+) in reducing conditions: the enhanced hydrogen permeation, i.e. ambipolar conduction, observed in Mo-substituted Nd6-yWO12-d is therefore explained by the higher Mo reducibility and the creation of additional – disordered – oxygen vacancies.
Corrosion Science Meets X-Rays, Neutrons and Electrons. The presentation gives an overview on current research activities applying in-situ X-ray diffraction and spectroscopy for a better understanding of fundamental mechanisms of high temperature corrosion. Additionally the knowledge gain by applying neutron powder diffraction and EBSD analysis is presented.
Konventionelle und innovative Hochtemperaturwerkstoffe sind im technischen Betrieb einer Vielzahl an Belastungen ausgesetzt. Neben mechanischen Beanspruchungen stellt die chemische Belastung durch das Vorhandensein von aggressiven und korrosiven Medien (SO2, CO2, O2, H2O…) bei hoher Temperatur einen Schlüsselfaktor dar, der die Langlebigkeit der Materialien im Einsatz beeinflusst. Neben konventionellen, mikroskopischen Analyseverfahren bieten röntgenbasierte Techniken Möglichkeiten, die Grenzflächenreaktionen zwischen dem Werkstoff und den Medien während der chemischen Belastung (in situ) zu untersuchen. Neuartige Einblicke in die zugrunde liegenden Prozesse der Schädigungsmechanismen werden anhand von klassischen ferritischen Legierungen beschrieben. Das Verständnis von Schlüsselfaktoren zur Induzierung eines Schutzmechanismus ist insbesondere für die Entwicklung von neuartigen Materialklassen wie Hochentropie- und chemisch komplexe Legierungen notwendig. Erste Einblicke in Schädigungsmechanismen durch Gaskorrosion dieser innovativen Materialsysteme werden vorgestellt.
The precise analysis of cation diffusion profiles through corrosion scales is an important aspect to evaluate corrosion phenomena under multicomponent chemical load, as during high‐temperature corrosion under deposits and salts. The present study shows a comprehensive analysis of cation diffusion profiles by electron microprobe analysis and microbeam X‐ray absorption near edge structure (µ‐XANES) spectroscopy in mixed oxide/sulfide scales grown on Fe–Cr model alloys after exposing them to 0.5% SO2. The results presented here correspond to depth‐dependent phase identification of oxides and sulfides in the corrosion scales by µ‐XANES and the description of oxidation‐state‐dependent diffusion profiles. Scales grown on low‐ and high‐alloyed materials show both a well‐pronounced diffusion profile with a high concentration of Fe3+ at the gas and a high concentration of Fe2+ at the alloy interface. The distribution of the cations within a close‐packed oxide lattice is strongly influencing the lattice diffusion phenomena due to their different oxidation states and therefore different crystal‐field preference energies. This issue is discussed based on the results obtained by µ‐XANES analysis.
The prediction of structural parameters and optoelectronic properties of compound semiconductors is very important. However, calculations often neglect chemical variability and structural defects. In chalcopyrite type semiconductors one of the major defects are copper vacancies (V Cu). The four cation neighbors of the anion determine its position in the chalcopyrite type structure expressed by the Wyckoff position 8d (x, 1/4, 1/8). Intrinsic point defects like V
Cu and anti-sites may cause variations of the Anion position in the middle of the cation tetrahedron, especially in the Anion position Parameter x. For stoichiometric chalcopyrite type compounds a formalism according to the principle of conservation of tetrahedral bonds (CTB) can be applied to calculate the anion position parameter, but it fails in the case of off-stoichiometric chalcopyrites. This case study of chalcopyrite type CuGaS 2 and Mn-substituted GuGaS 2
shows that the experimentally determined anion position Parameter x
deviate from values calculated by CTB approach. The systematic investigation of off-stoichiometric CuGaS 2 and Mn-substituted GuGaS
2 demonstrates the effect of copper vacancies on the average radii of the cation sites (Wyckoff positions 4a and 4b) as well as on the anion position Parameter x. By applying an elaborated CTB Approach implementing copper vacancies an agreement between experimental and calculated anion position Parameter x can be obtained.