Corrosion of metals and alloys in molten glasses. Part 2: nickel and cobalt high chromium superalloys behaviour and protection

Electrochemical methods have been used for the characterisation of high chromium alloys corrosion in molten glasses (cobalt and nickel base alloys in a borosilicate glass at 1050 °C, with rotating working electrodes). All the tested alloys are active but passivable materials. The active state is characterised by a rapid dissolution of the constitutive elements of the alloy in the glass melt. The passive state can be obtained by an air oxidation of the alloys (called preoxidation) or with a temporary anodic polarisation of the alloy. The obtained passive state is due to the presence of a thin protective chromia scale.     

Control of polymorphism in Al2O3 scale formed by oxidation of alumina-forming alloys

The selective oxidation of specific components in alumina-forming alloy such as CoNiCrAlY under precisely regulated oxygen partial pressures (P_O2) can be used to control polymorphism in Al₂O₃ scale formed on the alloy. Dense, smooth α-Al₂O₃ scale was formed rapidly by treatment at 1323 K under a thermodynamically determined P_O2, where both aluminum and chromium in the alloy were oxidized and elements such as cobalt and nickel were not oxidized. By contrast, under a higher P_O2 all the components in the alloy were oxidized, the transformation was obviously retarded, and (Co,Ni)(Al,Cr)₂O₄ was produced.     

Metal dusting and coking of alloy 803

Investigation was made by SEM examination on metal dusting and coking behaviours of alloy 803 in a flowing gas mixture of H₂-CO-H₂O. It was found that an oxide scale arisen on the sample surface at the beginning of exposure. Metal dusting started when graphite deposition occurred earlier at the local defects in the oxide scale than the defects were repaired by enough supply of chromium from the interior of alloy matrix. Coke consisted of graphite filaments and metallic particles produced by disintegrating of alloy matrix, and grew up from the defects in the oxide scale with pit left in the sample surface. Increasing chromium content, doping a small amount of silicon and reducing grain size to create fast diffusion paths for chromium and silicon to alloy surface, all promote the formation of a dense oxide scale and favor early self-repairing of the defects in the oxide scale before occurrence of graphite deposition. The resistance of an alloy to metal dusting can be improved generally by means of these methods.     

Evolution of carbides and chromium depletion profiles during oxidation of Alloy 602 CA

The microstructure evolution in carbide strengthened Alloy 602 CA during exposure to a synthetic flue gas (N₂–2.5%O₂–8.6%H₂O–16.4%CO₂) at 1100 °C has been studied. The chromium and aluminium loss resulted in a chromium depleted alloy subsurface area and the dissolution of the carbides within this area. An increase of the carbide fraction in the sample core was observed and quantified. Phase equilibria calculations revealed that the depletion of aluminium as well as that of chromium triggers carbon to leave the depleted area. The overall carbon depletion in that area corresponded to the observed increase in carbide fraction in the sample core.     

Characterization of microstructure and corrosion properties of cold worked Alloy 800

X-ray diffraction studies indicated that cold worked (∼50%) Alloy 800 was austenitic and transmission electron microscopy revealed the presence of a small volume fraction of hexagonal ε-martensite along with deformation bands, high dislocation density and primary TiN particle with a few dislocations within it. The passivity of cold worked alloy was very stable in H₂SO₄ solution but unstable in HCl solution at room temperature. The exposure of cold worked alloy in 673 K steam (initial pH of water was 10.1) for a period of 264 h showed almost nil corrosion rate. Scanning electron microscopy revealed a number of small oxide particles on the surface exposed in steam indicating initiation of oxide formation. Energy dispersive X-ray analyses of the surface containing small oxide particles indicated that the surface composition was similar to bulk composition of the alloy. X-ray photoelectron spectroscopy revealed that the alloy surface exposed in steam contained mixed oxides of iron and chromium as well as elemental form of iron, nickel and chromium.     

Isothermal oxidation behavior of FeCo–2V intermetallic alloy

Isothermal oxidation behavior and the nature of oxide layer formed during oxidation of FeCo–2V alloy were characterized in the temperature range of 500–600 °C. Oxidation kinetics of the alloy follows a parabolic rate law. SEM and XRD studies indicate the formation of an iron rich outer oxide layer and an inner solute rich layer containing cobalt and vanadium rich oxides. The oxidation mechanism of the FeCo–2V alloy is similar to that of low alloy steels. During the initial stages, preferential oxidation of iron and cobalt occurs at the alloy surface and leads to the formation of a solute rich inner layer. Continued oxidation occurs through oxidation of iron and cobalt at the outer layer and internal oxidation of inner layer. The iron rich oxide layer formed at the surface on oxidation of FeCo alloy is semi-conducting in nature and may not provide the necessary insulating barrier required at the surface to minimize eddy current losses during A.C. applications.     

Temperature dependence of oxide scale formation on high-Cr ferritic steels in Ar–H2–H2O

Four high chromium ferritic steels were oxidized in Ar/H₂/H₂O at temperatures between 500 and 900 °C. Polished specimens of all steels formed iron-rich oxides at temperatures below 600 °C, whereas increasing the temperature resulted in local formation of protective chromia scales. As the temperature was raised further, the specimens were totally covered with chromia scales. For the higher chromium steels this was also observed at 900 °C but not for the steel with a chromium content of 16%. The temperature dependence of the oxidation rates is governed by the competing diffusion processes in the alloy and the growing scales.     

The role of chromium and molybdenum in passivation of amorphous Fe-Cr-Mo-P-C alloys in deaerated 1 M HCl

The effect of open circuit immersion on the passivation behavior of amorphous Fe-8Cr-Mo-13P-7C alloys with 0, 2 and 6 at.% molybdenum by potentiostatic polarization in de-aerated 1 M HCl was investigated. The polarization was made at 400 mV (SCE) which is in the passive region of chromium but in the transpassive region of molybdenum, whereas the open circuit potential of these alloys is in the passive region of molybdenum but in the active region of chromium. Open circuit immersion of molybdenum-bearing alloys results in the formation of molybdenum-enriched passive film, but passivation at 400 mV is based on the formation of chromium-enriched passive film and the molybdenum-enriched film formed by open circuit immersion is converted to the chromium-enriched film at 400 mV. Polarization at 400 mV immediately after immersion leads to rapid enrichment of chromium to the level of 50% cations within 100 s, but polarization after open circuit immersion of molybdenum-bearing alloys for 10 min results in a gradual increase in chromium content to the level of 50% of cations in 5 h. The current density of molybdenum-bearing alloys after open circuit immersion is always higher than that of the alloys polarized immediately after immersion. Open circuit immersion of molybdenum-free alloy for 10 min gives rise to serious damage of the alloy surface and hence prevents passivation even if prolonged polarization is carried out.     

The effect of T4 heat treatment on the microstructure and corrosion behaviour of Zn27Al1.5Cu0.02Mg alloy

The effect of heat treatment on the microstructure and corrosion behaviour of Zn27Al1.5Cu0.02Mg alloy was examined. The alloy was prepared by melting and casting route and then thermally processed (T4 regime). Corrosion behaviour of the as-cast and heat treated alloy was studied in 3.5 wt.% NaCl solution using immersion method and electrochemical polarization measurements. The applied heat treatment affected the alloy microstructure and resulted in increased ductility and higher corrosion resistance of the heat treated alloy. Electrochemical measurements of the corrosion rate at the free corrosion potential are in agreement with the results obtained using the weight loss method.     

Improvement of the oxidation resistance of Tribaloy T-800 alloy by the additions of yttrium and aluminium

The microstructures and oxidation behaviour of the modified Tribaloy T-800 alloys by additions of yttrium and yttrium plus aluminium have been studied. At the presence of yttrium alone, the oxidation rate decreased, and the selective oxidation of chromium was promoted, which was related to the refinement of alloy phase size. The addition of yttrium plus aluminium further reduced the oxidation rate. The selective oxidation of chromium and aluminium were both promoted significantly. The benefits were especially pronounced at 1000 °C, with the formation of protective alumina external layer and no internal oxides, which may be detrimental to the alloy mechanical property.     

Effects of heat-treatment on the extent of chromium depletion and caustic corrosion resistance of Alloy 690

To quantify the extent of chromium depletion, electrochemical potentiokinetic reactivation tests were performed on solution-annealed (1393 K) and solution-annealed followed by ageing at 973 K for 4 h or 16 h samples of austenitic Alloy 690. The electrochemical studies indicated very high equilibrium chromium concentration at the chromium carbide/matrix interface for the aged samples. A new electrochemical test parameter that is the ratio of peak activation to maximum passive current density (defined by I_a/I_f) was considered to express the extent of chromium depletion. The alloy, in three different heat-treated conditions, revealed unstable passivity in deaerated 5% and 10% NaOH solutions at 295 K. A comparatively higher passive current density of the aged samples in deaerated caustic environments than the annealed one could be attributed to reactivity of Cr-carbides with the caustic. Microscopic studies indicated that the TiN inclusion/matrix interface may provide a preferred site for pit initiation in caustic environments, which could be attributed to large degree of misfit between TiN inclusion and austenite matrix.     

Electrochemical behaviour and corrosion of Mg–Y alloys

Corrosion of cast magnesium–yttrium (Y) alloys with systematic Y additions up to a nominal 18 wt.% were studied. Corrosion performance was related to the quantitative alloy microstructure and found to increase significantly with the level of alloying and volume fraction of the Mg–Y intermetallic present. In the alloy microstructures, Mg₂₄Y₅ was principally formed; the electrochemistry of which was characterised using the electrochemical microcell method. Electrochemical testing revealed the fundamental corrosion behaviour of Mg–Y alloys and elucidated the corrosion mechanisms at play.     

The influence of temperature on the passivation behaviour of a super duplex stainless steel in a boric-borate buffer solution

The passivation behaviour of a super duplex stainless steel has been investigated in a boric-borate buffer solution with and without chloride additions, at different temperatures, by means of potentiodynamic and potentiostatic techniques. X-ray photoelectron spectroscopy was used to detect surface compositional changes of anodic passive films formed as a function of electrode potential and temperature. The resulting passive films were all chromium enriched with respect to the bulk composition, and their thickness and ratio were found to vary significantly. In particular, the films formed in the passive domain were more enriched with chromium compared with those grown in the secondary passive region. At a constant potential the temperature increase produced a reduction in the chromium content of the film. These findings can be explained by the different ionic mobilities and dissolution rates at the film/solution and film/alloy interfaces. Pitting corrosion was observed only in the transpassive zone. A temperature increase from 23 to 60 °C did not produce a decrease in the pitting potential. This behaviour can be explained by the parallel action of two different phenomena, the change in the composition and structure of the passive film and the velocity increase in the process, which yield localized rupture of the passivity by the nucleation and growth of pits in connection with chromium depletion at high potentials.     

Corrosion stability of ferritic stainless steels for solid oxide electrolyser cell interconnects

Long-term oxidation behaviour of eight ferritic steels with 20-29 wt.% chromium (F 20 T, TUS 220 M, AL 453, Crofer 22 APU, Crofer 22 H, Sanergy HT, E-Brite and AL 29-4C) has been studied. The samples were cut into square coupons, ground and annealed for 140-1000 h at 1173 K in flowing, wet hydrogen, air and pure oxygen. The reaction kinetics was followed by mass increase of individual samples over time. Parabolic rate law was observed for most measurements. The respective rate constants have been evaluated and compared. The chemical composition of the oxide scale was investigated by XRD and SEM/EDXS. The major constituent is chromium oxide. Other oxides, such as (Mn, Cr)₃O₄, MnTiO₃, SiO₂ or Al₂O₃, are also present in different amounts depending on the chemical composition of the steel. The oxidation rate increases with increasing oxygen partial pressure and decreasing chromium concentration. Chromium diffusion coefficients in Cr₂O₃ and parabolic rate constants are compared. The reaction mechanism for the chromia formation is suggested. The results are discussed with respect to the applications of the steels in a working solid oxide electrolyser cell stack. Furthermore, suggestions for the development of a superior alloy composition are given.     

Protection of cobalt-based refractory alloys by chromium deposition on surface: Part I: Sub-surface enrichment in chromium by pack-cementation and diffusion

The feasibility of surface chromium enrichment by pack-cementation was assessed for different low chromium-containing cobalt alloys, in order to improve their resistance against high temperature oxidation. A binary Co-10Cr alloy, two ternary Co-10Cr-0.5C and Co-10Cr-1.0C alloys and two TaC-containing Co-10Cr-based alloys were elaborated by foundry for the study. 7.5 h-long and 15 h-long cementations at 1050 °C, followed or not by a 75 h-long heat treatment at 1200 °C were performed on these alloys. Microstructure examinations performed using a Scanning Electron Microscope and concentration profiles using Electron Probe Micro Analysis-Wavelength Dispersion Spectrometry were realized in order to analyze the level of Cr-enrichment of the sub-surface region, with as studied criteria: the nature of the external Cr-enriched zone, the maximal chromium content on surface and the depth of chromium enrichment. The Cr-enrichment of the sub-surface succeeded for the Co-10Cr alloy and for the two tantalum-containing alloys, with the formation of an external metallic zone containing around 30 wt.% Cr. In contrast the chromium carbides-containing alloys were effectively enriched in chromium in surface but in the form of a continuous chromium carbide layer which can induce other problems such as spallation and then possible fast oxidation of the denuded alloy. Finally it appeared that only the carbon-free alloys, and the alloys reinforced by carbides more stable than chromium carbides, are potentially able to be successful enriched in chromium in their sub-surface by pack-cementation.     

XPS study of duplex stainless steel oxidized by oxygen atoms

Surface oxidation of the duplex stainless steel DSS alloy 2205 was studied by X-ray photoelectron spectroscopy (XPS) and SEM imaging. The experiments were performed on the alloy after controlled oxidation with oxygen atoms created in an inductively coupled plasma. Experiments were performed at temperatures from room temperature up to 700 °C. Compositions of the modified oxidized surfaces were obtained from XPS survey scans, and the chemistries of selected elements from higher energy resolution scans of appropriate peaks. The morphologies of the surfaces were obtained using field emission scanning electron microscopy at different magnifications, up to 10,000×. Different Fe/Cr/Mn oxidized layers and different oxide thicknesses were observed and correlated with temperature.     

Corrosion of cupronickel alloy in permanganate under acidic condition

Cupronickel alloys are used as heat exchanger tube materials in nuclear power plant auxiliary coolant systems. In this work, the corrosion behaviour of cupronickel (70:30) alloy in permanganic acid medium was studied. Corrosion rate was found to follow logarithmic kinetics. Cyclic polarization studies showed that cupronickel did not undergo pitting in permanganic acid medium but uniform corrosion was observed. Presence of 0.43 mol/m³ chromate in 2.5 mol/m³ permanganic acid was found to decrease the corrosion rate of cupronickel by 50%. EIS and XPS studies revealed that the film formed on cupronickel was protective in nature and contained oxides of copper, nickel and manganese (mainly MnOOH). The composition of the film on cupronickel that had undergone chromate treatment also showed similar film except that it contained some chromium (III).     

High temperature oxidation of metallic chromium exposed to eight different metal chlorides

The influence of eight different chlorides (BaCl₂, CaCl₂, KCl, LiCl, MgCl₂, NaCl, PbCl₂, and ZnCl₂) on the oxidation of metallic chromium powder was studied at four different temperatures (400 °C, 500 °C, 550 °C, and 600 °C) under dry conditions in synthetic air by using a DTA/TG-apparatus. BaCl₂, CaCl₂, and MgCl₂ did not react with chromium at any of the studied temperatures. ZnCl₂ evaporated already before the air was introduced. KCl, LiCl, NaCl, and PbCl₂ were all found to be reactive and to accelerate the oxidation of chromium. LiCl reacted only at 600 °C, whereas the other three chlorides mentioned above reacted from 500 °C upwards.     

Effect of cobalt on the corrosion resistance of low alloy steel in sulfuric acid solution

This study examines the effect of cobalt addition on the corrosion resistance of low alloy steel in a 10 wt.% sulfuric acid solution at room temperature. All specimens show passive behaviors over the potential range, 0.5–1.55 V_SCE, and the passive current density decreased with increasing Co addition. The Co-containing steels also show higher polarization resistance and lower corrosion rate. The beneficial effect of Co is attributed to the formation of a uniform and continuous rust layer due to an interaction between Co and other elements such as Fe, O and S.     

Corrosion of metals and alloys in molten glasses. Part 1: glass electrochemical properties and pure metal (Fe, Co, Ni, Cr) behaviours

Corrosion of pure metals Fe, Ni, Co, Cr in molten glass was studied at 1050 °C by electrochemical techniques and thickness losses measurements. These two techniques are in good agreement. The electrochemical apparatus was used to determine the formal potential of some redox couples, to identify the corrosion reactions and to evaluate the corrosion rates.Among tested metals, only chromium is a passivable material. The passivation is due to the formation of a chromium oxide (Cr₂O₃) protective layer at the glass/metal interface. Then superalloys used in molten glass must contain a high chromium level to resist to corrosion.