High temperature corrosion of pure Fe, Cr and Fe-Cr binary alloys in O2 containing trace KCl vapour at 750 °C

Pure Fe, Cr and Fe-Cr binary alloys were corroded in O₂ containing 298 ppm KCl vapour at 750 °C. The corrosion kinetics were determined, and the microstructure and the composition of oxide scales were examined. During corrosion process, KCl vapour reacted with the formed oxide scales and generated Cl₂ gas. As Cl₂ gas introduced the active oxidation, a multilayer oxide scales consisted of an outmost Fe₂O₃ layer and an inner Cr₂O₃ layer formed on the Fe-Cr alloys with lower Cr concentration. In the case of Fe-60Cr or Fe-80Cr alloys, monolayer Cr₂O₃ formed as the healing oxidation process. However, multilayer Cr₂O₃ formed on pure Cr.     

Effects of cerium and manganese on corrosion of Fe–Cr and Fe–Cr–Ni alloys in Ar–20CO2 gas at 818 °C

Model alloys Fe–9Cr, Fe–20Cr and Fe–20Cr–20Ni (wt.%) with Ce (0.05%, 0.1%) or Mn (1%, 2%) were exposed to Ar–20CO₂ gas at 818 °C. Scales on Fe–9Cr alloys consisted of FeO and FeCr₂O₄, Fe–20Cr–(Ce) alloys formed only Cr₂O₃, and Fe–20Cr–(Mn) alloys formed Cr₂O₃ and MnCr₂O₄. All Fe–20Cr–20Ni alloys formed Fe₃O₄, FeCr₂O₄ and FeNi₃. Cerium additions had little effects, but additions of 2% Mn significantly improved oxidation resistance of Fe–20Cr and Fe–20Cr–20Ni alloys. Most alloys also carburized. All alloys developed protective chromium-rich oxide scales in air. Different behavior in the two gases is attributed to faster Cr₂O₃ scaling rates induced by CO₂.     

Effect of water vapour on cyclic oxidation of Fe–Cr alloys

Model Fe–Cr alloys containing 9, 17 or 25 wt% Cr were subjected to repeated 1 h cycles of exposure at 700 °C to flowing gas mixtures of Ar‐20O₂, Ar‐20O₂‐5H₂O and Ar‐5O₂‐20H₂O (all in volume %) for up to 400 cycles. The kinetics and morphological development of these reactions were compared with those found during isothermal exposure to the same gases. Under isothermal conditions, all alloys developed thin protective chromium‐rich scales in dry oxygen. Addition of 5% H₂O induced breakaway for Fe‐9Cr within 48 h, but had little effect on higher chromium alloys. Isothermal chromia scale growth on Fe‐17Cr and Fe‐25Cr was accelerated by the addition of 20% H₂O, but breakaway did not result. Under cyclic conditions in dry oxygen, Fe‐9Cr quickly entered breakaway, oxidising according to fast, linear kinetics, but the higher chromium alloys exhibited protective behaviour. When 5% H₂O was added to the oxygen, the 17% Cr alloy also underwent fast breakaway oxidation, but Fe‐25Cr continued to be protected by a chromia scale. In the 20% H₂O gas, all alloys failed under cyclic conditions, producing thick, iron‐rich oxide scales. The synergistic effects of water vapour and temperature cycling are discussed in terms of alloy chromium depletion and the effects of H₂O(g) on oxide transport properties.     

Water Vapour Effects on Fe–Cr Alloy Oxidation

Isothermal oxidation at 700 °C of binary Fe–Cr alloys containing 9, 17 and 25 wt% chromium was measured using continuous thermogravimetric analysis. All alloys developed thin, protective chromia scales in Ar–20O₂ (vol%). Chromia scale growth on the 17 and 25 Cr alloys was faster in Ar–20O₂–5H₂O and Ar–5O₂–20H₂O. In these gases, the Fe–9Cr failed to form a chromia scale and suffered rapid breakaway oxidation, growing iron-rich oxides instead. A low oxygen potential gas, Ar–10H₂–5H₂O caused chromia scaling on Fe–17Cr and Fe–25Cr, but internal oxidation of Fe–9Cr. Application of Wagner’s criterion for sustaining external scale growth is shown to account satisfactorily for these observations.     

High temperature oxidation of Fe13CrxAl alloys in airH2O vapour mixtures

High-temperature oxidation in air of Fe13CrxAl alloys containing up to 4.5 Al has been studied in the temperature range 680–980°C. A primary aim was to study the oxidation as a function of the Al concentration in the alloys and the water vapour content (from 0.03 to 2.3 vol. % H₂O) in the oxidizing gas.The Fe13Cr alloy exhibits an initial protective behaviour due to formation of protective Cr₂O₃ and $\text{Cr}{}_2\text{O}{}_3\text{Fe}{}_2\text{O}{}_3$ films. This protective stage is succeeded by breakaway oxidation due to depletion of chromium in the alloy beneath the oxide scale; double-layered, porous scales develop and chromium is internally oxidized. Under these conditions the oxidation rate increases significantly with increased water vapour content.Additions of aluminium modify the oxidation behaviour. At sufficiently high Al concentrations protective scales of AL₂O₃ (α-AL₂O₃) are found. The critical Al concentration necessary for selective Al oxidation increases as the temperature increases. Thus at 980°C 4Al is necessary while at 680°C 1Al provides excellent oxidation resistance. When continuous Al₂O₃ scales are formed the oxidation is not significantly dependent on the water vapour content in the air.At Al contents below the critical Al concentration, porous, multilayered scales are formed enriched with Al₂O₃ in the innermost layer. Under these conditions the oxidation rate increases significantly with water vapour content.The results strongly suggest that the increased rate of oxidation with water vapour content is due to gaseous transport across voids and pores with H₂O, H₂, and O₂ as carrier gases.     

High-temperature oxidation behavior of minor Hf doped NiAl alloy in dry and humid atmospheres

Oxidation behavior of NiAl and 0.05 at.% Hf doped NiAl alloys were investigated at 1100 °C in dry and humid atmospheres. Hf doping significantly improved the cyclic oxidation resistance. Water vapour promoted the formation of voids at the scale/alloy interface and accelerated scale spallation. Also, water vapour had effect on the phase transformation from θ- to α-Al₂O₃ at the initial oxidation stage. In humid atmosphere, more Hf segregated at the scale/alloy interface to form oxide pegs. Pre-oxidation process in O₂ + Ar could compromise the effect of humid atmosphere on the oxidation kinetics of the NiAl alloys.     

Protective and non-protective scale formation of NiCr alloys in water vapour containing high- and low-pO2 gases

The oxidation behaviour of NiCr alloys with Cr contents of 10, 20 and 25 wt.%, respectively, were studied in Ar-O₂, Ar-O₂-H₂O and Ar-H₂O mixtures. TG and SEM analysis revealed that the chromia scales formed on Ni-25Cr in the wet gases did not differ substantially from those formed in Ar-O₂. For the two “borderline” alloys Ni-10Cr and Ni-20Cr, addition of water vapour to Ar-O₂ hampered the formation of a protective chromia scale which, especially for Ni-10Cr, resulted in substantially increased scale growth rates compared to exposures in dry gas. Different from numerous observations described in the literature for “borderline” FeCr alloys with intermediate Cr contents of 10-20%, the corresponding NiCr alloys showed in Ar-H₂O a smaller tendency for non-protective scale formation than in Ar-O₂-H₂O. This is caused by the decreasing growth rate of NiO with decreasing pO₂ of the test gas, with the secondary effect that external chromia scale formation is promoted in low-pO₂ gases such as Ar-H₂O. Even if the alloy Cr content was too low to obtain external chromia scale formation, the oxidation rate in Ar-H₂O would, in contrast to low-Cr FeCr alloys, be quite small due to the very slow growth rate of NiO in this low-pO₂ gas.     

Temperature and gas composition dependence of internal oxidation kinetics of an Fe?10%Cr alloy in water vapour containing environments

Recently it was proposed, that the hampered formation of external protective chromia scales on FeCr‐alloys in water vapour containing, low‐pO₂ gases is correlated with enhanced internal oxidation of chromium. In the present study the internal oxidation kinetics of Fe? 10Cr (in mass%) during isothermal oxidation in Ar? H₂? H₂O mixtures at temperatures in the range 800–1050 °C has been investigated. It was found that the tendency for Cr to become internally oxidized decreased with decreasing temperature. At the higher test temperatures the internal oxide precipitates consisted of Fe/Cr‐spinel. With decreasing temperature the precipitates near the oxidation front gradually exhibited increasing amounts of chromia. At 900 °C the oxidation morphology in the Ar? H₂ base gas mixture changed from exclusive internal oxidation of Cr at a water vapour content of 2% towards a combined internal Cr oxidation and external Fe‐oxide formation at higher water vapour partial pressures.     

Oxidation of FeCr alloys in O2/3% H2O

A range of FeCr binary alloys containing 2–100%Cr was exposed in O₂/3%H₂O at 1023–1223K to determine whether the presence of the water had a significant effect on oxidation. Oxidation rates were not significantly different from those in dry oxygen and decreased with increasing time of oxidation. The kinetics of oxidation and the oxide structures both suggested that the early stages of oxidation were controlled by lattice diffusion through layers of FeCr spinel for Fe-2 1/4Cr and Fe-8 1/2Cr, or through (Cr, Fe)₂O₃ scale for alloys containing 16%Cr or more.     

Oxidation of 310 steel in H2O/O2 mixtures at 600 °C: the effect of water-vapour-enhanced chromium evaporation

The oxidation of type 310 stainless steel was investigated at 600 °C in the presence of O₂ and O₂+10% and 40% H₂O. The effect of gas velocity was studied. The oxidized samples were investigated by grazing angle X-ray diffraction, SEM/EDX and SAM. The addition of H₂O to O₂ resulted in a change of oxidation behaviour. A strong dependence on flow rate was observed in O₂/H₂O mixtures. At low flow rates a thin (30-50 nm) protective α-(Cr,Fe)₂O₃ formed, the outer part being depleted in chromium. When the flow rate was increased beyond a critical value the protective oxide failed. Under these conditions ?5 μm thick α-Fe₂O₃/(Cr,Fe)₃O₄, oxide islands formed on the part of the surface corresponding to the centre of the alloy grains. The effect of water vapour is attributed to the water-vapour-assisted evaporation of chromium from the oxide, in the form of a chromium oxide hydroxide, probably CrO₂(OH)₂. The oxidation behaviour is rationalized using a qualitative mechanism proposed previously and parallels that of the 304L alloy.     

The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.     

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.     

Oxidation of iron at 400-600 °C in dry and wet O2

The oxidation of iron in dry and wet O₂ at 400-600 °C has been re-investigated using gravimetry, SEM/EDX, XRD and FIB. In the presence of O₂, water vapour accelerates iron oxidation at 500 and 600 °C. At 400 and 500 °C the magnetite layer is duplex and exposure to water vapour results in the formation of blades on top of a fine-grained hematite layer. At 600 °C it results in a surface without needles and blades. The increased oxidation rate at 500 and 600 °C is attributed to a smaller grain size in the hematite layer resulting in faster ion transport.     

A first quantitative XPS study of the surface films formed, by exposure to water, on Mg and on the Mg-Al intermetallics: Al3Mg2 and Mg17Al12

An XPS investigation was carried out of the surface films, formed by exposure to ultrapure water, on mechanically ground Mg and the two Mg-Al intermetallic compounds: Al₃Mg₂ and Mg₁₇Al₁₂. The mechanically ground Mg surface had a film of MgO at the Mg metal surface covered by a Mg(OH)₂ layer, formed by the reaction of the MgO with water vapour in the air. Upon immersion in ultrapure water, this film converted to a duplex film with an inner MgO layer next to the Mg metal and an external porous hydroxide layer. For both intermetallics, the XPS data is consistent with (i) preferential dissolution of Mg and (ii) a 10 nm thick film on the surface after immersion in ultrapure water; the film composition on Al₃Mg₂ was AlMg_1.4O_0.2(OH)_5.4 whilst on Mg₁₇Al₁₂ the composition was AlMg_2.5(OH)₈.     

Oxidation and interfacial fracture behaviour of NiCrAlY/Al2O3 coatings on an orthorhombic-Ti2AlNb alloy

Al₂O₃ diffusion barriers of various thicknesses have been fabricated by filtered arc ion plating between the NiCrAlY coating and the O-Ti₂AlNb alloy. Isothermal oxidation tests and three-point bend tests have been conducted to investigate the influence of the Al₂O₃ diffusion barriers on the oxidation and interfacial fracture behaviour of the coatings. The results indicate that the Al₂O₃ diffusion barrier defers interdiffusion and gives oxidation resistance of the NiCrAlY coatings. The thickness of the Al₂O₃ interlayer not only influences the oxidation behaviour but also affects the interfacial fracture properties. Additionally, thermal exposure affects the critical load in three-point bend tests.     

Corrosion behaviour of cermet-based coatings with a bond coat in 0.5 M H2SO4

The corrosion behaviour of an HVOF Ni–5Al/WC–17Co coating on Al-7075 is investigated in 0.5 M H₂SO₄. In the temperature range of 25–45 °C, the coating exhibits pseudopassivity that effectively protects from localized corrosion. At 25 °C, pseudopassivity proceeds via three stages: during the first stage, oxidation of W in the binder phase occurs. The second stage is characterized by oxidation of W in both the binder and the carbide particles. The third stage is characterized by intensive hydration of WO₃ and formation of Co₃O₄. During the second and third pseudopassive stages, the formation of a bi-layer surface film is postulated. The inner layer, consisting of anhydrous oxides, has a barrier character. The outer layer, composed of WO₃ · xH₂O, is unstable. In case of surface film disruption, the bond coat successfully hinders corrosion propagation into the Al-alloy. Higher electrolyte temperatures lead to faster corrosion kinetics and higher tendency for pitting.     

Ion-plated Al-Al2O3 films as diffusion barriers between NiCrAlY coating and orthorhombic-Ti2AlNb alloy

Ion-plated Al-Al₂O₃ cermet films were fabricated as diffusion barriers between NiCrAlY coating and orthhombic-Ti₂AlNb alloy. The oxidation and interdiffusion behaviour of coatings with and without diffusion barrier were investigated in isothermal and cyclic oxidation tests at 800 °C. The results indicated that substantial interdiffusion and rapid oxidation degradation occurred in the coated specimens without diffusion barrier. With Al-Al₂O₃ diffusion barriers, deferred interdiffusion and improved oxidation resistance was observed. Among them, duplex coating containing 1Al-Al₂O₃ interlayer exhibited the best performance. Coefficient of diffusion hindering and factor of reaction hindering were proposed to compare and quantify the efficiency of the diffusion barriers.     

The role of microstructure in the high temperature oxidation mechanism of Cr3C2-NiCr composite coatings

Composites of Cr₃C₂-NiCr provide superior oxidation resistance to WC-Co composites, which has seen them applied extensively to components subjected to combined high temperature erosion and oxidation. This work characterises the variation in oxidation mechanism of thermally sprayed Cr₃C₂-NiCr composites at 700 °C and 850 °C as a function of heat treatment. Carbide dissolution during spraying increased the Ni alloy Cr concentration, minimising the formation of Ni oxides during oxidation. Compressive growth stresses resulted in ballooning of the oxide over the carbide grains. Carbide nucleation with heat treatment reduced the Ni alloy Cr concentration. The oxidation mechanism of the composite coating changed from being Cr based to that observed for NiCr alloys.     

Evolution of surface chemistry and morphology of oxide scale formed during initial stage oxidation of modified 9Cr–1Mo steel

Initial stage oxidation characteristics of the modified 9Cr–1Mo steel in ambient air at 650 °C have been investigated, for exposure times ranging from 5 to 500 h. Oxygen flux from the gas phase causes high initial oxidation rate, but the growth kinetics do not follow parabolic law. In “as-received” condition, binary oxides of Fe and Cr were found as native oxides. Upon oxidation, segregation of Mn resulted in the formation of MnCr₂O₄ along with FeCr₂O₄ and binary oxides of Fe, Cr and Mn. Thus, the initial oxide scale constitutes multiple oxides with delineated interface, unlikely to have a layered structure.