Oxidation of Fe-3 wt.% Cr alloy

The oxidation behavior and the oxide microstructure on Fe-3 wt. % Cr alloy were investigated at 800°C in dry air at atmospheric pressure. Two distinct oxidation rate laws were observed: initial parabolic oxidation was followed by nonparabolic growth. The change in the oxidation kinetics was caused by microchemical and microstructural developments in the oxide scale. Several layers developed in the oxide scale, consisting of an innermost layer of (Fe,Cr)₃O₄ spinel, an intermediate layer of (Fe,Cr)₂O₃ sesquioxide, and two outer layers of Fe₂O₃ hematite, each with different morphologies. Wustite (Fe_1–xO) and distorted cubic oxide (-(Fe,Cr)₂O₃) were observed during the iniital parabolic oxidation only.     

Cyclic oxidation behavior of Ni3Al-7.8% Cr-1.3% Zr-0.8% Mo-0.025% B between 900 and 1100°C

A Ni₃Al-based alloy, the composition of which was Ni-16.0% Al-7.8% Cr-1.3% Zr-0.8% Mo-0.025%B, was cyclically oxidized in the temperature range of 900 to 1100°C in air for up to 500 hr. The alloy displayed good cyclic oxidation resistance up to 1000°C, with little scale spallation. It, however, lost cyclic oxidation resistance during oxidation at 1100°C after about 200 hr, displaying large weight losses due to serious scale spallation. NiO, α-Al₂O₃, NiAl₂O₄ and ZrO₂ were formed. The oxide scales consisted primarily of an outer Ni-rich layer which was prone to spallation, and (Al, Cr, Zr, Mo, Ni)-containing internal oxides which were adherent due mainly to the formation of (Al₂O₃, ZrO₂)-containing oxides that keyed the oxide scale to the matrix alloy.     

Roles of Nb on the oxidation characteristics and oxide scale evolution of Fe-25Cr-35Ni-2.5Al-XNb alloys at 1000°C and 1100°C

The oxidation characteristics of Fe-25Cr-35Ni-2.5Al-_XNb (0, 0.6, and 1.2 wt%) alumina-forming austenitic alloys at 1000°C and 1100°C in air were investigated. Results show that Nb has an important effect on the high-temperature oxidation resistance. A bilayer oxide scale with a Cr₂O₃-rich outer layer and Al₂O₃-rich internal layer forms on the surface of the Nb-free alloy and exhibits a poor oxidation resistance at 1000°C and 1100°C. With Nb addition, both the 0.6Nb-addition and 1.2Nb-addition alloys exhibit better oxidation resistance at 1000°C. Because of the third element effect, Nb addition reduces the critical Al content and forms a single external protective Al₂O₃ scale, which greatly improves the oxidation resistance. After oxidation at 1100°C, niobium oxides (mainly Nb₂O₅) are formed on the surface of the 1.2Nb-addition alloy and destroy the integrity of the Al₂O₃ scale, which causes the formation of Cr-rich oxide nodules and eventually develops to be a loose bilayer oxide scale with NiCr₂O₄, Cr₂O₃, and Fe₂O₃ outer layers and Al₂O₃ inner layer.     

Oxidation Behavior of Ni-3, 6 wt% Al Alloys at 800 °C in Atmospheres Containing Water Vapor

The oxidation behavior of Ni, Ni–3Al, and Ni–6Al alloys at 800 °C in air + H₂O was investigated. The oxidation kinetics of Ni and the alloys in air + H₂O were very similar, but the mass gains of Ni and each alloy were smaller in air + H₂O than in air. Oxidation products formed on Ni-3 and 6Al alloys consisted of an outer NiO scale and internal Al₂O₃ precipitates. The growth rates of both NiO and the internal oxidation zone were much smaller in air + H₂O. The NiO scale formed in air + H₂O was duplex in structure with outer porous and inner dense layers. The outer porous layer consisted of fine powder-like NiO particles. A thicker metallic Ni(Al) layer formed at the NiO/alloy interface in air + H₂O, caused by extrusion of Ni from the substrate due to volume changes accompanying the internal oxide formation. Formation of the metallic Ni layer appeared to be the reason for the similarity between the oxidation kinetics of both Ni and the alloys in air + H₂O.     

Corrosion of Fe-(4.8, 9.2, 14.3) Wt%Al alloys at 700 and 800 °C in N2/H2O/H2S gases

Fe-(4.8, 9.2, 14.3)wt%Al alloys were corroded at 700 and 800 °C for up to 70 h in 1 atm of N₂/H₂O and N₂/H₂O/H₂S gases. Oxidation prevailed in N₂/H₂O gases. Fe-(4.8, 9.2)Al alloys formed a duplex scale that consisted of an outer iron oxide layer and an inner (Fe, Al, O)-mixed layer. The Fe-14.3Al alloy formed a thin layer consisting of α-Al₂O₃. Sulfidation dominated in N₂/H₂O/H₂S gases, resulting in rapid corrosion. Fe-(4.8, 9.2)Al alloys formed a duplex scale that consisted of an outer FeS layer and an inner (Fe, Al, S, O)-mixed layer. The high growth rate of FeS impeded the formation of a continuous, protective aluminium-rich oxide. The Fe-14.3Al alloy formed a thin layer consisting of α-Al₂O₃ that was incorporated with a bit of sulfur.     

High-temperature oxidation of Fe-16.7% Mn-2.1% Ni-6.6% Si alloy in SO2

The oxidation of an austenitic Fe-16.7% Mn-2.1% Ni-6.6% Si (by weight) alloy in SO₂ in the temperature range 600–900°C is described. The corrosion products formed on this alloy in this environment below 800°C consist only of oxides, rather than a mixture of oxides and sulfides as is observed for unalloyed Fe or Mn. The kinetics of oxidation of the alloy in SO₂ in this temperature range are similar to those in O₂. It is proposed that these characteristics result from the presence of a thin silicate layer near the scale-metal interface that alters the gradient of oxygen potential within the scale.     

Modification of the oxidation behavior of high-purity austenitic Fe-14Cr-14Ni by the addition of silicon

The oxidation behavior of Fe-14Cr-14Ni (wt.%) and of the same alloy with additions of 1 and 4% silicon was studied in air over the range of 900-1100° C. The presence of silicon completely changed the nature of the oxide scale formed during oxidation. The base alloy (no silicon) formed a thick outer scale of all three iron oxides and an internally oxidized zone of (Fe,Cr,Ni) spinels. The alloy containing 4% silicon formed an outer layer of Cr₂O₃ and an inner layer of either (or possibly both) SiO₂ and Fe₂SiO₄. The formation of the iron oxides was completely suppressed. The oxidation rate of the 4% silicon alloy was about 200 times less than that of the base alloy, whereas the 1% silicon alloy exhibited a rate intermediate to the other two alloys. The actual ratio of the oxidation rates may be less than 200 due to possible weight losses by the oxidation of Cr₂O₃ to the gaseous phase CrO₃. The lower oxidation rate of the 4% silicon alloy was attributed to the suppression of iron-oxide formation and the presence of Cr₂O₃, which is a much more protective scale.     

The influence of manganese on the High-temperature oxidation of iron-chromium alloys

An investigation has been undertaken into the oxidation behaviour of manganese-containing Fe-28% Cr alloys in oxygen at 800° and 1000°C. The presence of the tertiary element has a detrimental effect on the oxidation resistance, resulting in enhanced scale-growth rates during isothermal exposure and increased incidences of scale failure at temperature. This is largely due to relatively rapid rates of diffusion of manganese across the Cr₂O₃ scale and formation of MnCr₂O₄ spinel on its outer surface. The scale on Fe-28% Cr-1% Mn consists of a layer of Cr₂O₃, containing a small concentration of manganese, with an outer layer of the spinel oxide. During the early stages, an inner layer of the spinel also develops, but, eventually, this almost completely disappears as the manganese diffuses into the outer scale. A similar scale forms on Fe-26% Cr-5% Mn, but the higher manganese concentration enables a significant amount of this element to be retained in the inner regions. The overall growth rate of the scale is significantly faster than on Fe-28% Cr or the 1% Mn-containing alloy.     

A TEM study of the oxide scale development in Ni-Cr-Al alloys

In the present study the isothermal oxidation behaviours of Ni-10Cr-5Al, Ni-20Cr-5Al and Ni-30Cr-5Al alloys were investigated. The alloys were oxidised in air for 50 h at 1000 °C. Analytical transmission electron microscopy was used to characterize the morphology, structure and composition of the oxide scale. The oxide formed adjacent to the alloy was α-Al₂O₃ such that the higher was the Cr content of the alloy the easier was its formation. The Ni-30Cr-5Al alloy formed a complete layer of α-Al₂O₃ in the initial stages of oxidation through ‘oxygen gettering’ by Cr. A decrease in scale thickness and an increase in scale adherence were observed with an increase in Cr content from 10 to 30 wt.%.     

Transient Oxidation of a γ-Ni–28Cr–11Al Alloy

γ-NiCrAl alloys with relatively low Al contents tend to form a layered oxide scale during the early stages of oxidation, rather than an exclusive α-Al₂O₃ scale, the so-called “thermally grown oxide” (TGO). A layered oxide scale was established on a model γ-Ni–28Cr–11Al (at.%) alloy after isothermal oxidation for several minutes at 1100°C. The layered scale consisted of an NiO layer at the oxide/gas interface, an inner Cr₂O₃ layer, and an α-Al₂O₃ layer at the oxide/alloy interface. The evolution of such an NiO/Cr₂O₃/Al₂O₃ layered structure on this alloy differs from that proposed in earlier work. During heating, a Cr₂O₃ outer layer and a discontinuous inner layer of Al₂O₃ initially formed, with metallic Ni particles dispersed between the two layers. A rapid transformation occurred in the scale shortly after the sample reached maximum temperature (1100°C), when two (possibly coupled) phenomena occurred: (i) the inner transition alumina transformed to α-Al₂O₃, and (ii) Ni particles oxidized to form the outer NiO layer. Subsequently, NiO reacted with Cr₂O₃ and Al₂O₃ to form spinel. Continued growth of the oxide scale and development of the TGO was dominated by growth of the inner α-Al₂O₃ layer.     

Oxidation behavior of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy at high temperature in Ar-H2O atmospheres

The oxidation of an Fe-38Ni-13Co-4.7Nb-1.5Ti-0.4Si superalloy (Incoloy 909 type alloy), was investigated at temperatures between 1000 K and 1400 K in Ar-(1, 10%)H₂0 atmosphere using metallographic, electron probe microanalysis, and X-ray diffraction techniques. The oxide scales consist of an external scale and an internal scale which has an intergranular scale (above 1200 K) and an intergranular scale. The oxide phases in each scale are identified as-Fe₂,O₃ (below 1200 K) or FeO (above 1300 K) and CoO · Fe₂O₃ and FeO · Nb₂O₅, respectively. The morphologies, the oxide phases and the oxidation rates do not depend on the partial pressure of H₂O in the range between one and ten percent in Ar gas. The rate constants for the intergranular-scale formation in this alloy are about one-tenth as large as those in Fe-36%Ni alloy reported previously. At all the temperatures the scales grow according to a parabolic rate law and the apparent activation energies for the processes are estimated.     

The oxidation of Fe-19.6Cr-15.1Mn stainless steel

The oxidation behavior in air of Fe-19.6Cr-15.1Mn was studied from 700 to 1000°C. Pseudoparabolic kinetics were followed, giving an activation energy of 80 kcal/mole. The scale structure varied with temperature, although spinel formation occurred at all temperatures. At both 700 and 800°C, a thin outer layer of -Mn₂O₃ formed. The inner layer at 700°C was (Fe,Cr,Mn)₃O₄, but at 800°C there was an intermediate layer of Fe₂O₃ and an inner layer of Cr₂O₃ + (Fe, Cr,Mn)₃O₄. Oxidation at 900°C produced an outer layer of Fe₃O₄ and an inner layer of Cr₂O₃+(Fe,Cr,Mn)₃O₄. Oxidation at 1000°C caused some internal oxidation of chromium. In addition, a thin layer of Cr₂O₃ formed in some regions with an intermediate layer of Fe₃O₄ and an outer layer of (Fe,Mn)₃O₄. A comparison of rates for Fe₃O₄ formation during oxidation of FeO as well as for the oxidation of various stainless steels, which form spinels, gave good agreement and strongly suggests that spinel growth was rate controlling. The oxidation rate of this alloy (high-Cr) was compared with that of an alloy previously studied, Fe-9.5Cr-17.8Mn (low-Cr) and was less by about a factor of 12 at 1000°C and by about a factor of 100 at 800°C. The marked differences can be ascribed to the destabilization of wustite by the higher chromium alloy. No wustite formation occurred in the high-Cr alloy, whereas, extensive wustite formed in the low-Cr alloy. Scale structures are explained by the use of calculated stability diagrams. The mechanism of oxidation is discussed and compared with that of the low-Cr alloy.     

Fe-30Ni-5NiO alloy as inert anode for low-temperature aluminum electrolysis

Fe-30Ni-5NiO alloy anodes were prepared by a spark plasma sintering process for aluminum electrolysis. NiO nano-particles with the size of ∼20 nm were dispersed in the anodes. The oxidation behaviors of the anodes were investigated at 800°C and 850°C, respectively. The electrolysis corrosion behaviors were tested in a cryolite-alumina electrolyte at a low temperature of 800°C with anodic current densities of ∼0.5 A/cm². The results indicated that the oxidation kinetic of the anodes followed a parabolic law. A continuous Fe₂O₃ film selectively formed on the surface of the anode during the electrolysis process. A semi-continuous Al₂O₃ layer was observed at oxide film/alloy interface, probably caused by an in-situ chemical dissolution process.     

Oxidation of Fe-8Cr-14Ni-Al-Si-Mn from 700 to 1000°C

This paper reports an investigation into reducing the Cr concentration in commercial-grade stainless steels while maintaining oxidation protection at elevated temperatures. Aluminum and Si were added as partial substitute alloy elements to enhance the reduced operation protection resulting from Cr concentration reduced by approximately 50 pct of that found in stainless steels. The goal of this study was to determine the oxidation mechanism of such an Fe, Al-Si alloy: Fe-8Cr-14Ni-1Al-3.5Si-1Mn. During the initial oxidation period the protection resulted from a thin film of Al₂O₃ over an Fe and Cr spinel. Long-term oxidation protection resulted from the gradual formation of a Cr sesquioxide (Cr₂O₂) inner oxide layer. Eventually an outer oxide layer formed that was a mixed composition spinel of Cr and Mn (MnO · Cr₂O₃). The Al₂O₃, which was part of the original protective layer flaked off early in the oxide testing, and the aluminum oxide that formed later appeared as an internal oxide precipitate.     

Short Term Oxidation Behavior of Si-Free Low-Cr Alloy Sputtered Coating

A sputtered coating of a low-Cr alloy without Si was deposited on the cast alloy with the same composition. The short term (100 h) oxidation behavior of the sputtered coating and the cast alloy was evaluated in air at 800 °C. The results indicated that the sputtered coating exhibited a higher oxidation resistance than the cast alloy. It was found that the mass gain of the cast alloy increased continuously with oxidation time and was higher than that of the sputtered coating, which demonstrated only a slight increase in mass gain with oxidation time after 5 h thermal exposure. During the initial thermal exposure of 0.5 h, the oxide scale formed on the cast alloy consisted of Fe₂O₃ and (Fe,Co,Cr)₃O₄ spinel with a small amount of Cr. However, (Fe,Co,Cr)₃O₄ spinel and Fe₂O₃ were thermally grown on the sputtered coating. After oxidation for 100 h, the oxide scale formed on the cast alloy consisted of Co₃O₄ and (Fe,Co)₃O₄ with internal oxide of Cr, while a double-layer oxide consisting of an outer (Fe,Co,Cr)₃O₄ spinel layer and an inner Cr₂O₃ layer was developed on the sputtered coating.     

High temperature oxidation of Ni-20Cr-12.5Al coatings containing 1% dispersed oxides

Oxidation studies were conducted on plasma sprayed coatings of Ni-20Cr-12.5Al containing one of the following: 1% MgO, 1% La₂O₃, 1% Y₂O₃, and 0.8% Y. The alloy powders containing dispersed oxides were prepared by a variety of processes employing attrition and ball milling. The TEM characterization of the plasma sprayed deposits of Ni-20Cr-12.5Al-1Y₂O₃ indicated that the oxide particles ranged from almost pure aluminum oxide to various compounds of aluminum and yttrium oxide. In cyclic tests conducted at 1150 and 1225°C, the coating containing 1% Y₂O₃ appeared to provide the best oxidation resistance. The oxidation resistance appeared to be influenced by the size and distribution of the oxide particles.     

Duplex scale formation during high-temperature oxidation of Ni-0.1 wt.% Al alloy

The development of a duplex NiO scale microstructure on a Ni-0.1 wt.% Al alloy at 900°C has been examined, principally using secondary-ion mass spectrometry and analytical transmission electron microscopy. The¹⁸O-tracer distribution following sequential oxidation in¹⁸O₂/¹⁸O₂ showed that the inner NiO layer formed as a result of gaseous-oxygen penetration of the scale. The provision of pathways for oxygen transport as well as the role of Al, Si, and Ce segregation at oxide grain boundaries in influencing the growth rate and spallation behavior of the scale are discussed.     

Corrosion Behavior of Fe–25Cr in a N2–0.1% SO2 Atmosphere at 973 K Under Mechanical Loading

The corrosion behavior of an Fe-25Cr alloy was investigated in a N₂-0.1 vol.% SO₂ atmosphere at 973 K with and without stress. Without stress, the surface scale formed at the very initial stage consisting of Cr oxides and sulfides, which later changed to a Cr₂O₃-rich scale with the initially formed sulfides remaining. Under relatively low constant stress, +15 and +20 MPa, as well as cyclic stress of ±30 or ±40 MPa, the total strain for 36 ks was less than 0.1% and there was little cracking of the external scale, which consisted of Cr₂O₃ and (Fe, Cr)₃O₄ with small amounts of sulfide, growing faster. The external scale here was poorly adhesive. Under high stress, +25 and +35 MPa, cracks formed in the external scale and both oxides and Fe sulfide grew rapidly through the cracks to form nodules. The nodules consisted of an FeS-rich core surrounded by Fe₃O₄. With increasing strain, the preformed Cr₂O₃-rich scale changed drastically to a multilayered scale with an alternating oxide layer-sulfide layer structure.     

Optimization of Cr-Content for High-Temperature Oxidation Behavior of Co–Re–Si-Base Alloys

The oxidation behavior of Co-17Re-xCr-2Si alloys containing 23, 25, 27 and 30 at.% chromium at 1,000 and 1,100 °C were investigated. Alloy Co–17Re–23Cr–2Si showed a poor oxidation resistance during exposure to laboratory air forming a two-layer external scale and a very thin discontinuous Cr₂O₃ layer at the oxide/substrate interface. The outer layer of the oxide scale consisted of CoO, whereas the inner layer was a porous mixture of CoCr₂O₄ spinel particles in a CoO matrix. The oxide scale was found to be non-protective in nature as the vaporization of Re-oxide took place during oxidation. An increase of chromium content from 23 at.% to 25 at.% improved significantly the alloy oxidation resistance; a compact protective Cr₂O₃-scale formed and prevented the rhenium oxide evaporation. The oxidation behavior of alloys containing 27 at.% and 30 at.% chromium were quite similar to that of Co–17Re–25Cr–2Si. The oxidation mechanism for Co–17Re–25Cr–2Si alloy was established and the subsurface microstructural changes were investigated by means of EBSD characterization.     

The oxidation of dilute iron-silicon alloys ([Si] ⩽ 1 wo) in carbon dioxide

The manner in which silicon, present as a minor alloy constituent, modifies the oxidation of iron in CO₂/1 %CO at 500°C has been studied. Increasing amounts of silicon progressively reduce the oxidation rate within the range $\text{[}\text{Si}\text{] = 0–1}\text{w}\text{o}$ and a variety of physical techniques have been used to examine oxidized specimens in pursuit of the origins of this beneficial influence. The scale forming on the alloys is composed of two layers in each of which iron is present as Fe₃O₄. The inner layer of scale contains silicon at approximately the same level (on a vol. % basis) as the original metal while the outer scale appears to contain no silicon. The boundary between the two layers is also marked by an abrupt change in grain size and in texture of the Fe₃O₄. At the boundary between the alloy and the scale there develops a thin layer of non-ferrous material in which the concentration of silicon is increased by more than an order of magnitude above that in the bulk alloy. This layer also includes a substantial accumulation of carbon which is thought to derive from carbon oxide gases which have penetrated to the base of the scale before taking part in the oxidation reaction. The observation of the layer of non-ferrous material between the alloy and the scale constitutes a qualitative agreement with theoretical studies which indicate that the reduction in oxidation rate conferred by the presence of silicon in the alloy is at least partly due to the impeded passage of Fe³⁺ ions from the alloy into the scale.