High-Temperature Oxidation of Al–Mg Alloys

The effect of the atmosphere on the oxidation rates of aluminum-can alloyswas studied using thermogravimetric methods. The atmospheres included: air,Ar+1%O₂, Ar+5%O₂, and CO₂. Temperaturesranged from 450 to 800°C. The oxidation rate was influenced by thesurface condition and by the time elapsed after specimen preparation. Increasingtemperature increased the oxidation rate of both AA 3004 and 5182. Parabolickinetics were observed for AA 3004 and linear kinetics were observed forAA 5182 at 450 and 500°C. From 550 to 800°C, parabolic behavior wasobserved for AA 5182. The reduction of free oxygen in the atmosphere reducedthe rate of oxidation. The reactivity of the atmospheres decreased in thefollowing sequence: air, Ar+5%O₂, Ar+1%O₂, and CO₂.     

Simultaneous Internal Oxidation and Nitridation of Ni–Cr–Al Alloys

A series of Ni–Cr–Al alloys was subjected to thermal cycling to 1100°C in air for up to 260 1-hr cycles. All alloys exhibited poor corrosion resistance. Repeated scale spallation led to subsurface alloy depletion in aluminum and, to a lesser extent, chromium. This caused transformation of the prior alloy three-phase structures (-Cr+-NiAl+-Ni) to single-phase -nickel solution. Destruction of the external scale allowed gas access to this metal, which was able to dissolve both oxygen and nitrogen. Inward diffusion of the two oxidants led to development of a complex internal-precipitation zone: Al₂O₃ and Cr₂O₃ beneath the surface, followed by Al₂O₃, then AlN, then AlN+Cr₂N, and, finally, AlN alone in the deepest region. This distribution is shown to reflect the relative stabilities of the precipitates and the higher permeability of nitrogen. Diffusion-controlled kinetics were in effect initially, but mechanical damage to the internal-precipitation zone led to more rapid gas access and approximately linear kinetics in the long term.     

Effect of Sulfur Partial Pressures on Oxidation Behavior of Fe–Ni–Cr Alloys

Fe–Ni–Cr alloys containing different contents of Si with and without pre-formed oxide scale at the surface were tested in oxidation environments at 1,050?°C with varied sulfur partial pressures. The oxide-scale growth on Fe–Ni–Cr alloys was accelerated by increasing sulfur partial pressures in the oxidizing-carburizing environments. This accelerated oxidation was characterized by the formation of plate-shaped MnCr₂O₄ spinel crystallites and the nodular clusters at the site of scale spallation. Pre-oxidized Fe–Ni–Cr alloys generally did not suffer from sulfur attack because of excellent protection of pre-formed oxide scale. Scale spallation and sulfur attack were found only on high-Si alloy subjected to the maximum sulfur potential, which was attributed to accelerated oxidation and selective oxidation and sulfidation at the sites where oxide scale spallation had occurred. For bare alloys in absence of pre-formed oxide layers, scale spallation was found to occur at lower level of sulfur potential on low-Si alloy than on high-Si alloy. A higher content of Si is necessary for the formation of protective silica sub-layer, which is believed to be the main cause of the difference in scale spallation observed.     

High-Temperature Oxidation of Two-Phase Nanocrystalline Ag–Cr Alloys in 1 atm O2

Two nanocystalline two-phase Ag–Cr alloys prepared by mechanical alloying and containing approximately 30 and 50 wt.% Cr were oxidized in 1 atm O₂ at 700 and 800°C. Under all conditions, a continuous layer of chromia formed at the surface of the alloys, in spite of the very low solubility of Cr in Ag. A layer of AgCrO₂ also formed externally to the chromia layer. In the case of the Ag–30Cr alloy, some Ag particles were also present on the scale, directly in contact with the gas phase. Moreover, Cr particles dissolved in the subsurface region of the alloy, while internal oxidation of Cr was absent. Ag–Cr alloys prepared by powder metallurgy with coarse grain sizes were able to form an irregular thin chromia layer only at a Cr content of 69 wt.%, while an alloy containing 35 wt.% Cr corroded much more rapidly than the nanocrystalline Ag–30Cr alloy. This difference in the scaling behavior is attributed to the large reduction in the alloy grain size, which favors the dissolution of the Cr-rich particles in a Cr-depleted silver matrix and thus provides a faster supply of chromium from the alloy to the scale.     

Influence of Fe on Microstructure and Mechanical Properties in Pdoped Ni–Cr–Fe Alloys

The influence of Fe on the microstructure and mechanical properties of P-doped Ni–Cr–Fe alloys has been investigated.Results showed that increasing Fe content refined the dendrite microstructure and enhanced the solubility of P in as-cast alloys. The change of microhardness in different dendrite regions was attributed to the segregation of P atoms in solid solution state, which had strengthening effects. Increasing Fe contents from 15.2 to 60.7 wt% reduced the yield strength and tensile strength but had little influence on the elongation of alloys. The stress rupture life of alloys after heat treatment decreased with the increment of Fe contents, and the failure fracture modes transferred from transgranular to intergranular fracture mode. The change of fracture modes was due to the weakness of grain boundaries caused by the increment of Fe.In addition, the precipitation of M_(23)C_6 was believed to be related to the segregation of P toward grain boundaries, which led to the fluctuation of carbon and chromium atoms near the grain boundaries in alloys with low Fe contents. Consequently, the increment of Fe decreased the strength of matrix and changed the existence of P atoms and the precipitates at grain boundaries.     

Water Vapor Effects on the Oxidation Behavior of Fe–Cr and Ni–Cr Alloys in Atmospheres Relevant to Oxy-fuel Combustion

The oxidation behavior of a number of Fe–Cr- and Ni–Cr-based alloys was studied in atmospheres relevant to oxyfuel combustion at 650?°C. Oxidation was greatly enhanced in ferritic model alloys exposed in low p(O₂) CO₂?+?30%H₂O and Ar?+?30%H₂O gases. Rapidly growing iron oxides appear to be porous and gas permeable. Transition from non-protective to protective oxidation occurs on alloys with higher Cr contents between 13.5 and 22?wt% in H₂O. Excess oxygen, usually found in the actual oxyfuel combustion environments, disrupts the selective oxidation of Fe–Cr alloys by accelerating vaporization of early-formed Cr₂O₃ in combination with accelerated chromia growth induced by the H₂O. Rapid Cr consumption leads to the nucleation and rapid growth of iron oxides. On the contrary, Ni–Cr alloys are less affected by the presence of H₂O and excess O₂. The difference between Fe–Cr and Ni–Cr alloys is not clear but is postulated to involve less acceleration of chromia growth by water vapor for the latter group of alloys.     

Modeling of Oxidation Kinetics of Y-Doped Fe–Cr–Al Alloys

Studies using advanced analytical techniques indicated that the reactiveelements (RE) segregate along the oxide grain boundaries and at theoxide–alloy interface during oxidation of -Al₂O₃forming alloys. The segregation results in inward oxygen diffusion along theoxide grain boundaries as the predominant transport process in the oxidegrowth. The present work establishes a mathematical model based on themechanisms of inward oxygen diffusion along the grain boundaries and oxidegrain coarsening. This model has been used to describe the oxidationkinetics of Y-doped Fe–Cr–Al alloys. The results showed a muchbetter agreement with the experimental data than the parabolic rate law. Byusing this model, the exponential number for the grain coarsening of aluminascales during oxidation was calculated to be 3. The activation energyfor oxygen diffusing along the grain boundaries was 450 kJ/mol. They arealso in good agreement with values reported in the literatures.     

Microstructure and High-Temperature Oxidation Behavior of Dy-Doped Nb–Si-Based Alloys

Microstructures and oxidation behaviors of four Dy-doped Nb–Si-based alloys at 1250℃ were investigated. The nominal compositions of the four alloys are Nb–15Si–24Ti–4Cr–2Al–2Hf–xDy(at.%), where x = 0, 0.05, 0.10 and 0.15,respectively. Results showed that the four alloys all consisted of Nbss, αNb_5Si_3 and γNb_5Si_3, and the addition of Dy produced no obvious effect on the phase constitution and the microstructures of Nb–Si-based alloys. After oxidation at 1250℃ for 58 h, it was found that the addition of Dy accelerated the oxidation rate of Nb–Si-based alloys and caused a larger weight gain, accompanied by the formation of a more porous and less protective oxide scale. The oxides of Nb_2O_5,Ti_2Nb_(10)O_(29), TiNb_2O_7, Ti_(0.4)Cr_(0.3)Nb_(0.3)O_2 and glassy SiO_2 were formed on Dy-doped Nb–Si-based alloys. The hightemperature oxidation mechanism of Dy-doped Nb–Si-based alloys was discussed.     

High-Temperature Oxidation Behavior of Iron–Chromium–Aluminum Alloys

The detailed oxidation behavior of Fe–10Cr alloys, containing aluminumin the range of 2–8% by weight, was studied in pure oxygen at 1 atmpressure. The investigations were performed over the temperature range950–1050°C under cyclic conditions (3-hr cycles) in each case. Thecyclic-oxidation resistance, as measured by the specific weight-gain values,was observed to progressively improve with increasing aluminum content inthe alloy. For a particular aluminum content, however, the oxidationresistance decreased with increasing temperature. Following the initialtransient-oxidation period, a healing layer of chromia was established onthe four alloys. The lower-aluminum alloys (2–4% Al) were observedto end up with Fe-rich oxide scales under the experimental conditions atall temperatures, whereas those containing aluminum in the range of6–8% formed -Al₂O₃ scales.     

Oxidation Characteristics of Fe–18Cr–18Mn-Stainless Steel Alloys

Air oxidation studies of Fe–18Cr–18Mn stainless steels were conducted at 525, 625, and 725 °C. Alloys were evaluated with respect to changes in oxidation properties as a result of interstitial additions of nitrogen and carbon and of minor solute additions of silicon, molybdenum, and nickel. Interstitial concentrations possibly had a small, positive effect on oxidation resistance. Minor solute additions significantly improved oxidation resistance but could also reduce interstitial solubility resulting in formation of chromium carbides. Loss of solute chromium resulted in a slight reduction in oxidation protection. Oxidation lasting over 500 h produced a manganese rich, duplex oxide structure: an outer sesquioxide and an inner spinel oxide.     

Oxidation Behavior of ODS Fe–Cr–Al Alloys: Aluminum Depletion and Lifetime

The oxidation kinetics of two ODS Fe–Cr–Al alloys, PM 2000 and MA 956, were studied in oxygen and in air under isothermal conditions from 1000 to 1300°C. They both form an -alumina scale and have good oxidation resistance, without any mass loss. Although the aluminum content in these alloys is higher than the minimum Al content necessary to ensure the growth of a continuous alumina scale, an aluminum depletion occurred in the substrate. This depletion allows the determination of aluminum diffusion coefficients in the ODS alloy. This method is very original and interesting as no Al-stable isotope is available. Moreover, the evolution of the aluminum concentration in the substrate allows one to determine the lifetime of these alloys: indeed, when the aluminum content decreases and becomes lower than a critical value, alumina can no longer form, and less-stable oxides grow very rapidly compared to alumina.     

Effect of Alloy Composition and Exposure Conditions on the Selective Oxidation Behavior of Ferritic Fe–Cr and Fe–Cr–X Alloys

Selective oxidation behavior of ferritic martensitic Fe–Cr base alloys, exposed in various atmospheres containing combinations of O₂, CO₂, and H₂O, were studied at various temperatures relevant to oxy-fuel combustion. This paper begins with a discussion of the required Cr content to form a continuous external chromia scale on a simple binary Fe–Cr alloy exposed in oxygen or air based on experiments and calculations using the classic Wagner model. Then, the effects of the exposure environment and Cr content on the selective oxidation of Fe–Cr alloys are evaluated. Finally, the effects produced by alloying additions of Si, commonly present in various groups of commercially available ferritic steels, are described. The discussion compares the oxide scale formation on simple binary and ternary Fe–Cr base model alloys with that on several commercially available ferritic steels.     

High-Temperature Oxidation of Fe3Al and Fe3Al–Zr Intermetallics

The oxidation behavior of Fe₃Al and Fe₃Al–Zr intermetallic compounds was tested in synthetic air in the temperature range 900–1200 °C. The addition of Zr showed a significant effect on the high-temperature oxidation behavior. The total weight gain after 100 h oxidation of Fe₃Al at 1200 °C was around three times more than that for Fe₃Al–Zr materials. Zr-containing intermetallics exhibited abnormal kinetics between 900 and 1100 °C, due to the presence and transformation of transient alumina into stable α-Al₂O₃. Zr-doped Fe₃Al oxidation behavior under cyclic tests at 1100 °C was improved by delaying the breakaway oxidation to 80 cycles, in comparison to 5 cycles on the undoped Fe₃Al alloys. The oxidation improvements could be related to the segregation of Zr at alumina grain boundaries and to the presence of Zr oxide second-phase particles at the metal–oxide interface and in the external part of the alumina scale. The change of oxidation mechanisms, observed using oxygen–isotope experiments followed by secondary-ion mass spectrometry, was ascribed to Zr segregation at alumina grain boundaries.     

Oxidation Behavior of Ni–Cr–Fe-Based Alloys: Effect of Alloy Microstructure and Silicon Content

The oxidation behavior of Ni–Cr–Fe-based alloys in a low oxygen partial pressure atmosphere (H₂–H₂O) was investigated in terms of the effect of alloy microstructure and their silicon content. It was found that the formation and growth kinetics of the oxide scale are rather sensitive to the alloy microstructure and their corresponding Si contents. Oxide ridges were found to form in areas with eutectic structure, while a thin and homogeneous oxide scale formed on austenite matrix. The thicknesses of the oxide ridges and the oxide layer on the austenite matrix were dependent of their corresponding Si contents. The austenite/carbide phase boundaries in eutectic structure can offer fast diffusion paths for metal outward diffusion, which leads to the formation of ridge-like oxide features. The continuous SiO₂ sub-layer formed at the oxide scale/metal interface on the austenitic matrix acted as an effective diffusion barrier to metal outward diffusion, resulting in rather thin and uniform oxide scales.     

The Effect of Water Vapor on Selective Oxidation of Fe–Cr Alloys

Binary Fe–Cr alloys containing 10 and 20 mass% Cr were studied with respect to isothermal oxidation behavior at 900 and 1,050 °C in Ar–20%O₂, Ar–7%H₂O and Ar–4%H₂−7%H₂O. Thermogravimetric analyses in combination with analytical studies using SEM/EDX and Raman Spectroscopy revealed, that in atmospheres in which water vapor is the source of oxygen, Cr exhibits a higher tendency to become internally oxidized than in the Ar–O₂ gas. Contrary to previous studies which showed the presence of water vapor to affect transport processes in the scale, the present results thus reveal that the presence of water vapor also affects the transport processes in the alloy. This mechanism is an “easy” explanation of the frequently observed effect that Fe–Cr alloys with intermediate Cr contents (e.g. 10–20%, depending on temperature) exhibit protective chromia-rich scale formation in dry gases but breakaway type Fe-rich oxides in wet gases, provided the oxygen partial pressure is sufficiently high for Fe to become oxidized.     

High-Temperature Oxidation Behavior and Mechanism of a New Type of Wrought Ni–Fe–Cr–Al Superalloy up to 1300°C

The oxidation behavior of a new type of wrought Ni–Fe–Cr–Alsuperalloy has been investigated systematically in the temperature range of1100 to 1300°C. Results are compared with those of alloy 214, Inconel600, and GH 3030. It is shown that the oxidation resistance of the newsuperalloy is excellent and much better than that of the comparisonalloys. Scanning electron microscopy (SEM), electron probe microanalysis(EPMA), and X-ray diffraction (XRD) experiments reveal that the excellentoxidation resistance of the new superalloy is due to the formation of adense, stable and continuous Al₂O₃ and Cr₂O₃ oxide layer at hightemperatures. Differential thermal analysis (DTA) shows that the formationof Cr₂O₃ and Al₂O₃ oxide layers on the new superalloy reaches a maximum at1060 and 1356°C, respectively. The Cr2O3 layer peels off easily, and thesingle dense Al₂O₃ layer remains, giving good oxidation resistance attemperatures higher than 1150°C. In addition, the new superalloypossesses high mechanical strength at high temperatures. On-site testsshowed that the new superalloy has ideal oxidation resistance and can beused at high temperatures up to 1300°C in various oxidizing andcorrosion atmospheres, such as those containing SO₂, CO₂ etc., for longperiods.     

High-Temperature Oxidation Behavior of ODS–Fe3Al

The high-temperature oxidation behavior of an oxide dispersion-strengthened (ODS) Fe₃Al alloy has been studied during isothermal and cyclic exposures in oxygen and air over the temperature range 1000 to 1300°C. Compared to commercially available ODS–FeCrAl alloys, it exhibited very similar short-term rates of oxidation at 1000 and 1100°C, but at higher temperatures the oxidation rate increased because of increased scale spallation. Over the entire temperature range, the oxide scale formed was -Al₂O₃, with the morphological features typical of reactive-element doping and was similar to those formed on the ODS–FeCrAl alloys. Although initially this scale appeared to be extremely adherent to the Fe₃Al substrate, an undulating metal–oxide interface formed with increasing time and temperature, which led to cracking of the scale in the vicinity of surface undulations accompanied by a loss of small fragments of the full-scale thickness. In some instances, the surface undulations appeared to have resulted from gross outward local extrusion of the alloy substrate. Similar features developd on the FeCrAl alloys, but they were typically much smaller after a given oxidation exposure. The ODS–Fe₃Al alloy has a significantly larger coefficient of thermal expansion (CTE) than typical FeCrAl alloys (approximately 1.5 times at 900°C) and this appears to be the major reason for the greater tendency for scale spallation. The stress generated by the CTE mismatch was apparently sufficient to lead to buckling and limited loss of scale at temperatures up to 1100°C, with an increasing amount of substrate deformation at 1200°C and above. This deformation led to increased scale spallation by producing an out-of-plane stress distribution, resulting in cracking or shearing of the oxide.     

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.