High-temperature oxidation of Fe-Cr-Al-Si alloys extruded into honeycomb structures

The oxidation behavior of Fe–20Cr–5Al–(0.5–5)Si and Fe–(12–20)Cr–(5–7)Al–(1–2)Si alloys extruded into honeycomb structures has been investigated at 1150°C in air for up to 500 hr. The oxidation weight gains decrease with increasing Si and Cr contents in the 5-Al alloys. Si additions are more efficient than Cr additions to reduce the weight gain. Increasing Si content in the 5-Al alloys suppresses the formation of an iron-chromium complex oxide, forming mullite and vitreous silica in the scale, although the location is not clearly indicated. The 5-Si alloy shows anisotropy in elongation of the honeycomb specimen during oxidation in the Fe–20Cr–5Al–xSi alloys, whereas alloying with Si and Cr does not improve the oxidation resistance of the 7-Al alloys significantly. These results are explained by Wagner's theory of a secondary getter. However, we point out additionally that the difference between Si and Cr in the Pilling-Bedworth ratio and the solubility of their oxides in the Al₂O₃ scale may contribute to the significant effect of Si additions. Finally, this paper demonstrates that the selected Fe–Cr–Al–Si honeycombs having walls 200 m thick show excellent oxidation resistance over 500 hr at 1150°C in air. The time to catastrophic oxidation is roughly proportional to the wall thickness in extruded honeycombs.     

Oxidation Behavior of ODS Fe–Cr Alloys

Four experimental oxide dispersion strengthened (ODS)Fe-(13–14 at. %)Cr ferritic alloys were exposed for up to 10,000 hr at 700–1100 °C in air and in air with 10vol.% water vapor. Their performance has been compared to other commercial ODS and stainless steel alloys. At 700–800°C, the reaction rates in air were very low for all of the ODS Fe–Cr alloys compared to stainless steels. At 900°C, a Y₂O₃ dispersion showed a distinct benefit in improving oxidation resistance compared to an Al₂O₃ dispersion or no addition in the stainless steels. However, for the Fe-13 %Cr alloy, breakaway oxidation occurred after 7,000 hr at 900°C in air. Exposures in 10 % water vapor at 800 and 900°C and in air at 1000 and 1100°C showed increased attack for this class of alloys. Because of the relatively low Cr reservoirs in these alloys, their maximum operating temperature in air will be below 900°C.     

Oxidation kinetics,breakaway oxidation,and inversion phenomenon in 9Cr-1Mo steels

The oxidation behavior of 9Cr-1Mo ferrritic steels has been studied in air, oxygen, and steam at 1 atm pressure at various temperatures. Long-term experiments in air were carried out from 500–800°C by measuring the weight gains by interrupting the experiment at regular intervals of time. Short-term experiments in oxygen from 500–950°C and in air at 900 and 950°C were carried out by continuous recording of weight gain versus time in a continuousrecording thermogravimetric balance. Short-term experiments in steam were carried out using a special atmosphere furnace attached to the thermogravimetric balance. In air/oxygen, the weight gains at 700°C were lower than those at 600°C, while in steam, the weight gains at 800°C were lower than those at 700°C. This inversion phenomenon was observed for all the three steels viz. 9Cr-1Mo (high Si), 9Cr-1Mo (low Si), and 9Cr-1Mo-Nb steel. Examination of the oxide scales was carried out using SEM/EDAX, AES/ESCA, and X-ray diffraction techniques, and a mechanism is proposed for the occurrence of the inversion phenomenon.     

Some observations on the effects of sulfur and active elements on the oxidation of Fe−Cr−Al alloys

A very-low-sulfur-content industrial Fe–Cr–Al alloy has been used both as a baseline and as a charge material for laboratory metlts with variable sulfur and rare-earth additions. No significant differences in behavior were observed in cyclic oxidation tests on 1-mm-thick coupons at 1100°C, except for an excessive rare-earth content, which led to accelerated scale growth. At 1300°C, alloys without rare-earth additions developed high growth stresses in the oxide, leading to large tensile strains in the substrate. The oxide-metal interface in the low-sulfur (<2ppm) material resisted these stresses and the oxide remained adherent. However, as little as 4ppm S was sufficient to cause considerable spalling. Rare-earth additions markedly reduced growth stresses and eliminated both dimensional instability and spalling.     

The corrosion of Ni3Al in a combustion gas with and without Na2SO4-NaCl deposits at 600–800°C

The corrosion behavior of Ni₃Al containing small additions of Ti, Zr, and B in combustion gases both with and without Na₂SO₄–NaCl deposits at 600–800°C has been studied for times up to four days. The corrosion of the saltfree Ni₃Al leads to the formation of very thin alumina scales at 600°C but of mixed NiO–Al₂O₃ scales containing also some sulfur compounds at higher temperatures, while the rate increases with temperature up to 800°C. The presence of the salt deposits considerably accelerates the corrosion rate, especially at 600 and 800°C. The duplex scales formed at 600°C are composed mostly of a mixture of NiO and unreacted salt in the outer layer and of alumina and aluminum sulfide with some nickel compounds in the inner layer. The scales grown at 700°C contain only one layer of complex composition, while those grown at 800°C are similar but have an additional outer layer containing similar amounts of nickel and aluminum. At 600 and 700°C NiSO₄ can be detected also in the salt layer. The samples corroded at 700°C and 800°C also show an Al-depleted zone containing titanium sulfide precipitates at the surface of the alloy. The hot corrosion of Ni₃Al involves a combination of various mechanisms, including fluxing of the oxide scale as well as mixed oxidation-sulfidation attack. At all temperatures Ni₃Al shows poor resistance to hotcorrosion attack as a result of the formation of large amounts of Ni compounds in the scales.     

The oxidation of Co−Nb alloys under low oxygen pressures at 600–800°C

The oxidation of two Co–Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800° C in H₂–CO₂ mixtures providing an oxygen pressure of 10^–24 atm at 600°C and 10^–20 atm at 700 and 800°C, below the dissociation pressure of cobalt oxide. At 600 and 700°C both alloys showed only a region of internal oxidation composed, of a mixture of alpha cobalt and of niobium oxides (NbO₂ and Nb₂O₅) and at 700°C also the double oxide CoNb₂O₆, which formed from the Nb-rich Co₃Nb phase. No Nb-depleted layer formed in the alloy at the interface with the region of internal oxidation at these temperatures. Upon oxidation at 800°C a transition between internal and external oxidation of niobium was observed, especially for Co–30Nb. This corrosion mode is associated with the development of a single-phase, Nb-depleted region at the surface of the alloy. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in cobalt and to the relation between the microstructures of the alloys and of the scales.     

The high-temperature oxidation of some oxidation-resistant copper-based alloys

The oxidation behavior of Cu-2Be, Cu-5Al, Cu-8Al, Cu-3Si, Cu-2Al-2Si, Cu-2.5Al-2.5Si, Cu-4.5Al-2Si, Cu-7.5 Al-2Si, Cu-6.5Al-4Si, and Cu-4.5Al-5Si, in the temperature range 100–800°C, in air, has been investigated by gravimetric measurements and by electron microscopical examination of stripped oxide films. Most of the alloys showed considerable resistance to oxidation. This was given mainly by a thermally grown film of -alumina on the Cu-Al and Cu-Al-Si alloys and by a beryllia film on the Cu-Be alloy. Other oxide phases, principally copper oxides, were also found to grow on the alloys and these are described. Silicon additions to Cu-Al alloys are found to improve their oxidation resistance, although no crystalline oxides containing silicon were observed in the oxide films stripped from the Cu-Al-Si alloys.     

The internal-nitriding behavior of 310 stainless steel with and without Al and Ti additions

The internal-nitriding behavior in ammonia-hydrogen atmospheres of type-310 stainless steel and 310 to which either 2 wt.% Ti or 3 wt.% Al were added was studied over the range of 550–950°C. An Fe-24Cr binary alloy was included to assess the role of a BCC crystal structure vs the FCC crystal structure of 310 stainless steel. The BCC alloy exhibited the most rapid kinetics as expected. X-ray diffraction showed only the presence of CrN in all the alloys up to 735°C. At 850°C and above, both CrN and Cr₂N were detected. The nonformation of TiN and AlN at lower temperatures is attributed to nucleation problems. Precipitates were extremely fine (unresolvable even at 20,000×) at 563°C and became much coarser with increasing temperature. The precipitate density, size, and shape varied across the internal-nitriding zone at the higher temperatures. External scaling was noted at 850°C and above, however, it was not a continuous film. The activation energy of internal nitriding from 563–735°C ranged from 3.8 kcal/mol for 310+2Ti to 18.2 kcal/mol for 310+3Al; from 850–950°C, the activation energy ranged from 44 (310+2Ti) to 56.6 kcal/mol (310+3Al). Microhardness profiles show that an intermediate zone exists between the nitride case and the base metal. The origin of this zone is discussed.     

Effect of Carbon on the Long-Term Oxidation Behavior of Fe3Al Iron Aluminides

Electroslag, remelted-iron aluminides having the compositions: (1) Fe–16Al–0.05C, (2) Fe–16Al–0.14C, (3) Fe–16Al–0.5C, and (4) Fe–16Al–1.0C were investigated to understand the effect of carbon on their oxidation behavior in the temperature range 700–1000°C. The oxidation behavior of these aluminides was compared with that of 310 SS, a reference alloy used in the study. Regardless of carbon content, the iron aluminides exhibit marginally higher oxidation tendency than that of 310 SS at 700°C. However, between 800 and 1000°C, they exhibit better oxidation resistance than 310 SS. Although the oxidation resistance of aluminides at 1000°C is better than that of 310 SS, they suffer severe spallation during long-term exposure and C exacerbates this effect. Examination of the early stages of oxidation of the alloys at 800 and 900°C shows that they do not gain a corresponding weight as they do for a temperature rise from 700 to 800°C. A further rise to 1000°C leads to a marginal inversion in the oxidation tendency of the alloys. Based on the literature, this inversion is attributed to the possible dissolution and/or change in compo- sition of Fe₃AlC_0.69 carbide phase with temperature.     

Oxidation characteristics of Ti3Al-Nb alloys and improvement in the oxidation resistance by pack aluminizing

The oxidation behavior of three T_i3-Al-Nb alloys: Ti-25Al-11Nb, Ti-24Al-20Nb, and Ti-22Al-20Nb was investigated in the temperature range of 700–900°C in air. The uncoated alloy Ti-25Al-11Nb showed the lowest weight gain with nearly parabolic oxidation rate; while the other two alloys had much higher weight gain, accompanied by excessive oxide scale spalling. The scale analysis, using XRD, SEMIEDAX, and AES revealed that the scale was a mixture of TiO₂, Al₂O₃, and Nb₂O₅ with the outer layer rich in TiO₂. The effect of variation in Al and Nb content on the oxidation behavior is discussed. A decrease in Al content of the alloy adversely affects the oxidation resistance; and it seems that a Nb content as high as 20 at.% is also not beneficial. Hence these alloys, especially Ti-24Al-20Nb and Ti-22Al-20Nb, should not be used in the as-received condition above 750°C. An attempt was made to improve the oxidation resistance of these alloys by pack aluminizing which led to the formation of an Al rich TiAl₃ surface layer doped with Nb. The coating process was gaseous-diffusion controlled with a parabolic Al deposition rate. The weight gains for the aluminized alloy specimens oxidized at 900°C in air were much lower than that of the uncoated specimens. The weight gains were further decreased in the case of Si-modified aluminized specimens. The scale analysis revealed an alumina-rich scale with some amount of titania doped with Nb. The improvement in the oxidation resistance of the pack-aluminized alloys at 900°C is attributable to the formation of the alumina-rich oxide scale. The addition of Si to the aluminizing pack seems to promote further the growth of an alumina-rich scale by lowering the oxygen partial pressure in the system.     

Codeposited chromium and silicon diffusion coatings for Fe-Base alloys via pack cementation

The simultaneous deposition of Cr and Si into plain carbon, low-alloy, and austenitic steels using a halide-activated pack-cementation process is described. Equilibrium partial pressures of gaseous species have been calculated using the STEPSOL computer program to aid in designing specific processes for codepositing the desired ratios of Cr and Si into a given alloy. The calculations indicate that NaCl-activated packs are chromizing, while NaF-activated packs deposit more Si with less Cr. The use of a dual activator (e.g., NaF+NaCl) allows for the deposition of both Cr and Si in the desired amounts. Single-phase ferritic coatings (150–250 microns thick) with a surface concentration of 20–35 wt.% Cr and 2–4% Si have been grown on AISI 1018, Fe-2.25 Cr-1.0Mo-0.15C, and Fe-0.5 Cr-0.5 Mo-0.2C steels using packs containing a 90 wt.% Cr-10Si binary source alloy, a NaF+NaCl activator, and a silica filler. Two-phase coatings (approximately 75 microns thick) containing 20–25 wt.% Cr and 2.0–2.4% Si have been obtained on 304 stainless steel using packs containing a 90 wt.% Cr-10Si binary source alloy, a NaF activator, and an alumina filler. The same pack chemistry allowed the diffusion of Cr and Si into the austenitic Incoloy 800 alloy without a phase change. A coated Fe-2.25 Cr-1.0 Mo-0.15 C coupon with a surface concentration of Fe-34 wt.% Cr-3Si was cyclically oxidized in air at 700°C for over four months and 47 cycles. The weight gain was very low (<0.2 mg/cm²) with no scale spalling detected. Coated coupons of AISI 1018 steel, and Fe-0.5 Cr-0.5 Mo-0.2C steel have shown excellent oxidation-sulfidation resistance in reducing, sulfur-containing atmospheres at temperatures from 400 to 700°C and in erosion and erosion-oxidation testing in air at 650 and 850°C.     

The third-element effect in the oxidation of Ni–xCr–7Al (x = 0, 5, 10, 15 at.%) alloys in 1 atm O2 at 900–1000 °C

The oxidation in 1 atm of pure oxygen of Ni–Cr–Al alloys with a constant aluminum content of 7 at.% and containing 5, 10 and 15 at.% Cr was studied at 900 and 1000 °C and compared to the behavior of the corresponding binary Ni–Al alloy (Ni–7Al). A dense external scale of NiO overlying a zone of internal oxide precipitates formed on Ni–7Al and Ni–5Cr–7Al at both temperatures. Conversely, an external Al₂O₃ layer formed on Ni–10Cr–7Al at both temperatures and on Ni–15Cr–7Al at 900 °C, while the scales grown initially on Ni–15Cr–7Al at 1000 °C were more complex, but eventually developed an innermost protective alumina layer. Thus, the addition of sufficient chromium levels to Ni–7Al produced a classical third-element effect, inducing the transition between internal and external oxidation of aluminum. This effect is interpreted on the basis of an extension to ternary alloys of a criterion first proposed by Wagner for the transition between internal and external oxidation of the most reactive component in binary alloys.     

The oxidation of Ni-Nb alloys at low-oxygen pressures at 600–800°C

The oxidation of two Ni–Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800° C in H₂–CO₂ mixtures providing an oxygen pressure of 10^–24 atm at 600° C and 10^–20 atm O₂ at 700 and 800° C, these pressures being less than the dissociation pressure of nickel oxide. The scales formed on both alloys at 600 and 700° C show only a region of internal oxidation composed of a mixture of alpha nickel and niobium oxides (Nb₂O₅ or/and NbO₂), which formed from both the metal phases present, i.e., Ni₈Nb and Ni₃Nb. Only small, or even no, Nb depletion was observed in the alloys close to the interface with the zone of internal oxidation at these temperatures. On the contrary, samples of both alloys corroded at 800° C produced a continuous external scale of niobium oxides without internal oxidation. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in nickel.     

An analysis of the internal oxidation of binary M-Nb alloys under low oxygen pressures at 600–800°C

The corrosion of M–Nb alloys based on iron, cobalt, and nickel and containing 15 and 30 wt% Nb has been studied at 600–800°C under low oxygen pressures (10^–24 atm at 600°C and 10^–20 atm at 700–800°C). Except for the Co–Nb and Ni–Nb alloys corroded at 800°C, which formed external scales of niobium oxides, corrosion under low O₂ pressures produced an internal oxidation of niobium. This attack was much faster than expected on the basis of the classical theory. Furthermore, the distribution of the internal oxide in the alloys containing two metal phases was very close to that of the Nb-rich phase in the original alloys. These kinetic, microstructural, and thermodynamic aspects are examined by taking into account the effects of the limited solubility of niobium in the various base metals and of the two-phase nature of the alloys.     

Metal Dusting of Fe–Cr and Fe–Ni–Cr Alloys Under Cyclic Conditions

Metal dusting is the disintegration of alloys into carbon and metal particles during high-temperature exposure to carbon-bearing gases. Model Fe–Cr and Fe–Ni–Cr alloys were studied to test the hypothesis that M₃C formation is necessary for metal dusting to occur. The alloys were exposed to a 68% CO–26% H₂–6% H₂O gas mixture at 680°C (a_c=2.9) under thermal cycling conditions. Equilibrium calculations predicted the formation of M₃C at the surface of Fe–25Cr, but not Fe–60Cr. All compositions were expressed in w/o, weight percent. Alloys of Fe–25Cr with 2.5, 5, 10, and 25 w/o nickel additions were also exposed to the same conditions to study the role of nickel in destabilizing the precipitation of M₃C and, hence, altering the resistance to metal dusting. Metal dusting was observed on all the alloys except Fe–60Cr. For Fe–25Cr, Fe–25Cr–2.5Ni, and Fe–25Cr–5Ni, the carbonization and dusting process was localized, and its incidence decreased in Fe–25Cr–2.5Ni, consistent with the increased destabilization of M₃C precipitation. However, Fe–25Cr–10Ni and Fe–25Cr–25Ni both underwent extensive dusting in the absence of protective Cr₂O₃ formation. The carbon deposits formed consisted of carbon filaments, which contained particles at their tips. These were shown by electron diffraction to be exclusively Fe₃C in Fe–25Cr, Fe–25Cr–2.5Ni, and Fe–25Cr–5Ni, and a mixture of austenite and (Fe,Ni)₃C in Fe–25Cr–10Ni and Fe–25Cr–25Ni.     

The corrosion of Nb-modified Ti3Al in a combustion gas with and without Na2SO4−NaCl deposits at 600–800°C

The corrosion behavior of a Nb-modified Ti₃Al intermetallic compound containing 11 at.% Nb in a simulated combustion gas with and without deposits of a Na₂SO₄–NaCl mixture was examined at 600–800°C for times up to four days. In the absence of salt deposits the corrosion rates were rather low and increased only slightly with temperature, producing very thin scales of mixed oxides of Ti, Al, and Nb without sulfides. The presence of the salt deposits produced higher weight gains during an initial stage of one to two days at 600 and 700°C, after which the reaction stopped. A more important and longlasting effect was observed instead at 800°C, when the kinetics of hot corrosion became nearly linear. The scales formed by hot corrosion were complex mixtures of various corrosion products at all temperatures and showed a porous outer region containing a mixture of unreacted salts with oxides (mainly TiO₂), an intermediate region of a mixture of variable composition of oxides of the three metals, and a TiO₂-rich layer beneath it. At 800°C the scales tended to form a thin, discontinuous Al₂O₃-rich layer in the middle and contained an additional innermost region presenting a large concentration of sulfur, very likely as Nb and Ti sulfides. The high rate of hot corrosion at 800°C is attributed to the appearance of sulfides in the inner region of the scale and to a more efficient scale fluxing.     

The effect of Si additions on the high temperature oxidation of a ternary Ni-10Cr-4Al alloy in 1 atm O2 at 1100 °C

The oxidation of four Ni-10Cr-ySi-4Al alloys was studied at 1100 °C to examine the effects of Si additions (from 2 to 6 at.%) on the behavior of the alloy Ni-10Cr-4Al. Addition of 2 at.% Si prevented completely nickel oxidation, but could not form alumina scales. Larger Si additions produced alumina only over part of the alloy surface (about 20% with 4 at.% Si and 30% with 6 at.% Si), but could not prevent completely the internal oxidation of Al. The results are interpreted by extending to quaternary alloys the mechanism of the third-element effect already proposed for ternary alloys.     

Oxygen solubility and a criterion for the transition from internal to external oxidation of ternary alloys

Smith's model is expanded in order to derive expressions to quantitatively describe the oxygen-solubility behavior in ternary alloys as a function of alloy composition. Multicomponent-diffusion theory is used to establish a criterion for the onset of internal oxidation beneath the external scale when oxidizing conditions favor formation of the oxide of the least-noble metal in a ternary alloy. The oxygen-solubility model and the criterion are applied to the oxidation of Ni–Cr–Al alloys in 76 torr of oxygen at 1100 and 1200°C, predicting the minimum Al concentrations required to form a protective Al₂O₃ scale. It shows that sufficient Cr additions would significantly reduce the oxygen solubility and also alter the oxygen distribution in the ternary alloys, avoiding the oxygen supersaturation necessary for the onset of internal oxidation. These two factors make it easier to establish the protective Al₂O₃ scale.     

The Effect of Water Vapor on the Oxidation Behavior of CVD Iron-Aluminide Coatings

The oxidation behavior of iron-aluminide coatings, Fe₃Al or (Fe,Ni)₃Al, produced by chemical-vapor deposition (CVD) was studied in the temperature range of 700–800°C in air + 10 vol.% H₂O. A typical ferritic steel, Fe–9Cr–1Mo, and an austenitic stainless steel, 304L, were coated. For both substrates, the as-deposited coating consisted of a thin (<5μm), Al-rich outer layer above a thicker (30–50 μm), lower-Al-content inner layer. In addition to coated and uncoated Fe–9Cr–1Mo and 304L, cast Fe–Al model alloys with similar Al contents (13–20 at.%) to the CVD coatings were included in the oxidation exposures for comparison. The specimens were cycled to 1000 1 hr cycles at 700°C and 500 1 hr cycles at 800°C, respectively. The CVD coating specimens showed excellent performance in the water-vapor environment at both temperatures, while the uncoated alloys were severely attacked. These results suggest that an aluminide coating can substantially improve resistance to water-vapor attack under these conditions.     

Corrosion of nickel-base and iron-base alloys in a simulated fluidized-bed coal-combustion environment

The modes of initiation and propagation of corrosion attack on a series of high-temperature alloys were studied in synthetic gas mixtures at 900°C. The gas mixtures were intended to simulate the oxygen and sulfur partial pressures experienced in reducing zones in a coal-fired fluidized-bed combustor and comprised mixtures of CO, CO₂, and SO₂. The alloys studied were candidates for in-bed heat exchanger tubing for an air-heater cycle operating at 843°C and 300–500 psig and so ranged from type 300-series stainless steels to nickel-base alloys. With the exception of two FeCrAlY alloys and types 304 and 347 stainless steels, it was found that sulfidation corrosion could be initiated on all the alloys within 0.25 hr; the rate of propagation of the corrosive attack depended on the flux of SO₂ in the environment and on the nickel content of the alloys. The presence of iron in the alloys appeared to slow the initiation of sulfidation, by forming a continuous iron oxide layer. The effects of various alloying additions are discussed, and a schematic model for the initiation of sulfidation is proposed.