Silicon contamination effects in the oxidation of carbide-containing cobalt-chromium alloys

Austenitic Co-25Cr(wt pct) and two phase γ + M₇ C₃ alloys of composition Co-25Cr-xC were reacted with pure, dry oxygen at 1000°C. All alloys reacted according to relatively fast parabolic kinetics if they were prepared without silicon contamination. However, if the alloys were contaminated with silicon during annealing in silica ampoules, or if 0.05 wt pct silicon was added to Co-25Cr-1.0C, parabolic oxidation kinetics two orders of magnitude lower resulted. In the case of the rapid reactions, the scales consisted of an inner layer of CoCr₂O₄ + CoO overlaid by CoO. The slow reactions corresponded to growth of a thin scale of Cr₂O₃ overlaid by CoCr₂ O₄. In the latter case the selective oxidation of chromium led to chromium carbide dissolution in a subsurface zone of the two-phase alloy, but the rates were the same as for the single-phase alloy. Consideration of gas phase conditions in the silica annealing ampoules showed that p_SiO values were high enough to transfer substantial amounts of silicon to the alloy if p_O2 was low enough. This situation arose in well evacuated ampoules where oxygen was consumed by reaction with alloy chromium, or in titanium gettered capsules. In contrast, annealing the alloys under moderate oxygen pressures led to the growth of a protective oxide film which prevented silicon contamination of the oxide surface. It is concluded that the presence or absence of carbon in Co-25Cr is irrelevant to the oxidation mechanism and that the silicon effect is critical. An approximate diffusion analysis shows that bulk alloy properties are not affected by the silicon, and it is concluded that silicon has its effect at the alloy surface, by promoting Cr₂O₃ nucleation.     

Carburization of W- and Re-rich Ni-based alloys in impure helium at 1000 °C

The surface and microstructure stability of experimental W- and Re-rich Ni-based alloys in an impure-helium environment containing only CO and CO₂ as impurities (ppm level) have been investigated at 1000 °C. All the alloys carburized during 50 h of exposure, and, depending on the alloy composition, different carbides of the type M₆C, M₇C₃ and M₂₃C₆ formed on the alloy surface, in grain interiors and at grain boundaries. Microprobe analysis and Calphad-based calculations indicated that the chromium carbides (particularly Cr₂₃C₆) were enriched by rhenium. Extended exposure (225 h) led to the disappearance of surface transient carbides and the growth of surface oxide Cr₂O₃ occurred.     

The influence of silicon and yttrium on isothermal scaling of an austenitic Fe-Cr-Ni alloy (IN 519) at 1000 °C

When present in austenitic Fe-Cr-Ni alloys, both silicon and yttrium influence scaling behaviour during oxidation tests in air at high temperatures. The former promotes the formation and maintenance of a continuous Cr₂O₃ scale and the latter improves scale adhesion. During the isothermal exposure of nominally Fe + 24%Cr + 24%Ni east alloys at 1000°C a silicon content above 0.8% reduces the rate of scaling by providing additional sites for the lateral growth of the Cr₂ O₃ layer. Yttrium gives rise to the formation of Fe₉Y particles which disrupt the continuity of the Cr₂O₃ scale. The beneficial influence of silicon dominates the potentially detrimental effect of yttrium in alloys containing both silicon and yttrium.     

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 oxidation behaviour of austenitic FeCrNi alloys containing dispersed phases

The high temperature oxidation behaviour of FeCrNi austenitic alloys containing 1% Ti which, in some cases, had been converted into an oxide dispersion has been examined. The oxide dispersions were produced by an internal oxidation treatment using a 50/50 Cr/Cr₂O₃ powder mixture in a sealed quartz capsule at 1100°C: the samples were not in direct contact with the powders. Generally, the effect of the dispersed oxide was much less pronounced than in corresponding nickel-free, ferritic alloys. Nevertheless, the time-to-breakaway of the protective Cr₃O₃ scale which developed on Fe18CrNi alloys was substantially increased, although the differences between the untreated and the internally oxidized alloys reduced with increasing nickel content. An Fe14Cr20Ni alloy did not show any improvement after internal oxidation. Unlike the ferritic alloys, no coarsening of the dispersoid phase was observed during exposure.     

Comparison of Oxidation Behavior and Electrical Properties of Doped NiO- and Cr2O3-Forming Alloys for Solid-Oxide, Fuel-Cell Metallic Interconnects

The goal of this paper was to determine if NiO-forming alloys are a viable alternative to Cr₂O₃-forming alloys for solid-oxide fuel-cell (SOFC) metallic interconnects. The oxide-scale growth kinetics and electrical properties of a series of Li- and Y₂O₃-alloyed, NiO-forming Ni-base alloys and La-, Mn-, and Ti-alloyed Fe–18Cr–9W and Fe–25Cr base ferritic Cr₂O₃-forming alloys were evaluated. The addition of Y₂O₃ and Li reduced the NiO scale growth rate and increased its electrical conductivity. The area-specific-resistance (ASR) values were comparable to those of the best (lowest ASR) ferritic alloys examined. Oxidation of the ferritic alloys at 800°C in air and air+10% H₂O (water vapor) indicated that Mn additions resulted in faster oxidation kinetics/thicker oxide scales, but also lower oxide scale ASRs. Relative in-cell performance in model SOFC stacks operated at 850°C indicated a 60–80% reduction in ASR by Ni+Y₂O₃, Ni+Y₂O₃, Li, and Fe–25Cr+La,Mn,Ti interconnects over those made from a baseline, commercial Cr₂O₃-forming alloy. Collectively, these results indicate that NiO-forming alloys show potential for use as metallic interconnects.     

The oxidation behaviour of cobalt-base alloys containing dispersed oxides formed by internal oxidation

CoCr alloys containing a dispersed oxide phase have been produced by internally oxidizing alloys to which 1 wt % of a reactive element—Hf, Ti or Zr—has been added. Internal oxidation was carried out in a sealed quartz capsule containing a 50/50 powder mixture of CrCr₂O₃, or X-40-Cr₂O₃. The alloys produced in this way show all the beneficial characteristics demonstrated by similar alloys made by other techniques: (a) a continuous protective Cr₂O₃ scale is established at a chromium level of 10%, considerably below that required (approximately 25%) in the absence of a dispersoid; (b) a reduction in the growth rate of the Cr₂O₃ compared to particle-free alloys, particularly at high temperatures, and (c) greatly improved adhesion of the protective scale to the substrate. The beneficial effects appear to be independent of the composition of the dispersoid, and also its distribution. Oxidation of the CoCr-1 Hf, Zr or Ti alloys without pre-treatment produces scales characteristic of the chromium content of a corresponding binary alloy, indicating that some internal oxidation treatment is necessary and it is not sufficient to rely on the internal oxides formed during normal oxidation.     

The development of internal and intergranular oxides in nickel-chromium-aluminium alloys at high temperature

The development of internal oxides, intergranular oxides and internal voids in Ni-15.1Cr-1.1Al and Ni-28.8Cr-1.0Al during oxidation in 1 atm oxygen at 1000° to 1200°C has been studied. In both cases, the formation of an external Cr₂O₃-rich scale causes vacancies to be generated in the alloy due to the different diffusion rates of chromium towards the alloy-scale interface and of nickel back into the bulk alloy. At 1000°C, condensation of these vacancies at the alloy grain boundaries facilitates formation of intergranular oxides while, at 1200°C, the vacancies condense to give voids in the grains and grain boundaries. Internal oxides are formed at both temperatures. The internal and intergranular oxides are mainly α-Al₂O₃, although some Cr₂O₃-rich oxides are produced near the alloy-scale interface. Possible mechanisms for the development of the internal and intergranular oxides in these alloys are discussed and related to the observed oxide morphologies and compositions.     

Effect of internal oxidation pretreatments and Si contamination on oxide-scale growth and spalling

Internal oxidation pretreatments carried out in quartz capsule with a Rhines pack were found to have a profound effect on the subsequent oxidation behavior of alloys. Specimens of Co-15 wt.% Cr, Co-25 wt.% Cr, Ni-25 wt.% Cr, and Ni-25 wt.% Cr-1 wt.% Al were tested at 1100°C after pre-oxidation treatments. Even without the development of internal oxide particles, pretreated binary CoCr and NiCr alloys oxidized with significantly lower rates. Selective oxidation of chromium was observed on the non-Cr₂O₃-forming Co-base alloys, whereas on the Cr₂O₃-forming Ni-base alloys, elimination of base-metal oxide, reduction in the Cr₂O₃ growth rate, and better scale adhesion were found. These effects were more apparent with pre-oxidation temperatures greater than 1000°C and with longer pretreatment times. Contaimination of Si from the quartz is believed to be the cause.     

Oxidation behavior of Ni-Cr-1ThO2 alloys at 1000 and 1200°C

The oxidation behavior of Ni-13.5-33.7Cr-1ThO₂ alloys in flowing oxygen at 150 Torr was investigated in the temperature range 1000–1200°C. Gravimetric measurements of the oxidation kinetics have been combined with microstructural studies of the reacted samples in order to evaluate the reaction mechanisms. The oxide products formed on the alloys were a function of Cr content, sample surface preparation, reaction time, and temperature. The presence of ThO₂ appears to produce two effects during alloy oxidation. First, enhanced Cr diffusion to the alloy surface results in rapid formation of a Cr₂O₃ subscale beneath NiO on Ni-13.5Cr-1ThO₂ and selective oxidation of Cr for Ni-22.6Cr-1ThO₂. Second, the mechanism of formation of Cr₂O₃ is apparently different from that for simple Ni-Cr alloys, resulting in about an order of magnitude reduction in the Cr₂O₃ growth rate. The oxidationvaporization of Cr₂O₃ to CrO₃ becomes rate controlling for the higher Cr alloys after only a few hours of exposure at 1200°C.     

Effect of yttrium on the sulfidation behavior of Ni-Cr-Al alloys at 700°C

The sulfidation of Ni-10Cr-5Al, Ni-20Cr-5Al, and Ni-50Cr-5Al, and of the same alloys containing 1% Y, was studied in 0.1 atm sulfur vapor at 700°C. The sulfidation process followed linear kinetics for all the alloys except Ni-50Cr-5Al-1Y, and possibly Ni-50Cr-5Al, which followed the parabolic law. The reaction rates decreased with increasing chromium content in alloys without yttrium, and the addition of yttrium reduced the rates by at least a factor of two for the alloys containing 10 and 20% Cr and by an order of magnitude for Ni-50Cr-5Al. Alloys containing 10 and 20% Cr (with and without yttrium) formed duplex scales consisting of an outer layer of NiS_1.03 and an inner lamellar layer of a very fine mixture of Cr₂S₃ and A1₂O₃ in a matrix of NiS_1.03. The two alloys containing 50% Cr formed only a compact layer of Cr₂S₃, which was brittle and spalled during cooling. The lamellae in the duplex scales were parallel to the specimen surface and bent around corners. The lamellae were thicker than those on Ni-Al binary alloys. The lamellae were also thicker in scales on the 20% Cr alloy than on the 10% Cr alloy. The presence of yttrium refined the lamellae and increased the lamellae density near the scale/metal interface in the 10% alloy, but in the 20% Cr alloy the lammellae were thicker and more closely spaced. Platinum markers were found in the inner portion of the exterior NiS_1.03 layer close to the lamellar zone. A counter-current diffusion mechanism is proposed involving outward cation diffusion and inward sulfur diffusion, although diffusion was not rate controlling for alloys containing 10 and 20% Cr. Auger analysis of scales formed on Ni-50Cr-1Y showed an even distribution of yttrium throughout the layer of Cr₂S₃, suggesting that some yttrium dissolved in the sulfide. The reduced sulfidation rate of samples containing yttrium is explained by the possible dissolution of yttrium as a donor. The presence of Y⁴⁺ would then decrease the concentration of interstitial chromium ions in the N-type layer of Cr₂S₃, which would decrease the reaction rate.     

Selective Oxidation and Sub-surface Phase Transformations in Chromium-bearing Austenitic Steels

A series of Fe–15Cr–(2–3)Mo–(0.7–2.5)C (compositions in weight percent) steels was oxidised at 850°C and P_{O_2} = 5.8 × 10^–20 atm, where iron oxide is unstable. All grew external Cr₂O₃ scales according to parabolic kinetics. Depletion of chromium from alloy subsurface regions led to dissolution of chromium-rich carbides if the original alloy carbon level was less than 1.2%. Simultaneous decarburisation caused a transformation of the original austenitic or austenoferritic structure into single-phase ferrite, stabilised by the molybdenum. Diffusion analysis of the concentration profiles within this transformed zone led to satisfactory agreement with the known diffusion coefficient for chromium in ferrite. At high carbon levels, decarburisation was slow, resulting in low chromium concentrations at the internal alloy–carbide interfaces. In these cases, the carbide dissolution did not proceed and chromia scaling rates were slowed.     

Effect of carbide volume fraction on the oxidation of austenitic Fe‐Cr‐C alloys

A series of Fe‐15Cr‐(2‐3)Mo alloys (compositions in weight percent) was produced with different carbon concentrations, to control the distribution of chromium between matrix metal and M₂₃C₆ precipitates. The alloys were oxidized in the austenitic state at 850°C in pure oxygen, with and without a pre‐oxidation treatment at low oxygen potential, where no iron oxide could form. Protective, chromia‐rich scaling took place if the chromium concentration at the metal‐scale interface was high enough. This concentration was controlled by the original alloy matrix chromium concentration, and whether or not a high diffusivity ferrite zone developed at the surface by decarburization. Ferrite zone formation was assisted by pre‐oxidation at low oxygen potentials. The value of the carbides as suppliers of additional chromium was demonstrated by comparison with the oxidation performance of carbide‐free alloys of corresponding matrix chromium levels. However, because dissolution of the coarse carbides could be slow, alloys with high volume fractions of large carbides were unsuccessful.     

High Temperature Corrosion of Cast Alloys in Exhaust Environments. II—Cast Stainless Steels

This paper describes in detail the oxidation of two cast stainless steels in synthetic diesel and gasoline exhaust gases. One alloy was ferritic (Fe18Cr1.4Nb2.1Mn0.32C) and one austenitic (Fe20Cr9Ni1.9Nb2.7W0.47C). Polished sections were exposed, mostly for 50 h, at temperatures between 650 and 1,050 °C. The oxidation product was characterized by means of SEM/EDX, AES, and XRD. Inter-dendritic non-Cr carbides initiated thick oxides. The ferritic steel formed a rather thin and adherent oxide scale at all temperatures. It consisted of (Mn, Cr) oxide on top of Cr₂O₃ and, starting at 850 °C, a thin silica film at the metal–oxide interface. Chromium depletion triggered dissolution of carbides providing Cr to the oxide. Water vapor did not accelerate the attack since the outer (Mn, Cr) spinel oxide reduced the Cr evaporation. The austenitic grade was very sensitive to water vapor. Chromium segregation directed pitting to the dendrites up to 950 °C whereas uniform catastrophic oxidation occurred at 1,050 °C.     

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.     

The influence of zirconium on the approach to steady-state scaling in a Ni-Cr alloy and the mechanism of inhibition of corrosion in an oxygen-sulphur environment

The corrosion behaviour of a binary Ni-15 Cr alloy and a ternary Ni-15 Cr'1 Zr alloy has been examined when exposed to a bioxidant O₂:SO₂ atmosphere at 850°C. The patterns of scaling exhibited by the two alloys, especially in the early stages of reaction, have been studied using optical and scanning electron microscopy and EDAX analysis. It has been established that the nucleation of Cr₂ O₃ on, and its subsequent growth over the sample surface was much more rapid with the ternary alloy than the binary material. Furthermore the steady-state scale formed on the ternary alloy was single-layered and contained no NiO, in contrast to the anticipated duplex-layered scale developed on the binary material. It is suggested that the pre-existing intermetallic network in the as-cast microstructure of the Ni-15 Cr-1 Zr alloy is a key factor in promoting the rapid formation of the thin protective layer of Cr₂O₃, free from NiO. These features are responsible for the reduced rate of corrosion of the Zr'bearing material, relative to that exhibited by the binary alloy. The observations are discussed in the light of the published literature concerning the effects of rare earth/reactive metal and inert oxide additions to chromia-forming alloy systems.     

Metal dusting of high temperature alloys

Metal dusting, i.e. disintegration into fine metal particles and carbon, was induced on a selection of chromia forming high temperature alloys in a flowing CO-H₂-H₂O atmosphere in exposures at 650°C, 600°C, 500°, and 450°C. The materials were pretreated by annealing in H₂ at 1000°C and electropolishing, this leads to large grain size and low surface deformation, both is disadvantageous for formation of a Cr₂O₃ scale. The resistance to metal dusting is only dependent on the ability to form a protective Cr₂O₃ scale, thus the high Cr ferritic steels proved to be very resistant, the ferritic steels with 12–13% Cr were less resistant. Due to the lower Cr diffusivity in the austenitic steels, these were very susceptible, especially two alloys with about 30% Ni (Alloy 800, AC 66). The appearance of metal dusting was somewhat different for Ni-base materials but they were also attacked under pitting. The metal dusting is preceded in all cases by internal carburization whereby the chromium is tied up, afterwards the remaining Fe or Fe-Ni matrix can react to the instable intermediate carbide M₃C which decomposes to metal particles and carbon, in case of Ni-base materials a supersaturated solid solution of carbon is the intermediate.     

Effects of Grit Blasting and Annealing on the High-Temperature Oxidation Behavior of Austenitic and Ferritic Fe-Cr Alloys

Grit blasting (corundum) of an austenitic AISI 304 stainless steel (18Cr-8Ni) and of a low-alloy SA213 T22 ferritic steel (2.25Cr-1Mo) followed by annealing in argon resulted in enhanced outward diffusion of Cr, Mn, and Fe. Whereas 3 bar of blasting pressure allowed to grow more Cr₂O₃ and Mn _x Cr_3?x O₄ spinel-rich scales, higher pressures gave rise to Fe₂O₃-enriched layers and were therefore disregarded. The effect of annealing pre-oxidation treatment on the isothermal oxidation resistance was subsequently evaluated for 48 h for both steels and the results were compared with their polished counterparts. The change of oxidation kinetics of the pre-oxidized 18Cr-8Ni samples at 850 °C was ascribed to the growth of a duplex Cr₂O₃/Mn _x Cr_3?x O₄ scale that remained adherent to the substrate. Such a positive effect was less marked when considering the oxidation kinetics of the 2.25Cr-1Mo steel but a more compact and thinner Fe _x Cr_3?x O₄ subscale grew at 650 °C compared to that of the polished samples. It appeared that the beneficial effect is very sensitive to the experimental blasting conditions. The input of Raman micro-spectroscopy was shown to be of ground importance in the precise identification of multiple oxide phases grown under the different conditions investigated in this study.     

General and local corrosion of as-cast 25cr-20ni steel in molten sulphates: The influence of Si and W additions

The corrosion of as-cast austenitic stainless steels 25Cr-20Ni (AISI 310) in alkaline sulphate melts was studied at 700°C. General corrosion occurred on the austenitic matrix and local corrosion in the interdendritic zones. Local corrosion depended on the type of solidification precipitates (carbides). A Cr-depleted zone was found around M₇C₃ type carbides. Electrochemical investigations with alloys and sintered carbides showed anodic behaviour of this Cr-depleted zone in relation to the austenitic matrix or M₇C₃ carbides. The influence of silicon and tungsten on general and local corrosion is discussed.