Oxidation of nickel-based alloys in dry and water vapour containing air

Abstract

Ni-based alloys are widely used in power generation and their oxidation behaviour in the uncoated state is of interest, especially the impact of water vapour in the air on the formation of a protective underlying alumina scale. High-temperature X-ray diffraction was applied to investigate in situ the oxide scale formation in the initial state on the alumina formers CM247DS and CMSX4 in comparison to the chromia formers IN792 and SCA425+. Post-oxidation analysis was performed by field emission scanning electron microscopy. The samples were oxidised for 100 h at 950°C in dry air and in air with 20% relative moisture in the high temperature device on the X-ray diffractometer. In dry air, CM247 and CMSX-4 form α-Al₂O₃ from the beginning simultaneously with spinels and nickel oxide. The alumina scale underlies the spinels which spall partially on cooling. When adding water vapour, the same oxides were formed simultaneously resulting in a comparable oxide scale. IN792 forms in dry air mainly NiAl₂O₄ and transitionally CrO₂ under laid by an alumina scale. With water vapour, Cr₂O₃ forms and the underlying alumina scale shows a non coherent dendritic structure. SCA425+ forms in dry air Cr₂O₃ and Cr containing mixed oxides and with water vapour a more coherent alumina scale than IN792.     

The influence of the moisture content of the atmosphere on alumina scale formation and growth during high temperature oxidation of PM2000

Abstract

Preliminary studies have been undertaken on cyclic and isothermal oxidation at 1,300°C of thin (125 μm) samples of commercial ODS alloy PM2000 for up to 350h in two different oxidising environments; dry and moist air. Scanning electron microscopy (SEM) and electron microprobe analysis (EPMA) have been used to study the influence of such environments on alumina scale formation and growth. Initial mass gain observations showed that the alumina scale, which formed on the samples oxidised in air+2.5vol% H₂O grew faster in the early stages of oxidation than in the case of dry air. However the SEM analysis revealed that the scale morphologies in both dry air and air+2.5vol% H₂O were similar. In both cases the scales consisted of equiaxed grains at the scale–gas interface with Ti-rich particles in the outermost part of the scale. The major factor for the total scale failure, the formation of non-protective iron oxide, is the depletion of Al levels to a critical value, below which no protective alumina scale can form; and this occurred slightly faster in moist air than in dry air     

Influence of the oxidation environment on scale morphology and oxidation rate of Fe–22Cr

Abstract

The oxidation behaviour of a commercial Fe–Cr alloy with 22 wt% Cr was investigated at 1173K in Ar–9 H₂ with 1% H₂O (pO₂ = 9.8 × 10^?19), in air with 1% H₂O (pO₂ = 0.208), and in a combination of the two atmospheres. The oxide morphology was investigated with X-ray diffraction and scanning electron microscopy. The oxide layer consisted of MnCr₂O₄ on top of Cr₂O₃.

Small oxide whiskers were present at the surface after oxidation in Ar–9 H₂ with 1% H₂O but not after oxidation in air with 1% H₂O. For samples initially oxidised in air with 1% H₂O, the oxide/alloy interface was wrinkled and covered with a SiO₂ layer. SiO₂ particles had developed at a rather flat oxide/alloy interface for samples initially oxidised in Ar–9% H₂ with 1% H₂O. The results obtained can be explained assuming that oxide growth occurs by cation diffusion only in Ar–9 H₂ with 1% H₂O, whereas both cation and anion diffusion contribute to the growth in air/H₂O.     

High temperature oxidation of hot-pressed aluminium nitride by water vapour

Hot pressed AIN without additives was oxidized et 1100 to 1400°C in dry air, wet air and wet nitrogen gas atmospheres with 1.5 to 20 kPa of water vapour pressure. AIN was oxidized by both air and water vapour, and formed -Al₂O₃ film on the surface above 1150°C. The oxidation kinetics in air were parabolic end were promoted by water vapour. On the other hand, the oxidation kinetics in wet nitrogen were linear below 1250°C and parabolic above 1350°C. The oxidation rate in wet nitrogen was much greater than that in wet air. The rate of oxidation increased with increasing temperature until 1350°C, and then decreased. The parabolic rate constant decreased with increasing temperature and increased linearly with increasing water vapour pressure. The linear rate constant at 1150 to 1250° C increased with increasing the temperature with the apparent activation energy of 250 kJ mol^–1. The relation between the linear rate constant and water vapour pressure was of the Langmuir type.     

Oxidation of silicon nitride in a wet atmosphere

The effect of water vapour on oxidation was studied with hot-pressed silicon nitride containing both yttria and alumina as sintering aids in wet air flow with 10, 20, 30, and 40 vol% H₂O at 1300°C for 100 h. The oxidation kinetics were determined in a wet air flow with 20 vol% H₂O and in a dry air flow at 1300°C for oxidation times up to 360 h. The water vapour in the atmosphere slightly influenced the oxidation and accelerated the reaction, and the weight gained on oxidation in a wet atmosphere had an increasing tendency with increasing water vapour content. The oxidation proceeded in a diffusion-controlled manner in both wet and dry atmospheres. The values of weight gained in wet oxidation varied to a greater degree than in dry oxidation. Water vapour had a strong effect on the devitrification of the amorphous oxide. This process was presumed to promote the rate of oxidation more than in dry atmosphere. The water vapour also had a strong roughening effect on the surface oxide layer grown during oxidation. The flexural strength at room temperature was degraded by oxidation in a wet atmosphere and it is presumed to be degraded by wet oxidation slightly and consecutively with time.     

Simulation of road salt corrosion in austenitic alloys for automotive exhaust systems

Abstract

Cyclic oxidation tests in air with intermittent salt spraying have been performed to simulate the conditions of road salt (NaCl–CaCl₂) enhanced corrosion in automotive exhaust systems.

Tests were carried out at 600 and 700°C on three austenitic alloys, including two stainless steels currently employed for exhaust components (AISI 316 Ti and AISI 302B) and a higher nickel heat resisting alloy.

The presence of salt causes internal corrosion, both along a regular front beneath an outer oxide scale and down alloy grain boundaries. An increase in temperature accelerates the corrosion rate and particularly enhances intergranular penetration.

The results of micrographic and microanalytical investigations are in general agreement with an active oxidation mechanism in which Na_xCl_x vapour species, and not only chlorine, appear to play an important role. The regions directly affected are depleted in chromium and iron and enriched in nickel.

Although internal oxidation of silicon is observed, a high silicon content (2%) does not necessarily ensure effective protection against this type of attack.     

Role of nickel in the oxidation of Fe–Cr–Ni alloys in air–water vapour atmospheres

Abstract

A series of experimental austenitic alloys has been produced in which the nickel content ranges from 14 to 43%, with constant levels of 20%Cr, 1%Mn and 0.5%Si. A combination of isothermal, discontinuous and cyclic oxidation testing has been used to elucidate the performance in dry air and in air with 10%, 45% or 62% water vapour at 700°C and 1000°C. Evaluation was by means of thermogravimetry, surface analysis with glow discharge optical emission spectroscopy and scanning electron microscopy.

Nickel is shown to have several roles: it accelerates the kinetics of chromia formation yet suppresses chromia spallation at 700°C. At 1000°C, it strongly decreases the breakaway oxidation and spalling associated with iron oxide formation. This effect is particularly marked in environments containing water vapour, where the material loss may be decreased 10-fold by an increase in the nickel content. Results correlate to thermodynamic and kinetic data which show nickel to increase the chromium activity and diffusivity in the alloy.     

The effect of water vapor in increasing growth stresses in the oxide scale on martensitic steam plant alloys

Abstract

Investigation of the oxidation behavior of 9% Cr steels at 650°C in dry air and air + 10% H₂O have shown that oxide scale growth stresses may play a significant role in breakaway. For this reason, preliminary studies on the development and characteristics of growth stresses in oxides on these materials have begun. These studies include in situ acoustic emission (AE) for monitoring scale cracking, deflection testing in monofacial oxidation (DTMO) and in situ X–ray measurements. The measurements were complemented by detailed post-experimental metallographic investigations.

From the DTMO measurements the stresses in the oxide on the specimens tested in humid environment are increased by about a factor of 5 compared to dry air at the beginning of oxidation for P91. In a humid environment the stresses decrease with oxidation time while in dry air they remain almost constant. Significant acoustic emission (AE) occurs in humid air for oxidation coupons while virtually no AE is observed for thin foils in a humid environment and for coupons in dry air. These first results seem to be in good agreement with weight gain data characterizing the breakaway behavior in these environments, indicating that, indeed, oxide growth stresses play a key role for oxidation resistance and, thus, component lifetimes of such steels.

The first X–ray results indicate that for E911 the scale structure and composition changes completely between the two environments. Furthermore, in humid air, a breakaway effect is observed with a change from protective spinel type oxide to locally non-protective Fe–rich oxide.     

High-temperature oxidation of silicon nitride-based ceramics by water vapour

Hot-pressed Si₃N₄, sintered Si₃N₄ and three kinds of sialon with different compositions were oxidized in dry air and wet nitrogen gas atmospheres at 1100 to 1350° C and 1.5 to 20 kPa water vapour pressure. All samples were oxidized by both dry air and water vapour at high temperature, and formed oxide films consisting of SiO₂, Y₂Si₂O₇ and Y4A1209. The oxidation rate was in the order sialon > sintered Si₃N₄ > hot-pressed Si3N4. The oxidation rate of sialon increased with increasing Y₂O₃ content, and oxidation kinetics obeyed the usual parabolic law. The oxidation rates in dry air and wet nitrogen were almost the same: the rate in wet nitrogen was unaffected by water vapour pressure above 1.5 kPa. The activation energy was about 800 kJ mol^–1.     

Chemical-mechanical failure of oxide scales on 9% Cr steels in air with H2O

Abstract

The oxidation behaviour of 9% Cr steels P91 and Nf616 has been investigated at 650°C in dry air and in air with water vapour, where particular attention was given to breakaway failure. Additional emphasis was given to the quantitative characterisation of the kinetics of chromium depletion in the metal subsurface zone resulting from scale growth, CrO₂H₄ evaporation, and scale cracking and healing, with scale cracking being monitored by acoustic emission measurements. While in dry air the steels show protective oxidation behaviour up to 10000 h, breakaway oxidation may occur already after 100 h in humid environments, which was correlated with the stronger Cr-depletion and the development of intrinsic oxide scale growth stresses exceeding a critical value, in the case of water vapour containing air. In the paper the different parameters that are responsible for breakaway oxidation were identified and discussed with regard to the role of water vapour in the environment. As a conclusion it turns out that breakaway is not a consequence of Intrinsic Chemical Failure (InCF) but of a Mechanically Induced Chemical Failure (MICF).     

High temperature isothermal oxidation behaviour of an oxide dispersion strengthened derivative of IN625

Abstract

Gas atomised IN625 powder was mechanically alloyed with <1·0 Wt.% nano-yttria and consolidated by spark plasma sintering (SPS) to produce an oxide dispersion strengthened (ODS) alloy. The isothermal oxidation rate constant of the ODS alloy, and wrought IN625, was determined by thermogravimetric analysis. This was performed at 900 °C in static laboratory air for exposure times of up to 1000 h. It was found that the ODS alloy oxidised ~40x slower than wrought IN625, which is attributed to the reactive element effect. It is further proposed that the improvement in oxidation resistance of the ODS alloy, and the superior morphology of the oxide scale formed on the ODS alloy, may be related to the presence of Nb carbide, rather than δ-phase, in the ODS alloy.     

Oxidation of silicon carbide in a wet atmosphere

The effects of water vapour on oxidation of pressureless-sintered silicon carbide containing alumina as a densifying aid were studied in a wet air flow with 10, 20, 30 and 40vol% H₂O at 1300° C for 100h. The oxidation kinetics were determined in a wet air flow with 20 vol % H₂O and in a dry air flow at 1300° C for times up to 360 h. The weight gain on oxidation showed an increasing tendency with increasing water vapour content. Water vapour in the atmosphere strongly influenced oxidation and accelerated the reaction. Oxidation in a wet atmosphere proceeded in a diffusion-controlled manner, in the same process as that for the dry atmosphere. No remarkable differences were noticed in the microstructure of the oxide layer and the surface roughness between the samples oxidized under the four wet conditions, but the surface roughness increased with increasing oxidation time. Water vapour evidently accelerated the devitrification of amorphous silica and promoted oxidation. Oxidation in a wet atmosphere (10 to 40 vol % H₂O for 100 h and 20 vol % H₂O up to 360 h) had a slight degrading effect on the flexural strength. The microstructure or surface roughness of the oxide layer formed during oxidation presumably had very little effect on the room-temperature strength.     

Morphological characteristics of oxide scales grown on H11 steel oxidised in dry or wet air

Abstract

The oxidation behaviour in dry and wet air of H11 steel was studied at 600 and 700°C by Thermo Gravimetric Analysis (TGA) and in situ oxidation in the specimen chamber of an Environmental Scanning Electron Microscope (ESEM) equipped with a hot stage specimen holder. The oxidation kinetics of H11 steels are quite sensitive to the presence of water vapour and, although the final mass gains show a good overall reproducibility, they are locally rather irregular. The morphology and microstructure of oxide scale are complex and often heterogeneous, particularly at 700°C. In situ oxidation tests permit to follow the evolution of oxide scales and to observe several growth modes of oxide scales. The diversity of the observed scale growth modes can explain the complexity and irregularity of scale growth mechanisms. Some additional in situ oxidation tests were performed in wet nitrogen. Morphology and growth modes of oxide scale grown in wet air and wet nitrogen differ strongly.     

Technical note Fabrication of alumina dispersion strengthened copper strips by internal oxidation and hot roll bonding

Abstract

Alumina dispersion strengthened copper strips were fabricated by internal oxidation and hot roll bonding of Cu–Al alloy strips. Cu–Al alloy strips were internally oxidised without using any oxidant powders by a surface oxidation method. Several of the internally oxidised alloy strips were stacked and bonded by rolling at high temperatures. The bonded strip was cold rolled to achieve tensile strengths of 484–539 MPa and yield strengths of 472–522 MPa with thermally stable mechanical properties.     

Oxidation behaviour of TiAlYN/CrN and CrAlYN/CrN nanoscale multilayer coatings with Al2O3 topcoat deposited on γ-TiAl alloys

Abstract

TiAlYN/CrN and CrAlYN/CrN nanoscale multilayer coatings were deposited on γ-TiAl specimens using magnetron sputtering techniques. The nitride layers were manufactured by unbalanced magnetron sputtering (UBM) and high power impulse magnetron sputtering (HIPIMS). The CrAlYN/CrN coatings had an oxy-nitride overcoat. On some of the coated samples an additional alumina topcoat was deposited. The oxidation behaviour of the different coatings was investigated at 750 and 850°C performing quasi-isothermal oxidation tests in laboratory air. Mass change data were measured during exposure up to failure or the maximum exposure length of 2500 h. When exposed to air at 750°C, the Ti-based nitride films exhibited higher oxidation resistance than the Ti – 45Al –8Nb substrate material. The alumina topcoat enhanced the oxidation protection of this coating system, acting as diffusion barrier to oxygen penetration. At 850°C, the TiAlYN/CrN films exhibited poor stability and rapidly oxidised, and therefore were not applicable for long-term protective coatings on γ-TiAl alloys. The beneficial effect of the additional Al₂O₃ layer was less pronounced at this exposure temperature. The Cr-based nitride films exhibited high oxidation resistance during exposure at 850°C. HIPIMS deposition improved the oxidation behaviour of the CrAlYN/CrN nanoscale multilayer coatings in comparison to UBM coatings. For these coatings, the decomposed and partially oxidised nitride films were an effective barrier to oxygen inward diffusion. The alumina topcoat did not significantly increase the oxidation resistance of the γ-TiAl alloy coated with Cr-based nitride films.     

PASSIVATION EFFECTS ON CRACK CLOSURE IN THE FATIGUE CRACK PROPAGATION OF A PEAK-AGED Al-Li-Zr ALLOY IN NaCl AND Na2SO4 SOLUTIONS

Abstract Fatigue cracking of a peak-aged Al-Li-Zr alloy was investigated by measuring crack closure as a function of applied anodic potential in 0.6 M NaCl and 0.5 M Na₂SO₄ solutions with an unloading elastic compliance technique, and by comparison with crack closure in dry air. The present work involves complementary anodic behaviour of the Al-Li-Zr alloy in both solutions by potentiodynamic polarization and potentiostatic current transient experiments. From the repassivation rates in the passivation potential range in both solutions, it is indicated that a more stable passive film is formed at lower applied anodic potential than at higher applied anodic potential. The intrinsic fatigue crack propagation (FCP) rates under unstable passivation potential in both solutions were significantly larger than those obtained in dry air. Under stable passivation potential in both solutions, however, the intrinsic FCP rates in the low ΔK_eff range were slightly lower than those obtained in dry air. The crack closure in the low ΔK_eff range increased under stable passivation potential, in dry air and under unstable passivation potential. The high crack closures appearing in the low ΔK_eff range were characterized by a tortuous fracture surface in dry air, and the occurrence of various crack paths such as rolling plane delamination under unstable passivation potential. The difference between environmental crack closures under stable and unstable passivation conditions is discussed in terms of environment-assisted crack-tip damage processes.     

Oxidation of potential SOFC interconnect materials,Crofer 22 APU and Avesta 353 MA,in dry and humid air studied in situ by X-ray diffraction

Abstract

Several stainless steels have been developed for the use as interconnect materials in solid oxide fuel cells in order to reduce costs, while maintaining the required performance. The materials however, are subjected to humid air, at high temperatures up to 800°C leading to enhanced oxidation. High temperature X-ray diffraction, combined with field emission – scanning electron microscopy, has been applied to study in situ the influence of water vapour on the chromia scale formation on the ferritic Crofer 22 APU and the austenitic Avesta 353 MA alloys in comparison to their dry air oxidation behaviour. Both materials form at 800°C, during the first 100h exposure, Cr₂O₃ and MnCr₂O₄, the latter mostly in the surface region of the oxide scale. Additionally, Crofer 22 APU forms internal Al₂O₃ precipitates, while on Avesta 353 MA a SiO₂ layer is found beneath the outer oxide scale. High temperature XRD indicates stress formation and relaxation in the Cr₂O₃ scale formed in humid air, especially for Crofer 22 APU.     

Effect of partial oxygen pressure on the initial stages of high-temperature oxidation of γ-NiCrAl alloys

Abstract

The effect of the partial oxygen pressure (pO₂) on the initial stages of oxide-layer growth of a γ-Ni-27Cr-9Al (at.%) alloy at 1373 K was studied using X-ray photoelectron spectroscopy, X-ray diffractrometry, scanning electron microscopy and electron probe X-ray microanalysis. The alloy was oxidised at a pO₂ of 0.1 and 0.2 × 105 Pa in an UHV processing chamber and a furnace, respectively. For both pressures, a double-layered oxide structure evolved upon oxidation, which consisted of a NiCr₂O₄/Cr₂O₃ layer on top of an α-Al₂O₃ layer. Two different oxidation stages were identified: an initial, very fast oxidation stage followed by a second stage of slow, parabolic growth. The initial oxidation stage was associated with the preferential oxidation of Al, followed by the internal oxidation of Al and simultaneous formation of Cr₂O₃ (and some NiO). The onset of the second stage ran parallel with the coalescence of internal α-Al₂O₃ crystallites into a continuous closed layer. Then, the internal oxidation of Al and growth of Cr₂O₃ ceased. A lower pO₂ reduced the activity of oxygen at the oxide/alloy interface during the initial, fast oxidation stage, thereby enhancing the rate of formation of a continuous closed α-Al₂O₃ layer and suppressing the formation of Cr₂O₃ (and NiO).     

Oxidation behaviour of Ti6Al4V titanium alloy in oxygen

Abstract

The isothermal oxidation behaviour of two phase (α + β) titanium base alloy Ti6Al4V (coupons) has been studied at 1050, 1150, 1250, and 1340 K in O₂ gas at atmospheric pressure for 2, 4, 6, 8, and 12 h. Investigations on kinetic behaviour followed by the metallographic examination of oxidised scale morphology was carried out. Thermogravimetric data (weight gain v time) exhibited parabolic behaviour. Below 1250 K, the rate of oxidation substantially decreased after 8 h exposure, however, at 1340 K the oxidation rate was markedly high over the whole 12 h period. Parabolic rate constants were 0.234×10^-7, 3.67×10^-7, 10.72×10 ^-7, and 31.17×10^-7 kg² m^-4 s^-1 at 1050, 1150, 1250, and 1340 K respectively. The effective activation energy of oxidation was 88 kJ mol^-1. The instantaneous rate constant k _i exhibited a marked deviation from parabolic behaviour at high temperatures e.g. 1150, 1250, and 1340 K, however, k _i at lower temperature (1050 K) remained broadly unchanged with time exhibiting no deviation from parabolic behaviour. Metallographic observation of the sample coupons treated at 1340 K revealed an identical oxide scale morphology with increased thickness over the time.     

Oxidation of Fe–Si alloys in CO2–H2O atmospheres

Abstract

Iron and model alloys containing 1, 2, and 3wt% Si were reacted with dry and wet CO₂ gases at 800°C. All oxidised in dry CO₂ according to approximately linear kinetics. Additions of H₂O accelerated the reaction until steady-state parabolic kinetics were achieved. However, the effect of H₂O was small in the steady-state reaction stage of Fe – 3Si. Alloy reaction products were a duplex scale consisting of an outer FeO+Fe₃O₄ layer and an inner FeO+Fe₂SiO₄ layer, plus an internal oxidation zone, in all gases. In Fe – 1Si, amorphous SiO₂ precipitates in the internal oxidation zone grew with rod-like morphologies in all gases. However, internal amorphous SiO₂ precipitates grown in Fe – 2Si and Fe – 3Si formed network patterns. Internal penetration rates were initially rapid in Fe – 1Si, but slowed considerably at longer times. In Fe – 3Si, the internal oxidation zone grew wider in the first 20 h of reaction, and then remained constant in dry gas. In the wet gases this zone subsequently diminished, and disappeared after 50 h reaction.