Protective and non-protective scale formation of NiCr alloys in water vapour containing high- and low-pO2 gases

The oxidation behaviour of NiCr alloys with Cr contents of 10, 20 and 25 wt.%, respectively, were studied in Ar-O₂, Ar-O₂-H₂O and Ar-H₂O mixtures. TG and SEM analysis revealed that the chromia scales formed on Ni-25Cr in the wet gases did not differ substantially from those formed in Ar-O₂. For the two “borderline” alloys Ni-10Cr and Ni-20Cr, addition of water vapour to Ar-O₂ hampered the formation of a protective chromia scale which, especially for Ni-10Cr, resulted in substantially increased scale growth rates compared to exposures in dry gas. Different from numerous observations described in the literature for “borderline” FeCr alloys with intermediate Cr contents of 10-20%, the corresponding NiCr alloys showed in Ar-H₂O a smaller tendency for non-protective scale formation than in Ar-O₂-H₂O. This is caused by the decreasing growth rate of NiO with decreasing pO₂ of the test gas, with the secondary effect that external chromia scale formation is promoted in low-pO₂ gases such as Ar-H₂O. Even if the alloy Cr content was too low to obtain external chromia scale formation, the oxidation rate in Ar-H₂O would, in contrast to low-Cr FeCr alloys, be quite small due to the very slow growth rate of NiO in this low-pO₂ gas.     

Microstructure and anti-oxidation behavior of laser clad Ni-20Cr coating on molybdenum surface

A Ni-20Cr coating was deposited on a molybdenum substrate by laser cladding. The observation of the microstructure by SEM demonstrates that the coating is free of cracks and pores, and metallurgically bonded to the substrate. XRD and EDS analysis results show that some dilution occurs at the coating/substrate interface and that Mo combines with Ni-20Cr, to form a Ni-Cr-Mo alloy coating with slight oxidation. The oxidation behavior of the coating indicates that the laser clad Ni-20Cr coating can effectively prevent oxidation of molybdenum at 600 °C in air. The oxide scale formed on the coating surface by oxidation in air is composed of NiO, Cr₂O₃ and NiMoO₄.     

Grain size effects on the oxidation of two ternary Cu-Ni-20wt.% Cr alloys at 700-800 °C in 1 atm O2

Two nanocrystalline two-phase Cu-Ni-Cr alloys, both prepared by mechanical alloying and containing about 20 at.% Cr but with different Ni contents (40 and 20 wt.%, respectively), have been oxidized in 1 atm O₂ at 700-800 °C. Their oxidation behavior has been compared with that of two cast alloys of the same composition, already studied previously, to examine the effects of a large reduction of the size of the individual phase grains and particles. The nanophase alloy with 40 wt.% Ni formed a flat external layer of chromia of regular thickness, while the corresponding cast alloy produced a very irregular chromia layer, often protruding deeply into the alloy, only after an initial stage of rather fast corrosion involving also copper and nickel, associated with some degree of internal oxidation. By oxidation at 700 °C the nanophase alloy with 20 wt.% Ni formed an irregular chromia layer associated with low corrosion rates. The corresponding cast alloy formed complex scales containing Cu, Ni and Cr oxides, extending into the alloy in the form of large pegs, even though a very irregular and discontinuous innermost chromia layer was still able to produce low corrosion rates. On the contrary, at 800 °C both alloys formed complex scales containing mixtures of the oxides of the three metal components. However, the scales grown on the cast alloy were much more irregular in thickness and formed large protrusions into the alloy. In spite of this, the corrosion kinetics of the nanophase 20 wt.% Ni alloy at 800 °C were more irregular and, except for an initial stage, less protective than that of the cast alloy with the same composition.     

High-temperature corrosion of titanium-, niobium-, and manganese-rich Fe-25Cr alloys in H2-H2O-H2S gas mixtures

The simultaneous sulfidation and oxidation of Fe-25Cr, Fe-25Cr-4.3Ti, Fe-25Cr-7.5Nb, and Fe-25Cr-9.0 Mn alloys were studied at 1023, 1123, and 1223 K, respectively, in H₂-H₂O -H₂S gas mixtures. The influences of titanium, niobium, and manganese on the transition from protective oxide formation to the formation of sulfide-rich corrosion products of Fe-25Cr alloys have been investigated. It has been found that additions of titanium and niobium can improve the scaling resistance of Fe-25Cr alloys against sulfidation in H₂ -H₂O -H₂S gas mixtures at high temperatures. However, the addition of manganese does not increase the resistance to sulfidation of Fe-25Cr alloy. The oxide Cr₂Ti₂O₇, which can suppress sulfide formation, formed on the Fe-25Cr-4.3Ti alloy. The addition of manganese to Fe-25Cr does not form more stable and protective oxides than Cr₂O₃ which formed on Fe-25Cr. Thermodynamic stability diagrams are used to explain the experimental results.     

Transient state scale formation on Fe 32 Ni 20 Cr and Fe 20 Cr in H2-H2O-H2S atmospheres

The transient state of simultaneous oxidation and sulfidation of Fe-32 Ni-20 Cr and Fe-20 Cr was studied at 700°C for short time exposures in H₂-H₂O-H₂S. After heating the specimens in pure, dry hydrogen they were corroded by introduction of the oxidizing and sulfidizing atmosphere for 2, 4 or 15 min. After quenching the layer was investigated by SEM, AES, X-ray and electron diffraction. Four different gas compositions were applied: pS₂ = 10^?12 bar and pO₂ = 10^?25, 10^?26, 10^?27, 10^?28 bar, all within the thermodynamic stability range of Cr₂O₃. After the short time exposures oxides and sulfides were present on the surface, Cr₂O₃ and Cr₃S₄ had grown side by side and in case of the alloy Fe-32 Ni-20 Cr Fe- and Ni-containing sulfides formed patches on top of the scale. The amount of sulfides was higher for the lower oxygen pressures. After a longer time exposure, 120 min, all sulfides had vanished. Simultaneous formation of oxides and sulfides occurs in the transient state during phase boundary reaction or transport control. Upon transition to diffusion control the sulfides vanish by dissolution into the alloy and reaction with the gas atmosphere. This is valid for low pS₂ where no iron and nickel sulfides are stable.     

Effect of water vapour on cyclic oxidation of Fe–Cr alloys

Model Fe–Cr alloys containing 9, 17 or 25 wt% Cr were subjected to repeated 1 h cycles of exposure at 700 °C to flowing gas mixtures of Ar‐20O₂, Ar‐20O₂‐5H₂O and Ar‐5O₂‐20H₂O (all in volume %) for up to 400 cycles. The kinetics and morphological development of these reactions were compared with those found during isothermal exposure to the same gases. Under isothermal conditions, all alloys developed thin protective chromium‐rich scales in dry oxygen. Addition of 5% H₂O induced breakaway for Fe‐9Cr within 48 h, but had little effect on higher chromium alloys. Isothermal chromia scale growth on Fe‐17Cr and Fe‐25Cr was accelerated by the addition of 20% H₂O, but breakaway did not result. Under cyclic conditions in dry oxygen, Fe‐9Cr quickly entered breakaway, oxidising according to fast, linear kinetics, but the higher chromium alloys exhibited protective behaviour. When 5% H₂O was added to the oxygen, the 17% Cr alloy also underwent fast breakaway oxidation, but Fe‐25Cr continued to be protected by a chromia scale. In the 20% H₂O gas, all alloys failed under cyclic conditions, producing thick, iron‐rich oxide scales. The synergistic effects of water vapour and temperature cycling are discussed in terms of alloy chromium depletion and the effects of H₂O(g) on oxide transport properties.     

Corrosion and Carburization Behaviour of Ni-<Emphasis Type="Italic">x</Emphasis>Cr Binary Alloys in a High-Temperature Supercritical-Carbon Dioxide Environment

Pure Ni and Ni-xCr (x = 7, 14, 22 and 27 wt%) binary alloys were exposed to supercritical-carbon dioxide environment at 600 °C and 20 MPa for 200 h. For pure Ni, a thick NiO layer was formed on the surface. Meanwhile, for Ni-7Cr alloy, an inner oxide layer consisted of rather irregular chromia and NiO was formed below the outer NiO layer. When Cr content was greater than 14%, a continuous chromia layer was formed, resulting in much lower weight gain and oxide thickness. However, amorphous carbon layers had developed along the oxide–matrix interface when chromia was formed. The presence of the carbon layer was explained in view of the high C activity corresponding to the low equilibrium oxygen potential of chromia.     

Interfacial segregation during oxidation in O2 at 1173 K of CeO2-coated Fe-20Cr alloys

The interfacial segregation of sulphur and carbon during the oxidation in 1 torr O₂ at 1173 K of Fe-20Cr alloy, which was either free of Ce, alloyed with 0.078 wt.% Ce, or sputter-coated with a 4 nm-thick CeO₂ layer, was studied using polyatomic SIMS. Oxidation periods were up to 19 hr. During oxidation, sulphur and carbon accumulated at the alloy-oxide interface region of both uncoated and coated alloys. The amount of segregated sulphur did not vary appreciably with time, whereas carbon increased with time. The total amount of segregants was similar for both uncoated and coated alloys, although the scales formed on the sputter-coated alloy maintained adhesion and were about 10 times thinner than those on the uncoated alloys.     

Oxidation of a Three-Phase Cu–45Ni–30Cr Alloy at 700–800°C Under 1 atm O2

The oxidation of a ternary Cu–Ni–Cr alloy containing approximately 45 wt.% Ni and 30 wt.% Cr has been studied in 1 atm O₂ at 700–800°C. The alloy contains a mixture of three phases: the one with the largest copper and lowest chromium content forms the matrix, the one with an intermediate chromium content has a rather large volume fraction and forms large islands, while the phase richest in chromium forms isolated particles dispersed in the other two phases. At variance with another Cu–Ni–Cr ternary three-phase alloy containing only 20 wt.% Cr and 20 wt.% Ni, which formed complex scales containing mixtures of the oxides of the various components and double oxides, plus an irregular region composed of a mixture of alloy and oxides, the present alloy is able to form protective, external chromia scales. A similar result could be obtained with alloys containing about 20 wt.% Cr, but composed of either a single phase (Cu–60Ni–20Cr) or of a mixture of two phases (Cu–40Ni–20Cr). The need for a larger chromium content for producing chromia scales for three-phase as compared to two-phase Cu–Ni–Cr alloys is attributed to the limitations of the diffusion of the alloy components in the metal substrate imposed by their multiphase nature.     

Oxidation of a quaternary three-phase Cu-20Ni-20Cr-5Fe alloy at 700-900 °C in 1 atm of pure O2

The oxidation of a quaternary Cu-Ni-Cr-Fe alloy containing approximately 20 at.% Ni, 20 at.% Cr and 5 at.% Fe, balance Cu (Cu-20Ni-20Cr-5Fe), was studied at 700-900 °C in 1 atm of pure oxygen. The alloy is composed of a mixture of three phases, where the lightest α phase with the largest Cu content forms the matrix, while the other two, much richer in Cr, form a dispersion of isolated particles. At variance with the ternary three-phase Cu-20Ni-20Cr alloy examined previously, which was unable to form protective chromia scales over the alloy surface even after an extended period of oxidation, the present alloy formed complex external scales containing mixtures of the oxides of the various components plus a deep internal region containing a mixture of alloy and oxide phases. With time, a very irregular and thin but essentially continuous chromia layer formed at the bottom of the mixed internal oxidation region, producing a gradual decrease of the oxidation rate. Thus, the addition of 5 at.% Fe to Cu-20Ni-20Cr alloy is able to decrease the critical Cr content required to form the most stable oxide and promotes the formation of a continuous chromia scale under a lower Cr content in spite of the simultaneous presence of three different phases.     

Oxide scale adhesion and impurity segregation at the scale/metal interface

The chemistry at scale/metal interfaces was studied using scanning Auger microscopy after removal of the scale in ultra-high vacuum using an in situ scratching technique. Al₂O₃ and Cr₂O₃ scales formed between 900°C and 1100°C on Fe-18 wt.% Cr-5 wt.% Al and on Ni-25 wt.% Cr alloys, respectively, were investigated. The adhesion of these scales was determined qualitatively by way of micro-indentation and scratching on the surface oxide. All of the alumina scales fractured to the same degree to expose the metal surface, regardless of the oxidation temperature. The chromia-forming alloy on the other hand, developed more adherent scales at lower oxidation temperatures. About 20 at.% sulfur was found at the metal surface in all cases, and its presence was not only detected on interfacial voids, but also on areas where the scale was in contact with the alloy at temperature. Results from this study clearly demonstrated that sulfur as an alloying impurity does segregate to the scale/alloy interface. However, for alumina scales and chromia scales, the effect of this segregation on oxide adhesion is noticeably different.     

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.     

Preparation and Oxidation of Novel Electrodeposited Cu–Ni–Cr Nanocomposites

The poor oxidation resistance of Cu-base alloys limits their applications at high temperatures, and it cannot be improved by conventional Cr alloying because that requires an extremely high Cr content. In this work a chromia scale has been formed on novel Cu-base nanocomposites which contain much less chromium. Cu–Ni–Cr nanocomposites, with the weight percentage ratio of Cu/Ni ≈1 and various amounts of Cr, were produced by co-electrodeposition of Cu–Ni alloy with Cr nanoparticles which subsequently acted as “seeds” for chromia formation. The results of oxidation tests in air at 800°C showed that only 15 wt.% Cr in the nanocomposite was required to form an external chromia scale. Furthermore, the scale consisted only of chromia rather than the duplex scales which form on the conventional alloy even when it contains significantly more chromium.     

The Effect of Si Additions on the High-Temperature Oxidation of a Ternary Ni–10Cr–4Al Alloy in 1 ATM O2 AT 900–1000 °C

The oxidation of four Ni–10Cr–ySi–4Al alloys has been studied in 1 atm O₂ at 900 and 1000 °C to examine the effects of various Si additions on the behavior of the ternary alloy Ni–10Cr–4Al, which during an initial stage formed external NiO scales associated with an internal oxidation of Cr + Al, later replaced by the growth of a chromia layer at the base of the scale plus an internal oxidation of Al. The addition of 2 at.% Si was able to prevent the oxidation of nickel already from the start of the test, but was insufficient to form external alumina scales at 1000 °C, while at 900 °C alumina formed only over a fraction of the alloy surface. At 1000 °C the addition of 4 at.% Si produced external chromia scales plus a region of internal oxidation of Al and Si, a scaling mode which formed over a fraction of the alloy surface in combination with alumina scales also by oxidation at 900 °C. Conversely, the presence of about 6 at.% Si produced external alumina scales over the whole sample surface at 900 °C, but only over about 60 % of the alloy surface at 1000 °C. The changes in the oxidation modes of the ternary Ni–10Cr–4Al alloy produced by Si additions have been interpreted by extending to these quaternary alloys the mechanism of the third-element effect based on the attainment of the critical volume fraction of internal oxides needed for the transition to the external oxidation of the most-reactive-alloy component, already proposed for ternary alloys.     

Water Vapour Effects on Fe–Cr Alloy Oxidation

Isothermal oxidation at 700 °C of binary Fe–Cr alloys containing 9, 17 and 25 wt% chromium was measured using continuous thermogravimetric analysis. All alloys developed thin, protective chromia scales in Ar–20O₂ (vol%). Chromia scale growth on the 17 and 25 Cr alloys was faster in Ar–20O₂–5H₂O and Ar–5O₂–20H₂O. In these gases, the Fe–9Cr failed to form a chromia scale and suffered rapid breakaway oxidation, growing iron-rich oxides instead. A low oxygen potential gas, Ar–10H₂–5H₂O caused chromia scaling on Fe–17Cr and Fe–25Cr, but internal oxidation of Fe–9Cr. Application of Wagner’s criterion for sustaining external scale growth is shown to account satisfactorily for these observations.     

Oxidation resistance of aluminum-coated Fe-20Cr alloys containing rare earths or yttrium

Aluminum-coated Fe-20Cr-(rare earth or yttrium) alloy foils were developed with oxidation resistance equivalent or superior to Fe-20Cr-5Al-(rare earth or yttrium) alloy foils. The coated foils were made by dipping Fe-20Cr sheet into a salt-covered aluminum bath and then rolling the sheet to foil. Oxidation resistance of the coated foil was enhanced by adding rare earths or yttrium to the Fe-20Cr substrate alloys to insure oxide adherence. Test results indicate that only sufficient addition to tie up sulfur as a stable sulfide is needed in the Fe-20Cr alloy. Aluminum-coated foils show lower oxide growth rates than similar Fe-Cr-Al alloys, most likely the result of fewer impurities (particularly Fe) is the coated foils' growing oxide scale.     

The influence of aluminum on the transition from oxide to sulfide of aluminum-rich Fe-25Cr alloys with low-oxygen and high sulphur pressures

The simultaneous oxidation and sulfidation of Fe-25Cr, Fe-25Cr-5Al and Fe-25Cr-10Al alloys were studied at 1023, 1123, and 1223 K in H₂-H₂O-H₂S gas mixtures. Fe-25Cr and aluminum-rich alloys with 0–10 wt.% Al show, in H₂H₂O-H₂S gas mixtures at high temperatures, a transition from protective oxide-scale formation to the formation of a sulfide-rich corrosion product. The kinetics boundary, which indicates the transition from oxide formation with slow weight gains to sulfide formation with rapid weight gains, has been found in these three alloys. The critical oxygen partial pressures to stabilize oxide formation at the constant-sulfur partial pressures of aluminum-rich Fe-25Cr alloys were systematically below those of Fe-25Cr alloy. When the oxygen partial pressure is much higher than the critical one, the oxide scale formed on the Fe-25Cr alloy was mainly Cr₂O₃ with a small amount of FeCr₂O₄; on the other hand, the oxide scale formed on the aluminum-rich Fe-25Cr alloys was mainly Fe(Cr,Al)₂O₄ with a small amount of Al₂O₃ and Cr₂O₃. The thermodynamic stability diagrams for (Fe, Cr, Al) -S-O systems were constructed, and the experimental results which show the existence of Fe(Cr, Al)₂O₄ in the simultaneous sulfidation and oxidation of aluminum-rich Fe-25Cr alloys are explained by these diagrams. The reaction kinetics were measured by a stainless-steel spring balance, and the reaction products were characterized by x-ray diffraction, Auger spectroscopy, and scanning electron microscopy. The reaction rate usually decreased with an increase of the oxygen partial pressure at a constant sulfur partial pressure. The existence of aluminum plays an important role to suppress the sulfidation of Fe-25Cr alloys.     

Effects of nitrogen on the passivity of Fe-20Cr alloy

Influences of nitrogen on the passivity of Fe-20Cr-(0, 1.1)N alloys were examined by in situ electrochemical techniques. Nitrogen was incorporated in the form of (Fe, Cr)-nitrides in the passive film, and Cr was enriched in the film of the alloy with nitrogen. Photocurrent analysis demonstrated that the structure of passive film formed on Fe-20Cr-1.1N alloy is Cr-substituted γ-Fe₂O₃ with (Fe, Cr)-nitrides. Mott-Schottky analysis revealed that the film formed on Fe-20Cr-1.1N contained higher Cr⁶⁺ and lower Cr³⁺ vacancy concentrations compared with that on Fe-20Cr alloy. All of these results were associated with the enhanced protectiveness of the film on Fe-20Cr-1.1N.     

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

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

Some interactions in the erosion-oxidation of alloys

The modes of interaction of erosion and high-temperature oxidation, occurring simultaneously on an alloy surface, have been studied using Ni-30Cr, MA754, Ni-20Al, and Co-22Cr-11Al-0.2Y alloys to examine the influence of chromia and alumina scale formation on the erosion of nickel and cobalt base alloys. The results have shown that, in the presence of a rapidly flowing oxidizing gas stream, the evaporation of volatile metal oxides becomes important at lower temperatures where normally it can be ignored. Otherwise, the erosion and oxidation of alloys parallels the behavior of pure metals but also introduces additional factors derived from lengthening of the period of transient oxidation and modification of concentration profiles in the alloy adjacent to the alloy/scale interface. Higher erosion intensities extend the transient oxidation behavior which adversely affects the formation of protective scales. As with pure metals, the presence of erosion and oxidation together always produced increased rates of degradation.