High-Temperature Oxidation of Al–Mg Alloys

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

Oxidation of La–Sr–Mn-Coated Interconnector Alloys for Steam Electrolysis Under Pressure in Pure Oxygen and in Pure Steam

Pressurized steam electrolysis enables an efficient conversion of electric power from renewable energy sources into hydrogen for power-to-liquids processes. The interconnector material Crofer 22 APU, uncoated and coated by La_1?x Sr _x MnO₃ (LSM), deposited by thermal spray and by roll coating was studied in pure water vapor and pure oxygen at 850 °C and 30 bar. The uncoated Crofer 22 APU forms in both atmospheres a homogeneous oxide scale from an inner Cr₂O₃ and an outer MnCr₂O₄ layer. The chromia is locally undergrown by pits of MnCr₂O₄. With the LSM coating, the oxide scale is notably thinner in water vapor and the formation of pits is significantly reduced. In oxygen, this effect of the LSM coating is less pronounced. Chromium from volatile species was detected in the LSM coating, more in oxygen than in water vapor. After 3000 h in pure oxygen, Crofer 22 APU with thermally sprayed LSM shows breakaway oxidation.     

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

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

High-Temperature Oxidation of Zircaloy-4 in Oxygen–Nitrogen Mixtures

Isothermal oxidation experiments with cladding tube segments of Zircaloy-4 (Zr-1.3%Sn) in oxygen–nitrogen model mixtures were performed at 800, 1000, and 1200 °C for 6, 1 h, and 15 min, respectively. The gas compositions varied between 0 and 100 vol% nitrogen including 1 and 99 vol%. A strong accelerating effect of nitrogen on the oxidation kinetics was seen for a wide range of boundary conditions. At 800 °C, oxidation in all mixtures with 1–99 % nitrogen resulted in higher reaction rates compared to the pure gases, especially after transition from protective to non-protective oxide scales. At 1000 and 1200 °C, only starvation of oxygen in mixtures with low oxygen contents resulted in lower rates compared to pure oxygen. The oxide scales formed in the mixtures were very porous due to the formation of zirconium nitride at the metal-oxide interface and its oxidation during continuing reaction. The extension of the oxide-nitride zone increased with temperature and with nitrogen content in the gas mixture. Nitrogen seems also to affect the pre-transition reaction kinetics. The mechanism of the faster oxidation kinetics of zirconium alloys in atmospheres containing nitrogen will be discussed in this paper.     

Theoretical Analysis of Anomalies in High-Temperature Oxidation of Fe–Cr, Fe–Ni, and Fe–Ni–Cr Alloys

The following anomalies are theoretically analyzed: weakening of the protective ability of dense Cr₂O₃ film during its long-term thermal exposure (because of iron oxidation under the film); lowering of the heat resistance of Fe–Cr and Fe–Ni–Cr alloys during the oxidation (800°C) with an increase in the chromium content over 40 at. %; improving of the protective ability of the films formed at Fe–Ni alloys because of nickel oxidation under the dense FeO film; and the internal oxidation of the Fe 30Ni alloys under the FeO films with the internal formation of FeO oxides and spinel of NiFe₂O₄ type. It is shown that these anomalies can be explained, and the composition of the most heat-resistant alloys calculated, if one takes into account that associates with significantly stronger interatomic bonds than those in ideal solutions can form in solid solutions and cause unlimited solubility of the metallic components in each other.     

Investigation of Fe content in Cu–Al–Ni Shape Memory Alloys

Polycrystalline Cu–Al–Ni–Fe-based shape memory alloys with different chemical composition were produced in an arc-melting furnace under an argon atmosphere. Homogenized and aged specimens were prepared for multiple analyses. The temperatures of reversible martensitic transformations, namely A_s, A_f, M_s, M_f, A_max and ΔH enthalpy values were determined by a DSC device. The phase transition analysis from the room temperature to 850°C was undertaken by DTA. To characterize the lattice structure, an XRD analysis was conducted, the results of which were confirmed by microstructure images obtained from optical microscope observations.     

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

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

Optimization of Cr-Content for High-Temperature Oxidation Behavior of Co–Re–Si-Base Alloys

The oxidation behavior of Co-17Re-xCr-2Si alloys containing 23, 25, 27 and 30 at.% chromium at 1,000 and 1,100 °C were investigated. Alloy Co–17Re–23Cr–2Si showed a poor oxidation resistance during exposure to laboratory air forming a two-layer external scale and a very thin discontinuous Cr₂O₃ layer at the oxide/substrate interface. The outer layer of the oxide scale consisted of CoO, whereas the inner layer was a porous mixture of CoCr₂O₄ spinel particles in a CoO matrix. The oxide scale was found to be non-protective in nature as the vaporization of Re-oxide took place during oxidation. An increase of chromium content from 23 at.% to 25 at.% improved significantly the alloy oxidation resistance; a compact protective Cr₂O₃-scale formed and prevented the rhenium oxide evaporation. The oxidation behavior of alloys containing 27 at.% and 30 at.% chromium were quite similar to that of Co–17Re–25Cr–2Si. The oxidation mechanism for Co–17Re–25Cr–2Si alloy was established and the subsurface microstructural changes were investigated by means of EBSD characterization.     

Influence of Alloy Composition and Exposure Conditions on the Selective Oxidation Behavior of Ni–Al Alloys

Ni–Al coating alloys, which are commonly used in gas turbine engines operating in marine environments, are highly susceptible to hot corrosion attack. The effect of alloy composition and exposure conditions on the development of a protective alumina scale, which is important for the hot corrosion resistance of the alloy, and how they affect the transition of alumina from the θ to the α polymorph have been evaluated. A series of Ni–Al model alloys with a base composition of Ni–36 at.% Al, and 5 at.% additions of Cr, Pt and Si were exposed in dry air and in air–10%H₂O at 900 °C. The presence of water vapor in the gas led to higher oxidation rates and retarded the θ- to the α-Al₂O₃ transformation. The oxidation behavior of the alloys and the alumina polymorph which formed differed depending on the alloying element considered. Additions of Cr accelerated the θ to α transformation, while Pt and Si retarded it.     

High-Temperature Oxidation of Fe3Al and Fe3Al–Zr Intermetallics

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

The Oxidation Behaviour of Alloys Based on the Ni–Co–Al–Ti–Cr System

The isothermal oxidation behaviour of a series of quinary Ni–Co–Al–Ti–Cr alloys were studied at 800 °C. Alloys with higher Cr concentrations exhibited lower mass gain after 100-h exposure, as did the alloys richest in Ni and Al for a given Cr concentration. Extensive internal oxidation and nitridation was also observed in all alloys, except those containing the highest concentrations of Ni and Al. All alloys studied generated continuous chromium oxide layers, beneath which alumina particles were observed. Compositional analysis of the subscales identified shallower Cr concentration gradients in alloys containing equiatomic levels of Ni and Co, suggesting increased availability of Cr in the alloy. Thermodynamic calculations confirmed that these alloys contained higher concentrations of Cr in their γ matrices as a result of a combination of both the elemental partitioning behaviour and the increased mole fraction of γ′ precipitates forming in the alloy.     

Effect of Zr Addition on the High-Temperature Oxidation Behaviour of Mo–Si–B Alloys

Mo–Si–B alloys are promising candidates for structural high-temperature applications due to their excellent high-temperature mechanical properties along with high melting temperatures and oxidation resistance. After an initial period with high weight loss rates as a consequence of the volatilization of Mo-oxide, a protective borosilica (glass) layer develops on the alloy surface and steady-state oxidation is achieved. Aiming at improved mechanical properties of Mo–Si–B alloys which exhibit a continuous Mo solid solution matrix as a consequence of a powder metallurgical production route, small amounts of Zr were added. The presence of oxygen in the alloy leads to the formation of thermodynamically very stable Zr-oxide precipitates in the bulk alloy causing an enhancement of its mechanical properties. It was observed that the addition of Zr (distributed in the alloy matrix) also has significant influence on the oxidation behaviour of Mo–Si–B alloys by reducing the period for the formation of the protective and stable silica scale. Furthermore, the weight loss due to vaporization of Mo-oxides is consequently reduced. Besides this beneficial effect, Zr is harmful for the oxidation resistance at temperatures beyond 1,200 °C. This is mainly due to the increased oxygen transport through defects in the silica scale.     

Depletion and Voids Formation in the Substrate During High Temperature Oxidation of Ni–Cr Alloys

A numerical model to treat the kinetics of vacancy annihilation at the metal/oxide interface but also in the bulk metal has been implemented. This was done using EKINOX, which is a mesoscopic scale 1D-code that simulates oxide growth kinetics with explicit calculation of vacancy fluxes. Calculations were performed for high temperature Ni–Cr alloys oxidation forming a single chromia scale. The kinetic parameters used to describe the diffusion in the alloy were directly derived from an atomistic model. Our results showed that the Cr depletion profile can be strongly affected by the cold work state of the alloy. In fact, the oversaturation of vacancies is directly linked to the efficiency of the sinks which is proportional to the density of dislocations. The resulting vacancy profile highlights a supersaturation of vacancy within the metal. Based on the classical nucleation theory, the possibility and the rate of void formation are discussed.     

On the Role of Yttrium in Alumina Formers: Comparative Oxidation Behavior of (Ni–Cr–Al)- and (Ni–Cr–Al–Y)-Based Alloys

It is shown that the addition of Y to an alloy based upon the Ni–Cr–Al system slightly reduces the growth rate of Al₂O₃ scale during isothermal oxidation in air at temperatures in the range of 950–1150 °C. However, Y segregation at grain boundaries of the oxide is found to refine its grain structure down to the nanoscale with improved mechanical strength as compared to the Y-free alloy. It is concluded that Y can have the effect of decelerating the kinetics of diffusion processes leading to grain growth of the oxide.     

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.     

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

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

High-Temperature Oxidation Kinetics and Behavior of Ti–6Al–4V Alloy

Owing to the high-temperature reactivity of titanium, the oxidation and alloying of titanium during hot working processes is an important variable. The oxidation behavior of Ti–6Al–4V alloy in air was investigated at various temperatures between 850 and 1100 °C for different times. The oxidation kinetics were determined by isothermal oxidation weight gain experiments. The results showed that the oxidation kinetics approximately obeyed a parabolic law. The activation energy of oxidation was estimated to be 199 and 281 kJ mol^?1 when temperature was above and below the beta transformation temperature (T _β), respectively. A model to predict oxidation extent was established based on experimental observations. The oxide scales mainly consisted of TiO₂ with a small amount of Al₂O₃ and TiVO₄. The alpha case was defined as solid solution formed because of oxygen diffusion into the substrate. The difference in the morphology and the formation mechanism of the alpha case at different temperature ranges was mainly owing to the participation of the grain boundary and grain orientation of the nucleation site.     

Microstructural Evolution of Alumina Layers on an Al–Cu–Fe Quasicrystal during High-Temperature Oxidation

The oxidation of a quasicrystal with the nominal compositionAl₆₃Cu₂₅Fe₁₂ was studied around 800°Cin environmental and synthetic air by means of thermogravimetric analysis,electron microscopy, and analytical electron spectroscopy. In an earlyoxidation stage, -Al₂O₃ formed with an orientational relationship tothe quasicrystal. At the oxide–metal interface, -Al₂O₃transformed into large hexagonal shaped -Al₂O₃grains. The change in surface morphology indicated that at theoxide–gas interface -Al₂O₃ continued togrow as -Al₂O₃. Locally the metastable aluminalayer was transformed thoroughly into -Al₂O₃,which then continued to grow with a nodular morphology. On top of the oxidenodules, several at.% of Cu²⁺ were detected.     

Effect of Nanocrystallization on the Oxidation Behavior of a Ni–8Cr–3.5Al Alloy

Magnetron-sputter deposition was used to produce a Ni–8Cr–3.5Al(wt.%) nanocrystalline coating on substrates of the same alloy. Theoxidation behavior of the cast Ni–8Cr–3.5Al alloy and itssputtered coating were investigated at 1000°C in air. Complex,layered-oxide scales composed of Cr₂O₃ outer layer,mixed spinel NiAl₂O₄ and NiCr₂O₄middle layer, and -Al₂O₃ inner layer were formedon the Ni–8Cr–3.5Al nanocrystalline coating during 200-hroxidation, whereas Cr₂O₃, with some NiCr₂O₄external layer with internal Al₂O₃, formed on the castalloy. Because of the formation of this -Al₂O₃inner layer on the coating, the sputtered Ni–8Cr–3.5Al coatingshowed better oxidation resistance than the cast alloy. The effect ofnanocrystallization on oxide formation is discussed. It was indicated thatthe formation of this -Al2O3 inner layer was closely related to therapid diffusion of Al through grain boundaries in the nanocrystallinecoating and the relatively high Cr content in Ni–8Cr–3.5Al.     

Thermal conductivity mapping of the Ni–Al system and the beta-NiAl phase in the Ni–Al–Cr system

Micron-scale-resolution thermal conductivity mapping on graded compositions created in diffusion-multiple samples can be used to rapidly establish composition-phase-property relationships and to reveal the effects of solid-solutioning, order-disorder transition, compositional point defect, and site preference on thermal conductivity.

1. Download : Download high-res image (231KB)
2. Download : Download full-size image