Experimental study and modeling of high temperature oxidation of Nb-base in situ composites

The oxidation behavior of Nb-base in situ composites in static air at 1100, 1200 and 1250 °C has been studied. The reaction followed the parabolic rate law. The oxide scales were mainly composed of TiNb₂O₇, TiNb₁₀O₂₉, TiO₂, Nb₂O₅ and SiO₂. The theoretical oxidation model proposed by Gesmundo et al. has been applied to analyze existing oxidation data of Nb-base in situ composites. The result shows that oxidation rate of the Nb-base in situ composites is basically accordance with the analytical results predicted by the theoretical oxidation model to a good approximation.     

Isothermal oxidation behaviour of Nb-W-Cr Alloys

A study of the effect of Cr content on the microstructure and isothermal oxidation behaviour of four alloys from the Nb-Cr-W system has been performed. Selection of specific alloy compositions has been based on the ternary isothermal sections. Oxidation experiments were conducted in air at 900 and 1300 °C for 24 h under isothermal conditions. Weight gain per unit area as function of the temperature has been used to evaluate the oxidation resistance. The phases present in the alloys and the oxide scales were characterized by XRD, SEM, and EDS. Microstructure consists of Nb solid solution and NbCr₂, Laves phase. The oxidation kinetics follows a parabolic behaviour at 1300 °C; the addition of 30% Cr resulted in the significant reduction of the parabolic oxidation rate. At 900 °C, alloys with higher Cr content exhibit higher oxidation rates in comparison to alloys with lower Cr content. The oxidation products are a mixture of CrNbO₄ and Nb₂O₅ and the amount of each oxide present in the mixture is related to the intermetallic phase content and the oxidation temperature. The characterization results delineate the effect of the Cr content on the oxidation mechanisms of these alloys that represent a promising base for high-temperature alloy development.     

High temperature oxidation characteristics of Nb–10W–XCr alloys

The effect of Cr content on the microstructure and cyclic oxidation behavior of Nb–10W–XCr alloys with four different compositions has been investigated. Experiments were conducted in air at 900 °C and 1300 °C; the oxidation kinetics have been evaluated in terms of weight change per unit area with respect to exposure time. Alloy's microstructure consists of Nb solid solution phase regions surrounded by a network of NbCr₂ Laves phase. A trend of improvement in oxidation resistance with increase of the intermetallic phase is observed at 1300 °C and oxidation kinetics follow a parabolic behavior. At 900 °C, alloys with higher Cr content exhibit higher oxidation rates than alloys with lower Cr content. The oxidation products are a mixture of CrNbO₄, and Nb₂O₅ and the amount of each oxide present in the mixture is related to the intermetallic phase content. Results delineate the influence of microstructure and composition on the oxidation mechanisms of these alloys that represent a promising base for high-temperature intermetallic alloy development.     

A diffusional analysis of the oxidation of binary multiphase alloys

A nonsteady-state diffusional analysis has been applied to the oxidation of binary multiphase alloys. In addition to the solubility of the solute element in the continuous solid-solution phase, the volume fraction and the size of the second-phase particles have been found to be crucial for the exclusive formation of the solute oxide. By solving the diffusion equations, the oxidation behavior of a multiphase alloy has been quantitatively related to a microstructure parameter, P _L ,which is a function of both the volume fraction and shape of the second phase. Moreover, the effectiveness of alloying for alloys with differently shaped second-phase particles on the oxidation of multiphase alloys has been discussed.     

Oxidation resistance coatings of Mo−Si−B alloys via a pack cementation process

Oxidation behavior of Si pack cementation coatings on a three-phase Mo−Si−B alloy was examined. During Si pack cementation of a three-phase Mo−Si−B alloy, a MoSi₂ outer layer was synthesized on the exterior layer. Following oxidation in air of the pack-coated alloys at 1200°C, the MoSi₂ phase layer was consumed and replaced by the Mo₅Si₃ (or T₁) phase. The synthesized T₁ phase provided excellent oxidation resistance when exposed to high temperatures. The silicide-coated alloys exhibit higher oxidation resistance compared with uncoated Mo−Si−B alloys. The enhanced oxidation behavior and its mechanism are discussed in terms of the thicknesses of the oxide layers under exposure to high temperatures.     

High-temperature oxidation behavior of minor Hf doped NiAl alloy in dry and humid atmospheres

Oxidation behavior of NiAl and 0.05 at.% Hf doped NiAl alloys were investigated at 1100 °C in dry and humid atmospheres. Hf doping significantly improved the cyclic oxidation resistance. Water vapour promoted the formation of voids at the scale/alloy interface and accelerated scale spallation. Also, water vapour had effect on the phase transformation from θ- to α-Al₂O₃ at the initial oxidation stage. In humid atmosphere, more Hf segregated at the scale/alloy interface to form oxide pegs. Pre-oxidation process in O₂ + Ar could compromise the effect of humid atmosphere on the oxidation kinetics of the NiAl alloys.     

Microstructural effects on the high temperature oxidation of two-phase Cu-Cr alloys in 1 atm O2

The oxidation of a Cu-Cr alloy containing about 60 wt% Cr and of two Cu-Cr alloys containing about 40 wt% Cr was studied at 700 and 800 °C in 1 atm O₂. The 60 wt% Cr alloy was prepared by powder metallurgy (PM) and had a phase particle size of 50-150 μm. One of the two alloys containing about 40 wt% Cr was prepared by mechanical alloying (MA) and had a phase grain size ranging from 10-50 nm to 200-300 nm, depending on the location, while the other was prepared by magnetron sputtering (MS) and had a phase grain size around 5-10 nm. The most important difference between the oxidation behavior of the three alloys is the formation of an exclusive chromia scale on the surface of the Cu-40 wt% Cr alloy prepared by magnetron sputtering and of a continuous chromia layer beneath an outermost layer of copper oxides on the corresponding alloy prepared by mechanical alloying, while the Cu-60 wt% Cr alloy prepared by powder metallurgy formed complex scales composed mostly of CuO, Cu₂O with some Cu₂Cr₂O₄ and Cr₂O₃. Thus, the microstructure of two-phase binary alloys has a strong effect of their oxidation behavior. In particular, a decrease of the alloy grain size favors the exclusive external oxidation of the most reactive component, reducing the corresponding critical content in the alloy. This effect is attributed to the presence of larger concentrations of rapid diffusion paths for the migration of the components in the alloy as well as to a faster dissolution of the particles of the Cr-rich phase in the copper matrix.     

High-temperature oxidation behavior of multi-phase Mo-containing γ-TiAl-based alloys

Intermetallic titanium aluminides are potential materials for a number of high-temperature components used in aero and automotive engines. In particular, alloys solidifying via the β-phase are of great interest because they possess a significant volume fraction of the disordered body-centered cubic β_o-phase at elevated temperatures ensuring good processing characteristics during hot-working. Nevertheless, the practical use of such alloys at a temperature as high as 800 °C requires improvement of their oxidation resistance. Various attempts have been made including alloying with additional elements such as Nb, Cr, Mo etc. or applying the so-called fluorine effect. However alloying could not provide a sufficient oxidation resistance above 850 °C whereas the fluorine effect protects the base material against environmental degradation up to over 1000 °C. This paper aims to investigate the influence of the phase composition on the oxide scale morphology without and with fluorine effect. The results refer to the oxidation behavior of three β-solidifying γ-TiAl-based alloys in the cast and hot-isostatically pressed condition at 800 °C in air. The behavior of the TNM alloy (Ti–43.5Al–4Nb–1Mo–0.1B, in at.%) was compared with that of two Nb-free TiAl alloys which contain different amounts of Mo (3 and 7 at.%, respectively) and hence a different microstructure (α₂/β_o/γ vs. β_o/γ). During testing in dry synthetic air at 800 °C a mixed oxide scale develops on all three alloys. This behavior was changed via the fluorine effect, as demonstrated for previously investigated TiAl alloys with an Al-content higher than 40 at.% based on α₂/γ and α₂/β_o/γ phases. The oxidation resistance of the fluorine treated samples was significantly improved compared to the untreated samples. The reason for this is the change in the oxidation mechanism triggered by the small additions of fluorine in the subsurface zone of the investigated alloys. The results of isothermal oxidation tests at 800 °C in air are presented and discussed in view of chemical composition and microstructure, along with the impact of the phase composition on the efficiency of the fluorine effect. From a microstructural perspective the fluorine effect leads to the formation of an even thinner oxide scale on the β-phase compared to the γ-phase.     

Corrosion behaviour of 16%Cr-4%Al and 16%Cr ODS ferritic steels under different metallurgical conditions in a supercritical water environment

The corrosion behaviour of 16%Cr and 16%Cr-4%Al ODS ferritic steels in different heat treatment conditions has been investigated in a supercritical water environment. The exposed coupons were analyzed using scanning electron microscopy (SEM), electron probe micro analysis (EPMA), Auger and X-ray diffraction analysis (XRD). It was found that the formation of oxides depends on the chemical composition and not on the metallurgical condition. The Al-free alloys formed a monolayer oxide film composed of (Cr, Fe)₂O₃. The Al-containing alloys formed an oxide film composed of an outer layer of hematite and magnetite and an inner layer of Al₂O₃. The oxidation mechanisms are discussed.     

Relation between corrosion behavior and microstructure of Mg-Zn-Y alloys prepared by rapid solidification at various cooling rates

The relation between corrosion resistance and microstructure of Mg-Zn-Y alloys with a long period stacking ordered (LPSO) phase has been investigated. In order to clarify the influence of microstructure evolution by rapid solidification on the occurrence of localized corrosion such as filiform corrosion, several Mg_97.25Zn_0.75Y₂ (at. %) alloys with different cooling rates were fabricated by the gravity casting, copper mould injection casting and melt-spinning techniques and their corrosion behavior and microstructures were examined by the salt immersion tests, electrochemical measurements, XRD and TEM. When the cooling rate was less than 3 × 10⁴ K s⁻¹, filiform corrosion propagated in the early stage of salt immersion test, due to formation of a massive block-shaped LPSO phase during casting. On the other hand, when the cooling rate was increased up to 3 × 10⁴ K s⁻¹, rapidly solidified (RS) alloys exhibited excellent corrosion resistance because of grain refinement and formation of a supersaturated single-phase solid solution. Large-sized Mg_97.25Zn_0.75Y₂ alloys fabricated by consolidation of the RS ribbons also exhibited excellent corrosion resistance with passivity. Enhancement of microstructural and electrochemical homogeneities in the Mg-Zn-Y alloys by rapid solidification techniques results in the passivity of substrate materials.     

Hot corrosion behaviour of Nbss/Nb5Si3 in situ composites in the mixture of Na2SO4 and NaCl melts

Hot corrosion behaviour of Nb–16Si–24Ti–6Cr–6Al–2Hf (at.%) in the mixture of Na₂SO₄ and NaCl melts at 900 °C was studied. The results show that the corrosion kinetics of the alloy fit parabolic law. The oxides consist of a loose and porous outer layer and an internal oxidation zone. Outer oxides are mainly composed of TiO₂, TiNb₂O₇, Nb₂O₅, CrNbO₄ and SiO₂ while the internal oxidation zone is composed of TiO₂. Hot corrosion mechanism of the alloy in the presence of Na₂SO₄ and NaCl deposits is discussed.     

The oxidation of two ternary Ni-Cu-10 at.% Al alloys in 1 atm of pure O2 at 800-900 °C

The oxidation of the ternary alloys Ni-45Cu-10Al and Ni-30Cu-10Al has been studied at 800-900 °C under 1 atm O₂. The presence of 10 at.% Al reduces significantly the oxidation rate of the corresponding Cu-Ni alloys during the initial oxidation stages, even before the establishment of a complete Al₂O₃ layer. The weight of individual sample of the two ternary Ni-Cu-10Al alloys at 800 °C increases more rapidly than at 900 °C during the initial oxidation stage. As oxidation proceeds, the weight gain at 800 °C slows down to a degree that the total weight gain after 24 h oxidation at 800 °C is less than that at 900 °C. Due to a faster formation of the Al₂O₃ layer, which suppresses earlier the further oxidation of Cu and Ni, the external region of the scales grown on Ni-45Cu-10Al contain much less Cu and Ni oxides than those grown on Ni-30Cu-10Al. The transition from the internal oxidation to the selective external oxidation of the most reactive component Al in Ni-Cu-Al alloys is favored by higher values of the Al content, of temperature and of the Cu/Ni ratio.     

Cyclic-Oxidation Resistance of Niobium-Base in situ Composites: Modeling and Experimentation

Despite significant improvements in recent years, the oxidation resistance of niobium-base in situ composites is still inadequate for high-temperature applications because of their fast oxidation and the difficulty to form a coherent, protective-oxide layer on the Nb solid solution. Recently, several oxidation models have been proposed in the literature for treating the oxidation behavior of two-phase materials, which show features that are applicable to niobium-base in situ composites. In this article, the theoretical oxidation model proposed by Gesmundo et al. [Oxidation of Metals 39, 1977–209 (1993)] for treating independent isothermal oxidation of two-phase binary alloys has been extended to cyclic oxidation and applied to analyze existing oxidation data of niobium-base in situ composites. The critical conditions required to form a protective-oxide layer on Nb-base in situ composites is predicted via existing models proposed by Wang et al. [Oxidation of Metals 35, 317–322, 333–348 (1991)]. The analytical results are then used to identify possible means for improving the oxidation properties of the Nb-base in situ composites. Key conditions required for achieving a continuous protective oxide are predicted and compared against critical experiments performed on Nb-base in situ composites.     

The microstructural engineering of Mo-Si-B alloys produced by reaction synthesis

Mo-Si-B alloys are candidate materials for next-generation jet engine turbine blades and have the potential to increase the service temperature of the base metals 200°C higher than nickel superalloys. These refractory alloys form a composite microstructure of molybdenum solid Solution (Mo_ss and two intermetallic phases, Mo₃Bi and Mo₅SiB₂, where the Mo_ss phase enhances toughness and the intermetallic phases provide oxidation resistance. The properties of the alloys are highly dependent on the morphology of the microstructure. A powder processing approach has been developed to synthesize the three-phase alloys through the reaction of molybdenum, Si₃N₄ and BN powders. Electron backscatter diffraction imaging has been used to map the location of individual phases and provide a method for quantifying the Cluster size distribution of a secondary phase to examine the effect of BN reactant powders on the dispersion of the intermetallic phases.     

The steady-State corrosion kinetics of two-phase binary alloys forming the most-stable oxide

The steady-state kinetics in the high-temperature oxidation of binary A-B alloys containing a mixture of the conjugated solid solutions of B in A (alpha phase) and A in B (beta phase) with exclusive formation of the most-stable oxide BO_v have been examined, assuming that the external scale grows on top of a subsurface layer of alpha phase. The results obtained are compared with the corresponding behavior of alloys which are single phase in the whole range of composition. Under identical values of all the parameters involved the concentration of B at the alloy-scale interface is smaller for two-phase than for single-phase alloys under the same concentration of B in the alloy as a result of the restricted flux of B through the alpha-phase layer. As a consequence of this, the two-phase alloys corrode more slowly than single-phase alloys and this difference increases as the solubility of B in the alpha phase decreases. Finally, the simultaneous formation of BO_v both externally and as internal oxide is more likely for two-phase than for single-phase materials.     

Transition Between Different Oxidation Modes of Binary Fe–Si Alloys at 600–800 °C in Pure O2

The oxidation behavior of three Fe–Si alloys containing approximately 5, 9 and 13 at.% Si has been studied at 600–800 °C under 1 atm O₂. Fe–5Si and Fe–9Si followed multi-stage parabolic kinetics, while Fe–13Si showed more complex kinetics at all temperatures. The increase in Si content resulted in a transition from the internal oxidation of Si beneath an external scale of iron oxides to the exclusive external formation of silica. The critical contents required for the transitions between the various possible oxidation modes of the binary Fe–Si alloys were calculated and compared with the experimental results. A thermodynamic mechanism for the formation of Fe-rich oxide nodules observed in the oxidation of Fe–5Si and Fe–9Si has been proposed.     

The oxidation of cobalt—tungsten alloys

The oxidation behaviour of CoCrW alloys containing from 0–25%Cr and up to 30%W in oxygen at 900–1100°C has been studied. In CoW alloys there is a slight reduction in the oxidation rate as the tungsten content is increased, hwoever this is much mor emarked in Co15CrW alloys. Tungsten has little effect in Co25CrW alloys. On the binary alloys and CoCrW alloys which do not form Cr₂O₃, the scale has two layers: an outer, tungsten-free layer of columnar-grained CoO, and an inner layer of CoO containing CoWO₄ precipitates together with CoCr₂O₄ particles in the ternary alloys. The relative thicknesses of the two layers and the distribution of the constituents in the inner layer depends in temperature and alloy composition. The CoWO₄ and CoCr₂O₄ particles appear to be responsible for the reduction in oxidation rate by a blocking mechanism in the inner layer. There is some evidence to suggest that tungsten additions to Co?25%Cr alloys assist the exclusive formation of Cr₂O₃.     

The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.     

High temperature oxidation behaviour of Ni–Fe–Co anodes for aluminium electrolysis

The oxidation behaviour of ternary Ni_xFe_yCo_z alloys (where x/y (wt) = 1 and 1.85; z = 0, 10, 30 and 50 wt.%) was studied in air at 800 °C. Alloys were found to follow complex oxidation kinetics, with the highest oxidation rates observed for alloys having 50 wt.% Co. Significant improvements in oxidation resistance were achieved by addition of 10 and 30 wt.% Co to the Ni–Fe system. The decrease in oxidation rate was associated with suppression of Fe₂O₃ formation in preference for (Co,Ni)_xFe_3−xO₄ growth. The results were discussed in light of the materials requirements for inert anodes for aluminium electrolysis.     

Modelling the anodizing behaviour of aluminium alloys in sulphuric acid through alloy analogues

Anodic film morphologies on aluminium aerospace alloys are strongly influenced by alloying elements. The present study uses model alloys to interpret the early stages of anodizing of AA2024-T3 and AA7075-T6 aluminium alloys in 0.4 M sulphuric acid electrolyte. Further, coupled model alloys, representative of matrix and second phase regions, are employed as alloy analogues. The findings enable assignment of transient anodic currents during potentiodynamic polarization of the commercial alloys to oxidation of Al₂CuMg phase at 0 V SCE and of Al₂Cu, Al₇Cu₂Fe and Al–Cu–Fe phases at 5–6 V SCE. The phases that oxidize at the latter potential also cause voltage arrests during galvanostatic anodizing.