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.     

Preparation and characterisation of melt-spun Al–Cu–Fe quasicrystals

Three Al–Cu–Fe alloys with compositions of Al_60–65Cu_20–27.5Fe_12.5–15 were prepared by conventional casting and further processed by melt-spinning. The structures formed were examined to get an insight into the interrelated effects of synthesis, processing and microstructure of Al–Cu–Fe alloys. The study aimed at answering the questions such as whether the production of single-phase quasicrystalline ribbons is possible by the melt-spinning process and what is the role of the degree of undercooling in the development of microstructure in melt-spun ribbons.The icosahedral ψ-Al₆₅Cu₂₀Fe₁₅ phase forms by a peritectic reaction between the primary β-AlFe phase and the liquid, as the temperature decreases. At the later stages of cooling, the monoclinic λ-Al₁₃Fe₄ phase and the tetragonal θ-Al₂Cu phase are formed in the cast alloys, as a result of peritectic reactions. In the rapidly solidified alloys, the formation of the tetragonal θ-Al₂Cu phase and, in the case of alloy Al₆₀Cu₂₅Fe₁₅, the monoclinic λ-Al₁₃Fe₄ phase is avoided, apparently due to high degree of undercooling. Thus, the production of single-phase quasicrystalline ribbons is not possible by the melt-spinning process, at least by using the cooling rate of 5–7×10⁴ °C/s. In addition to phase selection, the degree on undercooling influences, for example, the composition of the ψ-Al₆₅Cu₂₀Fe₁₅ phase and the grain morphology in melt-spun ribbons.     

Electronic structure and transport properties of Fe–Al alloys

Electronic structure of iron-aluminides (Fe_1−xAl_x) has been calculated for a range of aluminum concentration (0⩽x⩽0.5) by using first principles density functional theory to explain the variation of electrical resistivity with increasing Al content. The Fe–Al intermetallics are modeled by a cluster of 15 atoms confined to their bulk geometry. The location of Al atoms as a function of concentration, x was determined by minimizing the total energy of the clusters. The electronic structure was determined by calculating the total as well as partial density of states around each of the Fe and Al atoms. With increasing Al concentration, the transfer of Al 3p electrons into the minority 3d orbital of Fe not only has a profound effect on the magnetic properties of these intermetallics, but affects their transport properties as well. For example, the observed anomaly in the electrical resistivity of Fe_1−xAl_x that peaks at x=0.33 is found to be a direct consequence of the filling of the Fe 3d orbital with Al valence electrons. The density of states is characterized by three distinct features: a narrow 3d band just below the Fermi energy originating from the Fe atoms, an Al s-band lying deeper in energy, and an Al p-band above the Fermi energy. The energy gap between Al 3p and Fe 3d density of states decreases with increasing Al concentration and for x=0.40, the density of states at the Fermi energy is a strongly hybridized p–d state giving Fe_1−xAl_x metallic-like properties. These features are consistent with the recent photoemission studies carried out at the synchrotron facility at Lawrence Livermore National Laboratory. An anomaly in the temperature dependence of electrical resistivity is also explained in terms of the unique electronic and magnetic structure of these intermetallics.     

Oxidation of Fe–Si,Fe–Al and Fe–Si–Al alloys in CO2–H2O gas at 800 °C

Binary Fe–(1, 2, 3)Si and Fe–(2, 4, 6)Al, and ternary Fe–(2, 3)Si–(4, 6)Al alloys (all in wt%) were oxidised in Ar–20% CO₂, with and without H₂O, at 800 °C. All binary alloys except Fe–6Al, in all gases, formed a thin outer layer of Fe₃O₄, an intermediate Fe₃O₄ + FeO layer, an inner FeO + Fe₂SiO₄ (or FeAl₂O₄) layer and internally precipitated SiO₂ (or FeAl₂O₄). Ternary alloys and Fe–6Al developed a protective Al₂O₃ layer beneath Fe₂O₃ in Ar–20% CO₂. Water vapour affected ternary alloy oxidation only slightly, but Fe–6Al oxidized internally in high H₂O-content gas, and its scale was non-protective.     

Structure and properties of cast and splat-quenched high-entropy Al–Cu–Fe–Ni–Si alloys

The effect of the composition and cooling rate of the melt on the microhardness, phase composition, and fine-structure parameters of as-cast and splat-quenched (SQ) high-entropy (HE) Al–Cu–Fe–Ni–Si alloys was studied. The quenching was performed by conventional splat-cooling technique. The cooling rate was estimated to be ~10⁶ K/s. Components of the studied HE alloys were selected taking into account both criteria for designing and estimating their phase composition, which are available in the literature and based on the calculations of the entropy and enthalpy of mixing, and the difference between atomic radii of components as well. According to X-ray diffraction data, the majority of studied Al–Cu–Fe–Ni–Si compositions are two-phase HE alloys, the structure of which consists of disordered solid solutions with bcc and fcc structures. At the same time, the Al_0.5CuFeNi alloy is single-phase in terms of X-ray diffraction and has an fcc structure. The studied alloys in the as-cast state have a dendritic structure, whereas, after splat quenching, the uniform small-grained structure is formed. It was found that, as the volume fraction of bcc solid solution in the studied HE alloys increases, the microhardness increases; the as-cast HE Al–Cu–Fe–Ni–Si alloys are characterized by higher microhardness compared to that of splat-quenched alloys. This is likely due to the more equilibrium multiphase state of as-cast alloys.     

Corrosion Behavior of Ψ and β Quasicrystalline Al–Cu–Fe Alloy

Two nanostructured Al–Cu–Fe alloys, Al64Cu24Fe12 and Al62.5Cu25.2Fe12.3, have been studied. Icosahedral quasicrystalline(w) Al64Cu24Fe12 and crystalline cubic(b) Al62.5Cu25.2Fe12.3cylindrical ingots were first produced using normal casting techniques. High-energy mechanical milling was then conducted to obtain w icosahedral and b intermetallic nanostructured powders. Electrochemical impedance spectroscopy, linear polarization resistance, and potentiodynamic polarization were used to investigate the electrochemical corrosion characteristics of the powders in solutions with different p H values. Current density(icorr), polarization resistance(Rp), and impedance modulus(|Z|) were determined. The results showed that regardless of p H value, increasing the solution temperature enhanced the corrosion resistance of the both phases. However, the electrochemical behavior of the w phase indicated that its stability depends on the submerged exposure time in neutral and alkaline environments. This behavior was related to the type of corrosion products present on the surfaces of the particles along with the diffusion and charge-transfer mechanisms of the corrosion process.     

Phase equilibria and structural investigations in the system Al–Fe–Si

The Al–Fe–Si system was studied for an isothermal section at 800 °C in the Al-rich part and at 900 °C in the Fe-rich part, and for half a dozen vertical sections at 27, 35, 40, 50 and 60 at.% Fe and 5 at.% Al. Optical microscopy and powder X-ray diffraction (XRD) was used for initial sample characterization, and Electron Probe Microanalysis (EPMA) and Scanning Electron Microscopy (SEM) of the annealed samples was used to determine the exact phase compositions. Thermal reactions were studied by Differential Thermal Analysis (DTA). Our experimental results are generally in good agreement with the most recent phase diagram versions of the system Al–Fe–Si. A new ternary high-temperature phase τ₁₂ (cF96, NiTi₂-type) with the composition Al₄₈Fe₃₆Si₁₆ was discovered and was structurally characterized by means of single-crystal and powder XRD. The variation of the lattice parameters of the triclinic phase τ₁ with the composition Al_2+xFe₃Si_3?x (?0.3 < x < 1.3) was studied in detail. For the binary phase FeSi₂ only small solubility of Al was found in the low-temperature modification LT-FeSi₂ (ζ_β) but significant solubility in the high-temperature modification HT-FeSi₂ (ζ_α) (8.5 at.% Al). It was found that the high-temperature modification of FeSi₂ is stabilized down to much lower temperature in the ternary, confirming earlier literature suggestions on this issue. DTA results in four selected vertical sections were compared with calculated sections based on a recent CALPHAD assessment. The deviations of liquidus values are significant suggesting the need for improvement of the thermodynamic models.     

Workability Studies on High Al Ferritic Fe–Al–C Alloys

Iron-based alloys with high-carbide (Fe₃AlC_0.5) volume fractions (up to 40%) may be obtained by careful aluminum and carbon additions. These need to be hot worked to obtain a uniform distribution of the carbide. The workability of two alloy compositions (Fe–11 wt.% Al with 0.5 wt.% C and 1.1 wt.% C) was investigated using a strain-induced crack opening (SICO) test in a Gleeble 3800 thermomechanical simulator. SICO tests were conducted in the temperature range of 1,073–1,373 K at strain rates of 0.05–0.1 s^?1. Both alloys exhibited good workability with no tendency for cracking despite their high aluminum and carbon contents. However, refinement of microstructure due to thermomechanical processing could only be observed at 1,373 K for both alloys. At lower temperatures, a slightly aligned and elongated structure was observed. It is proposed that the higher solubility of carbon with an increase in temperature as well as the transformation of matrix from ferrite to austenite may play an important role in determining the optimum working temperature for these alloys.     

Microstructure and hot cracking susceptibility of high conductivity Al–Fe–Si alloys

Aluminium–silicon based casting alloys have been extensively utilised in various industrial applications, but their relatively low electrical and thermal conductivities make them unsuitable for high conductivity parts. In this research, Al–Fe–Si based high conductivity alloys containing limited silicon content were investigated. Al–0·5Fe–xSi alloys with silicon ranging from 0·5 to 2% showed significantly higher electrical conductivity than conventional Al–Si based alloys. The hot cracking susceptibility of Al–Fe–Si alloys became seriously high as the Si content increased up to 1·5%, then susceptibility rapidly reduced with the further increase in Si. The relationship between solidification characteristics and hot cracking susceptibility of Al–0·5Fe–xSi alloys was discussed based on the thermal and cooling curve analyses and microstructural observations.     

Kinetics of ordering and disordering in the Fe–Al–Ti ternary alloy

The kinetics of ordering and disordering in the ternary b.c.c. Fe–Al–Ti alloy is investigated by means of the micro-master equation method. It was found that there are transient ordered states in the ternary b.c.c. Fe–Al–Ti alloy during the ordering from a quenched disordered state to the equilibrium ordered state. Two different mechanisms account for the occurrence of the transient states. In the kinetics of disordering, the evolution of the order parameters shows fluctuations.     

Oxidation Behavior of ODS Fe–Cr–Al Alloys: Aluminum Depletion and Lifetime

The oxidation kinetics of two ODS Fe–Cr–Al alloys, PM 2000 and MA 956, were studied in oxygen and in air under isothermal conditions from 1000 to 1300°C. They both form an -alumina scale and have good oxidation resistance, without any mass loss. Although the aluminum content in these alloys is higher than the minimum Al content necessary to ensure the growth of a continuous alumina scale, an aluminum depletion occurred in the substrate. This depletion allows the determination of aluminum diffusion coefficients in the ODS alloy. This method is very original and interesting as no Al-stable isotope is available. Moreover, the evolution of the aluminum concentration in the substrate allows one to determine the lifetime of these alloys: indeed, when the aluminum content decreases and becomes lower than a critical value, alumina can no longer form, and less-stable oxides grow very rapidly compared to alumina.     

Hot Deformation and Dynamic Recrystallization Behavior of Austenite-Based Low-Density Fe–Mn–Al–C Steel

The hot deformation and dynamic recrystallization(DRX) behavior of austenite-based Fe–27Mn–11.5Al–0.95 C steel with a density of 6.55 g cm-3were investigated by compressive deformation at the temperature range of900–1150 °C and strain rate of 0.01–10 s-1. Typical DRX behavior was observed under chosen deformation conditions and yield-point-elongation-like effect caused by DRX of d-ferrite. The flow stress characteristics were determined by DRX of the d-ferrite at early stage and the austenite at later stage, respectively. On the basis of hyperbolic sine function and linear fitting, the calculated thermal activation energy for the experimental steel was 294.204 k J mol-1. The occurrence of DRX for both the austenite and the d-ferrite was estimated and plotted by related Zener–Hollomon equations. A DRX kinetic model of the steel was established by flow stress and peak strain without considering dynamic recovery and d-ferrite DRX. The effects of deformation temperature and strain rate on DRX volume fraction were discussed in detail. Increasing deformation temperature or strain rate contributes to DRX of both the austenite and the d-ferrite, whereas a lower strain rate leads to the austenite grains growth and the d-ferrite evolution, from banded to island-like structure.     

Effects of Cr and Fe Addition on Microstructure and Tensile Properties of Ti–6Al–4V Prepared by Direct Energy Deposition

The effects of Cr and Fe addition on the mechanical properties of Ti–6Al–4V alloys prepared by direct energy deposition were investigated. As the Cr and Fe concentrations were increased from 0 to 2 mass%, the tensile strength increased because of the fine-grained equiaxed prior β phase and martensite. An excellent combination of strength and ductility was obtained in these alloys. When the Cr and Fe concentrations were increased to 4 mass%, extremely fine-grained martensitic structures with poor ductility were obtained. In addition, Fe-added Ti–6Al–4V resulted in a partially melted Ti–6Al–4V powder because of the large difference between the melting temperatures of the Fe eutectic phase (Ti–33Fe) and the Ti–6Al–4V powder, which induced the formation of a thick liquid layer surrounding Ti–6Al–4V. The ductility of Fe-added Ti–6Al–4V was thus poorer than that of Cr-added Ti–6Al–4V.     

High-strain-rate superplasticity of the Al–Zn–Mg–Cu alloys with Fe and Ni additions

During high-strain-rate superplastic deformation, superplasticity indices, and the microstructure of two Al–Zn–Mg–Cu–Zr alloys with additions of nickel and iron, which contain equal volume fractions of eutectic particles of Al₃Ni or Al₉FeNi, have been compared. It has been shown that the alloys exhibit superplasticity with 300–800% elongations at the strain rates of 1 × 10^–2–1 × 10^–1 s^–1. The differences in the kinetics of alloy recrystallization in the course of heating and deformation at different temperatures and rates of the superplastic deformation, which are related to the various parameters of the particles of the eutectic phases, have been found. At strain rates higher than 4 × 10^–2, in the alloy with Fe and Ni, a partially nonrecrystallized structure is retained up to material failure and, in the alloy with Ni, a completely recrystallized structure is formed at rates of up to 1 × 10^–1 s^–1.     

Stability of B2 ordered phase in the Ti-rich portion of Ti–Al–Cr and Ti–Al–Fe ternary systems

The stability region of the B2 phase at 1000°C in the Ti-rich part of the Ti–Al–Cr and Ti–Al–Fe ternary systems are investigated by energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM) using two-phase alloys and diffusion couples. It is established that the critical boundaries of the A2/B2 continuous ordering transition are functions of both the Al and Fe or Cr contents, and the phase equilibria between the α₂ and the β and between the β and FeTi (B2) phases are strongly affected by the A2/B2 order–disorder transition. By extrapolating these ternary data to the Ti–Al binary and using the Bragg–Williams–Gorsky approximation a metastable A2/B2 ordering boundary is postulated to exist at 1000°C in the vicinity of 23.5 at%Al in the Ti–Al binary system.     

Mechanical properties and hardening mechanism of Fe–Al–Ni single crystals containing NiAl precipitates

The microstructures and mechanical properties of Fe–23.0 Al–6.0 Ni (at.%) single crystals containing NiAl precipitates were investigated and the hardening mechanism due to the precipitates was discussed, focusing on the activated slip systems. When these alloys were slowly cooled to room temperature after homogenization at 1373 K, the NiAl phase with the B2 structure precipitated in the body-centered cubic (bcc) Fe–Al matrix, satisfying the cube-on-cube relationship with a small misfit strain. The single crystals containing the NiAl precipitates exhibited a high yield stress above 1 GPa at room temperature. In addition, the activated slip system and deformation behavior depended strongly on the loading axis. For instance, 〈1 1 1〉 slip, which is the primary slip for the bcc matrix, occurred at 〈1 4 9〉 and 〈0 0 1〉 orientations and the NiAl precipitates were sheared by the slip. A critical resolved shear stress of 〈1 1 1〉 slip in the NiAl phase was known to be extremely high, which led to strong precipitation hardening. On the other hand, at 〈5 5 7〉 and 〈0 1 1〉 orientations, 〈0 0 1〉 slip, which is the primary slip system for the NiAl precipitates, forcibly sheared the bcc Fe–Al matrix, also leading to strong hardening. Thus, in the Fe–Al–Ni alloys, the difference in the primary slip system between the bcc Fe–Al matrix and the NiAl precipitates resulted in extreme hardening. This hardening mechanism caused by the NiAl precipitates effectively increased the yield stress even at high temperatures. In fact, the crystals exhibited a high yield stress at ～1 GPa up to 823 K.     

Deformation and creep modeling in polycrystalline Ti–6Al alloys

This paper develops an experimentally validated computational model for titanium alloys accounting for plastic anisotropy and time-dependent plasticity for analyzing creep and dwell phenomena. A time-dependent crystal plasticity formulation is developed for hcp crystalline structure, with the inclusion of microstructural crystallographic orientation distribution. A multi-variable optimization method is developed to calibrate crystal plasticity parameters from experimental results of single crystals of α-Ti–6Al. Statistically equivalent orientation distributions of orientation imaging microscopy data are used in constructing the polycrystalline aggregate model. The model is used to study global and local response of the polycrystalline model for constant strain rate, creep, dwell and cyclic tests. Effects of stress localization and load shedding with orientation mismatch are also studied for potential crack initiation.     

Microstructure evolution during homogenization of Al–Mn–Fe–Si alloys: Modeling and experimental results

Microstructure evolution during the homogenization heat treatment of Al–Mn–Fe–Si, or AA3xxx, alloys has been investigated using a combination of modeling and experimental studies. The model is fully coupled to CALculation PHAse Diagram (CALPHAD) software and has explicitly taken into account the two different length scales for diffusion encountered in modeling the homogenization process. The model is able to predict the evolution of all the important microstructural features during homogenization, including the inhomogeneous spatial distribution of dispersoids and alloying elements in solution, the dispersoid number density and the size distribution, and the type and fraction of intergranular constituent particles. Experiments were conducted using four direct chill (DC) cast AA3xxx alloys subjected to various homogenization treatments. The resulting microstructures were then characterized using a range of characterization techniques, including optical and electron microscopy, electron micro probe analysis, field emission gun scanning electron microscopy, and electrical resistivity measurements. The model predictions have been compared with the experimental measurements to validate the model. Further, it has been demonstrated that the validated model is able to predict the effects of alloying elements (e.g. Si and Mn) on microstructure evolution. It is concluded that the model provides a time and cost effective tool in optimizing and designing industrial AA3xxx alloy chemistries and homogenization heat treatments.     

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.     

Microstructure and mechanical properties of Fe–Si–Ti–(Cu,Al) heterostructured ultrafine composites

The influence of partial substitution of Fe by Cu or Al in Fe_75?xSi₁₅Ti₁₀(Cu, Al)_x (x = 0 and 4) ultrafine composites on the microstructure and mechanical properties has been investigated. The Fe₇₁Si₁₅Ti₁₀Cu₄ ultrafine composite exhibits a favorable microstructural evolution and improved mechanical properties, i.e., large plastic strain of ～5% and pronounced work hardening characteristics. The mechanical properties of the ultrafine eutectic composite are strongly linked to the length scale heterogeneity and the distribution of the constituent phases.