Precipitation and fracture behaviour of Fe–Mn–Ni–Al alloys

The effects of Al addition on the precipitation and fracture behaviour of Fe–Mn–Ni alloys were investigated. With the increasing of Al concentration, the matrix and grain boundary precipitates changed from L1₀ θ-MnNi to B2 Ni₂MnAl phase, which is coherent and in cube-to-cube orientation relationship with the α′-matrix. Due to the suppression of the θ-MnNi precipitates at prior austenite grain boundaries (PAGBs), the fracture mode changed from intergranular to transgranular cleavage fracture. Further addition of Al resulted in the discontinuous growth of Ni₂MnAl precipitates in the alloy containing 4.2?wt.% Al and fracture occurred by void growth and coalescence, i.e. by ductile dimple rupture. The transition of the fracture behaviour of the Fe–Mn–Ni–Al alloys is discussed in relation to the conversion of the precipitates and their discontinuous precipitation behaviour at PAGBs.     

Thermodynamics of phase equilibrium of binary alloys containing nanprecipitates

A model of phase equilibrium in binary alloys has been developed taking into account the formation of phase precipitates of arbitrary (including nanometer) size. It has been shown that the phase composition of alloys substantially depends on the size of phase precipitates and, in the case of the formation of nano-precipitates, the phase composition can differ by a factor of several times from the phase composition of macroscopic precipitates. The proposed model has been used for calculating the dependence of the phase composition of some binary alloys (α-Fe-Cr at the temperature T = 773 K and Zr-Nb at the temperature T = 853−873 K) on the size of precipitates. The results of the calculation agree with experimental data obtained by other authors.     

Normal and excess nitrogen uptake by iron-based Fe–Cr–Al alloys: the role of the Cr/Al atomic ratio

Upon nitriding ferritic iron-based Fe–Cr–Al alloys, containing a total of 1.50 at. % (Cr?+?Al) alloying elements with varying Cr/Al atomic ratio (0.21–2.00), excess nitrogen uptake occurred, i.e. more nitrogen was incorporated in the specimens than compatible with only inner nitride formation and equilibrium nitrogen solubility of the unstrained ferrite matrix. The amount of excess nitrogen increased with decreasing Cr/Al atomic ratio. The microstructure of the nitrided zone was investigated by X-ray diffraction, electron probe microanalysis, transmission electron microscopy and electron energy loss spectroscopy. Metastable, fine platelet-type, mixed Cr_{1? x} Al _x N nitride precipitates developed in the nitrided zone for all of the investigated specimens. The degree of coherency of the nitride precipitates with the surrounding ferrite matrix is discussed in view of the anisotropy of the misfit. Analysis of nitrogen-absorption isotherms, recorded after subsequent pre- and de-nitriding treatments, allowed quantitative differentiation of different types of nitrogen taken up. The amounts of the different types of excess nitrogen as function of the Cr/Al atomic ratio are discussed in terms of the nitride/matrix misfit and the different chemical affinities of Cr and Al for N. The strikingly different nitriding behaviors of Fe–Cr–Al and Fe–Cr–Ti alloys could be explained on this basis.     

Surface dependence of the magnetic configurations of the ordered B2 FeCr alloy

Tight-binding linear muffin tin orbitals calculations with generalized gradient approximation were carried out for the magnetic configurations at the surface of the ferromagnetic ordered B2 FeCr alloys. For both (001) and (111) crystallographic phases, non ferromagnetic configurations are shown to be more stable than the ferromagnetic configuration of the bulk alloy. For (001) surface we display a c ground state for either Cr or Fe at the surface. For Cr top layer the magnetic moments are larger than in the bulk B2 FeCr while they are slightly enhanced for Fe top layer. For (111) surface an antiferromagnetic coupling between surface and subsurface is always obtained i.e. for either Fe or Cr at the surface. This change of coupling between Fe and Cr (from ferromagnetic to antiferromagnetic) is expected to be fundamental to any explanation of the experimental results obtained for the interface alloying at the Fe/Cr interfaces. Received 23 March 1998     

Elastic moduli of nanocrystalline binary Al alloys with Fe,Co, Ti,Mg and Pb alloying elements

The paper studies the elastic moduli of nanocrystalline (NC) Al and NC binary Al–X alloys (X is Fe, Co, Ti, Mg or Pb) by using molecular dynamics simulations. X atoms in the alloys are either segregated to grain boundaries (GBs) or distributed randomly as in disordered solid solution. At 0 K, the rigidity of the alloys increases with decrease in atomic radii of the alloying elements. An addition of Fe, Co or Ti to the NC Al leads to increase in the Young’s E and shear μ moduli, while an alloying with Pb decreases them. The elastic moduli of the alloys depend on a distribution of the alloying elements. The alloys with the random distribution of Fe or Ti demonstrate larger E and μ than those for the corresponding alloys with GB segregations, while the rigidity of the Al–Co alloy is higher for the case of the GB segregations. The moduli E and μ for polycrystalline aggregates of Al and Al–X alloys with randomly distributed X atoms are estimated based on the elastic constants of corresponding single-crystals according to the Voigt-Reuss-Hill approximation, which neglects the contribution of GBs to the rigidity. The results show that GBs in NC materials noticeably reduce their rigidity. Furthermore, the temperature dependence of μ for the NC Al–X alloys is analyzed. Only the Al–Co alloy with GB segregations shows the decrease in μ to the lowest extent in the temperature range of 0–600 K in comparison with the NC pure Al.     

Reverse α–α´ phase separation in Fe-20Cr-6Al alloy

The reverse α–α′ phase separation in Fe-20Cr-6Al alloys has been monitored by differential scanning calorimetry in as-hot rolled and recrystallized samples previously aged at 435?°C. The splitting in the position of the minima, and the increasing enthalpy change involved, might be explained in terms of dissolution of α′ particles with different compositions and volume fractions. These results are fully consistent with the α–α′ phase separation kinetics determined by atom probe tomography during ageing at 435?°C. The monitoring of activation energy for α′ dissolution indicates that it is faster in as-hot rolled samples. Finally, the activation energy evolution indicates that there is first a dissolution of β′ Fe(AlTi) phase followed by α′ dissolution.     

Local configurations and atomic intermixing in as-quenched and annealed Fe1−xCrx and Fe1−xMox ribbons

Local atomic configuration, phase composition and atomic intermixing in Fe-rich Fe_1?xCr_x and Fe_1?xMo_x ribbons (x = 0.05, 0.10, 0.15), of potential interest for high-temperature applications and nuclear devices, are investigated in this study in relation to specific processing and annealing routes. The Fe-based thin ribbons have been prepared by induction melting, followed by melt spinning and further annealed in He at temperatures up to 1250 °C. The complex structural, compositional and atomic configuration characterisation has been performed by means of X-ray diffraction (XRD), transmission Mössbauer spectroscopy and differential scanning calorimetry (TG-DSC). The XRD analysis indicates the formation of the desired solid solutions with body-centred cubic (bcc) structure in the as-quenched state. The Mössbauer spectroscopy results have been analysed in terms of the two-shell model. The distribution of Cr/Mo atoms in the first two coordination spheres is not homogeneous, especially after annealing, as supported by the short-range order parameters. In addition, high-temperature annealing treatments give rise to oxidation of Fe (to haematite, maghemite and magnetite) at the surface of the ribbons. Fe_1?xCr_x alloys are structurally more stable than the Mo counterpart under annealing at 700 °C. Annealing at 1250 °C in He enhances drastically the Cr clustering around Fe nuclei.     

Enhancement in age hardenability of sintered Ti–5Fe alloy by Zr addition processed by pulsed electric current sintering

The age-hardenable Ti–5Fe–5Zr (wt. %, 5Zr) alloy has been consolidated by pulsed electric current sintering, following a β solution treatment, and the results are compared with a Ti–5Fe (0Zr) alloy. The precipitation sequence measured at 640°C ageing is β?+?athermal ω?→?β?+?isothermal ω?→?β?+?α. At the peak hardness isothermal ω phase forms at 20?s of ageing. The Zr addition retards the precipitation kinetics of the α phase; as a result, the α phase nucleates at latest at 300?s ageing in the overaged state. Fe is partitioned into β, while it is depleted from the α phases. There is Zr enrichment near the α/β interface when the α phase precipitates due to a solute drag effect; the growth rate of the α phase in the 5Zr alloy is significantly reduced compared with that in the 0Zr alloy.     

Coherency strain and precipitation kinetics: crystalline and amorphous nitride formation in ternary Fe–Ti/Cr/V–Si alloys

Specimens of iron-based binary Fe–Si alloy and ternary Fe–Me–Si alloys (with Me = Ti, Cr and V) were nitrided at 580 °C in a NH₃/H₂-gas mixture applying a nitriding potential of 0.1 atm^?1/2 until nitrogen saturation in the specimens was attained. In contrast with recent observations in other Fe–Me ₁–Me ₂ alloys, no “mixed” (Me ₁, Me ₂) nitrides developed in Fe–Me–Si alloys upon nitriding: first, all Me precipitates as MeN; and thereafter, all Si precipitates as Si₃N₄. The MeN precipitates as crystalline, finely dispersed, nanosized platelets, obeying a Baker–Nutting orientation relationship (OR) with respect to the ferrite matrix. The Si₃N₄ precipitates as cubically, amorphous particles; the incoherent (part of the) MeN/α-Fe interface acts as heterogeneous nucleation site for Si₃N₄. The Si₃N₄-precipitation rate was found to be strongly dependent on the degree of coherency of the first precipitating MeN. The different, even opposite, kinetic effects observed for the various Fe–Me–Si alloys could be ascribed to the different time dependences of the coherent?→?incoherent transitions of the MeN particles in the different Fe–Me–Si alloys.     

Mössbauer study of oxide films of Fe-, Sn-, Cr- doped zirconium alloys during corrosion in autoclave

Mössbauer investigations were used to compare iron atom states in oxide films of binary Zr-Fe, ternary Zr-Fe-Cu and quaternary Zr-Fe-Cr-Sn alloys. Oxide films are received in an autoclave at a temperature of 350–360 °C and at pressure of 16.8 MPa. The corrosion process decomposes the intermetallic precipitates in alloys and forms metallic iron with inclusions of chromium atoms α–Fe(Cr), α–Fe(Cu), α–Fe ₂O₃ and Fe ₃O₄ compounds. Some iron ions are formed in divalent and in trivalent paramagnetic states. The additional doping influences on corrosion kinetics and concentration of iron compounds and phases formed in oxide films. It was shown the correlation between concentration of iron in different chemical states and corrosion resistance of alloys.     

Continuous and discontinuous precipitation in Fe-1 at.%Cr-1 at.%Mo alloy upon nitriding; crystal structure and composition of ternary nitrides

The internal nitriding response of a ternary Fe–1 at.%Cr–1 at.%Mo alloy, which serves as a model alloy for many CrMo-based steels, was investigated. The nitrides developing upon nitriding were characterised by X-ray diffraction, scanning electron microscopy, electron probe microanalysis, transmission electron microscopy and atom probe tomography. The developed nitrides were shown to be (metastable) ternary mixed nitrides, which exhibit complex morphological, compositional and structural transformations as a function of nitriding time. Analogous to nitrided binary Fe–Cr and Fe–Mo alloys, in ternary Fe–Cr–Mo alloys initially continuous precipitation of fine, coherent, cubic, NaCl-type nitride platelets, here with the composition (Cr_½,Mo_½)N_¾, occurs, with the broad faces of the platelets parallel to the {1?0?0}_α-Fe lattice planes. These nitrides undergo a discontinuous precipitation reaction upon prolonged nitriding leading to the development of lamellae of a novel, hexagonal CrMoN₂ nitride along {1?1?0}_α-Fe lattice planes, and of spherical cubic, NaCl-type (Cr,Mo)N _x nitride particles within the ferrite lamellae. The observed structural and compositional changes of the ternary nitrides have been attributed to the thermodynamic and kinetic constraints for the internal precipitation of (misfitting) nitrides in the ferrite matrix.     

Positron annihilation study of the vacancy clusters in ODS Fe–14Cr alloys

Abstract

Oxide dispersion strengthened Fe14Cr and Fe14CrWTi alloys produced by mechanical alloying and hot isostatic pressing were subjected to isochronal annealing up to 1400 °C, and the evolution and thermal stability of the vacancy-type defects were investigated by positron annihilation spectroscopy (PAS). The results were compared to those from a non-oxide dispersion strengthened Fe14Cr alloy produced by following the same powder metallurgy route. The long lifetime component of the PAS revealed the existence of tridimensional vacancy clusters, or nanovoids, in all these alloys. Two recovery stages are found in the oxide dispersion strengthened alloys irrespective of the starting conditions of the samples. The first one starting at T > 750 °C is attributed to thermal shrinkage of large vacancy clusters, or voids. A strong increase in the intensity of the long lifetime after annealing at temperatures in the 800–1050 °C range indicates the development of new vacancy clusters. These defects appear to be unstable above 1050 °C, but some of them remain at temperatures as high as 1400 °C, at least for 90 min.     

Magnetic and structural properties of FeCr alloys

Synergistic synchrotron x-ray absorption experiments using imaging magnetic microspectroscopy, x-ray magnetic circular dichroism, and ab initio calculations on FeCr alloys reveal that the Cr content strongly influences the ferromagnetic microstructure and the Fe magnetic moments. The Cr local structure resolved by extended x-ray absorption fine structure (EXAFS) is also found to be affected by the alloy's composition. Both EXAFS and ab initio calculations show a change in the Cr local atomic structure above 10 at.% Cr content from the distance contraction of the first two coordination shells around the Cr absorbing atom. These results indicate the strong dependence of magnetic and structural properties of these alloys on Cr concentration.     

First-principles study on superconductivity of the gold–indium alloy under high pressure

The superconductivity of gold–indium alloys has been investigated using first-principles calculations based on the density functional theory. At ambient pressure, the calculated superconducting transition temperature (T _c) is 0.04 μ K in pure gold, but T _c dramatically increases by substituting indium atoms for gold atoms. The gold–indium alloy having 12.5 atomic percent indium (Au_0.875In_0.125) shows T _c of 0.1 K, and Au_0.75In_0.25 marks 1.7 K. The dramatic increase in T _c owing to the alloying effect is caused by the enhancement of the electron–phonon coupling. The superconductivity of gold is predicted to be drastically weakened with increasing pressure and virtually disappear at 10 GPa, but it continues up to at least 30 GPa by the inclusion of indium atoms.     

Mössbauer spectroscopic studies of Fe-20 wt.% Cr ball milled alloy

Interesting differences were noticed in the alloying process during ball milling of Fe-10 wt.% Cr and Fe-20 wt.% Cr alloys by ⁵⁷Fe Mössbauer spectroscopic studies. In both cases, there is almost no diffusion of Fe in Cr or vice versa up to 20 h of milling time. As the powders are milled for another 20 h substantive changes occur in the Mössbauer spectra showing atomic level mixing. But the two compositions behave differently with respect to alloying. Fe-20 wt.% Cr sample does not differ much in the hyperfine field distribution as it is milled from 40 to 100 h. On the other hand, the hyperfine field distribution keeps on changing with milling time for Fe-10 wt.% Cr sample even up to 100 h of milling. The average crystallite size is found to be 7.5 nm for Fe-10 wt.% Cr and 6.5 nm in Fe-20 wt.% Cr after milling.     

Mechanomaking of nanostructure in nitrided Fe–Cr alloys by cyclic “dissolution–precipitation” deformation-induced transformations

Structural-phase transformations in surface layers of iron and Fe? Cr? (Ni) alloys subjected to ion-plasma nitriding and subsequent cold plastic compression shear deformation in Bridgman anvils have been investigated by the methods of Mössbauer spectroscopy, transmission electron microscopy and X-ray analysis. It has been shown that the deformation-induced cyclic phase “dissolution–precipitation” transformations of nitrides in alloys lead to the formation of nitrogen oversaturated solid solutions, precipitation of secondary nitrides and nanostructurization of the metal matrix.     

Microstructural evolution and thermal stability of Fe–Zr metastable alloys developed by mechanical alloying followed by annealing

The effect of Zr (up to 1 at.%) addition on the formation of Fe–Zr metastable alloys and their thermal stability were investigated for their possible nuclear applications. Fe–xZr (x = 0.25, 0.5, 1%) alloys were synthesised by mechanical alloying under a high-purity argon atmosphere using stainless steel grinding media in a SPEX 8000M high energy mill. The milling was conducted for 20 h with a ball-to-powder weight ratio of 10:1. The formation of metastable solid solutions after milling was confirmed from the change in the Gibbs free energy analysis as per Miedema’s model. The microstructural characterisation was carried out by analysis of X-ray diffraction, atomic force microscopy and transmission electron microscopy. The effect of Zr on the thermal stability of Fe–Zr alloys was investigated by extensive annealing experiments followed by microstructural analysis and microhardness measurements. The stabilisation was found to occur at 800 °C and thereafter, no significant change in the crystallite size was observed for the samples annealed between 800 and 1200 °C. The supersaturated solid solution, especially 1% Zr alloy, found to be highly stable up to 800 °C and the microhardness value of the same measured to be as high as 8.8 GPa corresponding to a crystallite size of 57 nm. The stabilisation effect has been discussed in the light of both the thermodynamic and kinetic mechanisms and the grain size stabilisation is attributed to the grain boundary segregation of Zr atoms and/or Zener pinning by nanoscale precipitation of the Fe₂Zr phase.     

Performance and application of a high energy monochromated Cu Kα1 X-ray source for the electron spectroscopy of materials

A Cu Kα₁ sealed tube X-ray source (hν = 8047.8 eV) and LiF(2 2 0) Johansson geometry monochromator crystal have been interfaced to a Scienta ESCA300 spectrometer for high energy XPS studies of materials, in particular for the measurement of Auger parameters associated with deep core levels in metallic alloys. The detailed arrangement of the source, monochromator and spectrometer combination is described, and factors affecting the overall intensity and resolution are discussed. The optimisation and characterisation of the system are also described. Several examples of Cu Kα₁ excited survey spectra (Cr, Fe, stainless steel), deep core level spectra (Cr 1s, Fe 1s) and Auger spectra (Cr KLL, Cr LMM, Fe KLL) are presented, which illustrate the capability of the system. Auger vacancy satellites are identified in the Cr LMM spectrum. For a series of Cr–Si alloys measurements are reported of the change in the Cr Auger parameter on going from metal to alloy.     

Density functional theory-based cluster expansion to simulate thermal annealing in FeCrW alloys

Abstract

In this work, we develop a rigid lattice cluster expansion as an ultimate goal to track the micro-structural evolution of Eurofer steel under neutron irradiation. The fact that all (defect) structures are mapped upon a rigid lattice allows a simplified computation and fitting procedure, thus enabling alloys of large chemical complexity to be modelled. As a first step towards the chemical complexity of Eurofer steels, we develop a cluster expansion (CE) for the FeCrW-vacancy system based on density functional theory (DFT) calculations in the dilute alloy limit. The DFT calculations suggest that only CrW clusters containing vacancies are stabilised. The cluster expansion was used to simulate thermal annealing in Fe–20Cr–xW alloys at 773 K. It is found that the addition of W to the alloy results in a non-linear decrease in the precipitation kinetics. The CE was found suitable to describe the energetics of the FeCrW-vacancy system in the Fe-rich limit.