The behaviour of chromium during anodizing of Al–Cr alloys

The anodic oxidation of dilute Al–Cr alloys, containing 0.8 and 1.7 at% Cr, has been investigated in order to understand the oxidation behaviour of the alloying element and its influences on the film composition and morphology. The alloys reveal two stages of oxidation: an initial stage, in which only aluminium atoms are oxidized to form a chromium-free anodic alumina film, and a subsequent stage, in which both aluminium and chromium are oxidized, in their approximate alloy proportions, with generation of a chromium-contaminated anodic alumina film. In the first stage, chromium is enriched in a thin layer of alloy, immediately beneath the anodic film, to an amount corresponding to a layer of average thickness 1.5 nm and of average composition, Al–20 at% Cr. Following the oxidation of chromium, oxygen is produced electrochemically within the film at or near the alloy/film interface, probably associated with the development of chromium-rich clusters in the enriched alloy layer and, subsequently, formation of semiconducting chromium-rich oxide. Thus, the film material formed at the alloy/film interface by inward migration of O^2- ions contains many oxygen-filled bubbles with associated high pressures. The chromium species present in the film migrate outward more slowly than Al³⁺ ions. Hence, a layer of chromium-free anodic alumina, which thickens as the film grows, is maintained adjacent to the film/electrolyte interface.     

Effects of carbon addition and aging on the shape memory effect of Fe–Mn–Si–Cr–Ni alloys

The effects of carbon content and aging treatment on the microstructures and shape recovery ratio of Fe–Mn–Si–Cr–Ni alloys were studied. It was found that the carbon content possessed significant effects on the shape recovery ratio of Fe–Mn–Si–Cr–Ni alloys. The shape memory effect of alloys containing different carbon amount could be improved through aging.     

Microstructural evolution during containerless rapid solidification of Ni–Mo eutectic alloys

Ni–45%Mo hypoeutectic, Ni–47.7%Mo eutectic and Ni–50%Mo hypereutectic alloys are rapidly solidified during containerless processing in drop tube. The microstructures of Ni–47.7%Mo eutectic alloy are composed of lamellar eutectic plus anomalous eutectic of Ni and NiMo phases. When the droplet size decreases, the volume fraction of anomalous eutectic becomes larger. The structural morphology transforms into Ni dendrite plus lamellar eutectic in very small droplets which are highly undercooled. The microstructures of Ni–45%Mo hypoeutectic alloy are characterized by primary Ni dendrite plus lamellar eutectic, whereas those of Ni–50%Mo hypereutectic alloy consist of NiMo dendrite plus lamellar eutectic. For both off-eutectic alloys, the experimental results show that the microstructure evolution depends mainly on droplet size. In the case of Ni–45%Mo hypoeutectic alloy, with the decrease of droplet size, the primary Ni phase transforms from dendrites to equiaxed grains. As for Ni–50%Mo hypereutectic alloy, when droplets become smaller and smaller the microstructural transition proceeds from primary NiMo dendrite plus lamellar eutectic to anomalous eutectic. The calculated highest undercoolings of the three alloys are 226, 182 and 135 K, respectively. By classical nucleation theory, Ni phase is the primary phase to nucleate for Ni–47.7%Mo eutectic alloy. The TMK eutectic growth and LKT/BCT dendritic growth theories are applied to analyze the rapid solidification process and investigate the microstructural transition mechanisms. The coupled zone of Ni–Mo eutectic alloy has also been calculated on the basis of TMK and LKT/BCT models, which covers a composition range from 45.7% to 57.1% Mo.     

Structure of strengthening particles of niobium carbide in Fe–Cr–Ni cast refractory alloys

Methods of optical and electron microscopies were used to study the structure of particles of niobium carbide in a cast refractory Fe–Cr–Ni–C alloy modified by Nb and Ti. Particles of niobium carbide in the structure of the cast alloy are predominantly multiphase polycrystalline clusters that are inhomogeneous in the chemical composition and crystal structure. The misorientation angle between individual crystals that compose the carbide particles is 30°–60°. The polycrystalline character of carbides is probably associated with significant thermal stresses that arise at the interphase boundaries in the structure of the alloy upon the primary cooling of the ingot. To explain the polymorphism of the cluster of niobium carbide, a further analysis of the structural and geometrical crystallography is required.     

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.     

Microstructural evolution and strain hardening of Fe–24Mn and Fe–30Mn alloys during tensile deformation

High Mn steels demonstrate an exceptional combination of high strength and ductility owing to their sustained high work hardening rate during deformation. In the present work, the microstructural evolution and work hardening of Fe–30Mn and Fe–24Mn alloys during uniaxial tensile testing at 293 K and 77 K were investigated. The Fe–30Mn alloy did not undergo significant strain-induced phase transformations or twinning during deformation at 293 K, whereas these transformations were observed during deformation at 77 K. A modified Kocks–Mecking model was successfully applied to describe the strain hardening behavior of Fe–30Mn at both temperatures, and quantitatively identified the influence of stacking fault energy and strain-induced phase transformations on dynamic recovery. The Fe–24Mn alloy underwent extensive ε martensite transformation during deformation at both test temperatures. An analytical micromechanical model was successfully used to describe the work hardening of Fe–24Mn and permitted the calculation of the ε martensite stress–strain curve and tensile properties.     

Sluggish diffusion in Co–Cr–Fe–Mn–Ni high-entropy alloys

Sluggish diffusion kinetics is an important contributor to the outstanding properties of high-entropy alloys. However, the diffusion kinetics in high-entropy alloys has never been probed directly. Here, the diffusion couple method was used to measure the diffusion parameters of Co, Cr, Fe, Mn and Ni in ideal-solution-like Co–Cr–Fe–Mn–Ni alloys. These parameters were compared with those in various conventional face-centered cubic metals. The results show that the diffusion coefficients in the Co–Cr–Fe–Mn–Ni alloys are indeed lower than those in the reference metals. Correspondingly, the activation energies in the high-entropy alloys are higher than those in the reference metals. Moreover, the trend of the normalized activation energy is positively related to the number of composing elements in the matrix. A quasi-chemical model is proposed to analyze the fluctuation of lattice potential energy in different matrices and to explain the observed trend in activation energies. Greater fluctuation of lattice potential energy produces more significant atomic traps and blocks, leading to higher activation energies, and thus accounts for the sluggish diffusion in high-entropy alloys.     

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.     

The influence of Cr alloying on microstructures of Fe–Al–Mn–Cr alloys

The effects of increasing chromium content on the phase transformations in Fe–Al–Mn–Cr alloys have been investigated by means of transmission electron microscopy and energy-dispersive X-ray spectrometry. The experimental results revealed that increasing the chromium addition would expand both the A12α-Mn and DO₃ phase-field regions.     

Prediction of microstructure evolution during high temperature blade forging of a Ni−Fe based superalloy,Alloy 718

The mechanical properties of the Ni−Fe-based Alloy 718 depend very much on grain size, as well as the strengthening phases, γ’ and γ. The grain structure of the superalloy components is mainly controlled during thermo-mechanical processes by the dynamic, meta-dynamic recrystallization and grain growth. In this investigation, the evolution of the grain structure in the process of two-step blade forging was experimentally and numerically dealt with. The evolution of the grain structure in Alloy 718 during blade forging was predicted using a 2-DFE simulator with implemented constitutive models on dynamic recrystallization and grain growth. The comparison of the simulated microstructure with the actual grain structure of the forged parts validated the prediction of the grain structure evolution. The effect of dynamic recrystallization on the evolution of grain structure is highlighted in this article.     

Fabrication of W–Ni–Fe alloys with gradient structures

A sintering couple of green compacts with compositions of 88W–5Mo–4.9–2.1Fe and 93W–4.9Ni–2.1Fe respectively, were processed by liquid phase sintering. The microstructure and content of binding phase at different regions along the direction perpendicular to the original interface were investigated by scanning electron microscopy (SEM). The distribution of Mo content in composite was determined by energy dispersive analysis (EDS) and the micro hardness in different regions were measured by Vickers micro hardness tester. Results show that the grain size, volume fraction of binding phase and micro hardness vary gradually due to the graded distribution of molybdenum, which also introduces a solid/liquid interfacial tension gradient and the unbalanced liquid phase pressure serving as the driving force for liquid phase migration during liquid phase sintering.     

The resistance to stress corrosion cracking of some Cr–Ni–Fe austenitic steels and alloys

Abstract

Stress-corrosion cracking testing by a variety of methods has been carried out in chloride and caustic environments on a series of Cr–Ni–Fe austenitic steels and alloys containing between 10 and 25 % of chromium and 15 and 45% of nickel. Limited testing has also been carried out on alloys containing additions of molybdenum and copper. The tests have confirmed that increasing the nickel content reduces the susceptibility of Cr–Ni–Fe alloys to stress-corrosion cracking in chloride solutions. Chromium content also affects cracking susceptibility but to a lesser degree. Stress corrosion susceptibility in caustic solutions is affected by these alloying elements in a different way. The results are discussed in relation to currently proposed theories of stress-corrosion cracking.     

Effect of Cu on the evolution of precipitation in an Fe–Cr–Ni–Al–Ti maraging steel

The evolution of precipitates in an Fe–Cr–Ni–Al–Ti stainless maraging steel alloyed with Cu was investigated during aging at 525 °C. Atom probe tomography was used to reveal the development of precipitates and to determine their chemical composition. Two types of precipitates were observed to form during the aging process. Based on their chemical composition these are assumed to be NiAl B2 and Ni₃(Ti,Al) (η-phase). The two phases of precipitates were found to develop independently of each other and the addition of Cu was found to accelerate precipitation. However, the effect of Cu on the nucleation of these phases is different: on the one hand, in the case of NiAl, Cu is incorporated and thus reduces the activation energy by reducing the lattice misfit; on the other hand, Cu acts as a nucleation site for the precipitation of Ni₃(Ti,Al) by forming independent Cu clusters.     

Microstructural design of hardfacing Ni–Cr–B–Si–C alloys

This work reports the procedure for selection of alloying elements to refine the microstructure of hardfacing Ni–Cr–B–Si–C alloys by providing in situ formed nucleation agents. It is concluded that the refining element should be able to spontaneously produce precipitates at high temperatures with little solubility in their Cr-rich counterparts. After exploring the theoretical backgrounds on how to select the refining element, Nb and Zr were selected and the phase formation reactions of Zr- or Nb-modified Ni–Cr–B–Si–C alloys were calculated using Thermo-Calc® simulations. Detailed microstructural analyses of the rapidly solidified samples deposited from the modified alloys showed that addition of Nb in specific quantities induces a significant microstructural refinement in the original Ni–Cr–B–Si–C alloy without deteriorating its high hardness. The Nb-modified alloy could be used to further investigate the viability of microstructural refinement as an effective toughening mechanism for Ni–Cr–B–Si–C and similar alloy systems.     

Two-phase growth in peritectic Fe–Ni alloys

Bridgman crystal growth experiments were carried out to investigate the solidification behavior of Fe–Ni alloys containing nominally between 4 and 4.5 at.% Ni. Due to macrosegregation, a radial concentration gradient was established across the cylindrical specimens. Due to this gradient, a series of solid/liquid interface morphologies was observed. Oriented two-phase microstructures, which formed either lamellar or fibrous δ-ferrite in an austenite (γ) matrix, were found in the central region of specimens with a composition of some 4.2 at.% Ni and a G/V ratio close to the critical ratio for solid/liquid interface breakdown. At slightly smaller concentrations, oscillatory two-phase structures formed which were similar to the 2-λ instabilities of off-eutectic alloys. The observations confirm that at low solidification rates the stable growth morphology in peritectic alloys cannot be selected by the highest growth temperature criterion. A recently developed nucleation and constitutional undercooling criterion (NCU) was applied to establish a solidification microstructure selection map. Reasonable agreement was obtained between calculated and experimental results. Based on eutectic growth theory the possibility of simultaneous two-phase growth in peritectic alloys is discussed.     

Wear characteristics of Fe–25Cr–C–B eutectic cast alloys

Abstract

To clarify the characteristics of Fe–25Cr–C–B cast alloys, a pin on disc friction and wear test was conducted on Fe–25Cr–0C–2.2B, Fe–25Cr–2.2C–1.0B and Fe–25Cr–3.5C–0B eutectic alloys, at various sliding velocities ranging from 0.125 to 1.99 m s^-1. The effects of sliding velocity on the wear resistance of these alloys were studied by the pin on disc friction and wear test, SEM and an X-ray diffraction method. The results show that the effects of sliding velocity on the increase in wear loss were different due to the differences in structure among the alloys. The X-ray diffraction method shows the presence of Fe₂ O₃ and Fe₃ O₄ in the alloys after conducting wear tests for almost all of the wear conditions. From the sliding velocity dependence of wear loss, worn surface observation after the wear tests and X-ray diffraction results, the relationships between the type of oxide and wear loss for Fe–25Cr– 0C–2.2B and Fe–25Cr–2.2C–0B alloys are not clear. However, the wear loss of Fe–25Cr–3.5C–0B alloy decreases at a sliding velocity of 0.5 m s^-1 or lower, due to the presence of red Fe₂ O₃ oxide on the worn surface. The wear loss peaks at a sliding velocity of 0.95 m s^-1, and decreases again at a sliding velocity of 1.99 m ^-1 due to the presence of black Fe₃ O₄ oxide.     

Effects of cerium and manganese on corrosion of Fe–Cr and Fe–Cr–Ni alloys in Ar–20CO2 gas at 818 °C

Model alloys Fe–9Cr, Fe–20Cr and Fe–20Cr–20Ni (wt.%) with Ce (0.05%, 0.1%) or Mn (1%, 2%) were exposed to Ar–20CO₂ gas at 818 °C. Scales on Fe–9Cr alloys consisted of FeO and FeCr₂O₄, Fe–20Cr–(Ce) alloys formed only Cr₂O₃, and Fe–20Cr–(Mn) alloys formed Cr₂O₃ and MnCr₂O₄. All Fe–20Cr–20Ni alloys formed Fe₃O₄, FeCr₂O₄ and FeNi₃. Cerium additions had little effects, but additions of 2% Mn significantly improved oxidation resistance of Fe–20Cr and Fe–20Cr–20Ni alloys. Most alloys also carburized. All alloys developed protective chromium-rich oxide scales in air. Different behavior in the two gases is attributed to faster Cr₂O₃ scaling rates induced by CO₂.     

Evolution of physical properties of amorphous Fe–Ni–Nb–B alloys with different Ni/Fe ratio upon thermal treatment

Amorphous ribbons (Fe–Ni)₈₁Nb₇B₁₂ with Ni/Fe = 0, 1/6, 1/3 and 1 were prepared by planar flow casting. Thermal treatment of samples was performed in vacuum at temperatures chosen to map the evolution of selected properties in the course of transformation from amorphous state. The coefficient of thermal dilatation exhibits changes at temperatures close to the glass transition, Curie and crystallization temperatures; these effects are enhanced or suppressed by cyclic thermal treatments up to the vicinity of these temperatures. The values of saturation magnetostriction λ_S allow to infer about processes taking place in the investigated materials, especially with respect to formation of new magnetic phases or magnetic anisotropy.Complex processes of structural transformations induced by thermal treatment are strongly affected by Ni percentage. A transitional, magnetically harder phase, which is formed at lower temperatures preferentially near surfaces of the Ni-richest alloy, produces characteristic hysteresis loop shape. This shape disappears after annealing at higher temperatures and enables the material to show the lowest coercivity of the whole alloy series. The saturation magnetic polarization reflects mainly the resulting Curie temperature, which falls with increasing Ni percentage. Magnetic hysteresis loops were also used in the study of dynamics of magnetic domains by MOKE. Domain shape evolution is shown in dependence on composition and thermal treatment as well as a function of applied magnetic field, ranging from remanent sample state to magnetic saturation.     

Microstructure evolution of Cu-Pb monotectic alloys during directional solidification

1 Introduction Monotectic alloy is an important class of alloy whose binary phase diagram has a miscibility gap, in which the original single liquid will decompose into two distinct immiscible liquids within a few seconds. In the normal gravity field, a …