Influence of cooling rate on the microstructure and corrosion behavior of Al-Fe alloys

The effect of Fe in Al is technologically important for commercial Al-alloys, and in recycled Al. This work explores the use of the novel rapid solidification technology, known as direct strip casting, to improve the recyclability of Al-alloys. We provide a comparison between the corrosion and microstructure of Al-Fe alloys prepared with wide-ranging cooling rates (0.1. °C/s to 500. °C/s). Rapid cooling was achieved via direct strip casting, while slow cooling was achieved using sand casting. Corrosion was studied via polarisation and immersion tests, followed by surface analysis using scanning electron microscopy and optical profilometry. It was shown that the corrosion resistance of Al-Fe alloys is improved with increased cooling rates, attributed to the reduced size and number of Fe-containing intermetallics.

Microstructure development and solute behaviour in Fe-C and Fe-C-V alloys during strip casting and secondary processing

 Strip casting is a rapid, environment friendly technology for manufacturing thin sheets of steel directly from molten metal. Research presented in this thesis examines the effect of atomic location, cluster size and composition on internal microstructure development during strip casting. Current research potentially leads to green manufacturing of steel.

Systematic approach to the quantitative voltammetric analysis of the Fe III /Fe II component of the [α 2 -Fe(OH 2 )P 2 W 17 O 61 ] 7-/8- reduction process in buffered and unbuffered aqueous media

The one-electron reduction of [α2-FeIII(OH2)P2W17O61]7- at a glassy carbon electrode was investigated using cyclic and rotating-disk-electrode voltammetry in buffered and unbuffered aqueous solutions over the pH range 3.45−7.50 with an ionic strength of approximately 0.6 M maintained. The behavior is well-described by a square-scheme mechanism P + e- ↔ Q (E10/ = −0.275 V, k10/ = 0.008 cm s-1, and α1 = 1/2), PH+ + e- ↔ QH+ (E20/ = −0.036 V, k20/ = 0.014 cm s-1, and α2 = 1/2), PH+ ↔ P + H+ (KP = 3.02 × 10-6 M), and QH+ ↔ Q + H+ (KQ = 2.35 × 10-10 M), where P, Q, PH+, and QH+ correspond to [α2-FeIII(OH)P2W17O61]8-, [α2-FeII(OH)P2W17O61]9-, [α2-FeIII(OH2)P2W17O61]7-, and [α2-FeII(OH2)P2W17O61]8-, respectively; E10‘ and E20‘ are the formal potentials, k10‘ and k20‘ are the formal (standard) rate constants, and KP and KQ are the acid dissociation constants for the relevant reactions. The analysis for the buffered media is based on the approach of Laviron who demonstrated that a square scheme with fully reversible protonations, reversible or quasi reversible electron transfers with the assumption that α1 = α2, can be well-described by the behavior of a simple redox couple, ox + e- ↔ red, whose formal potential, Eapp0‘, and standard rate constant, kapp0‘, are straightforwardly derived functions of pH, as are the values of E10‘, k10‘, E20‘, k20‘, and KP (only three of the four thermodynamic parameters in a square scheme can be specified). It was assumed that αapp = 1/2, and the simulation program DigiSim was used to determine the values of Eapp0‘ and kapp0‘, which are required to describe the cyclic voltammograms obtained in buffered media in the pH range from 3.45 to 7.52 (buffer-related reactions which effect general acid−base catalysis are included in the simulations). DigiSim simulations of cyclic voltammograms obtained in unbuffered media yielded the values of E10‘ and k10‘; KQ was then directly computed from thermodynamic constraints. These simulations included additional reactions between the redox species and H2O. The value of the diffusion coefficient of the [α2-FeIII(OH2)P2W17O61]7-, 2.92 × 10-6 cm2 s-1, was determined using DigiSim simulations of voltammograms at a rotating disk electrode in buffered and unbuffered media at pH 3.45. The diffusion coefficients of all redox species were assumed to be identical. When the pH is greater than 6, instability of P (i.e., [α2-FeIII(OH)P2W17O61]8-) led to the loss of the reactant and precluded lengthy experimentation.

Combined atom probe tomography and density functional theory investigation of the Al off-stoichiometry of κ-carbides in an austenitic Fe-Mn-Al-C low density steel

We report on the investigation of the off-stoichiometry and site-occupancy of κ-carbide precipitates within an austenitic (γ), Fe-29.8Mn-7.7Al-1.3C (wt.%) alloy using a combination of atom probe tomography and density functional theory. The chemical composition of the κ-carbides as measured by atom probe tomography indicates depletion of both interstitial C and substitutional Al, in comparison to the ideal stoichiometric L′12 bulk perovskite. In this work we demonstrate that both these effects are coupled. The off-stoichiometric concentration of Al can, to a certain extent, be explained by strain caused by the κ/γ mismatch, which facilitates occupation of Al sites in κ-carbide by Mn atoms (MnγAl anti-site defects). The large anti-site concentrations observed by our experiments, however, can only be stabilized if there are C vacancies in the vicinity of the anti-site.

Investigation of nano-scale precipitation phenomena in Al-Fe and Al-Cu-(Fe) alloys processed via direct strip casting

The use of rapid solidification processes such as direct strip casting (DSC) is a good way to refine the Fe-intermetallics and decrease their detrimental effects. DSC creates out-ofequilibrium supersaturated microstructures. In this work, we explore the precipitation phenomena in direct strip cast Al-Fe and Al-Cu-Fe alloys and related corrosion and mechanical properties. The precipitates are characterised with differential scanning calorimetry and transmission electron microscopy. The corrosion performances are evaluated with immersion tests and weight loss measurements and the yield strength and ductility are estimated with tensile tests. A strong correlation between the microstructure and the bulk properties is revealed with a significant improvement of properties of DSC alloys.

Theoretical study on the (1-012) deformation twinning and cracking in coarse-grained magnesium alloys

This paper theoretically and systematically investigates: (1) the effect of local transformed strains within deformation twinning on twin intersection; (2) the fracture mode based on type I co-zone tensile twin intersection in coarse-grained magnesium alloys, as well as the impacts of twin intersection and grain diameter on interfacial crack nucleation along twin boundaries; and (3) the influence of the local stresses arising from the encountered twin bands on crack growth. A novel dislocation-based strain nucleus model and a Green's function method, which are applicable to any material with local transformations in which elastic properties are reasonably approximated as isotropic, are specifically employed to model the concentrated transformed strain and calculate the local stress field resulting from deformation twinning and the stress intensity factors at crack tips in the magnesium alloys, respectively. In addition, an electron backscatter diffraction (EBSD) measurement is provided for crack nucleation originating from Type I co-zone tensile twin intersection. The theoretical modeling indicates: (i) the local strains within barrier twins strongly dictate the growth of incident twins and enhance the twin propagation stress; (ii) larger grains favor brittle fracture. More specifically, the dislocation reactions and pile-ups at the junctions between tensile twins can result in interfacial crack nucleation and growth along the twin boundaries, which is a brittle fracture mode based on lower twinning stress and stress concentration in the coarse-grained magnesium alloys; and (iii) the direction of crack propagation is easily changed by high-density twin bands and twin intersections owing to the local strains.

Study of direct laser fabricated high entropy alloys

This work analysed the microstructure-property correlations and solidification behavior of high entropy alloys (based on 5 principal elements: Al,Co, Cr, Fe, Ni). The novel outcome of the work is the effect of dislocation activities, texture and phase distribution on the tension-compression asymmetry of FCC, BCC and dual phase high entropy alloys.