Precipitate characterisation of an advanced high-strength low-alloy (HSLA) steel using atom probe tomography

Increased fuel economy, combined with the need for the improved safety has generated the development of new hot-rolled high-strength low-alloy (HSLA) and multiphase steels such as dual-phase or transformation-induced plasticity steels with improved ductility without sacrificing strength and crash resistance. However, the modern multiphase steels with good strength-ductility balance showed deteriorated stretch-flangeability due to the stress concentration region between the soft ferrite and hard martensite phases [1]. Ferritic, hot-rolled steels can provide good local elongation and, in turn, good stretch-flangeability [2]. However, conventional HSLA ferritic steels only have a tensile strength of not, vert, similar600 MPa, while steels for the automotive industry are now required to have a high tensile strength of not, vert, similar780 MPa, with excellent elongation and stretch-flangeability [1]. This level of strength and stretch-flangeability can only be achieved by precipitation hardening of the ferrite matrix with very fine precipitates and by ferrite grain refinement. It has been suggested that Mo [3] and Ti [4] should be added to form carbides and decrease the coiling temperature to 650 °C since only a low precipitation temperature can provide the precipitation refinement [4]. These particles appeared to be (Ti, Mo)C, with a cubic lattice and a parameter of 0.433 nm, and they were aligned in rows [4]. It was reported [4] that the formation of these very fine carbides led to an increase in strength of not, vert, similar300 MPa. However, the detailed analysis of these particles has not been performed to date due to their nanoscale size. The aim of this work was to carry out a detailed investigation using atom probe tomography (APT) of precipitates formed in hot-rolled low-carbon steel containing additions Ti and Mo.

The investigated low-carbon steel, containing Fe–0.1C–1.24Mn–0.03Si–0.11Cr–0.11Mo–0.09Ti–0.091Al at.%, was produced by hot rolling. The processing route has been described in detail elsewhere [5] European Patent Application, 1616970 A1, 18.01.2006.[5]. The microstructure was characterised by transmission electron microscopy (TEM) on a Philips CM 20, operated at 200 kV using thin foil and carbon replica techniques. Qualitative energy dispersive X-ray spectroscopy (EDXS) was used to analyse the chemical composition of particles. The atomic level of particle characterisation was performed at the University of Sydney using a local electrode atom probe [6]. APT was carried out using a pulse repetition rate of 200 kHz and a 20% pulse fraction on the sample with temperature of 80 K. The extent of solute-enriched regions (radius of gyration) and the local solute concentrations in these regions were estimated using the maximum separation envelope method with a grid spacing of 0.1 nm [7]. A maximum separation distance between the atoms of interest of dmax = 1 nm was used.

The microstructure of the steel consisted of two types of fine ferrite grains: (i) small recrystallised grains with an average grain size of 1.4 ± 0.2 μm; and (ii) grains with a high dislocation density (5.8 ± 1.4 × 1014 m−2) and an average grain size of 1.9 ± 0.1 μm in thickness and 2.7 ± 0.1 μm in length (Fig. 1a). Some grains with high dislocation density displayed an elongated shape with Widmanstätten side plates and also the formation of cells and subgrains (Fig. 1a). The volume fraction of recrystallised grains was 34 ± 8%.

Atom probe tomography of solute distributions in mg-based alloys

Atom probe tomography (APT) has been carried out on three magnesium-based alloys: M1 (Mg-1 wt pct Mn), AZ31(Mg-3 pct Al-1 pct Zn), and ME10 (Mg-1 pct Mn- 0.4 pct misch metal). The aims of this experiment were to measure the composition of the matrix and to investigate solute clustering in the matrix of the three different alloys. For AZ31, the matrix composition was variable but close to the bulk composition. For ME10 and M1, the matrix was depleted in alloying additions, with the remainder residing in precipitates. Most alloying additions were found to exhibit clustering to some extent, with misch metal having the strongest partitioning behavior to clusters. Solute clusters did not appear to affect mechanical twinning. It has been proposed that the clustering behavior of misch metal contributes to its ability to modify the recrystallization texture.

Understanding the behavior of advanced high-strength steels using atom probe tomography

The key evidence for understanding the mechanical behavior of advanced high strength steels was provided by atom probe tomography (APT). Chemical overstabilization of retained austenite (RA) leading to the limited transformation-induced plasticity (TRIP) effect was deemed to be the main factor responsible for the low ductility of nanostructured bainitic steel. Appearance of the yield point on the stress-strain curve of prestrained and bake-hardened transformationinduced plasticity steel is due to the unlocking from weak carbon atmospheres of newly formed during prestraining dislocations.

Atom probe tomography as a tool to advance steels design and performance

Development of modern steels consisting of complex or nano-scale microstructures with advanced properties requires in-depth understanding of the mechanisms responsible for their microstructure/property relationships. The evolution of microstructure during processing is often associated with various changes taking place at atomic level. These include solute distribution between phases as a result of phase transformations, formation of atmospheres at dislocations, clustering and precipitation phenomena due to various thermo-mechanical processing schedules and/or heat treatments. Atom probe tomography (APT) is invaluable tool for gaining insight into events at atomic scale determining the steel properties. This technique also contributes to the fundamental understanding of phase transformations, which is essential for nano-scale engineering of modern steels and optimization of their performance. In this work application of APT to study solute segregation, clustering and precipitation in TRIP steels and nanostructured bainitic steels after isothermal heat-treatment and after thermomechanical processing will be discussed.

Analysis of strengthening in AA6111 during the early stages of aging: atom probe tomography and yield stress modelling

In this work, a series of aging treatments has been conducted on AA6111 alloy samples for various times at ambient temperature (so-called natural aging) and at temperatures between 60 and 180 °C (artificially aged). The time at artificial ageing was chosen such that samples with approximately the same yield stress were produced. The microstructures of these alloy samples have been carefully characterized using atom probe tomography together with advanced cluster-finding techniques in order to obtain quantitative information about the changes in distribution of both the solute clusters and early-stage precipitates that are formed. The size distribution of clusters has been mapped onto the glide plane and then the stress necessary for a dislocation to pass through the range of obstacles has been estimated using an areal glide model where the dislocation–obstacle interaction strength has been assumed to be related to the obstacle size on the glide plane. It is demonstrated that the contribution of cluster strengthening during artificial aging at higher temperatures is dominated by the high number density of small clusters (Guinier radius <1 nm), whereas the situation during room temperature natural aging is more complex.

Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography

We report on the characterization of grain boundary (GB) segregation in an Fe-28Mn-0.3C (wt.%) twinning-induced plasticity (TWIP) steel. After recrystallization of this steel for 24 h at 700 °C, ∼50% general grain boundaries (GBs) and ∼35% Σ3 annealing twin boundaries were observed (others were high-order Σ and low-angle GBs). The segregation of B, C and P and traces of Si and Cu were detected at the general GB by atom probe tomography (APT) and quantified using ladder diagrams. In the case of the Σ3 coherent annealing twin, it was necessary to first locate the position of the boundary by density analysis of the atom probe data, then small amounts of B, Si and P segregation and, surprisingly, depletion of C were detected. The concentration of Mn was constant across the interface for both boundary types. The depletion of C at the annealing twin is explained by a local change in the stacking sequence at the boundary, creating a local hexagonal close-packed structure with low C solubility. This finding raises the question of whether segregation/depletion also occurs at Σ3 deformation twin boundaries in high-Mn TWIP steels. Consequently, a previously published APT dataset of the Fe-22Mn-0.6C alloy system, containing a high density of deformation twins due to 30% tensile deformation at room temperature, was reinvestigated using the same analysis routine as for the annealing twin. Although crystallographically identical to the annealing twin, no evidence of segregation or depletion was found at the deformation twins, owing to the lack of mobility of solutes during twin formation at room temperature.

Atom probe tomography study of the nanoscale heterostructure around an Al20Mn3Cu2 dispersoid in aluminum alloy 2024.

Atom probe tomography (APT) has been used to investigate the surface and sub-surface microstructures of aluminum alloy 2024 (AA2024) in the T3 condition (solution heat treated, cold worked, and naturally aged to a substantially stable condition). This study revealed surface Cu enrichment on the alloy matrix, local chemical structure around a dispersoid Al20Mn3Cu2 particle including a Cu-rich particle and S-phase particle on its external surface. Moreover, there was a significant level of hydrogen within the dispersoid, indicating that it is a hydrogen sink. These observations of the nanoscale structure around the dispersoid particle have considerable implications for understanding both corrosion and hydrogen embrittlement in high-strength aluminum alloys.

On low temperature bainite transformation characteristics using in-situ neutron diffraction and atom probe tomography

In-situ neutron diffraction was employed to monitor the evolution of nano-bainitic ferrite during low temperature isothermal heat treatment of austenite. The first 10 peaks (austenite, γ and ferrite, α) were monitored during austenization, homogenization, rapid cooling and isothermal holding at 573 K. Changes in the α-110 and γ-111 peaks were analysed to determine the volume fraction changes and hence the kinetics of the phase transformation. Asymmetry and broadening in the α-200 and γ-200 peaks were quantified to lattice parameter changes due to carbon redistribution as well as the effects of size and dislocation density. Atom Probe Tomography was used to confirm that, despite the presence of 1.5 mass % Si, carbide formation was evident. This carbide formation is the cause of poor ductility, which is lower than expected in such steels.

Atomic scale analysis of light alloys using atom probe tomography

The present paper reviews recent progress in atomic-scale characterisation of composition and nanostructure of light alloy materials using the technique of atom probe tomography. In particular, the present review will highlight atom-by-atom analysis of solid solution architecture, including solute clustering and short-range order, with reference to current limitations of spatial resolution and detector efficiency of atom probe tomography and methods to address these limitations. This leads to discussion of prediction of mechanical properties by simulation and modelling of the strengthening effect exerted by solute clusters and the role of experimental atom probe data to assist in this process. The unique contribution of atom probe tomography to the study of corrosion and hydrogen embrittlement of light alloys will also be discussed as well as a brief insight into its potential application for the investigation of solute strengthening of twinning in Mg alloys.

Atom probe tomography investigation of heterogeneous short-range ordering in the 'komplex' phase state (K-state) of Fe-18Al (at.%)

We study an Fe-18Al (at.%) alloy after various thermal treatments at different times (24-336 h) and temperatures (250-1100 °C) to determine the nature of the so-called 'komplex' phase state (or "K-state"), which is common to other alloy systems having compositions at the boundaries of known order-disorder transitions and is characterised by heterogeneous short-range-ordering (SRO). This has been done by direct observation using atom probe tomography (APT), which reveals that nano-sized, ordered regions/particles do not exist. Also, by employing shell-based analysis of the three-dimensional atomic positions, we have determined chemically sensitive, generalised multicomponent short-range order (GM-SRO) parameters, which are compared with published pairwise SRO parameters derived from bulk, volume-averaged measurement techniques (e.g. X-ray and neutron scattering, Mössbauer spectroscopy) and combined ab-initio and Monte Carlo simulations. This analysis procedure has general relevance for other alloy systems where quantitative chemical-structure evaluation of local atomic environments is required to understand ordering and partial ordering phenomena that affect physical and mechanical properties.

Quantitative chemical-structure evaluation using atom probe tomography: Short-range order analysis of Fe-Al.

Short-range-order (SRO) has been quantitatively evaluated in an Fe-18Al (at%) alloy using atom probe tomography (APT) data and by calculation of the generalised multicomponent short-range order (GM-SRO) parameters, which have been determined by shell-based analysis of the three-dimensional atomic positions. The accuracy of this method with respect to limited detector efficiency and spatial resolution is tested against simulated D03 ordered data. Whilst there is minimal adverse effect from limited atom probe instrument detector efficiency, the combination of this with imperfect spatial resolution has the effect of making the data appear more randomised. The value of lattice rectification of the experimental APT data prior to GM-SRO analysis is demonstrated through improved information sensitivity.

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.

Atom probe tomography at the University of Sydney

Summary: The Australian Microscopy & Microanalysis Research Facility (AMMRF) operates a national atom probe laboratory at The University of Sydney. This paperprovides a brief review and update of the technique of atom probe tomography (APT),together with a summary of recent research applications at Sydney in the scienceand technology of materials. We describe recent instrumentation advances such asthe use of laser pulsing to effect time-controlled field evaporation, the introductionof wide field of view detectors, where the solid angle for observation is increased byup to a factor of ∼20 as well as innovations in specimen preparation. We concludethat these developments have opened APT to a range of new materials that werepreviously either difficult or impossible to study using this technique because of theirpoor conductivity or brittleness.

Three-dimensional atom probe analysis of solute distribution in thermomechanically processed TRIP steels

Complex multiphase microstructures were obtained in transformation induced plasticity C–Mn–Si–(Nb–Al–Mo) steels by simulated controlled thermomechanical processing. These microstructures were characterized using transmission electron microscopy, X-ray diffraction and three-dimensional atom probe tomography (APT), which was used to determine the partitioning of elements between different phases and microconstituents. The measured carbon concentration (not, vert, similar0.25 at%) in the ferrite of carbide-free bainite was higher than expected from para-equilibrium between the austenite and ferrite, while the concentrations of substitutional elements were the same as in the parent austenite suggesting that incomplete bainite transformation occurred. In contrast, the distribution of substitutional elements between the ferrite lath and austenite in carbide-containing bainite indicated a complete bainite reaction. The average carbon content in the retained austenite (3.2 ± 1.6 at%) was somewhat higher than the T0 limit. On the basis of the APT measured composition, the calculated Ms temperatures for retained austenite were above room temperature, indicating its low chemical stability.