Andrew J. Breen

Lattice rectification in atom probe tomography: toward true three-dimensional atomic microscopy

Atom probe tomography (APT) represents a significant step toward atomic resolution microscopy, analytically imaging individual atoms with highly accurate, though imperfect, chemical identity and three-dimensional (3D) positional information. Here, a technique to retrieve crystallographic information from raw APT data and restore the lattice-specific atomic configuration of the original specimen is presented. This lattice rectification technique has been applied to a pure metal, W, and then to the analysis of a multicomponent Al alloy. Significantly, the atoms are located to their true lattice sites not by an averaging, but by triangulation of each particular atom detected in the 3D atom-by-atom reconstruction. Lattice rectification of raw APT reconstruction provides unprecedented detail as to the fundamental solute hierarchy of the solid solution. Atomic clustering has been recognized as important in affecting alloy behavior, such as for the Al-1.1 Cu-1.7 Mg (at. %) investigated here, which exhibits a remarkable rapid hardening reaction during the early stages of aging, linked to clustering of solutes. The technique has enabled lattice-site and species-specific radial distribution functions, nearest-neighbor analyses, and short-range order parameters, and we demonstrate a characterization of solute-clustering with unmatched sensitivity and precision.

Atomically resolved tomography to directly inform simulations for structure–property relationships

Microscopy encompasses a wide variety of forms and scales. So too does the array of simulation techniques developed that correlate to and build upon microstructural information. Nevertheless, a true nexus between microscopy and atomistic simulations is lacking. Atom probe has emerged as a potential means of achieving this goal. Atom probe generates three-dimensional atomistic images in a format almost identical to many atomistic simulations. However, this data is imperfect, preventing input into computational algorithms to predict material properties. Here we describe a methodology to overcome these limitations, based on a hybrid data format, blending atom probe and predictive Monte Carlo simulations. We create atomically complete and lattice-bound models of material specimens. This hybrid data can then be used as direct input into density functional theory simulations to calculate local energetics and elastic properties. This research demonstrates the role that atom probe combined with theoretical approaches can play in modern materials engineering.

A new systematic framework for crystallographic analysis of atom probe data

In this article, after a brief introduction to the principles behind atom probe crystallography, we introduce methods for unambiguously determining the presence of crystal planes within atom probe datasets, as well as their characteristics: location; orientation and interplanar spacing. These methods, which we refer to as plane orientation extraction (POE) and local crystallography mapping (LCM) make use of real-space data and allow for systematic analyses. We present here application of POE and LCM to datasets of pure Al, industrial aluminium alloys and doped-silicon. Data was collected both in DC voltage mode and laser-assisted mode (in the latter of which extracting crystallographic information is known to be more difficult due to distortions). The nature of the atomic planes in both datasets was extracted and analysed.

An automated method of quantifying ferrite microstructures using electron backscatter diffraction (EBSD) data

The identification and quantification of the different ferrite microconstituents in steels has long been a major challenge for metallurgists. Manual point counting from images obtained by optical and scanning electron microscopy (SEM) is commonly used for this purpose. While classification systems exist, the complexity of steel microstructures means that identifying and quantifying these phases is still a great challenge. Moreover, point counting is extremely tedious, time consuming, and subject to operator bias. This paper presents a new automated identification and quantification technique for the characterisation of complex ferrite microstructures by electron backscatter diffraction (EBSD). This technique takes advantage of the fact that different classes of ferrite exhibit preferential grain boundary misorientations, aspect ratios and mean misorientation, all of which can be detected using current EBSD software. These characteristics are set as criteria for identification and linked to grain size to determine the area fractions. The results of this method were evaluated by comparing the new automated technique with point counting results. The technique could easily be applied to a range of other steel microstructures.

Overcoming challenges in the study of nitrided microalloyed steels using atom probe

Nitrided steels are widely used in the engineering field due to their superior hardness and other attractive properties. Atom probe tomography (APT) was employed to study two Nb-microalloyed CASTRIP steels with different N contents. A major challenge of using APT to study this group of materials is the presence of tails after Fe peaks in the mass spectra, which overestimates the composition for alloying elements such as Nb and Cu in the steels. One important factor that contributes to the tails is believed to be delayed field evaporation from Fe²⁺. This artefact of the mass spectrum was observed to be the most severe when voltage pulsing was used. The application of laser pulses with energy ranging from 0.2 to 1.2 nJ successfully reduced the tails and lead to better compositional measurement accuracy. Spatial resolution in the z-direction (along the tip direction) was observed to be less affected by changing laser energy but deteriorates in x-y direction with increasing laser energy. This investigation suggests that pulsed-laser atom probe with ∼0.4 nJ laser energy can be used to study this group of materials with improved mass resolution while still maintaining high spatial resolution.

Linking stress-driven microstructural evolution in nanocrystalline aluminium with grain boundary doping of oxygen

The large fraction of material residing at grain boundaries in nanocrystalline metals and alloys is responsible for their ultrahigh strength, but also undesirable microstructural instability under thermal and mechanical loads. However, the underlying mechanism of stress-driven microstructural evolution is still poorly understood and precludes rational alloy design. Here we combine quantitative in situ electron microscopy with three-dimensional atom-probe tomography to directly link the mechanics and kinetics of grain boundary migration in nanocrystalline Al films with the excess of O atoms at the boundaries. Site-specific nanoindentation leads to grain growth that is retarded by impurities, and enables quantification of the critical stress for the onset of grain boundary migration. Our results show that a critical excess of impurities is required to stabilize interfaces in nanocrystalline materials against mechanical driving forces, providing new insights to guide control of deformation mechanisms and tailoring of mechanical properties apart from grain size alone.

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.

Correlating Atom Probe Crystallographic Measurements with Transmission Kikuchi Diffraction Data

Correlative microscopy approaches offer synergistic solutions to many research problems. One such combination, that has been studied in limited detail, is the use of atom probe tomography (APT) and transmission Kikuchi diffraction (TKD) on the same tip specimen. By combining these two powerful microscopy techniques, the microstructure of important engineering alloys can be studied in greater detail. For the first time, the accuracy of crystallographic measurements made using APT will be independently verified using TKD. Experimental data from two atom probe tips, one a nanocrystalline Al-0.5Ag alloy specimen collected on a straight flight-path atom probe and the other a high purity Mo specimen collected on a reflectron-fitted instrument, will be compared. We find that the average minimum misorientation angle, calculated from calibrated atom probe reconstructions with two different pole combinations, deviate 0.7° and 1.4°, respectively, from the TKD results. The type of atom probe and experimental conditions appear to have some impact on this accuracy and the reconstruction and measurement procedures are likely to contribute further to degradation in angular resolution. The challenges and implications of this correlative approach will also be discussed.

Restoring the lattice of Si-based atom probe reconstructions for enhanced information on dopant positioning.

The following manuscript presents a novel approach for creating lattice based models of Sb-doped Si directly from atom probe reconstructions for the purposes of improving information on dopant positioning and directly informing quantum mechanics based materials modeling approaches. Sophisticated crystallographic analysis techniques are used to detect latent crystal structure within the atom probe reconstructions with unprecedented accuracy. A distortion correction algorithm is then developed to precisely calibrate the detected crystal structure to the theoretically known diamond cubic lattice. The reconstructed atoms are then positioned on their most likely lattice positions. Simulations are then used to determine the accuracy of such an approach and show that improvements to short-range order measurements are possible for noise levels and detector efficiencies comparable with experimentally collected atom probe data.

Resolving the Morphology of Niobium Carbonitride Nano-Precipitates in Steel Using Atom Probe Tomography

Atom probe is a powerful technique for studying the composition of nano-precipitates, but their morphology within the reconstructed data is distorted due to the so-called local magnification effect. A new technique has been developed to mitigate this limitation by characterizing the distribution of the surrounding matrix atoms, rather than those contained within the nano-precipitates themselves. A comprehensive chemical analysis enables further information on size and chemistry to be obtained. The method enables new insight into the morphology and chemistry of niobium carbonitride nano-precipitates within ferrite for a series of Nb-microalloyed ultra-thin cast strip steels. The results are supported by complementary high-resolution transmission electron microscopy.