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We report on comparative atom probe tomography investigations of I³/I³â�²-forming Co-12Ti-4Mo-Cr alloys. Moderate additions of Cr (2 and 4 at) reduced the I³/I³â�² lattice misfit and increased the I³â�² volume fraction of a Co-12Ti-4Mo alloy significantly. These microstructural changes were accompanied by changes in the elemental partitioning between I³ and I³â�² and site-occupancy in I³â�². Spatial distribution maps revealed that Mo occupied both Co and Ti sub-lattice sites in I³â�². In agreement with the experimental data, thermodynamic calculations predicted a stronger tendency for Mo to occupy the Co-sites than for Cr and an increase in Cr fraction on the Ti-sites with increasing Cr content. Copyright © The Author(s), 2021. Published by Cambridge University Press on behalf of the Microscopy Society of America.

Bimetallic nanoparticles are often superior candidates for a wide range of technological and biomedical applications owing to their enhanced catalytic, optical, and magnetic properties, which are often better than their monometallic counterparts. Most of their properties strongly depend on their chemical composition, crystallographic structure, and phase distribution. However, little is known of how their crystal structure, on the nanoscale, transforms over time at elevated temperatures, even though this knowledge is highly relevant in case nanoparticles are used in, e.g., high-temperature catalysis. Au-Fe is a promising bimetallic system where the low-cost and magnetic Fe is combined with catalytically active and plasmonic Au. Here, we report on the in situ temporal evolution of the crystalline ordering in Au-Fe nanoparticles, obtained from a modern laser ablation in liquids synthesis. Our in-depth analysis, complemented by dedicated atomistic simulations, includes a detailed structural characterization by X-ray diffraction and transmission electron microscopy as well as atom probe tomography to reveal elemental distributions down to a single atom resolution. We show that the Au-Fe nanoparticles initially exhibit highly complex internal nested nanostructures with a wide range of compositions, phase distributions, and size-depended microstrains. The elevated temperature induces a diffusion-controlled recrystallization and phase merging, resulting in the formation of a single face-centered-cubic ultrastructure in contact with a body-centered cubic phase, which demonstrates the metastability of these structures. Uncovering these unique nanostructures with nested features could be highly attractive from a fundamental viewpoint as they could give further insights into the nanoparticle formation mechanism under non-equilibrium conditions. Furthermore, the in situ evaluation of the crystal structure changes upon heating is potentially relevant for high-temperature process utilization of bimetallic nanoparticles, e.g., during catalysis.

Laser surface remelting can be used to manipulate the microstructure of cast material. Here, we present a detailed analysis of the microstructure of Fe$_2$VAl following laser surface remelting. Within the melt pool, elongated grains grow nearly epitaxially from the heat-affected zone. These grains are separated by low-angle grain boundaries with 1{\deg}-5{\deg} misorientations. Segregation of vanadium, carbon, and nitrogen at grain boundaries and dislocations is observed using atom probe tomography. The local electrical resistivity was measured by an in-situ four-point-probe technique. A smaller increase in electrical resistivity is observed at these low-angle grain boundaries compared to high-angle grain boundaries in a cast sample. This indicates that grain boundary engineering could potentially be used to manipulate thermoelectric properties.

Recently 1:12 magnets of Sm-(Fe,V) have shown promising coercivities and the potential to be alternative rare-earth-lean permanent magnets. In this work, we investigated the effects of partial substitution of Cu, Mo and Ti for V in the magnets prepared by hot compaction and hot deformation of mechanically milled powders. The microstructure of the Sm-Fe-(V,Cu) and Sm-Fe-(V,Ti) hot-deformed magnets consisted in fine grains with sizes between 50 and 150 nm. The Sm-Fe-(V,Cu) magnet showed the best performance with μ0H c = 0.96 T, μ0M r = 0.49 T, (BH) max = 42 kJ m − 3 and T C = 362 ∘ C. Atom probe tomography of this magnet revealed the presence of a thin Sm17.5Fe71.5V8Cu3intergranular phase of 3-6 nm surrounding the 1:12 nanograins. The addition of a small amount of Cu, not only improved the magnetic properties but also hindered the grain growth during hot deformation. Micromagnetic simulations of the magnetization reversal agreed with the experimental values of coercivity. The presence of the intergranular phase reduces the number of grains that switch simultaneously.

Nano-oxide precipitates in a modern nanostructured ferritic alloy were investigated after extreme thermomechanical processing into a thin-walled tube geometry. It was found that the morphology of the precipitates changed from spherical to rod-shaped, with some increasing to aspect ratios of up to 9, despite the precipitate volume fraction (0.3%) and number density (> 1023 m−3) of precipitates remaining unchanged. High-resolution electron microscopy showed that the precipitates likely remained coherent with the Fe-matrix, while atom probe tomography confirmed that the precipitate compositions remained unaffected by the transformation. The morphological change was attributed to the shearable nature of the (Y,Ti,O)-rich precipitates, indicating they should be considered as “soft” obstacles to dislocation motion. The elongation was most pronounced in larger (>5 nm) precipitates, which may be caused by preferential dissolution of the smallest (1–3 nm) precipitates followed by the competition between re-precipitation and solute diffusion to larger precipitates during recovery heat treatments.

The solute partitioning under dynamic strain-induced austenite reversion in a Fe-11Mn-1Al-0.07C (in wt.%) steel was studied by atom probe tomography. It was found that the concentrations of Mn and Al fluctuate in austenite at the nanoscale during warm deformation at 650 °C, leading to less stable chemical zones. It is proposed that stored energy in ferrite can change the thermodynamic equilibrium, leading to the formation of austenite with lower Mn and higher Al contents. This paper reveals evidence that stored strain can deviate the thermodynamic equilibrium, and hence could be a new path for engineering the nanostructures in austenite.

Quantifying chemical compositions around nanovoids is a fundamental task for research and development of various materials. Atom probe tomography (APT) and scanning transmission electron microscopy (STEM) are currently the most suitable tools because of their ability to probe materials at the nanoscale. Both techniques have limitations, particularly APT, because of insufficient understanding of void imaging. Here, we employ a correlative APT and STEM approach to investigate the APT imaging process and reveal that voids can lead to either an increase or a decrease in local atomic densities in the APT reconstruction. Simulated APT experiments demonstrate the local density variations near voids are controlled by the unique ring structures as voids open and the different evaporation fields of the surrounding atoms. We provide a general approach for quantifying chemical segregations near voids within an APT dataset, in which the composition can be directly determined with a higher accuracy than STEM-based techniques., Atom probe tomography can image chemical composition at the nanoscale, but our understanding of how it images voids, or empty spaces, is still lacking. Here, the authors combine atom probe tomography, scanning transmission electron microscopy, and field-evaporation theory to show how voids are imaged and subsequently measured.

We investigated the solute diffusional behavior active during compressive creep deformation at 150 MPa / 975 °C of a Co-Al-W-Ta single crystal superalloy in the [001] orientation. We report the formation of shear-bands that involves re-orientation of γ/γʹ rafts to {111} from {001} planes, referring to as γ/γ′ raft-rotation. In the shear-band regions, we observed abundant micro-twins, stacking faults (SFs), disordered zones within the γʹ termed as ‘γ pockets’ and also few geometrically-close-packed (GCP) phases. We used a correlative approach blending electron microscopy and atom probe tomography to characterize the structure and composition of these features. The SFs were identified as intrinsic and exhibit a W enrichment up to 14.5 at.% and an Al deficiency down to 5.1 at.%, with respect to the surrounding γʹ phase. The micro-twin boundaries show a solute enrichment similar to the SFs with a distinct W compositional profile gradients perpendicular from the boundaries into the twin interior, indicating solute diffusion within the micro-twins. The γ-pockets have a composition close to that of γ but richer in W/Ta. Based on these observations, we propose (i) a solute diffusion mechanism taking place during micro-twinning, (ii) a mechanism for the γ/γʹ raft-rotation process and evaluate their influence on the overall creep deformation of the present Co-based superalloy.

The population of all non-equilibrium lattice defects in materials is referred to as microstructure. Examples are point defects such as substitutional and interstitial atoms, and vacancies; line defects such as dislocations; planar defects such as interfaces and stacking faults; or mesoscopic defects such as second-phase precipitates. These types of lattice imperfections are usually described in terms of their structural features, breaking the periodicity of the otherwise regular crystalline structure. Recent analytical probing at the nanoscale has revealed that their chemical features are likewise important and characteristic. The structure of the defects as well as their individual chemical composition, that is their chemical decoration state, which results from elemental partitioning with the adjacent matrix, can significantly influence the electrical and thermal transport properties of thermoelectric materials. The emergence of atom probe tomography (APT) has now made routinely accessible the mapping of three-dimensional chemical composition with sub-nanometer spatial accuracy and elemental sensitivity in the range of tens of ppm. Here, we review APT-based investigations and results related to the local chemical decoration states of various types of lattice defects in thermoelectric materials. APT allows to better understand the interplay between thermoelectric properties and microstructural features, extending the concept of defect engineering to the field of segregation engineering so as to guide the rational design of high-performance thermoelectric materials.

Imaging individual vacancies in solids and revealing their interactions with solute atoms remains one of the frontiers in microscopy and microanalysis. Here we study a creep-deformed binary Ni-2 at.% Ta alloy. Atom probe tomography reveals a random distribution of Ta. Field ion microscopy, with contrast interpretation supported by density-functional theory and time-of-flight mass spectrometry, evidences a positive correlation of tantalum with vacancies. Our results support solute-vacancy binding, which explains improvement in creep resistance of Ta-containing Ni-based superalloys and helps guide future material design strategies., Submitted to Physics Review Letter

The local variation of grain boundary atomic structure and chemistry caused by segregation of impurities influences the macroscopic properties of polycrystalline materials. Here, the effect of co-segregation of carbon and boron on the depletion of aluminum at a Σ5 (3 1 0 )[0 0 1] tilt grain boundary in a α − Fe-4 at%Al bicrystal is studied by combining atomic resolution scanning transmission electron microscopy, atom probe tomography and density functional theory calculations. The atomic grain boundary structural units mostly resemble kite-type motifs and the structure appears disrupted by atomic scale defects. Atom probe tomography reveals that carbon and boron impurities are co-segregating to the grain boundary reaching levels of >1.5 at%, whereas aluminum is locally depleted by approx. 2 at.%. First-principles calculations indicate that carbon and boron exhibit the strongest segregation tendency and their repulsive interaction with aluminum promotes its depletion from the grain boundary. It is also predicted that substitutional segregation of boron atoms may contribute to local distortions of the kite-type structural units. These results suggest that the co-segregation and interaction of interstitial impurities with substitutional solutes strongly influences grain boundary composition and with this the properties of the interface., The local variation of grain boundary atomic structure and chemistry caused by segregation of impurities influences the macroscopic properties of polycrystalline materials. Here, the effect of co-segregation of carbon and boron on the depletion of aluminum in a α − Fe grain boundary is shown.

Three-dimensional field ion microscopy is a powerful technique to analyze material at a truly atomic scale. Most previous studies have been made on pure, crystalline materials such as tungsten or iron. In this article, we study more complex materials, and we present the first images of an amorphous sample, showing the capability to visualize the compositional fluctuations compatible with theoretical medium order in a metallic glass (FeBSi), which is extremely challenging to observe directly using other microscopy techniques. The intensity of the spots of the atoms at the moment of field evaporation in a field ion micrograph can be used as a proxy for identifying the elemental identity of the imaged atoms. By exploiting the elemental identification and positioning information from field ion images, we show the capability of this technique to provide imaging of recrystallized phases in the annealed sample with a superior spatial resolution compared with atom probe tomography.

The grain boundary (GB) microchemistry and precipitation behaviour in high-strength Al-Zn-Mg-Cu alloys has an important influence on their mechanical and electrochemical properties. Simulation of the GB segregation, precipitation, and solute distribution in these alloys requires an accurate description of the thermodynamics and kinetics of this multi-component system. CALPHAD databases have been successfully developed for equilibrium thermodynamic calculations in complex multi-component systems, and in recent years have been combined with diffusion simulations. In this work, we have directly incorporated a CALPHAD database into a phase-field framework, to simulate, with high fidelity, the complex kinetics of the non-equilibrium GB microstructures that develop in these important commercial alloys during heat treatment. In particular, the influence of GB solute segregation, GB diffusion, precipitate number density, and far-field matrix composition, on the growth of a population of GB η-precipitates, was systematically investigated in a model Al-Zn-Mg-Cu alloy of near AA7050 composition. It is shown that the GB solute distribution in the early stages of ageing was highly heterogeneous and strongly affected by the distribution of GB η-precipitates. Significant Mg and Cu GB segregation was predicted to remain during overageing, while Zn was rapidly depleted. This non-trivial GB segregation behaviour markedly influenced the resulting precipitate morphologies, but the overall precipitate transformation kinetics on a GB were relatively unaffected. Furthermore, solute depletion adjacent to the GB was largely determined by Zn and Mg diffusion, which will affect the development of precipitate free zones during the early stages of ageing. The simulation results were compared with scanning transmission electron microscopy and atom probe tomography characterisation of alloys of the similar composition, with good agreement.

Atom probe tomography (APT) provides three-dimensional compositional mapping with sub-nanometre resolution. The sensitivity of APT is in the range of parts per million for all elements, including light elements such as hydrogen, carbon or lithium, enabling unique insights into the composition of performance-enhancing or lifetime-limiting microstructural features and making APT ideally suited to complement electron-based or X-ray-based microscopies and spectroscopies. Here, we provide an introductory overview of APT ranging from its inception as an evolution of field ion microscopy to the most recent developments in specimen preparation, including for nanomaterials. We touch on data reconstruction, analysis and various applications, including in the geosciences and the burgeoning biological sciences. We review the underpinnings of APT performance and discuss both strengths and limitations of APT, including how the community can improve on current shortcomings. Finally, we look forwards to true atomic-scale tomography with the ability to measure the isotopic identity and spatial coordinates of every atom in an ever wider range of materials through new specimen preparation routes, novel laser pulsing and detector technologies, and full interoperability with complementary microscopy techniques. This Primer on atom probe tomography introduces the fundamentals of the technique and its experimental set-up, describes recent developments in specimen preparation, highlights aspects of data reconstruction and analysis, and showcases various applications of atom probe tomography in the materials sciences, geosciences and biological sciences.

The longevity of a lithium-ion battery is limited by cathode degradation. Combining atom probe tomography and scanning transmission electron microscopy reveals that the degradation results from atomic-scale irreversible structural changes once lithium leaves the cathode during charging, thereby inhibiting lithium intercalation back into the cathode as the battery discharges. This information unveils possible routes for improving the lifetime of lithium-ion batteries.

International audience; We have investigated the partitioning of solutes at crystal defects in intergranular Cr-rich M2B borides after creep at 850°C/185MPa and annealing at 850°C for approximately 3000 hours in a polycrystalline nickel-based superalloy. Borides were found to coarsen in both cases, with the borides after creep to be the thickest (800-1100nm), compared to borides annealed in the absence of external applied load (400-600nm). Transmission electron microscopy revealed that the coarsened borides have either a tetragonal I4/mcm structure, or an orthorhombic Fddd, with those two structures coexisting in a single particle. The presence of a very high density of planar faults is systematically 2 observed within the coarsened borides. The faults were correlated with chemical fluctuations of B and Cr, revealed by atom probe tomography. In addition, partitioning of Ni and Co was observed at dislocations within the borides after creep providing insights into the deformation of borides.

Partitioning of C during tempering of quenched Fe-9.6Ni-0.5C-0.6Mn-0.6Mo-0.7Cr-0.1V (at.%) steel is determined by atom probe tomography and the resulting microstructure is described. The precipitated austenite size, together with its C and Ni content control its thermal stability and these can vary differently with tempering time and temperature. Thus, both austenite and strong carbide formers compete for the available C early in the process. Due to widely different transport kinetics, C likely plays a dominant role early but is either fully consumed or its role diminishes by dilution, and Ni partitioning eventually takes over as the austenite stability-controlling species.

Elemental segregation to grain boundaries (GBs) can induce structural and chemical transitions at GBs along with significant changes in material properties. The presence of multiple principal elements interacting in high-entropy alloys (HEAs) makes the GB segregation and interfacial phase transformation a rather challenging subject to investigate. Here, we explored the temporal evolution of the chemistry for general high-angle GBs in a typical equiatomic FeMnNiCoCr HEA during aging heat treatment through detailed atom probe tomography (APT) analysis. We found that the five principal elements segregate heterogeneously at the GBs. More specifically, Ni and Mn co-segregate to some regions of the GBs along with the depletion of Fe, Co and Cr, while Cr is enriched in other regions of the GBs where Ni and Mn are depleted. The redistribution of these elements on the GBs follow a periodic characteristic, spinodal-like compositional modulation. The accumulation of elements at the GBs can create local compositions by shifting their state from a solid solution (like in the adjacent bulk region) into a spinodal regime to promote interfacial phase-like transitions as segregation proceeds. These results not only shed light on phase precursor states and the associated nucleation mechanism at GBs in alloy systems with multiple principal elements but also help to guide the microstructure design of advanced HEAs in which formation of embrittling phases at interfaces must be avoided.

The successful development of advanced materials such as nanostructured ferritic alloys (NFA) for next generation nuclear reactor concepts and ultra-supercritical steam power plants requires information on long term thermal creep. To support this initiative, this work examines the NFA MA957 (Fe-14Cr-1.0Ti-0.3Mo + 0.3Y2O3 in wt%) crept to 61,251 h at 825 °C and 70 MPa, the longest creep test available to date for this material. Using atom probe tomography and electron microscopy, it is shown that the grain size and nanoprecipitate size/composition are unaffected following this 7 yr creep test, although significant porosity is noted throughout the microstructure attributed to microvoid coalescence and growth.

Fast reactor fuel cladding candidate materials require proficiency in extreme environments consisting of high temperatures and irradiation doses in excess of 150 displacements per atom (dpa). Nanostructured oxide dispersion strengthened (ODS) alloys have been developed extensively for this purpose due to their notable high temperature strength, creep resistance, and irradiation resistance. However, their properties can deteriorate if interstitial impurities such as C and N are not well controlled during the fabrication process. A new Fe-12Cr nanostructured ODS alloy OFRAC ( O ak Ridge F ast R eactor A dvanced Fuel C ladding) with solute additions of Mo, Ti, and Nb has been developed to provide the desired properties mentioned above while simultaneously sequestering impurities within the matrix. After extrusion at 850 °C, the as-extruded microstructure consists of an average 490 nm grain size and a high number density (6.8 × 1023 m-3) of 2.2 nm diameter (Y,Ti,O) nanoclusters distributed homogeneously in the matrix. Atom probe tomography investigations suggest non-stochiometric compositions for the smallest nanoclusters. In addition, a second population of nanometer scale (Nb,Ti) rich carbonitrides is also present in the microstructure that captures the potentially detrimental C and N impurity atoms present in the matrix. Atom probe tomography results indicate elemental segregation of Cr, Mo, and Nb to grain boundaries in the as-extruded material, consistent with previous investigations of solid solution strengthening by solute additions. The ability of OFRAC to sequester impurities introduced from the powder metallurgical approach to nanostructured ferritic alloy development, compounded with its beneficial mechanical properties, makes this alloy a competitive candidate for fast reactor applications. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).

We introduce a new perspective on the classical massive mode of solid-state phase transformation enabled by the correlative use of atomic-scale electron microscopy and atom probe tomography. This is demonstrated in a binary MnAl alloy which has Heusler-like characteristics. In this system, the τ phase formed by a massive transformation from the high-temperature e phase is metastable and ferromagnetic. The transformation results in a high density of micro-twins inside the newly grown τ phase. Atomic-scale compositional analysis across the interface boundaries and atomic structure of the micro-twins reveals the involvement of both structural modification and also the compositional partitioning during the growth of the τ phase. This is assisted by the migrating τ/e interface boundary during transformation. Finally, the role of micro-twins on nucleating the equilibrium phases and the influence of the defects and phase formation on the magnetic properties are discussed.

We explore the effects of the elemental site occupancy in γ′-A3B (L12) intermetallic phases and their partitioning across the γ/γ′ interface in a class of multicomponent W-free Co-based superalloys. Atom probe tomography and first principles density functional theory calculations (DFT) were used to evaluate the Cr site occupancy behavior in the γ′ phase and its effect on the γ/γ′ partitioning behavior of other solutes in a series of Co-30Ni-10Al-5Mo-2Ta-2Ti-XCr alloys, where x is 0, 2, 5, and 8 at.% Cr, respectively. The increase in Cr content from 0 to 2 to 5 at.% leads to an inversion of the partitioning behavior of the solute Mo from the γ′ phase ( K M o > 1 ) into the γ matrix ( K M o 1 ) . At 5 at.% Cr, the Cr also has a preference to replace the excess anti-site Co atoms from the B-sites. At 8 at.% Cr, the Cr develops an additional preference to replace Co atoms from the A-sites. These compositional changes in the phases and the site partitioning behavior in the γ′ phase are accompanied by an overall decrease in the lattice misfit (δ) across the γ/γ′ interfaces as measured by high-resolution X-ray diffraction at room temperature. The reduction in misfit triggers a change in morphology of the γ′ phase from cuboidal (δ ∼ +0.48% at 0 at.% Cr) to round-cornered (δ ∼ +0.34% at 5 at.% Cr) to spheroidal shaped (δ ∼ +0.19% at 8 at.% Cr) precipitates. We also observed an increase in the solvus temperature from 1066 °C to 1105 °C when adding 5 at.% Cr to the alloy. These results on the effects of Cr in Co-base superalloys enable tuning the microstructure of these alloys and widening the alloy spectrum for designing improved high temperature alloys.

Atom probe tomography is often introduced as providing "atomic-scale" mapping of the composition of materials and as such is often exploited to analyse atomic neighbourhoods within a material. Yet quantifying the actual spatial performance of the technique in a general case remains challenging, as they depend on the material system being investigated as well as on the specimen's geometry. Here, by using comparisons with field-ion microscopy experiments and field-ion imaging and field evaporation simulations, we provide the basis for a critical reflection on the spatial performance of atom probe tomography in the analysis of pure metals, low alloyed systems and concentrated solid solutions (i.e. akin to high-entropy alloys). The spatial resolution imposes strong limitations on the possible interpretation of measured atomic neighbourhoods, and directional neighbourhood analyses restricted to the depth are expected to be more robust. We hope this work gets the community to reflect on its practices, in the same way, it got us to reflect on our work., Submitted to Microscopy & Microanalysis to be part of the special issue assocaited to the APT&M 2020 conference

The long-term safety of water-based nuclear reactors relies in part on the reliability of zirconium-based nuclear fuel cladding. Yet the progressive ingress of hydrogen during service makes zirconium alloys subject to delayed hydride cracking. Here, we use a combination of electron back-scattered diffraction and atom probe tomography to investigate specific microstructural features from the as-received sample and in the blocky-α microstructure, before and after electrochemical charging with hydrogen/deuterium followed by a low temperature heat treatment at 400 °C for 5 h followed by furnace cooling at a rate of 0.5 °C/min. Specimens for atom probe were prepared at cryogenic temperature to avoid the formation of spurious hydrides. We report on the compositional evolution of grains and grain boundaries over the course of the sample's thermal history, as well as the ways the growth of the hydrides modifies locally the composition and the structure of the alloy. We observe a significant amount of deuterium left in the matrix, even after the slow cooling and growth of the hydrides. Stacking faults form ahead of the growth front and the segregation of Sn at the hydride/matrix interface and on these faults. We propose that this segregation may facilitate further growth of the hydride. Our systematic investigation enables us discuss how the solute distribution affects the evolution of the alloy's properties during its service lifetime.

Analyzing porous (nano)materials via atom probe tomography has been notoriously difficult. Voids and pores act as concentrators of the electrostatic pressure, which results in premature specimen failure, and the electrostatic field distribution near voids leads to aberrations that are difficult to predict. In this study, we propose a new encapsulating method for porous samples using a low melting point Bi–In–Sn alloy, known as Field's metal. As a model material, we used porous iron made by direct-hydrogen reduction of single-crystalline wüstite. The complete encapsulation was performed using in situ heating on the stage of a scanning electron microscope. No visible corrosion nor dissolution of the sample occurred. Subsequently, specimens were shaped by focused ion-beam milling under cryogenic conditions at −190°C. The proposed approach is versatile and can be applied to provide good quality atom probe datasets from micro/nanoporous materials.

Atom probe tomography (APT) helps elucidate the link between the nanoscale chemical variations and physical properties, but it has limited structural resolution. Field ion microscopy (FIM), a predecessor technique to APT, is capable of attaining atomic resolution along certain sets of crystallographic planes albeit at the expense of elemental identification. We demonstrate how two commercially-available atom probe instruments, one with a straight flight path and one fitted with a reflectron-lens, can be used to acquire time-of-flight mass spectrometry data concomitant with a FIM experiment. We outline various experimental protocols making use of temporal and spatial correlations to best discriminate field evaporated signals from the large field ionised background signal, demonstrating an unsophisticated yet efficient data mining strategy to provide this discrimination. We discuss the remaining experimental challenges that need be addressed, notably concerned with accurate detection and identification of individual field evaporated ions contained within the high field ionised flux that contributes to a FIM image. Our hybrid experimental approach can, in principle, exhibit true atomic resolution with elemental discrimination capabilities, neither of which atom probe nor field ion microscopy can individually fully deliver - thereby making this new approach, here broadly termed analytical field ion microscope (aFIM), unique., Comment: 20 pages, 10 figures

The size, distribution and chemical composition of grain boundary η-phase precipitates (GBPs) and micro-segregation present in thick plate (140 mm) 7xxx Al alloys has been quantified across a range of length scales. To address the known limitations of individual characterisation methods, a number of cross-correlated, high resolution techniques have been used, including atom probe tomography (APT). A new-generation high-Zn alloy (AA7085) has been compared to a more established material, AA7050, in T7651 temper conditions. The results show that high angle grain boundaries in both alloys are dominated by quench-induced GBPs (Q-GBPs), covering up to ~40% of the area in AA7050. When viewed on brittle intergranular fracture surfaces and in 3D, the Q-GBPs appear much larger than previously reported and exhibit complex branched, dendritic-like morphologies. In AA7050, the Q-GBPs contain substantially higher levels of Cu (by 29 %) and Al (by 37%) and lower Zn (by 33 %) than AA7085. Classical modelling demonstrates that these differences result from different transformation pathways, with precipitates in the more quench sensitive AA7050 alloy nucleating at higher temperatures, which exaggerates the effect of alloy chemistry. In both alloys GB segregation was limited, with low levels of Zn detected relative to the matrix, but more Mg and less Cu in AA7050. It is, therefore, proposed that the higher Cu and Al, and lower Zn content, of the large Q-GBPs present in AA7050 is the main difference in GB microchemistry between the two materials and is the primary reason its GBs are less chemically active. The implications for the relative susceptibilities of the alloys to environmentally assisted cracking are briefly discussed.

International audience; Nd2Fe14B-type materials exhibit the highest energy product around room temperature and hence dominate the high-performance permanent magnet market. Intensive research efforts aim at alternative material systems containing less critical elements with similar or better magnetic properties. Nd-and Sm-based compounds with a ThMn12-type structure exhibit intrinsic properties comparable or even superior to Nd2Fe14B. However, it has not been possible to achieve technically relevant coercivity and remanent magnetization in ThMn12-based bulk sintered magnets. Using SmFe11Ti as a prototypical representative, we demonstrate that one important reason for the poor performance is the formation of twins inside micro-crystalline grains. The nature of the twins in SmFe11Ti was investigated in twinned "single crystals" and both bulk and thin film poly-crystalline samples, using advanced electron microscopy and atom probe tomography as well as simulations and compared with benchmark Nd2Fe14B. Both micro-twins and nano-twins show a twin orientation of 57±2 • and an enrichment in Sm, which could affect domain wall motion in this 2 material. Micromagnetic simulations indicate that twins act as nucleation centers, representing the magnetically weakest link in the microstructure. The relation between twin formation energies and geometrical features are briefly discussed using molecular dynamic simulations.

The mechanism of inverse precipitation of γ-like shells forming around primary γ' leading to heteroepitaxial recrystallization after thermomechanical processing was studied. The wrought nickel-based AD730™ alloy was subjected to a sub-solvus heat treatment at 1050°C and cooled at 5°C/min in order to form heteroepitaxial γ-like shells on primary γ'. Electron backscattered diffraction analysis confirmed no measurable crystal misorientation between the γ-like shells and primary γ'. Atom probe tomography revealed segregation of Cr, Co and Fe at dislocations within the primary γ', while the γ-like shell was found enriched in these solutes compared to the γ matrix. A mechanism rationalizing the inverse precipitation of γ-like shells is proposed aiming to better understand the nucleation process of heteroepitaxial recrystallization in polycrystalline Ni-based superalloys.

Segregation to grain boundaries affects their cohesion, corrosion and embrittlement and plays a critical role in heterogeneous nucleation. In order to quantitatively study segregation and phase separation at grain boundaries, we derive a density-based phase-field model. In this model, we describe the grain boundary free energy based on available bulk thermodynamic data while an atomic grain boundary density is obtained using atomistic simulations. To benchmark the performance of the model, we study Mn grain boundary segregation in the Fe--Mn system. 3D simulation results are compared against atom probe tomography measurements. We show that a continuous increase in the alloy composition results in a discontinuous jump in the Mn grain boundary segregation. This jump corresponds to an interfacial spinodal phase separation. For alloy compositions above the interfacial spinodal, we found a transient spinodal phase separation phenomenon which opens opportunities for knowledge-based microstructure design through the chemical manipulation of grain boundaries. The proposed density-based model provides a powerful tool to study thermodynamics and kinetics of segregation and phase separation at grain boundaries., 36 Pages, 8 Figures, Full paper &Supplementary Information, 85 References

International audience; Fe2VAl exhibits promising properties for thermoelectric applications. Here, we investigated the microstructure of melt spun Fe2VAl using electron microscopy, atom probe tomography and field ion microscopy. We observe platelet-shaped VCxNy precipitates in the vicinity of antiphase boundaries (APB) oriented along the {010}-plane. The mean distance between these precipitates is (140 ± 40) nm. This distance is shorter than the mean free phonon path at room temperature in Fe2VAl, thus, these VCxNy precipitates, combined with the APB may efficiently lower the thermal conductivity of the alloy.

International audience; Crack initiation mechanisms in the very high cycle fatigue (VHCF) regime of nickel-based single-crystal (SX) superalloys have been investigated at high temperature (1000 °C) and under fully reversed conditions (R = −1). For all Ni-based SX alloys tested, a discernible area called rough zone has been identified around the crack initiation site on the fracture surface and is for the first time described. By means of electron microscopy and atom probe analyses, localized and severe plastic activity occurring in the rough zone is evidenced. The high dislocation density provided by the slip bands induces single-phase recrystallized grains and phases precipitation (intermetallics or carbides) via the redistribution of interacting solutes in the rough zone. A crack initiation mechanism based on these observations and on the stress intensity parameter determined around the rough zone – which has been demonstrated to be a constant threshold dependent on the material – is finally proposed.

In recent years, increasing developments in microscopy and microanalysis have allowed for the direct observation of nanoscale crystalline defects (i.e. dislocations). These defects are particularly important in naturally deformed materials yet this avenue of research remains understudied within the Earth Sciences. Dislocations can now be documented through the use of new and innovative structural and chemical analytical techniques such as electron channeling contrast imaging (ECCI), transmission electron microscopy, and atom probe tomography (APT). The presence and migration of dislocations in crystalline materials, including their role in trace element mobility, play a vital function in the way these materials respond to an applied stress. However, the mechanisms by which dislocations nucleate in minerals remain poorly understood. Prevailing models for dislocation nucleation include generation by Frank-Read sources, stress localization at crack-tips, atomic segregation, and free surface nucleation by critical stress-gradient criterion. Based on recent APT data from naturally-deformed pyrite, combined with electron backscatter diffraction (EBSD) mapping and ECC imaging, we propose a new nucleation mechanism where dislocations are generated by the local stress field in the vicinity of fluid inclusions. The investigated sample consists of a polycrystalline pyrite aggregate within a black shale host rock that has witnessed a peak temperature of 300°C. The combined EBSD and ECCI results reveal crystal plasticity in the form of lattice misorientation up to 8.5° and low-angle grain boundary development. APT data reveals nanoscale fluid inclusions enriched in As, O (H2O), Na and K as well as As- and Co-rich dislocations linked by fluid inclusions. This new model is the first documentation with APT methods of fluid inclusions (voids) in minerals, nanoscale features that are commonly misinterpreted as element clusters or chemically-enriched crystal-defects. The combined data has significant trans-disciplinary implications to the geosciences (structural geology, geochemistry, economic geology, geochronology), the material sciences (metals, ceramics, polymers), and analytical microscopy. Within geochronology voids and dislocations such as these in dated minerals may host elements or isotopes that negatively affect their age. Within ore deposit geology, voids in precious metal-hosting minerals may act as the necessary traps to structurally prevent the metals (gold, silver, copper) from migrating or diffusing out of the host mineral. In material sciences, the presence of such crystalline features can either limit or enhance the performance of engineering materials. Thus, performing APT analysis on crystalline material can help us better understand and predict their physical properties.

The spatial correlation between defects in crystalline materials and trace element segregation plays a fundamental role in determining the physical and mechanical properties of a material, which is particularly important in naturally deformed materials. Herein, we combine electron backscatter diffraction, electron channelling contrast imaging, scanning transmission electron microscopy and atom probe tomography on a naturally occurring metal sulphide in an attempt to document mechanisms of element segregation in a brittle-dominated deformation regime. Within APT reconstructions, features with a high point density comprising O-rich discs stacked over As-rich spherules are observed. The combined microscopy data allow us to interpret these as nanoscale fluid inclusions. Our observations are confirmed by simulated APT experiments of core-shell particles with a core exhibiting a very low evaporation field and the shell emulating a segregated layer at the inclusion interface. Our data has significant trans-disciplinary implications to the geosciences, the material sciences, and analytical microscopy.

Observing solute hydrogen (H) in matter is a formidable challenge, yet, enabling quantitative imaging of H at the atomic-scale is critical to understand its deleterious influence on the mechanical strength of many metallic alloys that has resulted in many catastrophic failures of engineering parts and structures. Here, we report on the APT analysis of hydrogen (H) and deuterium (D) within the nanostructure of an ultra-high strength steel with high resistance to hydrogen embrittlement. Cold drawn, severely deformed pearlitic steel wires (Fe–0.98C–0.31Mn–0.20Si–0.20Cr–0.01Cu–0.006P–0.007S wt%, e = 3.1 ) contains cementite decomposed during the pre-deformation of the alloy and ferrite. We find H and D within the decomposed cementite, and at some interfaces with the surrounding ferrite. To ascertain the origin of the H/D signal obtained in APT, we explored a series of experimental workflows including cryogenic specimen preparation and cryogenic-vacuum transfer from the preparation into a state-of-the-art atom probe. Our study points to the critical role of the preparation, i.e. the possible saturation of H-trapping sites during electrochemical polishing, how these can be alleviated by the use of an outgassing treatment, cryogenic preparation and transfer prior to charging. Accommodation of large amounts of H in the under-stoichiometric carbide likely explains the resistance of pearlite against hydrogen embrittlement.

Single crystal Ni-based superalloys have long been an essential material for gas turbines in aero engines and power plants due to their outstanding high temperature creep, fatigue and oxidation resistance. A turning point was the addition of only 3 wt.% Re in the second generation of single crystal Ni-based superalloys which almost doubled the creep lifetime. Despite the significance of this improvement, the mechanisms underlying the so-called “Re effect” have remained controversial. Here, we provide direct evidence of Re enrichment to crystalline defects formed during creep deformation, using combined transmission electron microscopy, atom probe tomography and phase field modelling. We reveal that Re enriches to partial dislocations and imposes a drag effect on dislocation movement, thus reducing the creep strain rate and thereby improving creep properties. These insights can guide design of better superalloys, a quest which is key to reducing CO2 emissions in air-traffic., Adding minute amounts of rhenium to Ni-based single crystal superalloys extends their high temperature performance in engines, but the reasons behind that are still unclear. Here, the authors combine high resolution imaging and modelling to show that rhenium enriches and slows down partial dislocations to improve creep performance.

PLOS ONE 15(1), e0227920 (2020). doi:10.1371/journal.pone.0227920, Published by PLOS, San Francisco, California, US

We used atom probe tomography to complement electron microscopy for the investigation of spinodal decomposition in alkali feldspar. To this end, gem-quality alkali feldspar of intermediate composition with a mole fraction of $$a_{\text {K}}=0.43$$ a K = 0.43 of the K end-member was prepared from Madagascar orthoclase by ion-exchange with (NaK)Cl molten salt. During subsequent annealing at $$550\,^\circ \hbox {C}$$ 550 ∘ C and close to ambient pressure the ion-exchanged orthoclase unmixed producing a coherent lamellar intergrowth of Na-rich and K-rich lamellae. The chemical separation was completed, and equilibrium Na–K partitioning between the different lamellae was attained within four days, which was followed by microstructural coarsening. After annealing for 4 days, the wavelength of the lamellar microstructure was $$\approx 17\,\hbox {nm}$$ ≈ 17 nm and it increased to $$\approx 30\,\hbox {nm}$$ ≈ 30 nm after annealing for 16 days. The observed equilibrium compositions of the Na-rich and K-rich lamellae are in reasonable agreement with an earlier experimental determination of the coherent solvus. The excess energy associated with compositional gradients at the lamellar interfaces was quantified from the initial wavelength of the lamellar microstructure and the lamellar compositions as obtained from atom probe tomography using the Cahn–Hilliard theory. The capability of atom probe tomography to deliver quantitative chemical compositions at nm resolution opens new perspectives for studying the early stages of exsolution. In particular, it helps to shed light on the phase relations in nm scaled coherent intergrowth.

The $\ensuremath{\alpha}/\ensuremath{\beta}$ interface in Ti-6Al-2Sn-4Zr-6Mo (Ti-6246) was investigated via center of symmetry analysis, both as-grown and after 10% cold work. Semicoherent interface steps are observed at a spacing of $4.5\ifmmode\pm\else\textpm\fi{}1.13$ atoms in the as-grown condition, in good agreement with theory. Lattice accommodation is observed, with elongation along $\mathrm{[}\overline{1}2\overline{1}{0]}_{\ensuremath{\alpha}}$ and contraction along ${[10\overline{1}0]}_{\ensuremath{\alpha}}$. Deformed $\ensuremath{\alpha}$ exhibited larger, less coherent steps with slip bands lying in ${{110}}_{\ensuremath{\beta}}$. This indicates dislocation pile-up at the grain boundary, a precursor to globularization during heat treatment. Atom probe tomography measurements of secondary $\ensuremath{\alpha}$ plates in the fully heat-treated condition showed a Zr excess at the interface, which was localized into regular structures indicative of Zr association with interface defects, such as dislocations. Such chemo-mechanical stabilization of the interface defects would both inhibit plate growth during elevated temperature service and the interaction of interface defects with gliding dislocations during deformation.

The mechanism of inverse precipitation of γ-like shells forming around primary γ' leading to heteroepitaxial recrystallization after thermomechanical processing was studied. The wrought nickel-based AD730™ alloy was subjected to a sub-solvus heat treatment at 1050 o C and cooled at 5 o C/min in order to form heteroepitaxial γ-like shells on primary γ'. Electron backscattered diffraction analysis confirmed no measurable crystal misorientation between the γ-like shells and primary γ'. Atom probe tomography revealed segregation of Cr, Co and Fe at dislocations within the primary γ', while the γ-like shell was found enriched in these solutes compared to the γ matrix. A mechanism rationalizing the inverse precipitation of γ-like shells is proposed aiming to better understand the nucleation process of heteroepitaxial recrystallization in polycrystalline Ni-based superalloys.

Interfaces play critical roles in materials and are usually both structurally and compositionally complex microstructural features. The precise characterization of their nature in three-dimensions at the atomic scale is one of the grand challenges for microscopy and microanalysis, as this information is crucial to establish structure–property relationships. Atom probe tomography is well suited to analyzing the chemistry of interfaces at the nanoscale. However, optimizing such microanalysis of interfaces requires great care in the implementation across all aspects of the technique from specimen preparation to data analysis and ultimately the interpretation of this information. This article provides critical perspectives on key aspects pertaining to spatial resolution limits and the issues with the compositional analysis that can limit the quantification of interface measurements. Here, we use the example of grain boundaries in steels; however, the results are applicable for the characterization of grain boundaries and transformation interfaces in a very wide range of industrially relevant engineering materials.

International audience; Atom probe tomography (APT) is particularly suited for the analysis of nanoscale microstructural features in metallic alloys. APT has become important in the quantitative assessment at high spatial resolution of light elements, which are notoriously difficult to analyze by electron- or X-ray-based techniques. These control the physical properties of high-strength materials and semiconductors. However, the mass spectrometer of state-of-the-art commercial atom probes with the highest spatial precision and detection efficiency are optimized for elements with mass-to-charge ratios corresponding to Fe and neighboring elements. Little is known on the theoretical performances for light elements. Here, we discuss the theoretical instrumental performance of one such instrument using accurate three-dimensional transient electrostatic simulations in a time-varying field approach. We compare the simulations to experimental measurements obtained on an FeBSi bulk-metallic glass. Dynamics effects during the ion's flight are revealed when examining multi-hit mass-to-charge correlations, and we demonstrate their influence on the mass resolution. The model reveals significant differences in ion projection as a function of the mass. We discuss how these chromatic aberrations affect the spatial precision. This approach shows that by tuning the shape of the voltage pulses used to trigger field evaporation, minimizing the influence of these detrimental dynamic effects is possible.

We propose a protocol for near-atomic–scale analysis of frozen water and embedded nanostructures by cryo–atom probe tomography., Transmission electron microscopy went through a revolution enabling routine cryo-imaging of biological and (bio)chemical systems, in liquid form. Yet, these approaches typically lack advanced analytical capabilities. Here, we used atom probe tomography to analyze frozen liquids in three dimensions with subnanometer resolution. We introduce a specimen preparation strategy using nanoporous gold. We report data on 2- to 3-μm-thick layers of ice formed from both high-purity deuterated water and a solution of 50 mM NaCl in high-purity deuterated water. The analysis of the gold-ice interface reveals a substantial increase in the solute concentrations across the interface. We explore a range of experimental parameters to show that atom probe analyses of bulk aqueous specimens come with their own challenges and discuss physical processes that produce the observed phenomena. Our study demonstrates the viability of using frozen water as a carrier for near-atomic–scale analysis of objects in solution by atom probe tomography.

The development of efficient acidic water electrolyzers relies on understanding dynamic changes of the Ir-based catalytic surfaces during the oxygen evolution reaction (OER). Such changes include degradation, oxidation, and amorphization processes, each of which somehow affects the material’s catalytic performance and durability. Some mechanisms involve the release of oxygen atoms from the oxide’s lattice, the extent of which is determined by the structure of the catalyst. While the stability of hydrous Ir oxides suffers from the active participation of lattice oxygen atoms in the OER, rutile IrO2 is more stable and the lattice oxygen involvement is still under debate due to the insufficient sensitivity of commonly used online electrochemical mass spectrometry. Here, we revisit the case of rutile IrO2 at the atomic scale by a combination of isotope labeling and atom probe tomography and reveal the exchange of oxygen atoms between the oxide lattice and water. Our approach enables direct visualization of the electrochemically active volume of the catalysts and allows for the estimation of an oxygen exchange rate during the OER that is discussed in view of surface restructuring and subsequent degradation. Our work presents an unprecedented opportunity to quantitatively assess the exchange of surface species during an electrochemical reaction, relevant for the optimization of the long-term stability of catalytic systems.

We investigated the origin of the deleterious grain boundary α phase formed during the aging of the β-titanium alloy, Ti–5Al–5Mo–5V–3Cr–0.5Fe (wt.%). We probed the composition of low and high-angle grain boundaries from the as-quenched β condition correlating electron microscopy and atom probe tomography. Our analysis reveals strong segregation of some α-stabilizing elements at both types of boundaries, especially oxygen, along with a depletion of β-stabilizing elements. The grain boundary maintains the body-centered-cubic structure despite the presence of this local composition. Our thermodynamic calculations, based on the measured grain boundary compositions, indicate that the segregation significantly increases the chemical driving force for α nucleation upon aging. Our work provides essential insight into the formation of the undesired grain boundary α layers along prior-β grain boundaries in metastable β-Ti alloys and paves the way for microstructural engineering of these alloys with enhanced mechanical properties.

There is an increasing reckoning that the thermoelectric performance of a material is dependent on its microstructure. However, the microstructure-properties relationship often remains elusive, in part due to the complexity of the hierarchy and scales of features that influence transport properties. Here, we focus on the Heusler-Fe2VAl compound, which shows promising thermoelectric properties, is non-toxic, cheap, and consist of earth-abundant elements. We directly correlate microstructure and local properties, using advanced scanning electron microscopy methods including in-situ four-point-probe technique for electron transport measurements. The local thermal conductivity is investigated by scanning thermal microscopy. Finally, atom probe tomography provides near-atomic scale compositional analysis. To locally manipulate the microstructure, we use laser surface remelting. The rapid quenching creates a complex microstructure with a high density of dislocations and small, elongated grains. We hence showcase that laser surface remelting can be employed to manipulate the microstructure to reduce the thermal conductivity and electrical resistivity, leading to a demonstrated enhancement of the thermoelectric performance at room temperature.

Atom probe tomography (APT) is rising in influence across many parts of materials science and engineering thanks to its unique combination of highly sensitive composition measurement and three-dimensional microstructural characterization. In this invited article, we have selected a few recent applications that showcase the unique capacity of APT to measure the local composition at structural defects. Whether we consider dislocations, stacking faults, or grain boundary, the detailed compositional measurements tend to indicate specific partitioning behaviors for the different solutes in both complex engineering and model alloys we investigated.

Electron microscopy and atom probe tomography were combined to investigate the crystallography and chemistry of a single twin boundary (TB) in a rare-earth-free ferromagnetic MnAl Heusler alloy. The results establish a significant segregation of Mn along the twin boundaries. An enrichment of approx. ~8 at.% Mn was measured along the twin boundary with a confined depletion outside the twin boundary, suggesting short range solute diffusion occurring during massive transformation.