Atom Probe Research Articles

Systematic quantification of hydrogen in pipeline steel by atom probe tomography after ambient charging and transfer

Systematic quantification of hydrogen in pipeline steel by atom probe tomography after ambient charging and transfer

Bringing atom probe tomography to transmission electron microscopes.

For the purpose of enhancing the structural insights within the three-dimensional composition fields revealed by atom probe tomography, correlative microscopy approaches, combining (scanning) transmission electron microscopy with atom probe tomography, have emerged and demonstrated their relevance. To push the boundaries further and facilitate a more comprehensive analysis of nanoscale matter by coupling numerous two- or three-dimensional datasets, there is an increasing interest in combining transmission electron microscopy and atom probe tomography into a unified instrument. This study presents the tangible outcome of an instrumental endeavour aimed at integrating atom probe tomography into a commercial transmission electron microscope. The resulting instrument demonstrates the feasibility of combining in situ 3D reconstructions of composition fields with the detailed structural analysis afforded by transmission electron microscopy. This study shows a promising approach for converging these two important nanoscale microscopy techniques.

Laser-Assisted Field Evaporation of Chromia with Deep Ultraviolet Laser Light.

In this work, samples of chromia (Cr2O3) scale have been prepared for atom probe tomography and field evaporated with deep ultraviolet laser light (258 nm wavelength). The investigated range of laser energies spans more than three orders of magnitude between 0.03 and 90 pJ. Furthermore, the effects of detection rate and temperature were investigated. Simultaneous voltage and laser pulses were employed on additional needle specimens to reduce the standing voltage and minimize background noise during the measurement. Smooth evaporation with minimal mass spectrum peak tails was maintained over the whole range of measurement parameters. High laser energies result in significant underestimation of the oxygen content. Only laser energies below 1 pJ resulted in measured values near the expected oxygen content of 60 at%, the closest being about 58 at%.

Stacking Fault Segregation Imaging With Analytical Field Ion Microscopy.

Stacking faults (SFs) are important structural defects that play an essential role in the deformation of engineering alloys. However, direct observation of SFs at the atomic scale can be challenging. Here, we use the analytical field ion microscopy, including density functional theory-informed contrast estimation, to image local elemental segregation at SFs in a creep-deformed solid-solution single-crystal alloy of Ni-2 at% W. The segregated atoms are imaged brightly, and time-of-flight spectrometry allows for their identification as W. We also provide the first quantitative analysis of trajectory aberration, with a deviation of approximately 0.4 nm, explaining why atom probe tomography could not resolve these segregations. Atomistic simulations of substitutional W atoms at an edge dislocation in face-centered cubic Ni using an analytic bond-order potential indicate that the experimentally observed segregation is due to the energetic preference of W for the center of the SF, contrasting with, for example, Re segregating to partial dislocations. Solute segregation to SF can hinder dislocation motion, increasing the strength of Ni-based superalloys. Yet, direct substitution of Re by W, envisaged to lower the superalloys' costs, requires extra consideration in alloy design since these two solutes do not have comparable interactions with structural defects during deformation.

Microstructure, electrical resistivity, and tensile properties of neutron-irradiated Cu–Cr–Nb–Zr

High strength, high conductivity copper alloys that can resist creep at high temperatures are one of the primary candidates for efficient heat exchangers in fusion reactors. Cu–Cr–Nb–Zr (CCNZ) alloys, which were designed to improve the strength and creep life of ITER Cu–Cr–Zr (CCZ) reference alloys, have been found to have comparable electrical conductivity and tensile properties to CCZ alloys. The measured creep rupture times for these improved alloys is about ten times higher than the ITER reference alloys at 90–125 MPa at 500 °C. However, the effects of neutron irradiation on these alloys, and the ensuing material properties, have not been studied; thus, their utility in a fusion reactor environment is not well understood. This study characterizes the room temperature mechanical and electrical properties of a neutron-irradiated CCNZ alloy and compares them to a neutron-irradiated ITER reference heat sink CCZ alloy. Tensile specimens were neutron irradiated in the High Flux Isotope Reactor (HFIR) to 5 dpa between 250 °C and 325 °C. Post-irradiation characterization included electrical resistivity measurements, hardness, and tensile tests. Microstructural evaluation used scanning electron microscopy, energy dispersive x-ray spectroscopy, and atom probe tomography to characterize the irradiation-produced changes in the microstructure and investigate the mechanistic processes leading to post-irradiation properties. Transmutation calculations were validated with composition measurements from atom probe data and used to calculate contributions to the increased electrical resistivity measured after irradiation. Comparisons with CCZ alloys in the same irradiation heat found that the post-irradiated CCNZ and CCZ alloys had comparable electrical resistivity. Although CCNZ alloys suffered more irradiation hardening than CCZ, the overall tensile behavior deviated very little from non-irradiated values in the temperature range studied.

Atom Probe Tomography: a Local Probe for Chemical Bonds in Solids.

Atom probe tomography is frequently employed to characterize the elemental distribution in solids with atomic resolution. Here the potential of this technique to locally probe chemical bonds is reviewed and discussed. Two processes characterize the bond rupture in laser-assisted field emission, the probability of molecular ions (PMI), i.e., the probability that molecular ions are evaporated instead of single (atomic) ions, and the probability of multiple events (PME), i.e., the correlated field-evaporation of more than a single fragment upon laser- or voltage pulse excitation. Here it is demonstrated that one can clearly distinguish solids with metallic, covalent, and metavalent bonds based on their bond rupture, i.e., their PME and PMI values. These findings open new avenues in understanding and designing advanced materials, since they allow a quantification of bonds in solids on a nanometer scale, as will be shown for several examples. These possibilities would even justify calling the present approach bonding probe tomography (BPT).

Atom probe tomography of deuterium-charged optimised ZIRLO

AbstractThis study investigates the morphology and composition of hydrides in Optimized ZIRLO following electrochemical deuterium charging. Both ZrO and ZrDx phases were formed upon charging. The interfaces between these phases are investigated by using atom probe tomography aided by cryogenic sample transfer. The Ga and Sn have formed a “net”-like structure at the original atom probe specimen surface, which is assumed to be associated with the boundaries between individual hydride laths/needles, as it thought to have formed as these species were excluded from the hydrides. Calculation of the D/Zr ratio throughout the sample allows for identification of the ZrDx phases, revealing the specimen consists of a complex arrangement of different hydride phases. In some areas there is small excess of D in the hydride, i.e. ZrD2+y. This result is interpreted as deuterium which was “frozen” as it was passing through the hydride during electrochemical charging. The observed microstructural changes and interfacial phenomena contribute valuable insights that may prove useful for improving the performance and safety of Zr alloys.

Insights into heat treatments of biodegradable Mg-Y-Nd-Zr alloys in clinical settings: Unveiling roles of β' and β1 nanophases and latent in vivo hydrogen evolution

Heat treatment serves as a viable strategy to effectively mitigate the intense corrosion of biodegradable WE43 alloys. However, limited comprehension of the passivation mechanisms underlying heat treatment and the dilemma to quantitatively examine the evolution of hydrogen gas in vivo introduce uncertainties in designing heat treatments for developing clinically applicable WE43. This work aims to advance this knowledge by applying cutting-edge atom probe tomography to provide atomic-scale insights into the passivation roles of rare earth (RE)-rich β1 (Mg3(Y, Nd)) and β' (Mg12NdY) nanophases induced by T6 heat treatment at 250 °C, and employing machine learning-based image analysis techniques to quantitatively unveil WE43’s in vivo gas evolution during a 12-week implantation. It was found that nanosized β1 and β' phases can effectively improve WE43′s corrosion resistance by inducing an accelerated passivation effect on the surface and confining the distribution of hydrogen ions in the matrix. Female rats presented slightly higher corrosion rates than male rats in weeks 1 and 4 but lower hydrogen gas volumes in vivo, while male rats possessed a superior ability to metabolise hydrogen gas in vivo. Notably, latent gas evolution against the corrosion rates was found which peaked at week 4 and subsided at week 12 despite the gradually decreased corrosion rates from week 1 to 12. This study offers insights for engineering heat treatments to develop clinically applicable WE43 with acceptable corrosion rates and in vivo gas generation at various implantation stages. Statement of SignificanceThe study aimed to reveal the role of β1 and β' nanophases on the good corrosion resistance of WE43. The influence of these nanophases on WE43′s corrosion performance has not been totally understood. Similarly, the understanding of hydrogen gas evolution as it relates to the magnesium implant's corrosion rate lacks clarity. Atom probe tomography (APT) indicates β1 and β' nanophases trap hydrogen, removing H2 from the lattice and disabling its catalytic role in Mg oxidation. Machine learning-aided analyses of computed tomography (CT) scan images indicate latent gas evolution, contradicting the monotonic in vivo H2 evolution that is widely accepted.

Tunable macroscopic self-healing of supramolecular gel through host–guest inclusion

Supramolecular gels (SGs) consisted of noncovalent cross-linking network structures are fascinating due to their efficient energy dissipation and reversible self-healing properties. However, it is unknown how the noncovalent interactions alter the macroscopic self-healing and mechanical properties of SGs. Herein, the peculiar nature of SGs manufactured by combining covalent and noncovalent (host–guest inclusion of β-cyclodextrin and C16 hydrophobic chain) cross-linking structures was studied and compared with covalent cross-linking preformed particle gels. The macroscopic self-healing behaviors, rheology, mechanical tensile properties, as well as the tunable mechanisms of self-healing were explored by visual inspection, rheological, and atomic force microscopy probing methods. The results show that the SGs exhibit excellent self-healing efficiency and mechanical strength after interfacial cutting. Moreover, the SGs exhibited excellent mechanical tensile properties, including loading–unloading, successive loading–unloading, and recovery loading–unloading tensile performances. Notably, the macroscopic self-healing of SGs has good tunability by changing the covalent and noncovalent crosslinker contents and salt contents. This peculiar phenomenon is attributed to certain host–guest inclusion forces (4.7 and 0.3 nN) between different SGs under the distilled and high-salinity water conditions, respectively. This study is beneficial for the development of stimuli–response supramolecular gels in different applications, such as oil recovery in fractured reservoirs.

The origin and control of interstitial impurities in refractory complex concentrated alloys

Interstitial impurities, primarily O and N, inadvertently introduced during the processing of refractory complex concentrated alloys (RCCAs) significantly limit the mechanical properties of the alloys at room temperature. Plasma arc melting (PAM) has facilitated the quest for RCCAs, showcasing remarkable combinations of strength and ductility. In this work, the composition and chemistry of residual gases in the PAM chamber environment during arc melting and the interstitial impurities in elemental feedstocks were analyzed to quantify the origin of O and N during synthesis. Moreover, the thermodynamic mechanisms governing the origin of interstitial impurities in arc-melted MoNbTaW RCCAs were discussed. With an understanding of the mechanisms governing the content of interstitial impurities in RCCAs during PAM, arc-melted MoNbTaW RCCAs with fewer than 100 ppm O were synthesized. The arc-melted MoNbTaW RCCAs were then characterized using electron microscopy and atom probe tomography to establish the compositional architecture of grain boundaries and thereby elucidate the thermodynamic drive for segregation and oxide formation in MoNbTaW. Additionally, density functional theory calculations of a MoNbTaW grain boundary were employed to analyze the effect of local chemical fluctuations on the O segregation and oxide formation at the grain boundary. This detailed understanding of the thermodynamic mechanisms governing the origin of interstitial impurities and their grain boundary segregation in MoNbTaW RCCAs provides greater context surrounding O interactions in RCCAs, which is key for the successful development of refractory alloys with unique combinations of strength and ductility.

Machine learning assisted crystallographic reconstruction from atom probe tomographic images

Atom probe tomography (APT) is a powerful technique for three-dimensional (3D) atomic-scale imaging, enabling the accurate analysis on the compositional distribution at the nanoscale. How to accurately reconstruct crystallographic information from APT data, however, is still a great challenge due to the intrinsic nature of the APT technique. In this paper, we propose a novel approach that consists of the modified forward simulation process and the backward machine learning process to recover the tested crystal from APT data. The high-throughput forward simulations on Al single crystals of different orientations generate 10 000 original 3D images and data augmentation is implemented on the original images, resulting in 100 000 3D images. The big data allows the development of deep learning models and three deep learning algorithms of Convolutional Neural Network (CNN), Vision Transformer (ViT), and Variational Autoencoder (VAE) are used in the backward process. After training, the ViT model performs superior than the CNN and VAE models, which can recover the crystalline orientation outstandingly, as evaluated by the coefficient of determinationR2and the Mean Percent Error (MPE), viz.,R2= 0.93 and MPE = 0.43%,R2= 0.97 and MPE = 0.35%, andR2= 0.93 and MPE = 0.77% for the rotation anglesϕ,ψandθ, respectively, on the test dataset. The present work clearly demonstrates the capability of deep learning models in the recovery of the tested crystals from APT data, thereby paving the way for the further development of large artificial intelligent models of APT.

Revealing Yukon’s hidden treasure: an atomic-scale investigation of Carlin-type gold mineralization in the Nadaleen Trend, Canada

AbstractThe invisible-gold deposits known as Carlin-type are becoming more important as easier to find deposits are progressively depleted. The combination of the invisible nature of the Au in these deposits, as well as the limited surface indicators of these deposits, makes exploration to find new Carlin-type deposits extremely difficult. Comprehensive mineralization models are essential to find new Carlin-type deposits in similar geologic settings. The Nadaleen Trend of Yukon, Canada, is one such district where an improved understanding of this deposit type has led to new discoveries. Previous studies compared and contrasted the tectonic setting, host rock depositional setting, structural preparation, and mineralization style of the Nadaleen Trend with those in Carlin-type localities, Nevada. However, the comparisons at an atomic scale, between Carlin-type Au deposits in the Nadaleen Trend and those in Nevada, has yet to be investigated. This study fills this knowledge gap by combining high resolution microanalytical techniques with atom probe tomography to examine the distribution of Au and other trace elements in the Nadaleen Trend, compare them to a representative Carlin-type deposit in Nevada (Turquoise Ridge), and determine how widespread the mineralization model is. Our findings show that in the Nadaleen Trend, as in Nevada, Au is generally directly linked with As at the macro to atomic scale, and is incorporated into As/Au rich overgrowths on sedimentary/diagenetic pyrite. Gold-rich pyrite rims in the Nadaleen Trend are generally smaller than those found in Nevada (0.5–2 µm vs > 10 µm), although the ore grades appear comparable. We find that the Au in the pyrite of the Nadaleen Trend is homogenously distributed (i.e. lattice bound) at the atomic scale, but that there is a notable enrichment of As surrounding individual Au atoms. These findings are in agreement with those from previous work on a representative deposit in Nevada, and support the assertation that As is the key ingredient in facilitating the incorporation of Au into the pyrite lattice. Arsenic as an essential component in the trapping mechanisms of Au in CTG deposits, is something that has been as to yet underappreciated in the current models of CTG deposit formation.

Precipitation strengthening behavior of Custom 455 stainless steel during tempering at 420 °C

After solid solution at 850 °C, the Custom 455 was aged at 420 °C for different times. The hardness changes were measured using a Vickers hardness tester, and the microstructure and composition of the second phase were studied using atom probe tomography (APT) and high-resolution transmission electron microscopy (HRTEM). The APT results indicate that in the early stage of aging, Cu atoms first segregate and attract Ti to form CuTi clusters; As the aging time increases, Ti atoms in CuTi clusters attract Ni and form CuTiNi clusters, resulting in a rapid increase in sample hardness; Subsequently, CuNiTi clusters grew and gradually separated into Cu-rich and NiTi-rich particles; As the aging time further increases, some NiTi-rich particles grow into rod-shaped Ni3Ti precipitates, while others have Si atoms and grow into spherical G phase particles. The orientation relationship between Cu-rich phase, Ni3Ti phase, and G phase is: [100]M//[0–11]Cu//[-12–10]Ni3Ti//[100]G, (011)M//(111)Cu//(0004)Ni3Ti//(022)G. The formation of the Cu-rich, Ni3Ti, and G phase resulted in a hardness peak of 538 HV after 16 h of aging. Subsequently, the decrease in hardness caused by the coarsening of the Cu-rich and Ni3Ti particles was offset by the newly formed G phase, resulting in a slow decrease in hardness.

The role of magnesium oxide addition in densification of AlON transparent ceramics by pressureless sintering

AbstractPressureless sintering processing was adopted to fabricate transparent aluminum oxynitride (AlON) ceramics by using magnesium oxide (MgO) as a sintering additive into synthetic single phased aluminum oxynitride powder. Under the condition of adding 0.6 wt% magnesium oxide, the relative density of aluminum oxynitride ceramics increased from 98.67% with no addition to 99.9% after being held at 1800°C for 24 h, coupled by a reducing of average grain size from 190 µm to 130 µm. The optical linear transmittance of the AlON ceramic sample (thickness 1.2 mm) reached 84.2% at the wavelength of 1100 nm. The microstructural characterizations by energy dispersive spectroscopy and atom probe tomography indicated that the doping Mg element was uniformly dispersed inside aluminum oxynitride grains of as‐sintered ceramics. It was demonstrated that magnesium oxide played a key role in inhibiting the movement of grain boundaries, eliminating pores, leading to the fully densification of aluminum oxynitride ceramics.

Boosting Coercivity of 3D Printed Hard Magnets through Nano-Modification of the Powder Feedstock.

The demand for strong, compact permanent magnets essential for the energy transition drives innovation in magnet manufacturing. Additive manufacturing, particularly Powder Bed Fusion of metals using a laser beam (PBF-LB/M), offers potential for near-net-shaped Nd-Fe-B permanent magnets but often falls short compared to conventional methods. A less explored strategy to enhance these magnets is feedstock modification with nanoparticles. It is demonstrated that modifying a Nd-Fe-B-based feedstock with 1wt.%Ag nanoparticles boost the coercivity of the magnets to a record value of 935±6kAm-1 without further post-processing or heat treatments. Suitable volumetric energy densities for the PBF-LB/M process are determined using finite element simulations predicting melt pool behavior and part density. Microstructural analyses reveal finer grain sizes and more equiaxed nanocrystalline structures due to the modification. Atom probe tomography identifies three phases in the Ag-modified samples, with Ag forming nanophase regions with rare-earth elements near the amorphous Zr-Ti-B-rich intergranular phase, potentially decoupling the Nd2Fe14B primary phase. The study shows that superior magnetic properties primarily result from microstructure modification rather than part density. These findings highlight inventive material design approaches via feedstock surface modification to achieve superior magnetic performance in additively manufactured Nd-Fe-B magnets.

Specimen preparation for atom probe tomography

Abstract In the past 20 years or so, atom probe tomography has gone from a niche technique in physical metallurgy to a well-established method in many parts of materials science and beyond. This is owing to the improvement in both instrumentation and specimen preparation. Given the availability of instruments, successful specimen preparation is often the bottleneck in atom probe projects. In this article, the authors want to give an overview of the types of preparation techniques that are available and which challenges they pose. This includes basic electropolishing, which was dominant until the introduction of focused ion beam-based preparation some 25 years ago. Nowadays, focused ion beam-based preparation methods possibly represent the largest share, as they allow for site-specific specimen preparation, non-conductive specimens and often a higher throughput. They are continuously improved, i. e., through higher current plasma ion columns, cryo preparation for sensitive materials and room temperature liquids and ‘additive’ techniques for nanomaterials. This steadily increases the types of materials that can be analyzed using atom probe tomography.

Chemical origins of β-Ti stabilization via B4C additions in metastable β-Ti alloys and composites

The aerospace industry relies on Ti alloys owing to their strength-to-weight ratio and corrosion resistance. In metastable β-Ti alloys, slow cooling from the β-transus leads to partial transformation into coarse α laths, which is detrimental to the mechanical properties. A refinement and decrease of α laths has been previously achieved in β-Ti alloys with B4C additions. In these materials, the ductility of β-Ti is preserved, and the TiB and TiC particles promote strengthening. However, the mechanism of the β-Ti stabilization remains unclear. Using atom probe tomography, we propose that Mo enrichment in the α-phase limits its growth by reducing the influx of Al from the β-phase. The complex chemical environment near eutectic TiB is enriched in Al and TiO, promoting heterogeneous nucleation of fine α-phase. Increased TiO concentration is observed with the introduction of B4C. A fundamental understanding of the α-refinement mechanism in Ti-alloys is critical for aerospace applications demanding high performance and reliability.

Revealing the embrittlement phenomena after post-weld heat treatment of high-strength weld metal using high-resolution microscopy

High strength combined with sufficient toughness is a fundamental prerequisite for steel in the field of lightweight construction. Joining high-strength steels by means of welding requires the use of highly advanced filler metals and a stress-relief post-weld heat treatment (PWHT) for optimum performance of the joint. However, such a heat treatment can lead to embrittlement in the weld metal. In this context, the present work deals with the influence of different PWHT holding temperatures on the microstructure and mechanical properties of a high-strength multipass all-weld metal to reveal the embrittlement phenomena. The all-weld metal was fabricated via gas metal arc welding using a metal cored wire with a minimum yield strength of 690 MPa. Charpy V-notch impact testing and tensile testing were carried out to characterize the strength and toughness of the all-weld metal in the as-welded condition and after a 2 h stress-relief PWHT at 520 °C, 580 °C, and 620 °C. The microstructure was characterized utilizing high-resolution techniques such as atom probe tomography and high-energy X-ray diffraction. The strength and toughness of the all-weld metal both decrease after PWHT with different holding temperatures. The cause for the observed embrittlement was found to be the formation of Mn-rich cementite precipitates. These carbides increase in size and phase fraction with increasing holding temperature and lead to a brittle transcrystalline cleavage fracture. Consequently, it was concluded that a gas metal arc welded joint with the investigated filler metal should not be exposed to stress-relief PWHT at temperatures higher than 580 °C.

Effect of intrinsic heat treatment on the precipitate formation of X40CrMoV5–1 tool steel during laser-directed energy deposition: A coupled study of atom probe tomography and in situ synchrotron X-ray diffraction

Additively manufactured components are generally heat treated to remove the undesired microstructure formed during the repeated heating-cooling cycles inherent to the process, known as intrinsic heat treatment (IHT). Recently, the IHT has been explored as a driving force for precipitation hardening in steels which can potentially shorten the manufacturing chain of AM components. However, the mechanisms behind the formation of secondary phase precipitates during the complex thermal history remains unclear. In this work, a combination of in situ high energy X-ray diffraction, atom probe tomography, scanning and transmission electron microscopy were used to reveal the precipitation sequence in an X40CrMoV5–1 tool steel during laser-directed energy deposition (L-DED). V-rich MCN and V8CN7 carbonitrides, as well as, Fe-Cr-rich M3C and M7C3 carbides were formed at different stages of the L-DED. Their evolution and resulting chemical stoichiometry was correlated to the exact phase transformation occurring in the microstructure during the IHT over different regions along the built direction. Finally, the combined results from the in situ and ex situ experiments enabled us to retrace the history of the full microstructure during the L-DED process. The findings lead to the conclusion that secondary hardening effect in tool steel is, as expected, sensitive to the severity of the IHT, and if limited, can result in a tempered microstructure comparable to the ones conventionally obtained after tempering heat treatments.

Impact of stacking faults on the luminescence of a zincblende InGaN/GaN single quantum well

Abstract In this paper, we investigate the optical properties of a zincblende InGaN single quantum well structure containing stacking faults. Cathodoluminescence studies revealed the presence of sharp emission features adjacent to stacking faults, identified as quantum wires via their spatial anisotropy. Scanning transmission electron microscopy provided evidence of indium rich regions adjacent to stacking faults which intersect the quantum well along the [110] and [1-10] directions, whilst atom probe tomography revealed that the indium rich regions have an elongated structure, creating a quantum wire. This work sheds light on the intricate relationship between stacking faults and quantum wires in zincblende InGaN single quantum well structures, offering insights into the underlying mechanisms governing their optical behaviour.