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Stacking faults (SF) are important structural defects that play an essential role in the deformation of engineering alloys. However, direct observation of stacking faults at the atomic scale can be challenging. Here, we use the analytical field ion microscopy (aFIM), 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 fcc 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 stacking fault, contrasting with e.g., 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 superalloys' costs, requires extra consideration in alloy design since these two solutes do not have comparable interactions with structural defects during deformation.

The understanding of protein structure, folding, and interaction with other proteins remains one of the grand challenges of modern biology. Tremendous progress has been made thanks to X-ray- or electron-based techniques that have provided atomic configurations of proteins, and their solvation shell. These techniques though require a large number of similar molecules to provide an average view, and lack detailed compositional information that might play a major role in the biochemical activity of these macromolecules. Based on its intrinsic performance and recent impact in materials science, atom probe tomography (APT) has been touted as a potential novel tool to analyse biological materials, including proteins. However, analysis of biomolecules in their native, hydrated state by APT have not yet been routinely achieved, and the technique's true capabilities remain to be demonstrated. Here, we present and discuss systematic analyses of individual amino-acids in frozen aqueous solutions on two different nanoporous metal supports across a wide range of analysis conditions. Using a ratio of the molecular ions of water as a descriptor for the conditions of electrostatic field, we study the fragmentation and behavior of those amino acids. We discuss the importance sample support, specimen preparation route, acquisition conditions and data analysis, to pave the way towards establishing guidelines for cryo-APT analysis of biomolecules.

Cryogenic atom probe tomography (cryo-APT) is being developed to enable nanoscale compositional analyses of frozen liquids. Yet, the availability of readily available substrates that allow for the fixation of liquids while providing sufficient strength to their interface, is still an issue. Here we propose the use of 1-2 microns thick binary alloy film of gold-silver (AuAg) sputtered onto flat silicon, with sufficient adhesion without an additional layer. Through chemical dealloying, we successfully fabricate a nanoporous substrate, with open-pore structure, which is mounted on a microarray of Si posts by lift out in the focused-ion beam, allowing for cryogenic fixation of liquids. We present cryo-APT results obtained after cryogenic sharpening, vacuum cryo-transfer and analysis of pure water on top and inside the nanoporous film. We demonstrate that this new substrate has the requisite characteristics for facilitating cryo-APT of frozen liquids, with a relatively lower volume of precious metals. This complete workflow represents an improved approach for frozen liquid analysis, from preparation of the films to the successful fixation of the liquid in the porous network, to cryo-atom probe tomography.

The influence of microstructure on thermoelectricity is increasingly recognized. Approaches for microstructural engineering can hence be exploited to enhance thermoelectric performance, particularly through manipulating crystalline defects, their structure, and composition. Here, we focus on a full-Heusler Fe2VAl-based compound that is one of the most promising thermoelectric materials containing only Earth-abundant, non-toxic elements. A Fe2VTa0.05Al0.95 cast alloy was atomized under a nitrogen-rich atmosphere to induce nitride precipitation. Nanometer- to micrometer-scale microstructural investigations by advanced scanning electron microscopy and atom probe tomography (APT) are performed on the powder first and then on the material consolidated by spark-plasma sintering for an increasing time. APT reveals an unexpected pick-up of additional impurities from atomization, namely W and Mo. The microstructure is then correlated with local and global measurements of the thermoelectric properties. At grain boundaries, segregation and precipitation locally reduce the electrical resistivity, as evidenced by in-situ four-point probe measurements. The final microstructure contains a hierarchy of structural defects, including individual point defects, dislocations, grain boundaries, and precipitates, that allow for a strong decrease in thermal conductivity. In combination, these effects provide an appreciable increase in thermoelectric performance.

Permanent magnets draw their properties from a complex interplay, across multiple length scales, of the composition and distribution of their constituting phases, that act as building blocks, each with their associated intrinsic properties. Gaining a fundamental understanding of these interactions is hence key to decipher the origins of their magnetic performance and facilitate the engineering of better-performing magnets, through unlocking the design of the "perfect defects" for ultimate pinning of magnetic domains. Here, we deployed advanced multiscale microscopy and microanalysis on a bulk Sm2(CoFeCuZr)17 pinning-type high-performance magnet with outstanding thermal and chemical stability. Making use of regions with different chemical compositions, we showcase how both a change in the composition and distribution of copper, along with the atomic arrangements enforce the pinning of magnetic domains, as imaged by nanoscale magnetic induction mapping. Micromagnetic simulations bridge the scales to provide an understanding of how these peculiarities of micro- and nanostructure change the hard magnetic behaviour of Sm2(CoFeCuZr)17 magnets. Unveiling the origins of the reduced coercivity allows us to propose an atomic-scale defect and chemistry manipulation strategy to define ways toward future hard magnets.

Climate change motivates the search for non-carbon-emitting energy generation and storage solutions. Metal hydrides show promising characteristics for this purpose. They can be further stabilized by tailoring the negative pressure of microstructural and structural defects. Using systematic ab initio and atomistic simulations, we demonstrate that an enhancement in the formation of hydrides at the negatively pressurized crack tip region is feasible by increasing the mechanical tensile load on the specimen. The theoretical predictions have been used to reassess and interpret atom probe tomography experiments for a high-strength 7XXX-aluminium alloy that show a substantial enhancement of hydrogen concentration at structural defects near a stress-corrosion crack tip. These results contain important implications for enhancing the capability of metals as H-storage materials., Comment: 22 pages, 9 figures

Hydrogen embrittlement in Zr alloy fuel cladding is a primary safety concern for water based nuclear reactors. Here we investigated the stabilisation of planar defects within the forming hydrides by Sn, the primary alloying element of Zircaloy-4 used in the cladding. In order to explain formation of hydrides and planar defects observed in our experiments, we performed atomic-scale ab initio calculations focusing on the solute interactions with generalized stacking faults in hcp $\alpha$-Zr and fcc zirconium hydrides. Our calculations showed that an increase in Sn concentration leads to a stabilisation of stacking faults in both $\alpha$-Zr and hydride phases. However, the solution enthalpy of Sn is lower in the $\alpha$-Zr as compared to the other hydride phases indicative of two competing processes of Sn depletion/enrichment at the Zr hydride/matrix interface. This is corroborated by experimental findings, where Sn is repelled by hydrides and is mostly found trapped at interfaces and planar defects indicative of stacking faults inside the hydride phases. Our systematic investigation enables us to understand the presence and distribution of solutes in the hydride phases, which provides a deeper insight into the microstructural evolution of such alloy's properties during its service lifetime., Comment: 17 pages, 8 figures

Fe- and steelmaking is the largest single industrial CO2 emitter, accounting for 6.5% of all CO2 emissions on the planet. This fact challenges the current technologies to achieve carbon-lean steel production and to align with the requirement of a drastic reduction of 80% in all CO2 emissions by around 2050. Thus, alternative reduction technologies have to be implemented for extracting iron from its ores. The H-based direct reduction has been explored as a sustainable route to mitigate CO2 emissions, where the reduction kinetics of the intermediate oxide product FexO wustite into Fe is the rate-limiting step of the process. The total reaction has an endothermic net energy balance. Reduction based on a H plasma may offer an attractive alternative. Here, we present a study about the reduction of hematite using H plasma. The evolution of both, chemical composition and phase transformations was investigated in several intermediate states. We found that hematite reduction kinetics depends on the balance between the initial input mass and the arc power. For an optimized input mass-arc power ratio, complete reduction was obtained within 15 min of exposure to the H plasma. The wustite reduction is also the rate-limiting step towards complete reduction. Nonetheless, the reduction reaction is exothermic, and its rates are comparable with those found in H-based direct reduction. Chemical and microstructure analysis revealed that the gangue elements partition to the remaining oxide regions, probed by energy dispersive spectroscopy and atom probe tomography. Si-enrichment was observed in the interdendritic fayalite domains, at the wustite/Fe hetero-interfaces and in the primarily solidified oxide particles inside the Fe. With proceeding reduction, however, such elements are gradually removed from the samples so that the final iron product is nearly free of gangue-related impurities.

The softening and strengthening contributions in pre-deformed and aged Al-Mg-Cu alloys containing 3wt.%Mg and 0.5wt.%Cu are evaluated by a combination of microscopy, mechanical testing and modelling. A refined phenomenological model for the work hardening response, accounting for the separate effects of recovery and precipitation, is shown to be suitable for an unambiguous determination of the precipitation hardening contribution in these alloys. Significantly, it is found that the mechanical response of these alloys is not strongly impacted by Cu content (in the low Cu content regime), pre-deformation level or aging temperature meaning that the alloys are robust with respect to variations in composition. This is interesting from the perspective of alloy design concepts based on `recycling friendly' compositions in applications that include paint-baking., Comment: 33 pages, 10 figures

Advanced characterisation techniques were used on LPBF Ti-6Al-4V samples produced on a heated base plate. When the substrate temperature is 100{\deg}C the elongation is 6\%, which increases and peaks at 10\% at 570{\deg}C, then sharply decreases to zero ductility at 770{\deg}C. At 100{\deg}C, a heavily strained and twinned microstructure, primarily composed of {\alpha}+{\alpha}', was observed and it was comparable to asbuilt microstructures obtained by conventional LPBF methods. At higher temperatures, twins are no longer present and instead nano-scale {\beta} precipitates are observed within {\alpha}' and {\alpha}, as well as dislocation networks (570{\deg}C) and tangles (770{\deg}C). Solute segregation at crystal defects was observed in all pre-heating conditions. Al and V segregation at microtwins was observed in the 100{\deg}C sample, reporting for the first time `selective' and mutually exclusive Al- and V-rich regions forming in adjacent twins. V segregation at dislocations was observed in the 570{\deg}C and 770{\deg}C samples, consistent with the higher preheating temperatures. High O contents were measured in all samples but with apparent opposing effects. At 100{\deg}C and 570{\deg}C was estimated to be below the critical threshold for O embrittlement and locally aids in maintaining a strength high by solid solution strengthening, whereas at 770{\deg}C it was above the threshold, therefore failing in a brittle fashion. Based on these observations, the initial increase in ductility from 100{\deg}C to 570{\deg}C is attributed to a reduction in microtwins and the dislocation networks acting as `soft barriers' for slip within a coarser microstructure. The lack of ductility at 770{\deg}C was attributed to local solute redistribution causing dislocation pinning and an increase of O content in this sample.

In this study, the effect of rhenium (Re) addition on microstructural evolution of a new low-density Co-Ni-Al-Mo-Nb based superalloy is presented. Addition of Re significantly influences the {\gamma}' precipitate morphology, the {\gamma}/{\gamma}' lattice misfit and the {\gamma}/{\gamma}' microstructural stability during long term aging. An addition of 2 at.% Re to a Co-30Ni-10Al-5Mo-2Nb (all in at.%) alloy, aged at 900{\deg}C for 50 hours, reduces the {\gamma}/{\gamma}' lattice misfit by {\approx} 40% (from +0.32% to +0.19%, measured at room temperature) and hence alters the {\gamma}' morphology from cuboidal to round-cornered cuboidal precipitates. The composition profiles across the {\gamma}/{\gamma}' interface by atom probe tomography (APT) reveals Re partitions to the {\gamma} phase (K_Re=0.34) and also results in the partitioning reversal of Mo to the {\gamma} phase (K_Mo=0.90) from the {\gamma}' precipitate. An inhomogeneous distribution of Gibbsian interfacial excess for the solute Re ({\Gamma}_Re, ranging from 0.8 to 9.6 atom.nm-2) has been observed at the {\gamma}/{\gamma}' interface. A coarsening study at 900{\deg}C (up to 1000 hours) suggests that the coarsening of {\gamma}' precipitates occurs solely by an evaporation--condensation (EC) mechanism. This is contrary to that observed in the Co-30Ni-10Al-5Mo-2Nb alloy as well as in some of the Ni-Al based and high mass density Co-Al-W based superalloys, where {\gamma}' precipitates coarsen by coagulation/coalescence mechanism with extensive alignment of {\gamma}' along <100> directions as a sign of microstructural instability. The {\gamma}' coarsening rate exponent (K_r) and {\gamma}/{\gamma}' interfacial energy are estimated to be 1.41 x 10-27 m3/s and 8.4 mJ/m2, which are comparable and lower than Co-Al-W based superalloys.

Zircaloy-4 (Zr-1.5%Sn-0.2%Fe-0.1%Cr wt. %) was electrochemically charged with deuterium to create deuterides and subsequently analysed with atom probe tomography and scanning transmission electron microscopy to understand zirconium hydride formation and embrittlement. At the interface between the hexagonal close packed (HCP) \alpha-Zr matrix and a face centred cubic (FCC) \delta deuteride (ZrD1.5-1.65), a HCP \zeta phase deuteride (ZrD0.25-0.5) has been observed. Furthermore, Sn is rejected from the deuterides and segregates to the deuteride/\alpha-Zr reaction front.

To understand the mechanisms by which Fe and Cr additions increase the corrosion rate of irradiated Zr alloys, a combination of experimental (atom probe tomography, x-ray diffraction and thermoelectric power measurements) and modelling (density functional theory) techniques are employed to investigate the non-equilibrium solubility and clustering of Fe and Cr in binary Zr alloys. Cr occupies both interstitial and substitutional sites in the {\alpha}-Zr lattice, Fe favours interstitial sites, and a low-symmetry site that was not previously modelled is found to be the most favourable for Fe. Lattice expansion as a function of alloying concentration (in the dilute regime) is strongly anisotropic for Fe additions, expanding the $c$-axis while contracting the $a$-axis. Defect clusters are observed at higher solution concentrations, which induce a smaller amount of lattice strain compared to the dilute defects. In the presence of a Zr vacancy, all two-atom clusters are more soluble than individual point defects and as many as four Fe or three Cr atoms could be accommodated in a single Zr vacancy. The Zr vacancy is critical for the increased solubility of defect clusters, the implications for irradiation induced microstructure changes in Zr alloys are discussed., Comment: 15 pages including figure, 9 figures, 2 tables. Submitted for publication in Acta Mater, Journal of Nuclear Materials (2015)

Due to their graphene-like properties after oxygen reduction, incorporation of graphene oxide (GO) sheets into correlated-electron materials offers a new pathway for tailoring their properties. Fabricating GO nanocomposites with polycrystalline MgB2 superconductors leads to an order of magnitude enhancement of the supercurrent at 5 K/8 T and 20 K/4 T. Herein, we introduce a novel experimental approach to overcome the formidable challenge of performing quantitative microscopy and microanalysis of such composites, so as to unveil how GO doping influences the structure and hence the material properties. Atom probe microscopy and electron microscopy were used to directly image the GO within the MgB2, and we combined these data with computational simulations to derive the property-enhancing mechanisms. Our results reveal synergetic effects of GO, namely, via localized atomic (carbon and oxygen) doping as well as texturing of the crystals, which provide both inter and intra granular flux pinning. This study opens up new insights into how low-dimensional nanostructures can be integrated into composites to modify the overall properties, using a methodology amenable to a wide range of applications.

Local fluctuations in the distribution of dopant atoms are a suspected cause of nanoscale electronic disorder or phase separation observed within the pnictide superconductors. Atom probe tomography results present the first direct observations of dopant nano-clustering in a K-doped 122-phase pnictides. First-principles calculations suggest the coexistence of static magnetism and superconductivity on a lattice parameter length scale over a large range of doping concentrations. Collectively, our results provide evidence for a mixed scenario of phase coexistence and phase separation originating from variation of dopant atom experiments distroibutions., Comment: 4 pages, 4 figures and 1 table, accepted by Physical Review Letter 2011