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Enamel and dentin are susceptible to acids from food sources leading to dental erosion, a global problem affecting millions of individuals. Particulate hydroxyapatite (HAP) on the tooth surface can influence the effects of acid attacks. Standardized bovine enamel and dentin samples with artificial saliva are used in an in vitro cyclic demineralization–remineralization protocol to analyze the structural changes experienced by tooth surfaces using high-resolution scanning electron microscopy and to evaluate the potential of a HAP-based oral care gel in the protection of teeth from erosive attacks. The interfaces between HAP particle and enamel HAP crystallites are investigated using focused ion beam preparation and transmission electron microscopy. The results show that erosion with phosphoric acid severely affects enamel crystallites and dentin tubules, while artificial saliva leads to remineralization effects. The HAP-gel forms a microscopic layer on both enamel and dentin surfaces. Upon acid exposure, this layer is sacrificed before the native tooth tissues are affected, leading to significantly lower degrees of demineralization compared to the controls. This demonstrates that the use of particulate HAP as a biomaterial in oral care formulations can help protect enamel and dentin surfaces from erosive attacks during meals using a simple and effective protection principle.

We report the development of a fully automatic large-volume 3D electron backscatter diffraction (EBSD) system (ELAVO 3D), consisting of a scanning electron microscope (ZEISS crossbeam XB 1540) with a dedicated sample holder, an adapted polishing automaton (Saphir X-change, QATM), a collaborative robotic arm (Universal Robots UR5), and several in-house built devices. The whole system is orchestrated by an in-house designed software, which is also able to track the process and report errors. Except for the case of error, the system runs without any user interference. For the measurement of removal thickness, the samples are featured with markers put on the perpendicular lateral surface, cut by plasma focused ion beam (PFIB) milling. The individual effects of both 1 μm diamond suspension and oxide polishing suspension polishing were studied in detail. Coherent twin grain boundaries (GBs) were used as an internal standard to check the removal rates measured by the side markers. The two methods for Z-spacing measurements disagreed by about 10%, and the inaccurate calibration of the PFIB system was found to be the most probable reason for this discrepancy. The angular accuracy of the system was determined to be ∼2.5°, which can be significantly improved with more accurate Z-spacing measurements. When reconstructed grain boundary meshes are sufficiently smoothed, an angular resolution of ±4° is achieved. In a 3D EBSD dataset of a size of 587 × 476 × 72 μm3, we focused on the investigation of coincidence site lattice ∑9 GBs. While bearing predominantly a pure tilt character, ∑9 GBs can be categorized into three groups based on correlative 3D morphologies and crystallography.

Severe plastic deformation leads to cementite decomposition in pearlitic and martensitic alloys, resulting in high-strength nanocrystalline ferrite. This effect can be employed to strengthen pearlitic wires but it can also be associated with material failure by white etching cracks (WECs) that are primarily known to concern bearings or rails. We investigate the decomposition of spheroidal cementite in the martensitic bearing steel 100Cr6 with 62 Rockwell hardness during high pressure torsion at 9.5 GPa applied pressure. The hard martensitic matrix and the even harder spheroidal cementite precipitates behave plastically very differently. The enforced macroscopic plastic deformation is almost entirely carried by the matrix. Plastic material flow of the matrix around the spheroidal cementite leads to wear of the spheroidal cementite as indicated by continuously increasing levels of chromium in the matrix. Plastic deformation of spheroidal cementite via dislocation gliding supposedly accelerates this process as slip steps generated thereby are preferential sites of wear at the matrix/cementite interface. Larger spheroidal cementite precipitates are more prone to plastic deformation and to decomposition than smaller ones. The mechanism likely holds true in general for multiphase materials with large strain difference between phases subjected to high pressure torsion. Although the formation of WECs in 100Cr6 bearings might be slowed down by reducing the size of the spheroidal cementite precipitates, it is unlikely that this could entirely prevent this failure mechanism.

Material failure by white-etching-cracks (WECs) can cause enormous economic costs. The formation of WECs emerges from the decomposition of the original, usually cementite-containing, microstructure...

Failure in engineering materials like steels is strongly affected by in-service deleterious alterations in their microstructure. White Etching Layers (WELs) are an example of such in-service alterations in the pearlitic microstructure at the rail surface. Cracks initiate in the rails due to delamination and fracture of these layers and propagate into the base material posing severe safety concerns. In this study, we investigate the microscale fracture behaviour of these WELs. We use in situ elastic-plastic fracture mechanics using J-integral to quantify the fracture toughness. Although usually assumed brittle, the fracture toughness of 21–25 MPa√m reveals a semi-brittle nature of WELs. Based on a comparison of the fracture toughness and critical defect size of WELs with the undeformed pearlitic steels, WELs are detrimental for rails. In the micro fracture tests, WELs show crack tip blunting, branching, and significant plasticity during crack growth due to their complex microstructure. The fracture behaviour of the WELs is governed by their microstructural constituents such as phases (martensite/austenite), grain size, dislocation density and carbon segregation to dislocations and grain boundaries. We observed dislocation annihilation in some martensitic grains in the WELs which also contributes to their fracture behaviour. Additionally, the strain-induced transformation from austenite to martensite affects the crack growth and fracture.

The formation of White (WEL) and Brown Etching Layers (BEL) on rail raceways during service causes the initiation of microcracks which finally leads to failure. Detailed characterization of the WEL and the BEL in a pearlitic rail steel is carried out from micrometer to atomic scale to understand their microstructural evolution. A microstructural gradient is observed along the rail depth including martensite, austenite and partially dissolved parent cementite in the WEL and tempered martensite, ultrafine/nanocrystalline martensite/austenite, carbon saturated ferrite and partially dissolved parent cementite in the BEL. Plastic deformation in combination with a temperature rise during wheel-rail contact was found to be responsible for the initial formation and further microstructural evolution of these layers. The presence of austenite in the WEL/BEL proves experimentally that temperatures rise into the austenite range during wheel-rail contact. This is in agreement with finite element modelling results. Each wheel-rail contact must be considered as an individual short but intense deformation and heat treatment cycle that cumulatively forms the final microstructure, as shown by diffusion length calculations of C and Mn. The presence of secondary carbides in the BEL indicates that the temperature in the BEL during individual loading cycles reaches levels where martensite tempering occurs. Partially fragmented primary cementite laths, enriched in Mn, depleted in Si, and surrounded by a C-gradient and dislocations were found in the BEL. The initial step in the formation of BEL and WEL is the defect- and diffusion-assisted decomposition of the original microstructure.

In this article, we probe the strain partitioning between the microstructural features present in a continuously cooled carbide-free bainitic steel together with damage nucleation and propagation. These features mainly comprise of phases (bainitic ferrite, martensite, and blocky/thin film austenite), interfaces between them, grain size and grain morphology. A micro Digital Image Correlation (μ-DIC) technique in scanning electron microscope is used to quantify the strain distribution between these microstructural features. The results show a strong strain partitioning between martensite, bainitic ferrite and retained austenite that provides weak links in the microstructure and creates conditions for the crack initiation and propagation during deformation. Blocky austenite islands accommodate maximum local strains in the global strain range of 0–2.3% and undergo strain-induced austenite to martensite transformation governing the local strain evolution in the microstructure. However, the local strains are minimum in martensite regions during entire in-situ deformation stage. Narrow bainitic ferrite channels in between martensitic islands and martensite-bainitic ferrite interfaces are recognised as primary damage sites with high strain accumulation of 30 ± 2% and 20 ± 3% respectively, at a global strain of 9%. The inclination of these interfaces with the tensile direction also affects the strain accumulation and damage.

When metals are mechanically loaded at elevated temperatures for extended periods of time, creep damage will occur in the form of cavities at grain boundaries. In the present experiments it is demonstrated that in binary iron-tungsten alloys creep damage can be self healed by selective precipitation of a W-rich phase inside these cavities. Using synchrotron X-ray nano-tomography the simultaneous evolution of creep cavitation and precipitation is visualized in 3D images with a resolution down to 30 nm. The degree of filling by precipitation is analysed for a large collection of individual creep cavities. Two clearly different types of behaviour are observed for isolated and linked cavities, where the isolated cavities can be filled completely, while the linked cavities continue to grow. The demonstrated self-healing potential of tungsten in iron-based metal alloys provides a new perspective on the role of W in high-temperature creep-resistant steels.

The properties of polycrystalline materials are related to their microstructures and hence a complete description, including size, shape, and orientation of the grains, is necessary to understand the behavior of materials. Here, we use Scanning Precession Electron Diffraction (SPED) in the Transmission Electron Microscope (TEM) combined with a tilt series to reconstruct individual grains in 3D within a polycrystalline dual-phase cold wire-drawn pearlitic steel sample. Nanoscale ferrite grains and intragranular cementite particles were indexed using an Automated Crystallographic Orientation Mapping (ACOM) tool for each tilt dataset. The grain orientations were tracked through the tilt datasets and projections of the individual grains were reconstructed from the diffraction data using an orientation-specific Virtual Dark Field (VDF) approach for tomographic reconstruction. The algorithms used to process and reconstruct such datasets are presented. These algorithms represent an extension to the ACOM approach that may be straightforwardly applied to other multi-phase polycrystalline materials to enable 3D spatial and orientation reconstructions.

Many materials science phenomena require joint structural and chemical characterization at the nanometer scale to be understood. This can be achieved by correlating electron microscopy (EM) and atom probe tomography (APT) subsequently on the same specimen. For this approach, specimen yield during APT is of particular importance, as significantly more instrument time per specimen is invested as compared to conventional APT measurements. However, electron microscopy causes hydrocarbon contamination on the surface of atom probe specimens. Also, oxide layers grow during specimen transport between instruments and storage. Both effects lower the chances for long and smooth runs in the ensuing APT experiment. This represents a crucial bottleneck of the method correlative EM/APT. Here, we present a simple and reliable method based on argon ion polishing that is able to remove hydrocarbon contamination and oxide layers, thereby significantly improving APT specimen yield, particularly after EM.

Premature failure of rail and bearing steels by White-Etching-Cracks leads to severe economic losses. This failure mechanism is associated with microstructure decomposition via local severe plastic deformation. The decomposition of cementite plays a key role. Due to the high hardness of this phase, it is the most difficult obstacle to overcome in the decaying microstructure. Understanding the mechanisms of carbide decomposition is essential for designing damage-resistant steels for industrial applications. We investigate cementite decomposition in the bearing steel 100Cr6 (AISI 52100) upon exposure to high-pressure torsion (maximum shear strain, Ƴmax = 50.2). Following-up on our earlier work on cementite decomposition in hardened 100Cr6 hardened steel (Qin et al., Act. Mater. 2020 [1]), we now apply a modified heat treatment to generate a soft-annealed microstructure where spherical and lamellar cementite precipitates are embedded in a ferritic matrix. These two precipitate types differ in morphology (spherical vs. lamellar), size (spherical: 100–1000 nm diameter, lamellar: 40–100 nm thickness) and composition (Cr and Mn partitioning). We unravel the correlation between cementite type and its resistance to decomposition using multi-scale chemical and structural characterization techniques. Upon high-pressure torsion, the spherical cementite precipitates did not decompose, but the larger spherical precipitates (>∼1 μm) deformed. In contrast, the lamellar cementite precipitates underwent thinning followed by decomposition and dissolution. Moreover, the decomposition behavior of cementite precipitates is affected by the type of matrix microstructure. We conclude that the cementite size and morphology, as well as the matrix mechanical properties are the predominating factors influencing the decomposition behavior of cementite. The compositional effects of Cr and Mn on cementite stability calculated by complementary density functional theory (DFT) calculations are minor in the current scenario.

For several decades, the formation of carbon(C)-rich domains upon room temperature aging of supersaturated martensite has been a matter of debate. C-rich tweed-like patterns are observed to form after short aging times at room temperature and coarsen upon further aging. Here, we present a systematic atomic-scale investigation of carbide formation in Fe-15Ni-1C (wt.%) martensite after two to three years of isothermal room temperature aging by a combination of atom probe tomography and transmission electron microscopy. Owing to the sub-zero martensite start temperature of −25 °C, a fully austenitic microstructure is maintained at room temperature and the martensitic phase transformation is initiated during quenching in liquid nitrogen. In this way, any diffusion and redistribution of C in martensite is suppressed until heating up the specimen and holding it at room temperature. The microstructural changes that accompany the rearrangement of C atoms have been systematically investigated under controlled isothermal conditions. Our results show that after prolonged room temperature aging nanometer-sized, plate-shaped η-Fe2C carbides form with a macroscopic martensite habit plane close to {521}. The orientation relationship between the η-Fe2C carbides and the parent martensite grain (α′) follows [001]α’//[001]η, ( 1 ¯ 10 ) α’//(020)η. The observation of η-Fe2C–carbide formation at room temperature is particularly interesting, as transition carbides have so far only been reported to form above 100 °C. After three years of room temperature aging a depletion of Fe is observed in the η carbide while Ni remains distributed homogenously. This implies that the substitutional element Fe can diffuse several nanometers in martensite at room temperature within three years.

Performing electron microscopy and atom probe tomography at the same location on the same specimen combines the strengths of electron microscopy, which is primarily the analysis of defects and crystal structures, with the strengths of atom probe tomography, which is primarily the robust, accurate and sensitive three dimensional compositional analysis. This viewpoint article provides a summary of the broad range of electron microscopy techniques that have been performed on atom probe specimens to date. It describes what technique is best suited to address a specific materials science question and finishes with an outlook on possible future developments in the field.

Nanoscale solute segregation to or near lattice defects is a coupled diffusion and trapping phenomenon that occurs in superalloys at high temperatures during service. Understanding the mechanisms underpinning this crucial process will open pathways to tuning the alloy composition for improving the high-temperature performance and lifetime. Here, we introduce an approach combining atom probe tomography with high-end scanning electron microscopy techniques, in transmission and backscattering modes, to enable direct investigation of solute segregation to defects generated during high-temperature deformation such as dislocations in a heat-treated Ni-based superalloy and planar faults in a CoNi-based superalloy. Three protocols were elaborated to capture the complete structural and compositional nature of the targeted defect in the alloy.

The authors wish to make the following corrections to this paper [...]

In this study, we investigate the fundamentals of deformation-driven cementite decomposition during rolling contact fatigue in a binary Fe-0.74C (wt.%) steel with pearlitic microstructure. To reveal the involved nano-scale mechanisms, we apply transmission electron microscopy and atom probe tomography, as well as the combination of both techniques on the same probe volume for correlative structural and chemical analysis. After ~32,500 individual ball contacts under a nominal Hertzian contact stress of ~1,250 MPa, cementite lamellae are consistently depleted in carbon (C) down to ~20 at.%, which is a reduction of 20% in comparison to the original stoichiometric composition of 25 at.% before deformation. By electron diffraction on atom probe tip volumes, we show that this under-stoichiometric cementite still maintains its crystal structure. The potential effect of temperature increase during rolling contact fatigue on cementite decomposition is addressed by carrying out annealing experiments at 150°C and 250°C for 30 minutes after rolling contact fatigue. Our results show that slip transmission across cementite lamellae is primarily responsible for the observed C-depletion in cementite. We quantitatively discuss slip transmission from ferrite to cementite using slip trace analysis and correlate the amount of slip activity with the observed C-depletion. In this way, we explain the formation of under-stoichiometric cementite by combined slip transmission and solute drag by dislocations, where C is transported out of cementite by dislocation gliding through cementite lamellae. Only afterward, cementite decomposition in terms of phase dissolution is suggested to occur by the dislocation-shuffle mechanism.

Premature failure of bearings during rolling contact fatigue is often associated with the formation of white etching cracks (WECs). Crack surface rubbing of WECs transforms the original bainitic/martensitic microstructure into white etching areas (WEAs), comprised of nanocrystalline ferrite. The grain size and carbon content vary within the WEA. Here, we show by atom probe tomography and scanning electron microscopy, that there is an inversely proportional relationship between grain size and carbon content in WEAs formed in 100Cr6 bearings that failed by WECs in service. We explain this phenomenon by the reduction of grain boundary energy through carbon segregation. Depending on the carbon content, this reduces the driving force for recrystallization and grain coarsening, thereby stabilizing the nanocrystalline microstructure. No such effect is observed for the substitutional element chromium. The smallest grain size (

Background Column damage is a unique degradation pattern observed in cobalt-chromium-molybdenum (CoCrMo) femoral head taper surfaces that resemble column-like troughs in the proximal-distal direction. We investigate the metallurgical origin of this phenomenon. Methods Thirty-two severely damaged CoCrMo femoral head retrievals from 7 different manufacturers were investigated for the presence of column damage and chemical inhomogeneities within the alloy microstructure via metallographic evaluation of samples sectioned off from the femoral heads. Results Column damage was found to affect 37.5% of the CoCrMo femoral heads in this study. All the column-damaged femoral heads exhibited chemical inhomogeneities within their microstructures, which comprised of regions enriched or depleted in molybdenum and chromium. Column damage appears as a dissolution of the entire surface with preferential corrosion along the molybdenum and chromium depleted regions. Conclusion Molybdenum and chromium depleted zones serve as initiation sites for in vivo corrosion of the taper surface. Through crevice corrosion, the degradation spreads to the adjacent non-compositionally depleted areas of the alloy as well. Future improved alloy and processing recipes are required to ensure no chemical inhomogeneity due to segregation of solute elements are present in CoCrMo femoral heads.

We report on the strengthening and strain hardening mechanisms in an aged high-Mn lightweight steel (Fe-30.4Mn-8Al-1.2C, wt.%) studied by electron channeling contrast imaging (ECCI), transmission electron microscopy (TEM), atom probe tomography (APT) and correlative TEM/APT. Upon isothermal annealing at 600 °C, nano-sized κ-carbides form, as characterized by TEM and APT. The resultant alloy exhibits high strength and excellent ductility accompanied by a high constant strain hardening rate. In comparison to the as-quenched κ-free state, the precipitation of κ-carbides leads to a significant increase in yield strength (∼480 MPa) without sacrificing much tensile elongation. To study the strengthening and strain hardening behavior of the precipitation-hardened material, deformation microstructures were analyzed at different strain levels. TEM and correlative TEM/APT results show that the κ-carbides are primarily sheared by lattice dislocations, gliding on the typical face-centered-cubic (fcc) slip system {111} , leading to particle dissolution and solute segregation. Ordering strengthening is the predominant strengthening mechanism. As the deformation substructure is characterized by planar slip bands, we quantitatively studied the evolution of the slip band spacing during straining to understand the strain hardening behavior. A good agreement between the calculated flow stresses and the experimental data suggests that dynamic slip band refinement is the main strain hardening mechanism. The influence of κ-carbides on mechanical properties is discussed by comparing the results with that of the same alloy in the as-quenched, κ-free state.

We investigated a high-purity cold-rolled martensitic Fe-9wt%Mn alloy. Tensile tests performed at room temperature after tempering for 6 h at 450 °C showed discontinuous yielding. Such static strain ageing phenomena in Fe are usually associated with the segregation of interstitial elements such as C or N to dislocations. Here we show by correlative transmission electron microscopy (TEM)/atom probe tomography (APT) experiments that in this case Mn segregation to edge dislocations associated with the formation of confined austenitic states causes similar effects. The local chemical composition at the dislocation cores was investigated for different tempering temperatures by APT relative to the adjacent bcc matrix. In all cases the Mn partitioning to the dislocation core regions matches to the one between ferrite and austenite in thermodynamic equilibrium at the corresponding tempering temperature. Although a stable structural and chemical confined austenitic state has formed at the dislocation cores these regions do not grow further even upon prolonged tempering. Simulation reveals that the high Mn enrichment along the edge dislocation lines (25 at.%Mn at 450 °C) cannot be described merely as a Cottrell atmosphere formed by segregation driven by size interaction. Thermodynamic calculations based on a multiscale model indicate that these austenite states at the dislocation cores are subcritical and defect-stabilized by the compression stress field of the edge dislocations. Phenomenologically, these states are the 1D equivalent to the so-called complexions which have been extensively reported to be present at 2D defects, hence have been named linear complexions.

Atom probe tomography was employed to characterize the microstructure and C distribution in the white etching area (WEA) of a martensitic 100Cr6 bearing steel subjected to rolling contact fatigue. Different from its surrounding matrix where a plate-like martensitic structure prevails, the WEA exhibits equiaxed grains with a uniform grain size of about 10 nm. Significant C grain boundary enrichment (>7.5at.%) and an overall higher C concentration than the nominal value are observed in the WEA. These results suggest that the formation of WEA results from severe local plastic deformation that causes dissolution of carbides and the redistribution of C.

A density variation in shear bands visible by electron microscopy is correlated with compositionally altered locations measured by atom-probe tomography in plastically-deformed Al85.6Y7.5Fe5.8 metallic-glass ribbons. Twocompositionally distinct regions are identified along shear bands, one is Al-rich (~92 at.%), the other is Al depleted(~82.5 at.%) and both regions show marginal concentration fluctuations of Y and Fe. The elementalre-distribution is observed within shear bands only, and no chemical exchange with the surrounding glassy matrixis observed. Macroscopic deformation of metallic glasses (MGs) is mainly confinedto shear bands (SBs), which limits the ductility to often less thana fewpercent intension[1–6].Much effort has been devoted to enhancethe ductility by controlling SBs initiation and propagation [7–18]. Due tothe key role of SBs in the deformation, better understanding of theirstructure and chemical composition is of interest. Transmission electron microscopy (TEM) has been extensively usedto study the underlying mechanisms of vitrification and nanocrystallizationin Al-based MGs [19–22] in order to obtain glass/crystalcomposites with enhanced ductility [23,24]. High-angle annular darkfieldscanning TEM(STEM-HAADF) has revealed a periodic spatial variationof dark and bright regions of intensity along thin SBs in plasticallydeformedAl88Y7Fe5 [7], Pd40Ni40P20 [8] andZr52.5Cu17.9Ni14.6Al10Ti5 [25]MGs (all compositions are given in at.% throughout the text). Since thedark field intensity corresponds to a resultant atomic (Z) contrast, theobserved periodic variations can originate from the combination oflocal compositional and mass-density fluctuations. The variationswere also observed for Zr-, Pd- and Mg-based MGs [26] by a synchrotronX-ray tomography. For an Al88Y7Fe5 MG ribbon, cold-rolled to~28% thickness reduction, mass-density changes between −9% and+6% and an average fluctuation length of ~50–110 nm in b10 nmthick SBs were observed [7]. Periodic-density fluctuations along SBswere also reported for cold-rolled Pd40Ni40P20 MGs with up to 20%thickness reduction [8]. Some reports correlate the fluctuations to ahigh volumetric strain during SBs formation [11]. Although the structureof SBs has been described by atomistic simulations [27–29], it is unclearwhether density variation inside SBs is a generally-observedphenomenon. Unlike the observations reported in Ref. [8], no densityfluctuations inside SBs were observed in Pd40Ni40P20 bulk MGs compressedto an engineering plastic strain of 0.4 [30]. Despite the effortsto characterize the local low- and high-mass-density variations in SBsfor Al88Y7Fe5 glass, the corresponding compositional changes have notbeen rigorously analyzed except by Rösner et al. [25] using STEMenergy-dispersive spectroscopy (STEM-EDS). Nevertheless, varying foil thickness and a projection plane of SBs in the EDS analyzed volumecauses practical challenges to accurately quantify the composition insideSBs, which are clearly visible in the edge-on perspective only, andhence characterizing 3-D aspects of the elemental re-distribution bySTEM is difficult.Atom-probe tomography (APT) enables quantitative 3-D compositionalanalysis with the near atomic resolution with equal sensitivityin the range of 10 ppm for all elements [31], which makes it an idealprobe for chemical changes associated with SBs. Typically, APT hasbeen used to study solute partitioning [32], vitrification and crystallization [33,34] in Al-basedMGs. There have been relatively a fewattemptsto investigate both, the mass-density and the compositional fluctuationsalong SBs by APT. Hunter et al. [35] studied the origin of SBs initiationin a Ti-based glass/nanocrystalline composite and they observedno compositional fluctuations along SBs. For APT technique, theatomic-density and spatial resolutions are prone to artifacts due toion-trajectory aberrations and local magnification effects. It has beenargued that the apparent density change observed in SBs by APT couldbe an artifact due to the local lowering of the evaporation field at SBs positionsin a tip [35]. The presence of such aberration effects forbids to unambiguouslylocate SBs in terms of APT alone, especially when thechemical variations inside SBs and relative to the adjacent matrix aresubtle. In this paper, a combined TEM/APT characterization [36] is appliedto directly correlate density fluctuations along SBs visible bySTEM with chemical alterations analyzed by APT.

Analysis and understanding of the role of hydrogen in metals is a significant challenge for the future of materials science, and this is a clear objective of recent work in the atom probe tomography (APT) community. Isotopic marking by deuteration has often been proposed as the preferred route to enable quantification of hydrogen by APT. Zircaloy-4 was charged electrochemically with hydrogen and deuterium under the same conditions to form large hydrides and deuterides. Our results from a Zr hydride and a Zr deuteride highlight the challenges associated with accurate quantification of hydrogen and deuterium, in particular associated with the overlap of peaks at a low mass-to-charge ratio and of hydrogen/deuterium containing molecular ions. We discuss possible ways to ensure that appropriate information is extracted from APT analysis of hydrogen in zirconium alloy systems that are important for nuclear power applications.

The process of building an open source library of simulated field desorption maps for differently oriented synthetic tips of the face-centered cubic, body-centered cubic, and hexagonal-close-packed crystal structures using the open source software TAPSim is reported. Specifically, the field evaporation of a total set of 4 × 101 single-crystalline tips was simulated. Their lattices were oriented randomly to sample economically the fundamental zone of crystal orientations. Such data are intended to facilitate the interpretation of low-density zone lines and poles that are observed on detector hit maps during Atom Probe Tomography (APT) experiments. The datasets and corresponding tools have been made publicly available to the APT community in an effort to provide better access to simulated atom probe datasets. In addition, a computational performance analysis was conducted, from which recommendations are made as to which key tasks should be optimized in the future to improve the parallel efficiency of TAPSim.

Since white etching crack (WEC) phenomena primarily occur in high carbon steels, we elucidate the role of carbon in this failure mechanism in bearings. The nano-crystalline ferritic regions that make up the white etching area (WEA) are formed by crack surface rubbing leading to complete decomposition of the initial microstructure by severe plastic deformation. In order to analyze local carbon compositions on µm-nm length scales, we employ electron probe microanalysis, transmission electron microscopy and atom probe tomography. We focus on a 100Cr6 wind turbine gearbox bearing which failed in service due to extensive formation of WEC networks below the raceway surface and subsequent spalling. Our results show a significantly lower carbon content in the WEA as compared to the nominal alloy composition. At the same time, we find carbon deposits with a carbon content of > 85 at%, which are heterogeneously distributed across WEAs. We explain this observation by assuming segregation of excess carbon from the WEA to the open crack surfaces during crack surface rubbing. Further, the presence of a “lubricating” carbon film at the WEC surfaces might explain the accelerated failure by WECs as compared to classical rolling contact fatigue.

The strain hardening mechanism of a high-Mn lightweight steel (Fe-30.4Mn-8Al-1.2C (wt%)) is investigated by electron channeling contrast imaging (ECCI) and transmission electron microscopy (TEM). The alloy is characterized by a constant high strain hardening rate accompanied by high strength and high ductility (ultimate tensile strength: 900 MPa, elongation to fracture: 68%). Deformation microstructures at different strain levels are studied in order to reveal and quantify the governing structural parameters at micro- and nanometer scales. As the material deforms mainly by planar dislocation slip causing the formation of slip bands, we quantitatively study the evolution of the slip band spacing during straining. The flow stress is calculated from the slip band spacing on the basis of the passing stress. The good agreement between the calculated values and the tensile test data shows dynamic slip band refinement as the main strain hardening mechanism, enabling the excellent mechanical properties. This novel strain hardening mechanism is based on the passing stress acting between co-planar slip bands in contrast to earlier attempts to explain the strain hardening in high-Mn lightweight steels that are based on grain subdivision by microbands. We discuss in detail the formation of the finely distributed slip bands and the gradual reduction of the spacing between them, leading to constantly high strain hardening. TEM investigations of the precipitation state in the as-quenched state show finely dispersed atomically ordered clusters (size

High-entropy alloys (HEAs) and metallic glasses (MGs) are two material classes based on the massive mixing of multiple-principal elements. HEAs are single or multiphase crystalline solid solutions with high ductility. MGs with amorphous structure have superior strength but usually poor ductility. Here, the stacking fault energy in the high-entropy nanotwinned crystalline phase and the glass-forming-ability in the MG phase of the same material are controlled, realizing a novel nanocomposite with near theoretical yield strength (G/24, where G is the shear modulus of a material) and homogeneous plastic strain above 45% in compression. The mutually compatible flow behavior of the MG phase and the dislocation flux in the crystals enable homogeneous plastic co-deformation of the two regions. This crystal-glass high-entropy nanocomposite design concept provides a new approach to developing advanced materials with an outstanding combination of strength and ductility.

In article https://doi.org/10.1002/advs.201903008, Shanoob Balachandran, Zita Zachariah, and co‐authors reveal the fretting corrosion mechanisms in a cobalt alloy/titanium alloy taper junction present in modular hip implants. Although the cobalt alloy is more wear resistant than the titanium alloy, microploughing phenomena on the titanium alloy surface promote tribocorrosion in the cobalt alloy, resulting in metal ion release into the body.

The high nitrogen bearing steel X30CrMoN15-1, marketed under commercial names such as Cronidur30, VC444, NitroMax and N360, is well-known for its outstanding rolling contact fatigue and corrosion properties. More importantly, there are no reports about failure by white etching cracks for this alloy, although this premature failure mode is frequently observed in conventional high carbon bearing steels. To understand the origin of this superior performance, we analyze in the current paper its microstructure prior to rolling contact fatigue by means of scanning electron microscopy, atom probe tomography and nano-indentation, and relate this to its thermal processing history. The origin of the exceptional white etching crack resistance of this alloy is rationalized in terms of the mechanical and thermodynamic stability of the precipitates, the different grain boundary segregation behavior between nitrogen and carbon as indicated by the atom probe results, and the cleanliness of the steel.

White etching cracks (WECs) and the associated white etching areas (WEAs) are responsible for failure of widely spread engineering applications such as bearings and railways. Although the phenomenon is known for more than 100 years, the underlying mechanisms are still a matter of debate. In this work, we thoroughly investigate a 100Cr6 wind turbine gearbox bearing after failure in service operation. Based on our findings from detailed microstructure characterization on multiple length scales we formulate a new consistent explanation for the formation of WEAs during rolling contact fatigue. We propose a mechanism of moving WECs - not only in terms of conventional crack propagation but also as a movement of the crack normal to its plane. During cyclic loading the crack continuously changes its position and leaves behind a severely plastically deformed area consisting of ferritic nano-grains, i.e. the WEAs. The atomic-scale delocalization of the crack plane in a single loading cycle adds up to micron-sized WEAs during repetitive loading/unloading. After the initial formation of a fatigue crack around inclusions, crack face rubbing occurs during compressive loading cycles. This leads to the formation of WEA by local severe plastic deformation. It also leads to partial cohesion of the abutting crack faces and material transport between them. As a result, the WEC opens at a slightly shifted position with respect to its former location during unloading.

We study the mechanisms of deformation driven chemical mixing in a metallic nanocomposite model system. More specific, we investigate shear banding at the atomic scale in an amorphous CuZr/ crystalline Cu nanolaminate, deformed by microindentation. Three CuZr/Cu multilayer systems (100 nm Cu/100 nm CuZr, 50 nm Cu/100 nm CuZr, and 10 nm Cu/100 nm CuZr) are fabricated to study the effect of layer thickness on shear band formation and deformation induced alloying. The chemical and structural evolution at different strain levels are traced by atom probe tomography and transmission electron microscopy combined with nano-beam diffraction mapping. The initially pure crystalline Cu and amorphous CuZr layers chemically mix by cross-phase shear banding after reaching a critical layer thickness. The Cu inside the shear bands develops a high dislocation density and can locally undergo transition to an amorphous state when sheared and mixed. We conclude that the severe deformation in the shear bands in the amorphous layer squeeze Zr atoms into the Cu dislocation cores in the Cu layers (thickness

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

a b s t r a c t Grain boundaries influence mechanical, functional, and kinetic properties of metallic alloys. They can be manipulated via solute decoration enabling changes in energy, mobility, structure, and cohesion or even promoting local phase transformation. In the approach which we refer here to as ‘segregation engineering’ solute decoration is not regarded as an undesired phenomenon but is instead utilized to manipulate specific grain boundary structures, compositions and properties that enable useful material behavior. The underlying thermodynamics follow the adsorption isotherm. Hence, matrix-solute combinations suited for designing interfaces in metallic alloys can be identified by considering four main aspects, namely, the segregation coefficient of the decorating element; its effects on interface cohesion, energy, structure and mobility; its diffusion coefficient; and the free energies of competing bulk phases, precipitate phases or complexions. From a practical perspective, segregation engineering in alloys can be usually realized by a modest diffusion heat treatment, hence, making it available in large scale manufacturing.

We have investigated the strain-hardening mechanisms across the relevant scales in a Fe-22Mn-0.6C (wt.%) twinning induced plasticity steel by multi-scale microstructure characterization. The approach makes use of electron microscopy techniques such as electron channeling contrast imaging (ECCI) to characterize microstructure features at the micro/nanoscale, and atomic-scale investigations of partitioning behavior across interfaces and solid solution/clustering effects by atom probe tomography (APT). The contribution of most relevant microstructure features to strain hardening is analyzed.

Carbon partitioning between ferritic and austenitic phases is essential for austenite stabilization in the most advanced steels such as those produced by the quenching and partitioning (Q&P) process. The atomistic analysis of the carbon partitioning in Q&P alloys is, however, difficult owing to the simultaneous occurrence of bainite transformation, which can also contribute to carbon enrichment into remaining austenite and hence overlap with the carbon partitioning from martensite into austenite. Therefore, we provide here a direct atomic-scale evidence of carbon partitioning from martensite into austenite without the presence of bainite transformation. Carbon partitioning is investigated by means of atom probe tomography and correlative transmission electron microscopy. A model steel (Fe–0.59 wt.% C (2.7 at.% C)–2.0 wt.% Si–2.9 wt.% Mn) with martensite finish temperature below room temperature was designed and used in order to clearly separate the carbon partitioning between martensite and austenite from the bainite transformation. The steel was austenitized at 900 °C, then water-quenched and tempered at 400 °C. Approximately 8 vol.% retained austenite existed in the as-quenched state. We confirmed by X-ray diffraction and dilatometry that austenite decomposition via bainite transformation did not occur during tempering. No carbon enrichment in austenite was observed in the as-quenched specimen. On the other hand, clear carbon enrichment in austenite was observed in the 400 °C tempered specimens with a carbon concentration inside the austenite of 5–8 at.%. The results hence quantitatively revealed carbon partitioning from martensite to austenite, excluding bainite transformation during the Q&P heat treatment.

Recent advances in synchrotron based X-ray imaging and diffraction techniques offer interesting new possibilities for mapping 3D grain shapes and crystallographic orientations in different classes of polycrystalline materials. X-ray diffraction contrast tomography (DCT) is a monochromatic beam imaging technique combining the principles of X-ray micro-tomography and three-dimensional X-ray diffraction microscopy (3DXRD). DCT provides simultaneous access to 3D grain shape, crystallographic orientation and attenuation coefficient distribution at the micrometer length scale. The microtexture of the material can be quantified in more detail by post-processing of the volume data provided by DCT. In particular one can determine the local crystallographic habit plane of the grain boundary by analysing the surface normal of the grain boundary with respect to the crystal orientation. The resulting five parameter description of the character of individual grain boundaries could previously be produced only by destructive characterization techniques. Statistical analysis of this kind of data can be expected to provide new insight into various physico-chemical processes, driven by the grain boundary energy (corrosion, coarsening). © 2009 Elsevier B.V.

Welcoming steel's new complexion Metals have a number of famous properties, including good strength and ductility. Controlling these properties frequently requires modifying the number and type of structural defects in a metal alloy. Kuzmina et al. produced a new type of defect, called a linear complexion, in magnesium-rich steel (see the Perspective by Kaplan). These complexions are chemically and structurally distinct regions located inside a linear defect and are isolated from the bulk by a layer of dislocations. The discovery suggests a new path for targeting defects and improving alloy development. Science , this issue p. 1080 ; see also p. 1059

The microstructure of complex steels can be manipulated by utilising the interaction between the local mechanical distortions associated with lattice defects, such as dislocations and grain boundaries, and solute components that segregate to them. Phenomenologically these phenomena can be interpreted in terms of the classical Gibbs adsorption isotherm, which states that the total system energy can be reduced by removing solute atoms from the bulk and segregating them at lattice defects. Here we show how this principle can be utilised through appropriate heat treatments not only to enrich lattice defects by solute atoms, but also to further change these decorated regions into confined ordered structural states or even to trigger localized decomposition and phase transformations. This principle, which is based on the interplay between the structure and mechanics of lattice defects on the one hand and the chemistry of the alloy's solute components on the other hand, is referred to as segregation engineering. In this concept solute decoration to specific microstructural traps, viz. lattice defects, is not taken as an undesired effect, but instead seen as a tool for manipulating specific lattice defect structures, compositions and properties that lead to beneficial material behavior. Owing to the fairly well established underlying thermodynamic and kinetic principles, such local decoration and transformation effects can be tuned to proceed in a self-organised manner by adjusting (i) the heat treatment temperatures for matching the desired trapping, transformation or reversion regimes, and (ii) the corresponding timescales for sufficient solute diffusion to the targeted defects. Here we show how this segregation engineering principle can be applied to design self-organized nano- and microstructures in complex steels for improving their mechanical properties.

In many cases, the three-dimensional reconstructions from atom probe tomography (APT) are not sufficiently accurate to resolve crystallographic features such as lattice planes, shear bands, stacking faults, dislocations or grain boundaries. Hence, correlative crystallographic characterization is required in addition to APT at the exact same location of the specimen. Also, for the site-specific preparation of APT tips containing regions of interest (e.g. grain boundaries) correlative electron microscopy is often inevitable. Here we present a versatile experimental setup that enables performing correlative focused ion beam milling, transmission electron microscopy (TEM), and APT under optimized characterization conditions. The setup was designed for high throughput, robustness and practicability. We demonstrate that atom probe tips can be characterized by TEM in the same way as a standard TEM sample. In particular, the use of scanning nanobeam diffraction provides valuable complementary crystallographic information when being performed on atom probe tips. This technique enables the measurement of orientation and phase maps as known from electron backscattering diffraction with a spatial resolution down to one nanometer.

Grain boundary segregation leads to nanoscale chemical variations that can alter a material's performance by orders of magnitude (e.g., embrittlement). To understand this phenomenon, a large number of grain boundaries must be characterized in terms of both their five crystallographic interface parameters and their atomic-scale chemical composition. We demonstrate how this can be achieved using an approach that combines the accuracy of structural characterization in transmission electron microscopy with the 3D chemical sensitivity of atom probe tomography. We find a linear trend between carbon segregation and the misorientation angle ω for low-angle grain boundaries in ferrite, which indicates that ω is the most influential crystallographic parameter in this regime. However, there are significant deviations from this linear trend indicating an additional strong influence of other crystallographic parameters (grain boundary plane, rotation axis). For high-angle grain boundaries, no general trend between carbon excess and ω is observed; i.e., the grain boundary plane and rotation axis have an even higher influence on the segregation behavior in this regime. Slight deviations from special grain boundary configurations are shown to lead to unexpectedly high levels of segregation.

Der Aufwand bei der Entwicklung eines neuen Abgassystems wird zu einem erheblichen Teil von Problemen der Schalldampfung bestimmt. Eine der wesentlichen Herausforderungen besteht darin, den Schall in unterschiedlichen Frequenzbereichen wirksam zu dampfen, ohne die Motorleistung zu beeintrachtigen. Die Friedrich Boysen GmbH & Co. KG, hat ein Abgassystem entwickelt, das einen Helmholtz-Resonator und eine Abgasklappe kombiniert. Das System, das Mitte 2001 zum ersten Mal serienmasig in einem Pkw zum Einsatz kommen soll, wurde zum Patent angemeldet.

Compared with the existent techniques, atom probe tomography is a unique technique able to chemically characterize the internal interfaces at the nanoscale and in three dimensions. Indeed, APT possesses high sensitivity (in the order of ppm) and high spatial resolution (sub nm). Considerable efforts were done here to prepare an APT tip which contains the desired grain boundary with a known structure. Indeed, site-specific sample preparation using combined focused-ion-beam, electron backscatter diffraction, and transmission electron microscopy is presented in this work. This method allows selected grain boundaries with a known structure and location in Cu(In,Ga)Se2 thin-films to be studied by atom probe tomography. Finally, we discuss the advantages and drawbacks of using the atom probe tomography technique to study the grain boundaries in Cu(In,Ga)Se2 thin-film solar cells.

Compared with the existent techniques, atom probe tomography is a unique technique able to chemically characterize the internal interfaces at the nanoscale and in three dimensions. Indeed, APT possesses high sensitivity (in the order of ppm) and high spatial resolution (sub nm). Considerable efforts were done here to prepare an APT tip which contains the desired grain boundary with a known structure. Indeed, site-specific sample preparation using combined focused-ion-beam, electron backscatter diffraction, and transmission electron microscopy is presented in this work. This method allows selected grain boundaries with a known structure and location in Cu(In,Ga)Se2 thin-films to be studied by atom probe tomography. Finally, we discuss the advantages and drawbacks of using the atom probe tomography technique to study the grain boundaries in Cu(In,Ga)Se2 thin-film solar cells.

Three-dimensional (3D) short fatigue crack growth behaviour in a cast magnesium alloy, Elektron 21, was studied using a combination of X-ray diffraction contrast tomography (DCT) and microtomography at the European Synchrotron Radiation Facility. A 3D map of grain shapes and crystallographic orientations was produced in a miniature fatigue specimen using DCT. A focused ion beam instrument was used to introduce small notches in selected grains. Synchrotron microtomography was used to study the evolution of fatigue cracks from these notches during interrupted in situ fatigue cycling. Stage I crack growth occurred preferentially on the basal plane of the magnesium hexagonal close packed crystal, with local crack growth rates between 4 and 40 nm cycle. Retardations in the local crack growth rate were observed in certain grains and at certain grain boundaries. The observed interactions between the crack and the polycrystalline microstructure can be explained using Schmid factors and a development of the tilt-twist model of Zhai and Wilkinson (Zhai T, Wilkinson AJ, Martin JW. Acta Mater 2000;48;4917). Copyright 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

International audience; no abstract