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Wear-related energy and material loss cost over 2500 Billion Euro per year. Traditional wisdom suggests that high-strength materials reveal low wear rates, yet, their plastic deformation mechanisms also influence their wear performance. High strength and homogeneous deformation behavior, which allow accommodating plastic strain without cracking or localized brittle fracture, are crucial for developing wear-resistant metals. Here, we present an approach to achieve superior wear resistance via in-situ formation of a strong and deformable oxide nanocomposite surface during wear, by reaction of the metal surface with its oxidative environment, a principle that we refer to as ‘reactive wear protection’. We design a TiNbZr-Ag alloy that forms an amorphous-crystalline oxidic nanocomposite surface layer upon dry sliding. The strong (2.4 GPa yield strength) and deformable (homogeneous deformation to 20% strain) nanocomposite surface reduces the wear rate of the TiNbZr-Ag alloy by an order of magnitude. The reactive wear protection strategy offers a pathway for designing ultra-wear resistant alloys, where otherwise brittle oxides are turned to be strong and deformable for improving wear resistance., Wear-resistant metals have long been a pursuit of reducing wear-related energy and material loss. Here the authors present the ‘reactive wear protection’ strategy via friction-induced in situ formation of strong and deformable oxide nanocomposites on a surface.

The recent development of electron-sensitive and pixelated detectors has attracted the use of four-dimensional scanning transmission electron microscopy (4D-STEM). Here, we present a precession electron diffraction-assisted 4D-STEM technique for automated orientation mapping using diffraction spot patterns directly captured by an in-column scintillator-based complementary metal-oxide-semiconductor (CMOS) detector. We compare the results to a conventional approach, which utilizes a fluorescent screen filmed by an external charge charge-coupled device camera. The high-dynamic range and signal-to-noise characteristics of the detector greatly improve the image quality of the diffraction patterns, especially the visibility of diffraction spots at high scattering angles. In the orientation maps reconstructed via the template matching process, the CMOS data yield a significant reduction of false indexing and higher reliability compared to the conventional approach. The angular resolution of misorientation measurement could also be improved by masking reflections close to the direct beam. This is because the orientation sensitive, weak, and small diffraction spots at high scattering angles are more significant. The results show that fine details, such as nanograins, nanotwins, and sub-grain boundaries, can be resolved with a sub-degree angular resolution which is comparable to orientation mapping using Kikuchi diffraction patterns. © 2021 Cambridge University Press. All rights reserved.

Additive manufacturing processes, such as laser powder bed fusion, require steady powder processing but often exhibit poor flowability and low powder bed densities. Reducing the attractive Van-der-Waals force through nanoparticle coating can enhance initially poor flowability. We investigated the effect of dry-coating nanosized SiO2 on gas-atomized CoCrFeNi powders containing different amounts of particles

The effects of hydrogen in metals are a pressing issue causing severe economic losses due to material deterioration by hydrogen embrittlement. A crucial understanding of the interactions of hydrogen with different microstructure features can be reached by nanoindentation due to the small volumes probed. Even more, in situ testing while charging the sample with hydrogen prevents the formation of concentration gradients due to hydrogen desorption. Two custom electrochemical cells for in situ testing were built in-house to charge the sample with hydrogen during nanoindentation: “front-side” charging with the sample and the indenter tip immersed into the electrolyte, and “back-side” charging where the analyzed region is never in contact with the solution. During front-side charging, surface degradation often occurs which also negatively influences analyses after hydrogen charging. The back-side charging approach proposed in this work is a promising technique for studying in situ the effects of hydrogen in alloys under mechanical loads, while completely excluding the influence of the electrolyte on the nanoindented surface. Hydrogen diffusion from the charged back-side toward the testing surface is here demonstrated by Kelvin probe measurements in ferritic FeCr alloys, used as a case study due to the high mobility of hydrogen in the bcc lattice. During nanoindentation, a reduction on the shear stress necessary for dislocations nucleation due to hydrogen was observed using both setups; however, the quantitative data differs and a contradictory behavior was found in hardness measurements. Finally, some guidelines for the use of both approaches and a summary of their advantages and disadvantages are presented. Graphical abstract

Homogeneous face-centered cubic (fcc) polycrystalline CoCrFeNi films were deposited at room temperature on (0001)alpha-Al2O3 (c-sapphire). Phase and morphological stability of 200 to 670 nm thick films were investigated between 973 K and 1423 K. The fcc-phase persists while the original texture of 30-100 nm wide columnar grains evolves into ~10 or ~1000 micron wide grains. Only the grains having specific orientation relationships to the sapphire grow; as in the case of pure fcc metal (M) films 4 orientation relationships (OR) are found: OR1 (M(111)[1-10]//alpha-Al2O3 (0001)[1-100]) and OR2 (M(111)[1-10]//alpha-Al2O3 (0001)[11-20]) and their twin-related variants (OR1t and OR2t). Below 1000 K, the film microstructure stabilizes into 10 micron wide OR1 and OR1t twin grains independent of film thickness. Above 1000 K, the OR2 and OR2t grains expand to sizes exceeding more than a 1000 times the film thickness. Upon annealing, the films either retain their integrity or break-up depending on the competing kinetics of grain growth and grain boundary grooving. Triple junctions of the grain boundaries, the major actors in film stability, were tracked. Thinner films and higher temperatures favor film break-up by dewetting from the holes grooved at the triple junctions down to the substrate. The grain boundaries of the OR2 and OR2t grains migrate fast enough to overcome the nucleation of holes from which break-up could initiate. The growth of the OR2 and OR2t grains in this complex alloy is faster than in pure fcc metals at equivalent homologous annealing temperatures., 6 figures and 3 tables

Molecular dynamics simulations are performed to investigate the role of a coherent {\Sigma}3 (111) twin boundary on the plastic deformation behavior of Cu nanopillars. Our work reveals that the mechanical response of pillars with and without the twin boundary is decisively driven by the characteristics of initial dislocation sources. In the condition of comparably large pillar size and abundant initial mobile dislocations, overall yield and flow stresses are controlled by the longest, available mobile dislocation. An inverse correlation of the yield and flow stresses with the length of the longest dislocation is established, and its extrapolation agrees well with experimental yield stress data. The experimentally reported subtle differences in yield and flow stresses between pillars with and without the twin boundary are thus likely related to the maximum lengths of the mobile dislocations. In the condition of comparably small pillar size, for which a reduction of mobile dislocations during heat treatment and mechanical loading occurs, the mechanical response of pillars with and without the twin boundary can be clearly distinguished. Dislocation starvation during deformation is more clearly present in pillars without the twin boundary than in pillars with the twin boundary because the twin boundary acts as a pinning surface for the dislocation network., Comment: - Main document: 29 pages, 12 figures, 3 tables - Supplementary Material: 13 pages, 11 figures, 2tables

We report on a multilayered structure comprising of rock-salt (rs) structured CrN layers of constant thickness and AlN layers of varying thicknesses, which surprisingly enables the growth of metastable zinc-blende (zb) AlN layers for certain layer-thickness combinations. The multilayer exhibits an atomic and electronic structure gradient as revealed using advanced electron microscopy and electron spectroscopy. Gradient structures are also accompanied by a modulation of the chemical compositions. A combined experimental analysis based on valence electrons and inner shell electrons allowed mapping the mechanical properties of the multilayer at the nanometer scale and further unveiled the effect of oxygen impurities on the bulk modulus. We found that the presence of oxygen impurities causes a remarkable reduction of the bulk modulus of rs-CrN while having no significant effect on the bulk modulus of the stable wurtzite structure wz-AlN layers. The findings are unambiguously validated by theoretical calculations using density functional theory. © 2020 Acta Materialia Inc.

Understanding deformation mechanisms in silicon is critical for reliable design of miniaturized devices operating at high temperatures. Bulk silicon is brittle, but it becomes ductile at about 540 °C. It creeps (deforms plastically with time) at high temperatures (∼800 °C). However, the effect of small size on ductility and creep of silicon remains elusive. Here, we report that silicon at small scales may deform plastically with time at lower temperatures (400 °C) above a threshold stress. We achieve this stress by bending single-crystal silicon microbeams using an in situ thermomechanical testing stage. Small size, together with bending, localize high stress near the surface of the beam close to the anchor. This localization offers flaw tolerance, allowing ductility to win over fracture. Our combined scanning, transmission electron microscopy, and atomic force microscopy analysis reveals that as the threshold stress is approached, multiple dislocation nucleation sites appear simultaneously from the high-stressed surface of the beam with a uniform spacing of about 200 nm between them. Dislocations then emanate from these sites with time, lowering the stress while bending the beam plastically. This process continues until the effective shear stress drops and dislocation activities stop. A simple mechanistic model is presented to relate dislocation nucleation with plasticity in silicon.

Microscale mechanical behaviour of single crystalline Barium Titanate (BaTiO3), a ferroelectric ceramic was studied by uniaxial in situ micropillar compression and nanoindentation. It was observed that pillars below 1 µm diameter reached the theoretical strength of BaTiO3 whereas larger pillars yielded at lower stress values with multiple stress drops confirming slip activity. A size scaling exponent of 0.96 ± 0.09 was estimated for BaTiO3 which is close to one of the soft fcc metals. The material's strength, hardness and deformation behaviour did not show any dependence on the character of the ferroelectric domain, within our error bars.

While the theory of grain boundary (GB) structure has a long history1 and the proposition that grain boundaries can undergo phase transformations was made already 50 years ago2,3, the search for these GB transitions has been in vain. The underlying assumption was that multiple stable and metastable states exist for different grain boundary orientations4,5,6. The terminology complexion was recently proposed to distinguish between those interfacial states that differ in any equilibrium thermodynamic property7. Different types of complexions and transitions between them have been characterized mostly in binary or multicomponent systems 8,9,10,11,12,13,14,15,16,17,18,19. Novel simulation schemes have provided a new perspective on the phase behavior of interfaces and showed that grain boundary transitions can occur in a multitude of material systems20,21,22,23,24. However, their direct experimental observation and transformation kinetics in an elemental metal remained elusive. Here, we show atomic scale grain boundary phase coexistence and transformations at symmetric and asymmetric [11-1] tilt grain boundaries in elemental copper (Cu). We found the coexistence of two different grain boundary structures at Σ19b grain boundaries by atomic resolution imaging. Evolutionary grain boundary structure search and clustering analysis21,25,26 finds the same structures and predicts the properties of these GB phases. Furthermore, finite temperature molecular dynamics simulations explore their coexistence and transformation kinetics. Our results demonstrate how grain boundary phases can be kinetically trapped enabling atomic scale room temperature observations. Our work paves the way for atomic scale in situ studies of grain boundary phase transformations in metallic grain boundaries. In the past, only indirect measurements have indicated the existence of interfacial transitions9,15,27,28,29. Now, their atomic scale role on the influence of abnormal grain growth, non-Arrhenius type diffusion or liquid metal embrittlement can be explored.

Extended diffusion layers of the cubic C15 and hexagonal C14 and C36 NbCo2 Laves phases with concentration gradients covering their entire homogeneity ranges were produced by the diffusion couple technique. Single-phase and single-crystalline micropillars of the cubic and hexagonal NbCo2 Laves phases were prepared in the diffusion layers by focused ion beam (FIB) milling. The influence of chemical composition, structure type, orientation and pillar size on the deformation behavior and the critical resolved shear stress (CRSS) was studied by micropillar compression tests. The pillar orientation influences the activated slip systems, but the deformation behavior and the CRSS are independent of orientation. The deformation of the smallest NbCo2 micropillars (0.8 µm in top diameter) appears to be dislocation nucleation controlled and the CRSS approaches the theoretical shear stress for dislocation nucleation. The CRSS of the 0.8 µm-sized NbCo2 micropillars is nearly constant from 26 to 34 at.% Nb where the C15 structure is stable. It decreases as the composition approaches the Co-rich and Nb-rich boundaries of the homogeneity range where the C15 structure transforms to the C36 and the C14 structure, respectively. The decrease in the CRSS at these compositions is related to the reduction of shear modulus and stacking fault energy. As the pillar size increases, stochastic deformation behavior and large scatter in the CRSS values occur and obscure the composition effect on the CRSS.

Nanostructuring metals through nanograins and nanotwins is an efficient strategy for strength increase as the mean free path of dislocations is reduced. Yet, nanostructures are thermally often not stable, so that the material properties deteriorate upon processing or during service. Here, we introduce a new strategy to stabilize nanotwins by an interfacial nanophase design and realize it in an interstitial high-entropy alloy (iHEA). We show that nanotwins in a carbon-containing FeMnCoCrNi iHEA can remain stable up to 900 °C. This is enabled by co-segregation of Cr and C to nanoscale 9R structures adjacent to incoherent nanotwin boundaries, transforming the 9R structures into elongated nano-carbides in equilibrium with the nanotwin boundaries. This nanoscale 9R structures assisted nano-carbide formation leads to an unprecedented thermal stability of nanotwins, enabling excellent combination of yield strength (~1.1 GPa) and ductility (~21%) after exposure to high temperature. Stimulating the formation of nanosized 9R phases by deformation together with interstitial doping establishes a novel interfacial-nanophase design strategy. The resulting formation of nano-carbides at twin boundaries enables the development of strong, ductile and thermally stable bulk nanotwinned materials.

Laves phases belong to the group of tetrahedrally close-packed intermetallic phases, and their crystal structure can be described by discrete layer arrangements. They often possess extended homogeneity ranges and the general notion is that deviations from stoichiometry are accommodated by anti-site atoms or vacancies. The present work shows that excess Nb atoms in a Nb-rich NbFe2 C14 Laves phase can also be incorporated in various types of planar defects. Aberration-corrected scanning transmission electron microscopy and density functional theory calculations are employed to characterize the atomic configuration of these defects and to establish stability criteria for them. The planar defects can be categorized as extended or confined ones. The extended defects lie parallel to the basal plane of the surrounding C14 Laves phase and are fully coherent. They contain the characteristic Zr4Al3-type (O) units found in the neighboring Nb6Fe7 µ phase. An analysis of the chemical bonding reveals that the local reduction of the charge transfer is a possible reason for the preference of this atomic arrangement. However, the overall layer stacking deviates from that of the perfect µ phase. The ab initio calculations establish why these exceptionally layered defects can be more stable configurations than coherent nano-precipitates of the perfect µ phase. The confined defects are observed with pyramidal and basal habit planes. The pyramidal defect is only ~1 nm thick and resembles the perfect µ phase. In contrast, the confined basal defect can be regarded as only one single O unit and it appears as if the stacking sequence is disrupted. This configuration is confirmed by ab initio calculations to be metastable.

Titanium thin films were deposited on silicon nitride (SiNx) coated Si, NaCl, and sapphire substrates varying the deposition conditions using e-beam evaporation to investigate thin film growth modes. The microstructure and texture evolution in dependence of substrate, deposition rate, film thickness, and substrate temperature were studied using X-ray diffraction, electron backscatter diffraction, and transmission electron microscopy. Thin films obtained on SiNx and NaCl substrates were nanocrystalline, while the films deposited on sapphire transformed from nanocrystalline to single crystalline at deposition temperatures above 200 °C. Predominantly, a surface plane orientation of (0002) was observed for the single crystalline films due to the minimization of surface energy. The orientation relationship of epitaxial single crystalline films grown on C-plane sapphire substrate is found to be (0002)Ti ‖ ( 0006 ) Sapphire , 〈 11 2 ¯ 0 〉 Ti ‖ 〈 03 3 ¯ 0 〉 Sapphire . In this orientation relationship, both the total surface and strain energy of the film are minimized. The results were complemented by resistivity measurements using the four-point probe method reporting an increase from ~ 60 μ Ω cm to ~ 95 μ Ω cm for single crystalline and nanocrystalline films, respectively.

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

Using in-situ nanoindentation experiments it is possible to study the dislocation mechanisms which unfold under an indenter.Large-scale atomistic simulations of the same are possible due to similarities in length scale, provided that defects can be included in the simulation. Yet, nanoindentation simulations have so far been mostly undertaken on defect free samples, while studies with pre-existing defects are few. The latter show that the average hardness is not affected by the presence of pre-existing defects, which justifies the use of ideal crystals in such simulations. However, this observation is counter-intuitive, as indenter-defect interactions should lead to work hardening and manifest themselves in hardness calculations. Our simulations along with a new look at the evolution of dislocations under the indenter, show for the first time, that hardness in atomistic simulations is influenced by pre-existing defects in the sample. Utilizing a face-centred tetragonal TiAl bicrystal with misfit dislocations at the interface, to populate the sample with defects, we correlate the contact-pressure variations to defect-indenter interactions. We show that the measured contact-pressure is affected by the presence and nature of defects under the indenter. Dislocation pile ups lead to intermittent rise in contact pressure, while seamless growth leads to steady convergence. The sensitivity to detect such defect interactions depends upon indenter size while convergence to average hardness is a result of curvature accommodation near the surface. Our findings prove that pre-existing defects have a profound influence on calculated hardness in indentation simulations which also corroborates with experimental observations in the literature. © 2021 Elsevier Ltd

Acta materialia 217, 117147 (2021). doi:10.1016/j.actamat.2021.117147, Published by Elsevier Science, Amsterdam [u.a.]

The iron aluminides discussed here are Fe–Al-based alloys, in which the matrix consists of the disordered bcc (Fe,Al) solid solution (A2) or the ordered intermetallic phases FeAl (B2) and Fe3Al (D03). These alloys possess outstanding corrosion resistance and high wear resistance and are lightweight materials relative to steels and nickel-based superalloys. These materials are evoking new interest for industrial applications because they are an economic alternative to other materials, and substantial progress in strengthening these alloys at high temperatures has recently been achieved by applying new alloy concepts. Research on iron aluminides started more than a century ago and has led to many fundamental findings. This article summarizes the current knowledge of this field in continuation of previous reviews.

Cu-Cr alloys with ∼32 at.% Cr were rapidly solidified by splat quenching or laser melting techniques with the intention to form a very fine grained, non-equilibrium nanostructure similar to those obtained by severe plastic deformation or thin film deposition. The rapidly solidified Cu-Cr alloys were analyzed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Both synthesis techniques lead to a similar two-phase microstructure with a nearly pure fcc Cu matrix with μm grain sizes and bcc Cr particles highly supersaturated with Cu. Splat quenching provides finer bcc particles with dimensions of less than 50 nm compared to laser melting with particle sizes of 100–2000 nm. In case of laser melting, (14 ± 2) at.% Cu are contained in the bcc phase, while splat quenching freezes (20 ± 2) at.% Cu in the bcc particles. The microstructures are discussed and compared to the non-equilibrium microstructures reported in literature using severe plastic deformation and thin films deposition.

In situ nanomechanical testing provides critical insight into the fundamental processes that lead to deformation phenomena in materials. Often, in situ tests are performed in relevant conditions such as high or low temperatures, tribological contact, gas environments, or under radiation exposure. Modern diffraction and imaging methods of materials under load provide high spatial resolution and enable extraction of quantitative mechanical data from local microstructure components or nano-sized objects. The articles in this issue cover recent advances in different types of in situ nanomechanical testing methods, spanning from dedicated nanomechanical testing platforms and microelectromechanical systems devices to deformation analyses via in situ diffraction and imaging methods. This includes scanning electron microscopy, advanced scanning transmission electron microscopy, electron diffraction, x-ray diffraction, and synchrotron techniques. Emerging areas such as in situ tribology enable novel insights into the origin of deformation mechanisms, while the evolution of microelectromechanical systems for controlled in situ testing provide opportunities for advanced control and loading strategies. Discussion on the current state of the art for in situ nanomechanical testing and future opportunities in imaging, strain sensing, and testing environments are also addressed.

Nanoindentation tests have shown that exposure to deuterium plasma causes a decrease in pop-in load and an increase in hardness of tungsten. In this work, we use micro-compression tests to investigate the plastic deformation and apparent strain hardening of tungsten exposed to deuterium plasma. In comparison with the pillars tested at reference state, the pillars tested after exposure showed an increased apparent strain hardening rate as well as an increased multitude of slip traces, which is attributed to the presence of deuterium. The micro-compression results are in agreement with the nanoindentation study on the pop-in and hardness of tungsten.

The dynamics of solid state dewetting phenomena of a 50nm thick, mazed bicrystalline Al film on single crystalline α-Al2O3(sapphire) substrates was studied in-situ using an environmental scanning electron microscope (ESEM). The bicrystalline Al thin films served as a model system where the influence of grain boundaries and texture effects are well determined compared to polycrystalline films. The experiments were performed in controlled oxidizing and reducing atmospheres at 773K and 823K, respectively, to shed light on the differences in dewetting mechanisms and dynamics.While the reducing atmosphere led to spontaneous dewetting at 823K after an incubation time of a few minutes, a hierarchical dewetting process was observed for the sluggish dewetting under oxidizing conditions. Voids initiated at (substrate or surface) defects and expanded trying to maintain a hexagonal shape. Pinning and depinning processes led to a discontinuous void growth and irregular void shapes including finger instabilities. As a consequence, the void growth followed a variety of power law exponents between 0.10 and 0.55. A new microkink-flow mechanism was discovered at the terminating Al planes at the void.

The important role of grain boundaries for the mechanical properties of polycrystalline materials has been recognized for many decades. Up to now, the underlying deformation mechanisms at the nano- and micro scale are not understood quantitatively. An overview of the synthesis and subsequent mechanical testing of specific grain boundaries at the micro and sub-micro scale is discussed in the present contribution, including various methods for producing one or multiple specific, crystallographically well-defined grain boundaries. Furthermore, established micromachining methods for isolating and measuring local dislocation-grain boundary interactions are portrayed. Examples of the techniques described are shown with to the aid of copper grain boundaries.

Metal-nanoparticles (M-NPs) were synthesized in a wet-chemical synthesis route in tunable aryl alkyl ionic liquids (TAAILs) based on the 1-aryl-3-alkyl-substituted imidazolium motif from Ru3(CO)12 and Ir4(CO)12 by microwave-heating induced thermal decomposition. The size and size dispersion of the NPs were determined by transmission electron microscopy (TEM) to an average diameter of 2.2(±0.1) to 3.9(±0.3) nm for Ru-NPs and to an average diameter of 1.4(±0.1) to 2.4(±0.1) nm for Ir-NPs. The TAAILs used contain the same bis(trifluoromethylsulfonyl)imide anion but differ in the substituents on the 1-aryl ring, e.g. 2-methyl-, 4-methoxy- and 2,4-dimethyl groups and in the 3-alkyl chain lengths (C4H9, C5H11, C8H17, C9H19, C11H23). All used TAAILs are suitable for the stabilization of Ru- and Ir-NPs over months in the IL dispersion. Different from all other investigations on M-NP/IL systems which we are aware of the particle separation properties of the TAAILs vary strongly as a function of the aryl substituent. Good NP separation can be achieved with the 4-methoxyphenyl- and 2,4-dimethylphenyl-substituted ILs, irrespective of the 3-alkyl chain lengths. Significant aggregation can be observed for 2-methylphenyl-substituted ILs. The good NP separation can be correlated with a negative electrostatic potential at the 4-methoxyphenyl or 4-methylphenyl substituent that is in the para-position of the aryl ring, whereas the 2-(ortho-)methylphenyl group assumes no negative potential. e-ePC-SAFT calculations were used to validate that the interactions between ILs and the washing agents (required for TEM analyses) do not cause the observed aggregation/separation behaviour of the M-NPs. Ru-NPs were investigated as catalysts for the solvent-free hydrogenation of benzene to cyclohexane under mild conditions (70 °C, 10 bar) with activities up to 760 (mol cyclohexane) (mol Ru)−1 h−1 and over 95% conversion in ten consecutive runs for Ru-NPs. No significant loss of catalytic activity could be observed.

We report evidence of Re and Mo segregation (up to 2.6 at.% and 1 at.%) along with Cr and Co to the dislocations inside of {\gamma}' precipitates in a second generation Ni-based single crystal superalloy, after creep deformation at 750{\deg}C under an applied stress of 800 MPa. The observed segregation effects can be rationalized through bridging the solute partitioning behavior across the {\gamma}/{\gamma}' interface and the pipe diffusion mechanism along the core of the dislocation line. This understanding can provide new insights enabling improved alloy design.

We unravel the nature of twin boundary-associated strengthening in Fe-Mn-C twinning-induced plasticity steel (TWIPs) by micro-pillar compression tests. Dislocation interactions with a coherent twin boundary and their role on strain hardening were investigated. The results indicate that twin-matrix bundles dynamically introduced by deformation twinning and their interaction with dislocations are required for strengthening Fe-Mn-C TWIPs, while single coherent twin boundaries enable dislocation transmission. Correlative studies on orientation dependent deformation mechanisms, detailed dislocation-twin boundary interactions, and the resulting local stress-strain responses suggest that twin boundary-associated strengthening is primarily caused by the reduction of the mean free dislocation path in nano-twinned microstructures.

International audience; The bulk quaternary equiatomic CoCrFeNi alloy is studied extensively in literature. Under experimental conditions, it shows a single-phase fcc structure and its physical and mechanical properties are similar to those of the quinary equiatomic CoCrFeMnNi alloy. Many studies in literature have focused on the mechanical properties of bulk nanocrystalline high entropy alloys or compositionally complex alloys, and their microstructure evolution upon annealing. The thin film processing route offers an excellent alternative to form nanocrystalline alloys. Due to the high nucleation rate and high density of defects in thin films synthesized by sputtering, the kinetics of microstructure evolution is often accelerated compared to those taking place in the bulk. Here, thin films are used to study the phase evolution in nanocrystalline CoCrFeNi deposited on Si/SiO 2 and c-sapphire substrates by magnetron cosputtering from elemental sources. The phases and microstructure of the films are discussed in comparison to the bulk alloy. The main conclusion is that second phases can form even at room temperature provided there are sufficient nucleation sites.

Materials and design 206, 109757 (2021). doi:10.1016/j.matdes.2021.109757, Published by Elsevier Science, Amsterdam [u.a.]

In this work, we experimentally establish the isothermal nanofacet evolution at an asymmetric ∑ 5 tilt grain boundary in the Cu-Ag system using a diffusion couple approach. We investigate the nanofacet formation along the grain boundary in dependence of the Ag solute excess concentration. The initial grain boundary dissociates into asymmetric Ag-lean segments and Ag-rich symmetric (210) segments. Increasing Ag excess leads to an increase in Ag-rich facet segment length, while the length of the asymmetric facets remains constant. From this, we construct a grain boundary nanofaceting diagram deduced from our experiments relating local atomic structure, overall inclination and Ag solute excess.

Grain boundaries (GBs) in metals usually increase electrical resistivity due to their distinct atomic arrangement compared to the grain interior. While the GB structure has a crucial influence on the electrical properties, its relationship with resistivity is poorly understood. Here, we perform a systematic study on the resistivity and structure relationship in Cu tilt GBs, employing high resolution in-situ electrical measurements coupled with atomic structure analysis of the GBs. Excess volume and energies of selected GBs are calculated using molecular dynamics simulations. We find a consistent relation between the coincidence site lattice (CSL) type of the GB and its resistivity. The most resistive GBs are high range of low-angle GBs (misorientation 14 to 18 degrees) with twice the resistivity of high angle tilt GBs, due to the high dislocation density and corresponding strain fields. Regarding the atomistic structure, GB resistivity approximately correlates with the GB excess volume. Moreover, we show that GB curvature increases resistivity by about 80%, while phase variations and defects within the same CSL type do not considerably change it., 20 pages, 7 Figures, 1 Table, Supplementary material

Scanning nano-beam electron diffraction with a pixelated detector was employed to investigate the orientation relationship of nanometer sized, irradiation induced G-phase (M$_6$Ni$_{16}$Si$_{7}$) precipitates in an austenite matrix. Using this detector, the faint diffraction spots originating from the small G-phase particles could be resolved simultaneously as the intense matrix reflections. The diffraction patterns were analyzed using a two-stage template matching scheme, whereby the matrix is indexed first and the precipitates are indexed second after subtraction of the matrix contribution to the diffraction patterns. The results show that G-phase forms with orientation relationships relative to austenite that are characteristic of face-centered cubic (FCC) to body-centered cubic (BCC) transformations. This work demonstrates that nano-beam electron diffraction with a pixelated detector is a promising technique to investigate orientation relationships of nano-sized precipitates with complex crystal structures in other material systems with relative ease., Comment: 12 pages double spaced text, 4 figures, accepted manuscript in Scripta Materialia

International audience; It is well-known that grain boundaries (GBs) increase the electrical resistivity of metals due to their enhanced electron scattering. The resistivity values of GBs are determined by their atomic structure; therefore, assessing the local resistivity of GBs is highly significant for understanding structure–property relationships. So far, the local electrical characterization of an individual GB has not received much attention, mainly due to the limited accuracy of the applied techniques, which were not sensitive enough to detect the subtle differences in electrical resistivity values of highly symmetric GBs. Here, we introduce a detailed methodology to probe in situ or ex situ the local resistivity of individual GBs in Cu, a metallic model system we choose due to its low resistance. Both bulk Cu samples and thin films are investigated, and different approaches to obtain reliable and accurate resistivity measurements are described, involving the van der Pauw technique for macroscopic measurements as well as two different four-point-probe techniques for local in situ measurements performed inside a scanning electron microscope. The in situ contacts are realized with needles accurately positioned by piezodriven micromanipulators. Resistivity results obtained on coincidence site lattice GBs (incoherent Σ3 and asymmetric Σ5) are reported and discussed. In addition, the key experimental details as well as pitfalls in the measurement of individual GB resistivity are addressed.

Materials and design 191, 108582 (2020). doi:10.1016/j.matdes.2020.108582, Published by Elsevier Science, Amsterdam [u.a.]

High entropy alloys are generally considered to be single phase material. This state is, however, typically a non-equilibrium state after fabrication at high cooling rates. Phase constitution after fabrication or heat treatment is mostly known for isothermal annealing only and for casts as well as rapidly quenched alloys. Knowledge on early phase separation stages of high entropy alloys and their mechanisms are missing so far. Here, we present results on phase separation at intermediate cooling rates, by characterization of gas atomized powder of the AlCoCr0.75Cu0.5FeNi alloy. Although investigation by X-ray diffraction and Electron Backscatter Diffraction indicates a single-phase nature of the powder particles, aberration-corrected scanning transmission electron microscopy and atom probe tomography reveal a nanoscale phase separation into Ni-Al-rich B2 and Fe-Cr-rich A2 regions as well as a high number density of 3.1x1024 Cu-rich clusters per m3 in the B2 matrix. The observed phase separation and cluster formation are linked to spinodal decomposition and nucleation processes, respectively. The study highlights that adequate characterization techniques need to be chosen when making statements about phase stability and structural evolution in compositionally complex alloys., 33 pages, 12 figures

Alloys based on titanium aluminides received a lot of attention because of their capability to substitute Ni-based superalloys in high-temperature applications. However, the phase equilibria between the main microstructure constituents (αTi), (βTi), γ (TiAl) and α2 (Ti3Al) can be shifted significantly by impurities such as oxygen especially at high temperatures. This behavior is investigated on the tie-triangle (αTi) + (βTi) + γ (TiAl) in the ternary Ti-Al-Nb system at 1300 °C. An explanation for this behavior could be the occupation of octahedral voids by impurities in certain phases.

Frontiers in Materials 7, 89 (2020). doi:10.3389/fmats.2020.00089, Published by Frontiers Media, Lausanne

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

The mechanical properties of high-entropy alloys (HEAs) are still not deeply understood. Detailed knowledge of the strengthening mechanism, especially, the atomistic origin of solid solution hardening and its interplay with dislocation plasticity is needed. Here, we report on the dislocation glide behavior of a FeCoCrNiMn face-centered cubic (FCC) single crystal studied by in situ deformation in a transmission electron microscope (TEM). The threshold shear stress for dislocation glide in a thin foil is measured from dislocation curvature as exceeding 400 MPa. Interestingly, dislocations are prevented from straightening upon unloading due to high frictional stresses.

A face-centered cubic (FCC) phase in electro-polished specimens for transmission electron microscopy of commercially pure titanium has sometimes been reported. Here, a combination of atom-probe tomography, scanning transmission electron microscopy and low-loss electron energy loss spectroscopy is employed to study both the crystal structural and chemical composition of this FCC phase. Our results prove that the FCC phase is actually a TiHx (x ≥ 1) hydride, and not a new allotrope of Ti, in agreement with previous reports. The formation of the hydride is discussed.

In conventional metallic materials, strength and ductility are mutually exclusive, referred to as strength-ductility trade-off. Here, we demonstrate an approach to improve the strength and ductility simultaneously by introducing micro-banding and the accumulation of a high density of dislocations in single-phase high-entropy alloys (HEAs). We prepare two compositions (Cr10Mn50Fe20Co10Ni10 and Cr10Mn10Fe60Co10Ni10) with distinctive different stacking fault energies (SFEs) as experimental materials. The strength and ductility of the Cr10Mn50Fe20Co10Ni10 HEA are improved concurrently by grain refinement from 347.5 ± 216.1 µm to 18.3 ± 9.3 µm. The ultimate tensile strength increases from 543 ± 4 MPa to 621 ± 8 MPa and the elongation to failure enhances from 43±2% to 55±1%. To reveal the underlying deformation mechanisms responsible for such a strength-ductility synergy, the microstructural evolution upon loading is investigated by electron microscopy techniques. The dominant deformation mechanism observed for the Cr10Mn50Fe20Co10Ni10 HEA is the activation of micro-bands, which act both as dislocation sources and dislocation barriers, eventually, leading to the formation of dislocation cell structures. By decreasing grain size, much finer dislocation cell structures develop, which are responsible for the improvement in work hardening rate at higher strains (>7%) and thus for the increase in both strength and ductility. In order to drive guidelines for designing advanced HEAs by tailoring their SFE and grain size, we compute the SFEs of Cr10MnxFe70–xCo10Ni10 (10 ≤ x ≤ 60) based on first principles calculations. Based on these results the overall changes on deformation mechanism can be explained by the influence of Mn on the SFE.

Wafer curvature measurements reported in literature for polycrystalline (often textured) and epitaxial fcc metal thin films on hard substrates show a characteristic “signature” in the stress-temperature evolution for either type of films. While epitaxial films reveal characteristic elastic – ideal plastic deformation with no dislocation storage and highly repeatable cycles, polycrystalline films show considerable hardening upon cooling in addition to the relaxation by diffusional creep at elevated temperatures. In the present study, we study the deformation characteristics of an electron beam deposited epitaxial nanotwinned Ag on Si (111) substrate. The twin spacing λ of the nanotwinned Ag is controlled by suitable heat treatment and the “signature” thermomechanical deformation curves by wafer curvature measurements are recorded for twin spacings varying from 20 nm to 1 μm. Further, deformation is compared to other small scale deformation studies on fcc metals such as epitaxial bicrystal films, bicrystal micropillars containing a coherent twin boundary and nanotwinned micropillars.

The indentation-induced plasticity and roughness have been investigated intensively by experiments and simulations during the last decades. However, the precise mechanisms of how dislocation flow leads to pile-up formation are still not completely understood, although this is one of the initial steps causing surface roughening in tribological contacts at low loads. In this work, $$\{001\}$${001}-, $$\{101\}$${101}- and $$\{111\}$${111}-grain orientations in an austenite stainless steel [(face-centered cubic (FCC) phase]) are indented with varying load forces. By using scanning electron-based methods and slip plane analysis, we reveal: (1) how slip-steps show the change of pile-up formation, (2) how the slip-plane inclination determines the dislocation flow and (3) how slip-plane interactions result in the final pile-up shape during indentation. We find that the flow direction transforms from the forward flow to the sideway at a transition angle of $$55^\circ{-}58^\circ $$55∘-58∘ between the slip-plane and the surface. We use large displacement finite element method simulations to validate an inversion of the resolved shear stress at this transition angle. We provide insights into the evolution of plasticity in dislocation-mediated FCC metal indentations, with the potential application of this information for indentation simulations and for understanding the initial stage of scratching during tribology in the future.

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.

Hydrogen exposure has been found to result in metal embrittlement. In this work, we use nanoindentation to study the mechanical properties of polycrystalline tungsten subjected to deuterium plasma exposure. For the purpose of comparison, nanoindentation tests on exposed and unexposed reference tungsten were carried out. The results exhibit a decrease in the pop-in load and an increase in hardness on the exposed tungsten sample after deuterium exposure. No significant influence of grain orientation on the pop-in load was observed. After a desorption time of td ≥ 168 h, both the pop-in load and hardness exhibit a recovering trend toward the reference state without deuterium exposure. The decrease of pop-in load is explained using the defactant theory, which suggests that the presence of deuterium facilitates the dislocation nucleation. The increase of hardness is discussed based on two possible mechanisms of the defactant theory and hydrogen pinning of dislocations.

Tensile tests were carried out in high-purity, polycrystalline copper alloys with three concentrations of sulfur impurities (14, 27 and 7920 at ppm) at temperatures between 20 °C and 400 °C. The ductility drops with increasing sulfur concentration and temperature while the ultimate tensile strength increases. The alloys exhibit a grain size of several millimeters and contain mostly random grain boundaries (GBs). The microstructure and composition is investigated by transmission electron microscopy (TEM) and atom probe tomography (APT). The microstructure of the samples with sulfur contents of 14 and 27 ppm consists of globular grains and neither of the microanalytical techniques employed reveals the formation of Cu-sulfides or sulfur segregation to GBs. Even after annealing at 500 °C, no sulfide formation or sulfur segregation to GBs was detected. In the alloy with a sulfur content of 7920 ppm, a dendritic structure is observed and in the interdendritic region monoclinic Cu2S precipitates with a size range from 5 nm to several μm are observed at GBs and also within the grains. The influence of S on the ductility is discussed considering the TEM and APT results.

The microstructural and mechanical characterization of an equiatomic YGdTbDyHo high entropy alloy with hexagonal close-packed structure was performed. The phase state and chemical homogeneity of the solid solution were analysed with respect to crystal structure, phase stability, and oxide formation. It was found that Y-rich precipitates form at grain boundaries and that the alloy is prone to oxidation, leading to a homogeneous distribution of ∼10 nm-sized oxides in the grain interiors. The plastic response at the sub-grain level was studied in terms of the activated slip systems, critical resolved shear stresses (CRSS), and strain hardening using micropillar compression tests. We observe plastic slip on the basal system, with a CRSS of 196 ± 14.7 MPa. Particle strengthening and strength dependence on sample size are discussed on the basis of dislocation particle interaction and mechanical size effects.

Nanoindentation has been used intensively during the last decades to characterize experimentally the elastic and plastic material properties of phases at the microscale. Accompanying simulations have investigated the plastic mechanisms during nanoindentation. While experiments and simulations have led to a thorough understanding of most mechanisms during nanoindentation, the plasticity on positively and negatively inclined slip planes is still not completely clear. In this work, {1 0 0}-, {1 0 1}- and {1 1 1}-grains of an austenitic stainless steel are indented to better understand the dislocation mediated plasticity through slip step analysis. We observe that slip occurs on positively and negatively inclined slip planes during nanoindentation and we propose methods to differentiate between both types of planes. We find that slip steps on positively inclined slip planes form preferentially during the early stage as compared to the formation of slip steps on negative inclination, which occurs during the later deformation stage due to the change in surface topography. By calculating the resolved shear stress in the presence and absence of pile-ups, we reveal the origin of slip on positively and negatively inclined planes as well as the reason for the sequence of occurrences. We conclude that accounting for the surface topography evolution in experiments and simulations is essential in predicting the plastic slip activation during nanoindentation. Keywords: Nanoindentation, Slip step, Plasticity, Austenitic stainless steel

Cubic and hexagonal NbCo2 Laves phases are known to have composition dependent hardness and yield strength. However, it is unknown whether this dependence is also reflected in their fracture toughness values. In order to elucidate the fracture behavior, single-crystalline micro-cantilevers of the cubic and hexagonal NbCo2 Laves phases having different compositions were fabricated in the diffusion layers grown by the diffusion couple technique. Micro-cantilever bending tests were performed to study the composition- and crystal-structure-dependence of the fracture toughness. To exclude the influence of micro-cantilever geometry, pentagonal and rectangular beams were tested and found to result in the same fracture toughness value. The present results reveal that neither a change of the crystal structure nor a change in chemical composition has a significant influence on the fracture toughness of NbCo2 Laves phase. Keywords: Laves phase, Fracture toughness, Micro-cantilever, Composition, Diffusion couple

A composition-spread Cu-Zr thin film library with Zr contents from 2.5 up to 6.5 at.% was synthesized by magnetron sputtering on a thermally oxidized Si wafer. The compositional and microstructural variations of the Cu-Zr thin film across the composition gradient were examined using energy dispersive X-ray spectroscopy, X-ray diffraction, and high-resolution scanning and transmission electron microscopy of cross-sections fabricated by focused ion beam milling. Composition-dependent hardness and elastic modulus values were obtained by nanoindentation for measurement areas with discrete Zr contents along the composition gradient. Similarly, the electrical resistivity was investigated by 4-point resistivity measurements to study the influence of Zr composition and microstructural changes in the thin film. Both, the mechanical and electrical properties reveal a significant increase in hardness and resistivity with increasing Zr content. The trends of the mechanical and functional properties are discussed with respect to the local microstructure and composition of the thin film library.

Micro- and nanomechanical testing has seen a rapid development over the last decade with miniaturized test rigs and MEMS-based devices providing access to the mechanical properties and performance of materials from the micrometer down to the tenths of nanometer length scale. In this overview, we summarize firstly the different testing concepts with excursions into recent imaging and diffraction developments, which turn micro- and nanomechanical testing into “quantitative mechanical microscopy” by resolving the underlying material physics and simultaneously providing mechanical properties. A special focus is laid on the pitfalls of micro-compression testing with its stringent boundary conditions often hampering reliable experiments. Additionally, the challenges of instrumented micro- and nanomechanical testing at elevated temperature are summarized. From the wide variety of research topics employing micro- and nanomechanical testing of materials we focus here on miniaturized samples and test rigs and provide three examples to elucidate the state-of-the-art of the field: (i) probing the “strength” of individual grain boundaries in metals, (ii) temperature dependent deformation mechanisms in metallic nanolayered and -alloyed structures, and (iii) the prospects and challenges of fracture studies employing micro- and nanomechanical testing of brittle and ductile monolithic materials, and materials containing interfaces. Proven concepts and new endeavors are reported for the topics discussed in this overview.