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The influence of temperature on the deformation behaviour of the C15 CaAl2 Laves phase, a key constituent for enhancing the mechanical properties of Mg alloys up to service temperatures of 200 °C, remains largely unexplored. This study presents, for the first time, the nanoscale brittle-to-ductile transition (BDT) of this intermetallic phase through in situ testing including nanoindentation and micropillar splitting conducted at elevated temperatures. By correlating observations from these techniques, changes in deformation of CaAl2 were identified in relation to temperature. High-temperature nanoindentation quantitatively determined the BDT temperature range, and revealed that CaAl2 undergoes a BDT at ∼0.55 Tm, exhibiting an intermediate region of microplasticity. A noticeable decrease in nanoindentation hardness was observed at ∼450–500 °C, while indentation cracking was not observed above 300 °C. Results from high-temperature micropillar splitting revealed cracking and brittle pillar splitting up to 300 °C, with an increase in apparent fracture toughness from 0.9 ± 0.1 MPa·√m to 2.8 ± 0.3 MPa·√m, and subsequent crack-free plastic deformation from 400 °C. Transmission electron microscopy analysis of the deformed material from nanoindentation revealed that the BDT of CaAl2 may be attributed to enhanced dislocation plasticity with increasing temperature.

Nano-structured copper thin films present numerous applications for miniaturization of electronic devices. Their long term stability is key for reliable functionality. This work explores the thermal stability and solid state dewetting of a Cu-Co solid solution thin film and compares it to pure Cu. As according to the phase diagram Co is practically immiscible in Cu at room temperature, a metastable solid solution of Cu-15 at. % Co was deposited as thin film on a sapphire wafer. The microstructural evolution of the Co super-saturated film at temperatures ranging from 673 to 1073 K was evaluated using X-ray diffraction and high resolution microscopy techniques such as scanning electron and transmission electron microscopy. Interestingly, there is a competition between grain growth and phase separation. Co precipitates at grain boundaries acting as pinning sites preventing rapid grain growth during heat treatment at intermediate annealing temperature. However, grain growth occurs very quickly at higher temperatures, once the elemental phases of Cu and Co are formed. The competition between grain growth and phase separation and their consequence for dewetting are discussed.

Abstract Grain boundaries, the two-dimensional defects between differently oriented crystals, tend to preferentially attract solutes for segregation. Solute segregation has a significant effect on the mechanical and transport properties of materials. At the atomic level, however, the interplay of structure and composition of grain boundaries remains elusive, especially with respect to light interstitial solutes like B and C. Here, we use Fe alloyed with B and C to exploit the strong interdependence of interface structure and chemistry via charge-density imaging and atom probe tomography methods. Direct imaging and quantifying of light interstitial solutes at grain boundaries provide insight into decoration tendencies governed by atomic motifs. We find that even a change in the inclination of the grain boundary plane with identical misorientation impacts grain boundary composition and atomic arrangement. Thus, it is the smallest structural hierarchical level, the atomic motifs, that controls the most important chemical properties of the grain boundaries. This insight not only closes a missing link between the structure and chemical composition of such defects but also enables the targeted design and passivation of the chemical state of grain boundaries to free them from their role as entry gates for corrosion, hydrogen embrittlement, or mechanical failure.

Hydrogen barrier coatings are protective layers consisting of materials with a low intrinsic hydrogen diffusivity and solubility, showing the potential to delay, reduce or hinder hydrogen permeation. Hydrogen barrier coatings are expected to enable steels, which are susceptible to hydrogen embrittlement, specifically cost-effective low alloy-steels or light-weight high-strength steels, for applications in a hydrogen economy. Predominantly, ceramic coating materials have been investigated for this purpose, including oxides, nitrides and carbides. In this review, the state of the art with respect to hydrogen permeation is discussed for a variety of coatings. Al2O3, TiAlN and TiC appear to be the most promising candidates from a large pool of ceramic materials. Coating methods are compared with respect to their ability to produce layers with suitable quality and their potential for scaling up for industrial use. Different setups for the characterisation of hydrogen permeability are discussed, using both gaseous hydrogen and hydrogen originating from an electrochemical reaction. Finally, possible pathways for improvement and optimisation of hydrogen barrier coatings are outlined.

Damage tolerance of a thin film attached to a substrate is dependent on several parameters such as film thickness, film orientation, residual stresses, nature of interfaces, microstructure and defects present. Here we study the fracture resistance and crack growth trajectory in BaTiO3 thin films attached to elasticially stiff substrates using micromechanical experiments and finite element modeling. Microcantilever fracture tests are carried out on bi-layered systems of BaTiO3 film on Pt-Si and SrTiO3 substrates to study the effect of interfaces, texture and elastic mismatch on fracture toughness. The substrates in the bi-layers are chosen to force the crack to experience a shielding effect in terms of a decrease in the crack driving force. Experiments revealed an unexpectedly large increase in fracture toughness when the crack tip is closer to a stiffer substrate, qualitatively matching the predictions from the numerical model. The bi-layered films attached to the substrate showed 125% (on Pt-Si) and 160% (on SrTiO3) increase in fracture toughness compared to the free-standing films, for the first time, revealing the significant effect of elastic modulus of the substrate on improving the fracture resistance at such micrometer length scales.

The role of a ∑3{112} incoherent twin boundary (ITB) on the shear stress of Cu at the micron scale has been investigated through microcompression of bi-crystalline pillars containing ITB, as well as single-crystalline pillars, in two different compression directions. The Cu sample containing ITBs was synthesized using magnetron sputtering on a sapphire substrate. Firstly, pillars along [111] compression direction were milled on the film surface. As multiple slip systems were activated upon loading, the dislocation-ITB interaction in this direction was dominated by the dislocation–dislocation interactions. Another set of pillars was milled from the side of the film (in the thickness of the film) in a nominally [134¯] compression direction. Compression in this direction activated a single slip in each grain, which facilitated the investigation of the interaction between dislocations and ITBs. Post-mortem images showed that slip traces were not distinctly connected at the boundary unlike ideal slip transmission in pillars containing a coherent twin boundary. Moreover, bi-crystalline pillars in the single slip direction are stronger than single-crystalline pillars. The observations indicate that ITBs are not impenetrable for dislocations, but the boundary demonstrates some resistance to transmission.

Hydrogen embrittlement is common in metallic materials and a critical issue in industries involving hydrogen-related processes. Here we investigate the mechanical response upon hydrogen loading of ferritic Fe-16Cr, Fe-21Cr and Fe-4Al alloys. We use a novel in situ setup for electrochemical backside hydrogen charging during nanoindentation. Single-phase ferritic Fe-Cr binary alloys with high hydrogen diffusivity and low solubility, are ideal for in situ studies during hydrogen charging, particularly the effect of diffusible and lightly trapped hydrogen is targeted. The hardness increases linearly with increasing hydrogen content until a quasi-equilibrium state between hydrogen absorption and desorption is reached while Young's modulus remains unaffected. Above this transient region, the slope of the absolute hardness experiences a drastic decrease. The hardness variation in Fe-21Cr is anisotropic as determined for (100), (110) and (111) oriented grains. Increasing the Cr content enhances the hardening effect in (100) orientation: a 16.7 % hardness increase is observed in Fe-21Cr, while Fe-16Cr, shows an increment of 10.8 %. A Fe-4Al alloy increases slightly in hardness by only 4.3 % at the applied current density of 3 mA/cm2. The hardening effect is caused by enhancing dislocation density, as revealed by studying the cross-section underneath the nanoindentation imprints.

Dislocations in high-entropy alloys encounter pinning during glide resulting in jerky motion. Here the authors demonstrate that the density of high local Peierls force is proportional to the critical stress required for their glide and mobility.

Additive manufacturing of pure copper (Cu) via laser-powder bed fusion (L-PBF) is challenging due to the low energy absorptivity under infra-red laser. As a result, 3-dimensional architectures, known for excellent load-bearing and energy absorption capabilities, have not been fabricated in pure Cu, so far. This study, for the first time, Cu lattice structures are fabricated through laser-powder bed fusion (L-PBF) with green laser (λ = 515 nm). Structural and microstructural analysis confirm that the lattice structures consist of well-defined unit-cells and show dense microstructure. The deformation behavior is investigated under a wide range of strain rates from ∼0.001 /s to ∼1000 /s. The stress–strain curves exhibit a smooth and continuous deformation without any post-yield softening, which can be attributed to the intrinsic mechanical properties of Cu. Correlated with post-mortem microscopy examination, the rate-dependent deformation behavior of pure Cu lattice structures is investigated and rationalized. The current work suggests that the complex Cu architectures can be fabricated by L-PBF with green laser and are suitable for dynamic loading applications.

The phase behavior of grain boundaries can influence the interfacial properties. Here the authors demonstrate nanoscale patterning of a grain boundary by two alternating phases in Cu that exhibit a congruent, diffusionless transition between the two phases.

Metal powders in laser-powder-bed-fusion (L-PBF) often exhibit cohesive flow resulting from interparticle adhesion. Nanoparticle dry-coating can improve powder flowability and promote powder layer densification. A Co25Cr25Fe25Ni25 metal powder (20–90 µm) is dry-coated with TiN particles with a diameter of 16 nm at low concentrations of up to 69 ppm. The dynamic angle of repose decreased and bulk powder density increased compared to the uncoated state from 49 ° and 4.67 g/cm3 to 29 ° and 4.81 g/cm3 with dry-coating of TiN, respectively. UV/Vis spectroscopy showed negligible alterations by TiN additions on the powder light absorption. The powder modifications strongly affected their corresponding processability in L-PBF and reduced the melt pool signatures of the in situ detected confocal single-color pyrometer signal as well as ex situ measured melt pool depth and width. With increasing flowability, a significant decrease in thermal emission and melt pool size was observed. The results demonstrate the impact of powder flowability and bulk powder density on the quality of L-PBF parts when particle interactions are actively modified.

Interstitials can substantially strengthen metals. Here the authors show a massive interstitial solid solution (MISS) approach enabling a model multicomponent alloy to achieve near-theoretical strength together with large deformability.

The development of sputtered coatings with improved hardness-toughness property combination is widely sought after. Multi-element ceramic carbide (Hf-Nb-Ta-Zr)C coatings with excess carbon, synthesized by DC co-sputtering is presented in this study as a promising candidate to achieve this objective. The specific roles of microstructure and residual stress are decoupled in order to understand their influence on the mechanical properties. Extensive mechanical characterization through in situ testing of focused ion beam fabricated microcantilevers and nanoindentation based approaches are adopted to quantitatively separate the effect of residual stresses on the fracture toughness of the (Hf-Nb-Ta-Zr)C coatings. Residual stress free, microcantilever testing in notched and unnotched conditions, in combination with microstructural characterization unambiguously reveals the intrinsic mechanical behavior of coatings, which solely depend on the microstructure. On the other hand, nanoindentation based testing techniques probe the influence of residual stress and microstructure on the measured mechanical properties. The segregation and thickening of carbon-rich clusters, especially to the grain boundaries with increasing deposition temperatures is speculated to lead to substantial degradation in all mechanical properties measured. An easier fracture path through grain boundaries leads to a reduction in fracture resistance, which is possibly related to carbon enrichment.

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.

Template-assisted electrodeposition is a promising microscale additive manufacturing technique allowing to deposit pure metals with high resolution. To allow the application-relevant design of metamaterials, it is necessary to establish microstructure-mechanical property relationships under extreme conditions. In this work, a novel process based on two-photon lithography was used to synthesize arrays of nanocrystalline nickel micropillars and complex microlattices. This allowed high throughput mechanical testing using a newly developed in situ nanoindenter at unprecedented combination of cryogenic temperatures (160 to 300 K) and strain rates (0.001 to 500 s−1). Strain rate sensitivity was found to increase from ∼ 0.004 at 300 K to ∼ 0.008 at 160 K. Thermal activation analysis showed a decrease in activation volume from 122b3 at 300 K to 45b3 at 160 K and an activation energy of 0.59 eV in line with collective dislocation nucleation as the rate limiting mechanism. Transmission Kikuchi Diffraction allowed quantifying microstructural changes during deformation. As such, a deformation map along with the responsible deformation mechanisms has been ascertained for additively micromanufactured nanocrystalline nickel at unique combinations of extreme temperatures and strain rates. Further, rate-dependent compression of microlattices and complementary finite element simulations using the results from micropillars as constitutive models exemplified the promise of such metal microarchitectures in space and aviation applications.

Thin film metallic glasses (TFMGs) are a novel class of materials showing a mutual combination of large plastic deformation in tension (>10% strain) and superior yield strength up to ∼ 3.5 GPa, which make them ideal candidates for applications such as flexible electronics. Nevertheless, a clear relationship between the atomic structure and mechanical properties of TFMGs has not yet been achieved. In particular, the role of composition in determining a different local atomic order and the effect of nanostructure on TFMGs properties must be further investigated. In this work, the mechanical properties and thermal stability of several amorphous Zr100-xCux TFMGs with either compact or fine columnar nanostructure were studied. The mediating role of composition in controlling crystallization temperature and hardness is here reported, which was found to increase from 4.6 to 7.7 GPa with increasing Cu content from 26 to 76 at.%. Moreover, plastic behavior and fracture resistance are shown to be highly dependent on both composition and nanostructure, with the Cu-rich and homogeneous film able to withstand elongation up to 2% strain before crack initiation. These results underline how atomic structure changes induced by composition can effectively influence TFMG properties, while demonstrating an approach to tune their behavior for various technological applications.

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.

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.

Experimental fracture mechanics at the microscale became an indispensable tool for understanding and developing advanced material systems. In case of linear elastic fracture mechanics, stringent requirements are typically only warranted for very brittle materials. The material properties of semi-brittle materials might be accessible by elasto-plastic fracture mechanics. However, challenges exist in determining the crack length, in producing geometry and notch geometry, in defining of the initiation toughness and in extracting the size independent crack resistance curves. In this study, we assess current approaches of measuring the fracture toughness of semi-brittle materials by elasto-plastic fracture mechanics. We investigate the notch geometry (through thickness notch and bridge notch), the notch depth and the method of determining in situ the crack length for ultrafine grained tungsten. Further challenges due to the overlap of sample size and crack process zone are identified. Finally, we propose a workflow for analyzing the elasto-plastic fracture toughness of material systems at the microscale.

Quantum mechanically guided materials design has been used to predict the mechanical property trends in crystalline materials. Thereby, the identification of composition-structure-property relationships is enabled. However, quantum mechanics based design guidelines and material selection criteria for ultra-strong metallic glasses have been lacking. Hence, based on an ab initio model for metallic glasses in conjunction with an experimental high-throughput methodology geared toward revealing the relationship between chemistry, topology and mechanical properties, we propose principles for the design of tough as well as stiff metallic glasses. The main design notion is that a low fraction of hybridized bonds compared to the overall bonding in a metallic glass can be used as a criterion for the identification of damage-tolerant metallic glass systems. To enhance the stiffness of metallic glasses, the bond energy density must be increased as the bond energy density is the origin of stiffness in metallic glasses. The thermal expansion, which is an important glass-forming identifier, can be predicted based on the Debye-Grüneisen model.

High fracture toughness is crucial for the application of metallic glasses as structural materials to avoid catastrophic failure of the material in a brittle manner. One fingerprint for fracture toughness in metallic glasses is the fraction of hybridized bonds, which is affected by alloying Pd57.4Al23.5Y7.8M11.3 with M = Fe, Ni, Co, Cu, Os, Ir, Pt, and Au. It is shown that experimental fracture toughness data is correlated to the fraction of hybridized bonds which scale with the localized bonds at the Fermi level. Thus, the localized bonds at the Fermi level are utilized quantitatively as a measure for fracture toughness. Based on ab initio calculations, the minimum fraction of hybridized bonds was identified for Pd57.4Al23.5Y7.8Ni11.3. According to the ansatz that the crystal orbital overlap population at the Fermi level scales with fracture toughness, for Pd57.4Al23.5Y7.8Ni11.3 a value of around 95 ± 20 MPa·m0.5 is predicted quantitatively for the first time. Consistent with this prediction, in micro-mechanical beam bending experiments Pd57.4Al23.5Y7.8Ni11.3 thin films show pronounced plasticity and absence of crack growth. Keywords: Metallic glass, Ab initio, Fracture toughness, Chemical bonding

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

Oxygen contamination during the mixing of precursor powders for nanocrystalline materials affects alloy microstructure, but exactly how remains unclear. Here, the authors show that stable nano-oxides can form easily inside severely deformed Cu-Fe grains during heating.

A reduction in synthesis temperature is favorable for hard coatings, which are designed for industrial applications, as manufacturing costs can be saved and technologically relevant substrate materials are often temperature-sensitive. In this study, we analyzed Mo2BC hard coatings deposited by direct current magnetron sputtering at different substrate temperatures, ranging from 380 °C to 630 °C. Transmission electron microscopy investigations revealed that a dense structure of columnar grains, which formed at a substrate temperature of 630 °C, continuously diminishes with decreasing substrate temperature. It almost vanishes in the coating deposited at 380 °C, which shows nanocrystals of ~1 nm in diameter embedded in an amorphous matrix. Moreover, Argon from the deposition process is incorporated in the film and its amount increases with decreasing substrate temperature. Nanoindentation experiments provided evidence that hardness and Young's modulus are modified by the nanostructure of the analyzed Mo2BC coatings. A substrate temperature rise from 380 °C to 630 °C resulted in an increase in hardness (21 GPa to 28 GPa) and Young's modulus (259 GPa to 462 GPa). We conclude that the substrate temperature determines the nanostructure and the associated changes in bond strength and stiffness and thus, influences hardness and Young's modulus of the coatings. Keywords: Mo2BC hard coating, Direct current magnetron sputtering, Substrate temperature, Transmission electron microscopy, Nanostructure evolution, Mechanical properties

The fracture behavior of a white etching layer formed on the rail surface in pearlitic steels during the rail-wheel contact is investigated using indentation-based microcantilever fracture tests. The sample thickness is in the order of 5 μm. The local fracture toughness of the white etching layer, its neighboring brown etching layer, martensite and pearlite with similar chemical composition are determined and compared to ferritic steels. All samples show stable crack growth accompanied by significant plasticity at the crack tip. The toughnesses scale inversely with the microhardness. The white etching layer exhibits a toughness of 16.0 ± 1.2 MPa m1/2 which is in the same range as the fully martensitic steel. It is shown that the local fracture toughness can be roughly estimated based on the Vickers hardness of the white etching layer. Also, an estimation of a critical defect size in white etching layers which considerably furthers the understanding of crack initiation is made in this study. Furthermore, various criteria for analyzing the elasto plastic fracture toughness are compared. Keywords: Rail steel, White etching layer, Elasto plastic fracture mechanics, Micro cantilever testing

An amendment to this paper has been published and can be accessed via a link at the top of the paper.