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The influence of temperature on the deformation behaviour of the C15 CaAl$_2$ Laves phase, a key constituent for enhancing the mechanical properties of Mg alloys up to service temperatures of 200 {\deg}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, scratch testing, and micropillar splitting conducted at elevated temperatures. By correlating observations from these techniques, changes in deformation of CaAl$_2$ were identified in relation to temperature. High-temperature nanoindentation quantitatively determined the temperature range for the BDT, and revealed that CaAl$_2$ undergoes a BDT at ~0.55T$_m$, exhibiting an intermediate region of microplasticity. A noticeable decrease in nanoindentation hardness was observed at ~450-500 {\deg}C, accompanied by an increase in residual indent size, while indentation cracking was not observed above 300 {\deg}C. Results from high-temperature micropillar splitting revealed cracking and brittle pillar splitting up to 300 {\deg}C, with an increase in apparent fracture toughness from 0.9 $\pm$ 0.1 MPa$\cdot\sqrt m$ to 2.8 $\pm$ 0.3 MPa$\cdot\sqrt m$, and subsequent crack-free plastic deformation from 400 {\deg}C. Transmission electron microscopy analysis of the deformed material from nanoindentation revealed that the BDT of CaAl$_2$ may be attributed to enhanced dislocation plasticity with increasing temperature.

A giant Zn segregation transition is revealed using CALPHAD-integrated density-based modelling of segregation into Fe grain boundaries (GBs). The results show that above a threshold of only a few atomic percent Zn in the alloy, a substantial amount of up to 60 at.\% Zn can segregate to the GB. We found that the amount of segregation abruptly increases with decreasing temperature, while the Zn content in the alloy required for triggering the segregation transition decreases. Direct evidence of the Zn segregation transition is obtained using high-resolution scanning transmission electron microscopy. Base on the model, we trace the origin of the segregation transition back to the low cohesive energy of Zn and a miscibility gap in Fe-Zn GB, arising from the magnetic ordering effect, which is confirmed by ab-initio calculations. We also show that the massive Zn segregation resulting from the segregation transition greatly assists with liquid wetting and reduces the work of separation along the GB. The current predictions suggest that control over Zn segregation, by both alloy design and optimizing the galvanization and welding processes, may offer preventive strategies against liquid metal embrittlement., Comment: Original work, Letter, 14 pages including supplementary material (SM), 8 figures (3 in SM), 2 tables in SM

The embrittlement of metallic alloys by liquid metals leads to catastrophic material failure and severely impacts their structural integrity. The weakening of grain boundaries by the ingress of liquid metal and preceding segregation in the solid are thought to promote early fracture. However, the potential of balancing between the segregation of cohesion-enhancing interstitial solutes and embrittling elements inducing grain boundary decohesion is not understood. Here, we unveil the mechanisms of how boron segregation mitigates the detrimental effects of the prime embrittler, zinc, in a $\Sigma 5\,[0\,0\,1]$ tilt grain boundary in $\alpha-$Fe ($4~at.\%$ Al). Zinc forms nanoscale segregation patterns inducing structurally and compositionally complex grain boundary states. Ab-initio simulations reveal that boron hinders zinc segregation and compensates for the zinc induced loss in grain boundary cohesion. Our work sheds new light on how interstitial solutes intimately modify grain boundaries, thereby opening pathways to use them as dopants for preventing disastrous material failure., Comment: 29 pages, 6 figures in the main text and 10 figures in the supplementary

Grain boundaries, the two-dimensional (2D) defects between differently oriented crystals, control mechanical and transport properties of materials. Our fundamental understanding of grain boundaries is still incomplete even after nearly a century and a half of research since Sorby first imaged grains. Here, we present a systematic study, over 9 orders of magnitude of size scales, in which we analyze 2D defects between two neighboring crystals across five hierarchy levels and investigate their crystallographic, compositional, and electronic features. The levels are (a) the macroscale interface alignment and grain misorientation (held constant here); (b) the systematic mesoscopic change in the inclination of the grain boundary plane for the same orientation difference; (c) the facets, atomic motifs (structural units), and internal nanoscopic defects within the boundary plane; (d) the grain boundary chemistry; and (e) the electronic structure of the atomic motifs. As a model material, we use Fe alloyed with B and C, exploiting the strong interdependence of interface structure and chemistry in this system. This model system is the basis of the 1.9 billion tons of steel produced annually and has an eminent role as a catalyst. Surprisingly, we find that even a change in the inclination of the GB plane with identical misorientation impacts GB composition and atomic arrangement. Thus, it is the smallest structural hierarchical level, the atomic motifs, which control the most important chemical properties of the grain boundaries. This finding 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.

The local variation of grain boundary atomic structure and chemistry caused by segregation of impurities influences the macroscopic properties of poylcrystalline materials. Here, the effect of co-segregation of carbon and boron on the depletion of aluminum at a $\Sigma 5\,(3\,1\,0\,) [0\,0\,1]$ tilt grain boundary in a $\alpha-$Fe-$4~at.~\%$Al bicrystal was 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., Comment: 26 pages, 10 Figures, 1 Table