arXiv subjects

Stefan Zaefferer

Publications and source records attributed to Stefan Zaefferer.

10 recordsLinked to original sources

arXiv2025

Domain Boundaries in a Metallic Distortive Polar Metal

Polar metals are an underexplored material class combining two properties that are typically incompatible, namely a polar crystal structure and reasonable electrical conductivity. These intriguing materials offer a unique combination of properties, potentially relevant to optoelectronics, catalysis, memory devices, among other applications. The distortive polar metal (DPM) subclass forms through a symmetry-lifting phase transformation into a non-centrosymmetric polar crystal structure. In the process, domains with uniform geometric polar directions form, oftentimes separated by domain boundaries with polarity discontinuities arranged in "charged" head-to-head (H-H) or tail-to-tail (T-T) morphologies. To date, only metallic oxide DPM microstructures have been studied. Here we reveal, in the intermetallic DPM Mn$_{5}$Al$_{8}$, different surface interactions and electron transfer reactivity at domain boundaries depending on their H-H or T-T character. Variable surface reactivity suggests localized changes in electronic work functions due to an increase (H-H) or decrease (T-T) in the electronic density of states. These findings suggest that metallic DPMs may offer functionalizable domain boundaries and deserve increased attention, given that they allow tunable chemistries and various thermomechanical processing or transformation protocols. Ultimately, this study proposes unconventional metal physics, propelling the discovery and design of advanced electronic materials and devices.

cond-mat.mtrl-sci↗

arXiv2025

Protection of metal interfaces against hydrogen-assisted cracking

Enabling a hydrogen economy requires the development of materials resistant to hydrogen embrittlement (HE). More than 100 years of research have led to several mechanisms and models describing how hydrogen interacts with lattice defects and leads to mechanical property degradation. However, solutions to protect materials from hydrogen are still scarce. Here, we investigate the role of interstitial solutes in protecting critical crystalline defects sensitive to hydrogen. Ab initio calculations show that boron and carbon in solid solutions at grain boundaries can efficiently prevent hydrogen segregation. We then realized this interface protection concept on martensitic steel, a material strongly prone to HE, by doping the most sensitive interfaces with different concentrations of boron and carbon. This segregation, in addition to stress relaxations, critically reduced the hydrogen ingress by half, leading to an unprecedented resistance against HE. This tailored interstitial segregation strategy can be extended to other metallic materials susceptible to hydrogen-induced interfacial failure

cond-mat.mtrl-sci↗

arXiv2025

Vacuum Dealloyed Brass as Li-Metal Battery Current Collector: Effect of Zinc and Porosity

"Anode-free" lithium-metal batteries promise significantly higher energy density than conventional graphite-based lithium-ion batteries; however, lithium dendrite growth can lead to internal short circuits with associated safety risks. While porous current collectors can suppress dendrite growth, optimal porosity and composition remain unknown. Here, we show that the temperature during vapor phase dealloying (VPD) of alpha-brass (Cu63Zn37) controls the surface Zn concentration, decreasing from 8 percent to below 1 percent from 500 to 800 degrees C. The surface composition is controlled by the temperature-dependent diffusion. A battery cell maintains greater than 90 percent Coulombic efficiency (CE) over 100 cycles when the Zn content is the lowest, whereas the higher-Zn samples degraded to approximately 70 percent CE. The difference in surface composition has hence dramatic effects on battery performance, and our results demonstrate how precise compositional control enables stable lithium-metal battery operation, establishing about 1 atomic percent surface Zn as optimal for preventing capacity fading and uniform lithium plating, while establishing predictive relationships between processing temperature and surface composition. This work provides design rules for multifunctional current collectors and demonstrates scalable VPD production for next-generation batteries.

cond-mat.mtrl-sci↗

arXiv2025

Electrochemically-driven formation of Intermetallic Cu3ZnLi2 alters Li-transport in nanostructured bimetallic battery anode

The role of Li-based batteries in the electrification of society cannot be understated, however their operational lifetime is often limited by the formation of dendrites, i.e. the localised deposition of Li that can cause shorts between the two electrodes leading to the failure of the battery. Nanocrystalline bimetallic current collectors can be used for anode-free Li-metal batteries, with improved Li plating and limited or suppressed formation of dendrites. Here, we demonstrate that the microstructure of an alpha-Brass current collector, Cu 63% Zn 37%, used in an anode-free Li-metal battery evolves during cycling. It initially had a nanocrystalline deformation layer approximately 80 nm in thickness after polishing. After 100 cycles, the initial deformed brass layer was partially converted to a ternary Laves phase Cu3ZnLi2 within a nanocrystalline brass matrix that grew to 200 - 250 nm in thickness. Upon Li stripping, the phase partially decomposes electrochemically, but what remains can sequester Li thus forming "dead Li" thereby contributing to capacity loss. We propose a mechanism for the microstructural evolution including dynamic recrystallization and phase formation. Since this ternary Laves phase emerges during electrochemical cycling alone, binary alloy current collectors must be assessed for metastable ternary phase formation under different cycling conditions to either stabilize and exploit such phases or electrochemically fully strip them.

cond-mat.mtrl-sci↗

arXiv2024

Segregation at prior austenite grain boundaries: the competition between boron and hydrogen

The interaction between boron and hydrogen at grain boundaries has been investigated experimentally and numerically in boron-doped and boron-free martensitic steels using thermal desorption spectrometry (TDS) and ab initio calculations. The calculations show that boron and hydrogen are attracted to grain boundaries but boron can repel hydrogen. This behavior has also been observed using TDS measurements, with the disappearance of one peak when boron is incorporated into the microstructure. Additionally, the microstructure of both steels has been studied through electron backscattered diffraction, electron channeling contrast imaging, synchrotron X-ray measurements, and atom probe tomography. While they have a similar grain size, grain boundary distribution, and dislocation densities, a pronounced boron segregation into PAGBs is observed for boron-doped steels. Then, the equilibrium hydrogen concentration in different trapping sites has been evaluated using the Langmuir-McLean approximation. This thermodynamic model shows that the distribution of hydrogen is identical for all traps when the total hydrogen concentration is low for boron-free steel. However, when it increases, traps of the lowest segregation energies (mostly PAGBs) are firstly saturated, which promotes failure initiation at this defect type. This finding partially explains why PAGBs are the weakest microstructure feature when martensitic steels are exposed to hydrogen-containing environments.

cond-mat.mtrl-sci↗

arXiv2023

Hydrogen-induced hardening of a high-manganese twinning induced plasticity steel

High-manganese twinning-induced plasticity (TWIP) steels exhibit high strain hardening, high tensile strength, and high ductility, which make them attractive for structural applications. At low tensile strain rates, TWIP steels are prone to hydrogen embrittlement (HE). Here though, we study the hardening and strengthening resulting from electrochemical hydrogen-charging of a surface layer of a Fe-26.9Mn-0.28C (wt.%) TWIP steel. We observed a 20% increase in yield strength following the electrochemical hydrogen-charging, accompanied by a reduction in ductility from 75% to 10% at a tensile strain rate of 10-3s-1. The microstructural evolution during tensile deformation was examined at strain levels of 3%, 5% and 7% by electron backscatter diffraction (EBSD) and electron channeling contrast imaging (ECCI) to study the dislocation structure of the hardened region. As expected, the microstructure of the hydrogen-hardened and the uncharged regions of the material evolve differently. The uncharged areas show entangled dislocation structures, indicating slip from a limited number of potentially coplanar slip systems. In contrast, hydrogen segregated to the grain boundaries, revealed by the deuterium-labelled atom probe tomography, delays the dislocation nucleation by blocking dislocation sources at the grain boundaries. The charged areas hence first show the formation of cells, indicating dislocation entanglement from more non-coplanar slip systems. With increasing strain, these cells dissolve, and stacking faults and strain-induced ε-martensite are formed, promoted by the presence of hydrogen. The influence of hydrogen on dislocation structures and the overall deformation mechanism is discussed in details.

cond-mat.mtrl-sci↗

arXiv2022

In-situ nitriding of Fe2VAl during laser surface remelting to manipulate microstructure and crystalline defects

Tailoring the physical properties of complex materials for targeted applications requires optimizing the microstructure and crystalline defects that influence electrical and thermal transport, and mechanical properties. Laser surface remelting can be used to modify the sub-surface microstructure of bulk materials and hence manipulate their properties locally. Here, we introduce an approach to perform remelting in a reactive nitrogen atmosphere, in order to form nitrides and induce segregation of nitrogen to structural defects. These defects arise from the fast solidification of the full-Heusler Fe2VAl compound that is a promising thermoelectric material. Advanced scanning electron microscopy, including electron channelling contrast imaging and three-dimensional electron backscatter diffraction, is complemented by atom probe tomography to study the distribution of crystalline defects and their local chemical composition. We reveal a high density of dislocations, which are stable due to their character as geometrically necessary dislocations. At these dislocations and low-angle grain boundaries, we observe segregation of nitrogen and vanadium, which can be enhanced by repeated remelting in nitrogen atmosphere. We propose that this approach can be generalized to other additive manufacturing processes to promote local segregation and precipitation states, thereby manipulating physical properties.

cond-mat.mtrl-sci↗

arXiv2022

Hierarchical nature of hydrogen-based direct reduction of iron oxides

Fossil-free ironmaking is indispensable for reducing massive anthropogenic CO2 emissions in the steel industry. Hydrogen-based direct reduction (HyDR) is among the most attractive solutions for green ironmaking, with high technology readiness. The underlying mechanisms governing this process are characterized by a complex interaction of several chemical (phase transformations), physical (transport), and mechanical (stresses) phenomena. Their interplay leads to rich microstructures, characterized by a hierarchy of defects ranging across several orders of magnitude in length, including vacancies, dislocations, internal interfaces, and free surfaces in the form of cracks and pores. These defects can all act as reaction, nucleation, and diffusion sites, shaping the overall reduction kinetics. A clear understanding of the roles and interactions of these dynamically-evolving nano-/microstructure features is missing. Gaining better insights in these effects could enable improved access to the microstructure-based design of more efficient HyDR methods, with potentially high impact on the urgently needed decarbonization in the steel industry.

cond-mat.mtrl-sci↗

arXiv2019

On the spatial resolution of EBSD in magnesium

We measured the physical lateral resolution of the electron backscatter diffraction (EBSD) technique for the case of pure magnesium and tungsten. Spatial resolution, among other parameters, depends significantly on the accelerating voltage and the atomic number of the material. For the case of lighter metals, it is supposed to be lower than in the case of heavier metals for a given accelerating voltage. In the present work, lateral resolution was measured in dependence of accelerating voltage on a straight high angle grain boundary which was positioned parallel (horizontal boundary) and perpendicular (vertical boundary) to the tilt axis of the specimen. For magnesium the best lateral resolution of 240 nm was obtained at an accelerating voltage of 5 kV. The resolution dramatically worsened to values as high as 3500 nm as the voltage was increased from 15 kV to 30 kV. The aspect ratio of horizontal and vertical lateral resolution tended to 1.0 at the accelerating voltage of 5 kV and to 2.5 at the accelerating voltage of 30 kV. These values as function of accelerating voltages were compared with those obtained on the high atomic number metal tungsten. Here resolution at 5 kV was about a quarter of that of magnesium. With increasing voltage, the value almost didnt change. For all voltages the resolution aspect ratio stayed close to 1.0.

cond-mat.mtrl-sci↗

arXiv2019

New techniques for imaging and identifying defects in electron microscopy

Defects in crystalline materials control the properties of materials, and their characterization focuses our strategies to optimize performance. Electron microscopy has served as the backbone of our understanding of defect structure and their interactions owing to beneficial spatial resolution and contrast mechanisms that enable direct imaging of defects. These defects reside in complex microstructures and chemical environments, demanding a combination of experimental approaches for full defect characterization. In this article, we describe recent progress and trends in methods for examining defects using scanning electron microscopy platforms, where several emerging approaches offer attractive benefits, for instance in correlative microscopy across length scales and in situ studies of defect dynamics.

cond-mat.mtrl-sci↗