arXiv subjects

Florian Spieckermann

Publications and source records attributed to Florian Spieckermann.

5 recordsLinked to original sources

arXiv2025

Core-Shell Confinement Blocks Hydride Formation: The Impact of Surface Oxides on Hydrogen Sorption in Nanoporous FeTi

Metal hydrides remain an intriguing alternative to conventional gaseous and liquid hydrogen storage methods, offering high volumetric storage density and enhanced hydrogen storage safety at ambient conditions. In this regard, the intermetallic compound FeTi is one of the most promising storage materials. However, its widespread industrial application remains challenging due to the need for activation, slow initial kinetics, large hysteresis, and high material costs. In this study, we aim to overcome these limitations by devising an alternative synthesis pathway to prepare nanoporous and ultra-fine porous FeTi with controlled grain and ligament sizes, allowing us to study the obtained well-defined microstructures in detail. In particular, we observe the confinement of the FeTi phase by surface oxides, which can be correlated with the hydrogen sorption properties of the respective material. These experimental results are further supported by an analytical model allowing the calculation of the absorption pressure as a function of microstructure-dependent elastic stresses. Additionally, we show that such stresses also influence the absorption-desorption hysteresis. This study lays the groundwork for the controlled and systematic study of the processing-structure-properties relations in metal hydrides and FeTi in particular, thereby paving the way to cost-effective and efficient hydrogen storage solutions based on metal hydrides.

cond-mat.mtrl-sci↗

arXiv2025

Hydrogen-Mediated Control of Phase Formation and Microstructure Evolution

Hydrogen is key in reducing greenhouse gas emissions in materials production. At the same time, it significantly affects mechanical properties, often causing unwanted embrittlement. However, rather than solely addressing these disadvantages, hydrogens inevitable role in sustainable metallurgy should be leveraged to create new and potentially superior materials. Here, we show that using hydrogen in the form of metal hydrides introduces a barrier to mechanical alloying, stabilizing otherwise unattainable microstructures. Severe plastic deformation of a composite of the high entropy alloy (HEA) TiVZrNbHf and Cu leads to amorphization while substituting the HEA by its hydride preserves the two-phase structure. Monte Carlo simulations confirm that the significantly different hydrogen affinities, together with the restricted dislocation motion in the hydride, create a barrier to mechanical alloying. This hydride route enables new microstructural states, even in well-studied material systems. It opens an additional dimension in designing materials with diverging hydrogen affinities, offering tighter control over mechanical alloying.

cond-mat.mtrl-sci↗

arXiv2024

Nano-Patterned Pt-Based Metallic Glass Electrocatalysts with In-Situ Copper Oxide Foam for Enhanced Hydrogen Evolution

Hydrogen is a promising energy carrier for replacing fossil fuels, and hydrogen production via hydrogen evolution reaction (HER) is an environmentally friendly option if electrocatalysts with low overpotentials and long-term stability are used. In this work, the electrocatalytic performance of $\mathrm{Pt_{57.5}Cu_{14.7}Ni_{5.3}P_{22.5}}$ bulk metallic glass (BMG) with flat, micro-patterned, and nano-patterned surfaces for HER in 0.5 M H2SO4 is studied. The nano-patterned Pt-BMG demonstrates outstanding long-term stability and self-improving behavior with a final overpotential of 150 mV and a Tafel slope of 42 $\mathrm{mV dec^{-1}}$ after 1000 linear sweep voltammetry (LSV) cycles, which is respectively 42% and 37% lower than in the first LSV cycle. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) indicate the formation of a layer of CuO/Cu2O foam deposited on top of the nano-patterned surface during the stability test of 1000 LSV cycles. A three-step process is proposed to explain the formation of CuxO foam via dynamic hydrogen bubble templating (DHBT) electrodeposition from Cu dissolution of the Pt-BMG without using copper salt. This work provides a method to create CuxO foams that could be used for various applications. Moreover, nano-patterned BMGs with DHBT deposition offer a feasible strategy to synthesize metal or metal-oxide foams.

cond-mat.mtrl-sci↗

arXiv2022

Magnetron Sputtered Non-Toxic and Precious Element-Free Ti-Zr-Ge Metallic Glass Nanofilms with Enhanced Biocorrosion Resistance

The chemical composition and structural state of advanced alloys are the decisive factors in optimum biomedical performance. This contribution presents unique Ti-Zr-Ge metallic glass thin-film compositions fabricated by magnetron sputter deposition targeted for nanocoatings for biofouling prevention. The amorphous nanofilms with nanoscale roughness exhibit a large relaxation and supercooled liquid regions as revealed by flash differential scanning calorimetry. Ti\textsubscript{68}Zr\textsubscript{8}Ge\textsubscript{24} shows the lowest corrosion (0.17 \textmu A cm\textsuperscript{\textminus2}) and passivation (1.22 \textmu A cm\textsuperscript{\textminus2}) current densities, with the lowest corrosion potential of \textminus0.648 V and long-range stability against pitting, corroborating its excellent performance in phosphate buffer solution at 37 {\textdegree}C. The oxide layer is comprised of TiO\textsubscript{2}, TiO\textsubscript{\emph{x}} and ZrO\textsubscript{\emph{x}}, as determined using X-ray photoelectron spectroscopy by short-term ion-etching of the surface layer. The two orders of magnitude increase in the oxide and interface resistance (from 14 to 1257 {\textOmega} cm\textsuperscript{2}) along with an order of magnitude decrease in the capacitance parameter of the oxide interface (from 1.402 x 10\textsuperscript{\textminus5} to 1.677 x 10\textsuperscript{\textminus6} S s\textsuperscript{n} cm\textsuperscript{\textminus2}) of the same composition is linked to the formation of carbonyl groups and reduction of the native oxide layer during linear sweep voltammetry.

cond-mat.mtrl-sci↗

arXiv2022

Structure-dynamics relationships in cryogenically deformed bulk metallic glass

The atomistic mechanisms occurring during the processes of aging and rejuvenation in glassy materials involve very small structural rearrangements that are extremely difficult to capture experimentally. Here we use in-situ X-ray diffraction to investigate the structural rearrangements during annealing from 77 K up to the crystallization temperature in Cu44Zr44Al8Hf2Co2 bulk metallic glass rejuvenated by high pressure torsion performed at cryogenic temperatures and at room temperature. Using a measure of the configurational entropy calculated from the X-ray pair correlation function, the structural footprint of the deformation-induced rejuvenation in bulk metallic glass is revealed. With synchrotron radiation, temperature and time resolutions comparable to calorimetric experiments are possible. This opens hitherto unavailable experimental possibilities allowing to unambiguously correlate changes in atomic configuration and structure to calorimetrically observed signals and can attribute those to changes of the dynamic and vibrational relaxations (α-, β- and γ-transition) in glassy materials. The results suggest that the structural footprint of the β-transition is related to entropic relaxation with characteristics of a first-order transition. Dynamic mechanical analysis data shows that in the range of the β-transition, non-reversible structural rearrangements are preferentially activated. The low-temperature γ-transition is mostly triggering reversible deformations and shows a change of slope in the entropic footprint suggesting second-order characteristics.

cond-mat.mtrl-sci↗