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Dierk Raabe

Publications and source records attributed to Dierk Raabe.

At least 73 records · Page 4Linked to original sources

Influence of microstructure and atomic-scale chemistry on iron ore reduction with hydrogen at 700°C

With 1.85 billion tons produced per year, steel is the most important material class in terms of volume and environmental impact. While steel is a sustainability enabler, for instance through lightweight design, magnetic devices, and efficient turbines, its primary production is not. For 3000 years, iron has been reduced from ores using carbon. Today 2.1 tons CO2 are produced per ton of steel, causing 30% of the global CO2 emissions in the manufacturing sector, which translates to 6.5% of the global CO2 emissions. These numbers qualify iron- and steel-making as the largest single industrial greenhouse gas emission source. The envisaged future industrial route to mitigate these CO2 emissions targets green hydrogen as a reductant. Although this reaction has been studied for decades, its kinetics is not well understood, particularly during the wustite reduction step which is dramatically slower than the hematite reduction. Many rate-limiting factors of this reaction are set by the micro- and nanostructure as well as the local chemistry of the ores. Their quantification allows knowledge-driven ore preparation and process optimization to make the hydrogen-based reduction of iron ores commercially viable, enabling the required massive CO2 mitigation to ease global warming. Here, we report on a multi-scale structure and composition analysis of iron reduced from hematite with pure H2, reaching down to near-atomic scale.

cond-mat.mtrl-sci↗

Magneto-electric Tuning of Pinning-Type Permanent Magnets through Atomic-Scale Engineering of Grain Boundaries

Pinning-type magnets maintaining high coercivity, i.e. the ability to sustain magnetization, at high temperature are at the core of thriving clean-energy technologies. Among these, Sm2Co17-based magnets are excellent candidates owing to their high-temperature stability. However, despite decades of efforts to optimize the intragranular microstructure, the coercivity currently only reaches 20~30% of the theoretical limits. Here, the roles of the grain-interior nanostructure and the grain boundaries in controlling coercivity are disentangled by an emerging magneto-electric approach. Through hydrogen charging/discharging by applying voltages of only ~ 1 V, the coercivity is reversibly tuned by an unprecedented value of ~ 1.3 T. In situ magneto-structural measurements and atomic-scale tracking of hydrogen atoms reveal that the segregation of hydrogen atoms at the grain boundaries, rather than the change of the crystal structure, dominates the reversible and substantial change of coercivity. Hydrogen lowers the local magnetocrystalline anisotropy and facilitates the magnetization reversal starting from the grain boundaries. Our study reveals the previously neglected critical role of grain boundaries in the conventional magnetisation-switching paradigm, suggesting a critical reconsideration of strategies to overcome the coercivity limits in permanent magnets, via for instance atomic-scale grain boundary engineering.

cond-mat.mtrl-sci↗

Defect segregation and its effect on the photoelectrochemical properties of Ti-doped hematite photoanodes for solar water splitting

Optimising the photoelectrochemical performance of hematite photoanodes for solar water splitting requires better understanding of the relationships between dopant distribution, structural defects and photoelectrochemical properties. Here, we use complementary characterisation techniques including electron microscopy, conductive atomic force microscopy (CAFM), Rutherford backscattering spectroscopy (RBS), atom probe tomography (APT) and intensity modulated photocurrent spectroscopy (IMPS) to study this correlation in Ti-doped (1 cat.%) hematite films deposited by pulsed laser deposition (PLD) on F:SnO2 (FTO) coated glass substrates. The deposition was carried out at 300 °C, followed by annealing at 500 deg C for 2 h. Upon annealing, Ti was observed by APT to segregate to the hematite/FTO interface and into some hematite grains. Since no other pronounced changes in microstructure and chemical composition were observed by electron microscopy and RBS after annealing, the non-uniform Ti redistribution seems to be the reason for a reduced interfacial recombination in the annealed films, as observed by IMPS. This results in a lower onset potential, higher photocurrent and larger fill factor with respect to the as-deposited state. This work provides atomic-scale insights into the microscopic inhomogeneity in Ti-doped hematite thin films and the role of defect segregation in their electrical and photoelectrochemical properties.

physics.chem-ph↗

Machine-learning-enhanced time-of-flight mass spectrometry analysis

Mass spectrometry is a widespread approach to work out what are the constituents of a material. Atoms and molecules are removed from the material and collected, and subsequently, a critical step is to infer their correct identities based from patterns formed in their mass-to-charge ratios and relative isotopic abundances. However, this identification step still mainly relies on individual user's expertise, making its standardization challenging, and hindering efficient data processing. Here, we introduce an approach that leverages modern machine learning technique to identify peak patterns in time-of-flight mass spectra within microseconds, outperforming human users without loss of accuracy. Our approach is cross-validated on mass spectra generated from different time-of-flight mass spectrometry(ToF-MS) techniques, offering the ToF-MS community an open-source, intelligent mass spectra analysis.

cond-mat.mtrl-sci↗

Solute hydrogen and deuterium observed at the near atomic scale in high-strength steel

Observing solute hydrogen (H) in matter is a formidable challenge, yet, enabling quantitative imaging of H at the atomic-scale is critical to understand its deleterious influence on the mechanical strength of many metallic alloys that has resulted in many catastrophic failures of engineering parts and structures. Here, we report on the APT analysis of hydrogen (H) and deuterium (D) within the nanostructure of an ultra-high strength steel with high resistance to hydrogen embrittlement. Cold drawn, severely deformed pearlitic steel wires (Fe-0.98C-0.31Mn-0.20Si-0.20Cr-0.01Cu-0.006P-0.007S wt.%, ε=3.1) contains cementite decomposed during the pre-deformation of the alloy and ferrite. We find H and D within the decomposed cementite, and at some interfaces with the surrounding ferrite. To ascertain the origin of the H/D signal obtained in APT, we explored a series of experimental workflows including cryogenic specimen preparation and cryogenic-vacuum transfer from the preparation into a state-of-the-art atom probe. Our study points to the critical role of the preparation, i.e. the possible saturation of H-trapping sites during electrochemical polishing, how these can be alleviated by the use of an outgassing treatment, cryogenic preparation and transfer prior to charging. Accommodation of large amounts of H in the under-stoichiometric carbide likely explains the resistance of pearlite against hydrogen embrittlement.

cond-mat.mtrl-sci↗

Comparative study of hydrogen embrittlement resistance between additively and conventionally manufactured austenitic stainless steels

Hydrogen embrittlement in 304L (18wt.% Cr, 8-10wt.% Ni) austenitic stainless steel (ASS) fabricated by laser powder-bed-fusion (LPBF) was investigated by tensile testing after electrochemical hydrogen pre-charging and compared to conventionally available 304L ASSs with two different processing histories, (i) casting plus annealing (CA) and (ii) CA plus thermomechanical treatment (TMT). It was revealed that hydrogen-charging led to a significant reduction in ductility for the CA sample, but only a small effect of hydrogen was observed for the LPBF and CA-TMT samples. Hydrogen-assisted cracking behavior was found to be strongly linked to strain-induced martensitic transformation. In addition, the amount of alpha' martensite was much higher in the CA sample than in other samples, suggesting that severe hydrogen embrittlement can be correlated with the low mechanical stability of austenite. Detailed microstructural characterization showed that low austenite stability of the CA sample was mainly attributed to the retained content of delta ferrite and the chemical inhomogeneity inside the gamma matrix (gamma close to delta has ~2 wt.% higher Cr but ~2 wt.% lower Ni), but TMT enhanced the chemical homogeneity and thus austenite stability. By contrast, the LPBF process led directly, i.e. without any thermomechanical treatment, to a fully austenitic structure with homogeneous elemental distribution in the ASS. These results confirmed that the presence of delta and the chemical inhomogeneity inside gamma matrix, which promoted the deformation-induced martensitic transformation and the associated H enrichment at the gamma-alpha' interface, was the primary reason for the severe H-assisted failure.

cond-mat.mtrl-sci↗

Strain rate dependency of dislocation plasticity

Dislocation slip is a general deformation mode and governs the strength of metals. Via discrete dislocation dynamics and molecular dynamics simulations, we investigate the strain rate and dislocation density dependence of the strength of bulk copper single crystals using 192 simulations spanning over 10 orders of magnitude in strain rate and 9 orders of magnitude in dislocation density. Based on these large set of simulations and theoretical analysis, a new analytical relationship between material strength, dislocation density, strain rate and dislocation mobility is proposed, which is in excellent agreement with the current simulations as well as with experimental data. The results show that the material strength is a non-monotonic function of dislocation density and displays two universal regimes (first decreasing, then increasing) as the dislocation density increases. The first regime is a result of strain rate hardening, while the second regime is dominated by the classical Taylor forest hardening. Accordingly, the strength displays universally, as a function of strain rate, a rate-independent regime at low strain rates (governed by forest hardening) followed by a rate hardening regime at high strain rates (governed by strain rate hardening). All the results can be captured by a single scaling function. Finally, the fluctuations of dislocation flow are analyzed in terms of the strain rate dependent distribution of dislocation segment velocities. It is found that the fluctuations are governed by another universal scaling function and diverge in the rate independent limit, indicating a critical behavior. The current analysis provides a comprehensive understanding on how collective dislocation motions are governed by the competition between the internal elastic interactions of dislocations, and the stress required to drive dislocation fluxes at a given externally imposed strain rate.

cond-mat.mtrl-sci↗

Segregation--Assisted Spinodal and Transient Spinodal Phase Separation at Grain Boundaries

Segregation to grain boundaries affects their cohesion, corrosion and embrittlement and plays a critical role in heterogeneous nucleation. In order to quantitatively study segregation and phase separation at grain boundaries, we derive a density-based phase-field model. In this model, we describe the grain boundary free energy based on available bulk thermodynamic data while an atomic grain boundary density is obtained using atomistic simulations. To benchmark the performance of the model, we study Mn grain boundary segregation in the Fe--Mn system. 3D simulation results are compared against atom probe tomography measurements. We show that a continuous increase in the alloy composition results in a discontinuous jump in the Mn grain boundary segregation. This jump corresponds to an interfacial spinodal phase separation. For alloy compositions above the interfacial spinodal, we found a transient spinodal phase separation phenomenon which opens opportunities for knowledge-based microstructure design through the chemical manipulation of grain boundaries. The proposed density-based model provides a powerful tool to study thermodynamics and kinetics of segregation and phase separation at grain boundaries.

cond-mat.mtrl-sci↗

Could face-centered cubic titanium in cold-rolled commercially-pure titanium only be a Ti-hydride?

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.

cond-mat.mtrl-sci↗

Atomic-scale grain boundary engineering to overcome hot-cracking in additively-manufactured superalloys

There are still debates regarding the mechanisms that lead to hot cracking in parts build by additive manufacturing (AM) of non-weldable Ni-based superalloys. This lack of in-depth understanding of the root causes of hot cracking is an impediment to designing engineering parts for safety-critical applications. Here, we deploy a near-atomic-scale approach to investigate the details of the compositional decoration of grain boundaries in the coarse-grained, columnar microstructure in parts built from a non-weldable Ni-based superalloy by selective electron-beam melting. The progressive enrichment in Cr, Mo and B at grain boundaries over the course of the AM-typical successive solidification and remelting events, accompanied by solid-state diffusion, causes grain boundary segregation induced liquation. This observation is consistent with thermodynamic calculations. We demonstrate that by adjusting build parameters to obtain a fine-grained equiaxed or a columnar microstructure with grain width smaller than 100 $μ$m enables to avoid cracking, despite strong grain boundary segregation. We find that the spread of critical solutes to a higher total interfacial area, combined with lower thermal stresses, helps to suppress interfacial liquation.

cond-mat.mtrl-sci↗

Multi-component chemo-mechanics based on transport relations for the chemical potential

A chemo-mechanical model for a finite-strain elasto-viscoplastic material containing multiple chemical components is formulated and an efficient numerical implementation is developed to solve the resulting transport relations. The numerical solution relies on inverting the constitutive model for the chemical potential. In this work, a semi-analytical inversion for a general family of multi-component regular-solution chemical free energy models is derived. This is based on splitting the chemical free energy into a convex contribution, treated implicitly, and a non-convex contribution, treated explicitly. This results in a reformulation of the system transport equations in terms of the chemical potential rather than the composition as the independent field variable. The numerical conditioning of the reformulated system, discretised by finite elements, is shown to be significantly improved, and convergence to the Cahn-Hilliard solution is demonstrated for the case of binary spinodal decomposition. Chemo-mechanically coupled binary and ternary spinodal decomposition systems are then investigated to illustrate the effect of anisotropic elastic deformation and plastic relaxation of the resulting spinodal morphologies in more complex material systems.

physics.comp-ph↗

Imaging individual solute atoms at crystalline imperfections in metals

Directly imaging all atoms constituting a material and, maybe more importantly, crystalline defects that dictate materials' properties, remains a formidable challenge. Here, we propose a new approach to chemistry-sensitive field-ion microscopy (FIM) combining contrast interpretation from density-functional theory (DFT) and elemental identification enabled by time-of-flight mass-spectrometry and data mining. Analytical-FIM has true atomic resolution and we demonstrate how the technique can reveal the presence of individual solute atoms at specific positions in the microstructure. The performance of this new technique is showcased in revealing individual Re atoms at crystalline defects formed in Ni during creep deformation. The atomistic details offered by A-FIM allowed us to directly compare our results with simulations, and to tackle a long-standing question of how Re extends lifetime of Ni-based superalloys in service at high-temperature.

cond-mat.mtrl-sci↗

Quantification challenges for atom probe tomography of hydrogen and deuterium in Zircaloy-4

Analysis and understanding of the role of hydrogen in metals is a significant challenge for the future of materials science, and this is a clear objective of recent work in the atom probe tomography (APT) community. Isotopic marking by deuteration has often been proposed as the preferred route to enable quantification of hydrogen by APT. Zircaloy-4 was charged electrochemically with hydrogen and deuterium under the same conditions to form large hydrides and deuterides. Our results from a Zr hydride and a Zr deuteride highlight challenges associated to accurate quantification of hydrogen and deuterium, in particular associated to the overlap of peaks at low mass-to-charge ratio and of hydrogen/deuterium containing molecular ions. We discuss possible ways to ensure that appropriate information is extracted from APT analysis of hydrogen in a zirconium alloy systems that is important for nuclear power.

cond-mat.mtrl-sci↗

Unraveling the Metastability of C_n^{2+} (n=2-4) Clusters

Pure carbon clusters have received considerable attention for a long time. However, fundamental questions such as what the smallest stable carbon cluster dication is remain unclear. Here, we investigated the stability and fragmentation behavior of C_n^{2+} (n=2-4) dications using state-of-the-art atom probe tomography. These small doubly charged carbon cluster ions were produced by laser-pulsed field evaporation from a tungsten carbide field emitter. Correlation analysis of the fragments detected in coincidence reveals that they only decay to C_{n-1}^+ + C^+. During C_2^{2+} => C^+ + C^+, significant kinetic energy release (\approx 5.75-7.8 eV) is evidenced. Through advanced experimental data processing combined with \textit{ab initio} calculations and simulations, we show that the field evaporated diatomic ^12C_2^{2+} dications are either in a weakly bound ^3Π_u and ^3Σ_g^- state, quickly dissociating under the intense electric field, or in a deeply bound electronic ^5Σ_u^- state with lifetimes longer than 180 ps.

physics.atm-clus↗

Influence of composition and precipitation evolution on damage at grain boundaries in a crept polycrystalline Ni-based superalloy

The microstructural and compositional evolution of intergranular carbides and borides prior to and after creep deformation at 850 $^\circ$C in a polycrystalline nickel-based superalloy was studied. Primary MC carbides, enveloped within intergranular $\rm γ'$ layers, decomposed resulting in the formation of layers of the undesirable $\rm η$ phase. These layers have a composition corresponding to Ni$_{3}$Ta as measured by atom probe tomography and their structure is consistent with the D0$_{24}$ hexagonal structure as revealed by transmission electron microscopy. Electron backscattered diffraction reveals that they assume various misorientations with regard to the adjacent grains. As a consequence, these layers act as brittle recrystallized zones and crack initiation sites. The composition of the MC carbides after creep was altered substantially, with the Ta content decreasing and the Hf and Zr contents increasing, suggesting a beneficial effect of Hf and Zr additions on the stability of MC carbides. By contrast, $\rm M_{5}B_3$ borides were found to be microstructurally stable after creep and without substantial compositional changes. Borides at 850 $^\circ$C were found to coarsen, resulting in some cases into $\rm γ'$-depleted zones, where, however, no cracks were observed. The major consequences of secondary phases on the microstructural stability of superalloys during the design of new polycrystalline superalloys are discussed.

cond-mat.mtrl-sci↗

Atomic-scale investigation of hydrogen distribution in a Ti-Mo alloy

Ingress of hydrogen is often linked to catastrophic failure of Ti-alloys. Here, we quantify the hydrogen distribution in fully \b{eta} and α+\b{eta} Ti-Mo alloys by using atom probe tomography. Hydrogen does not segregate at grain boundaries in the fully \b{eta} sample but segregates at some α/\b{eta} phase boundaries with a composition exceeding 20 at.% in the α+\b{eta} sample. No stable hydrides were observed in either sample. The hydrogen concentration in \b{eta} phases linearly decreases from ~13 at. % to ~4 at. % with increasing Mo-content, which is ascribed to the suppression of hydrogen uptake by Mo addition.

cond-mat.mtrl-sci↗

On the segregation of Re at dislocations in the γ' phase of Ni-based single crystal superalloys

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 γ' precipitates in a second generation Ni-based single crystal superalloy, after creep deformation at 750°C under an applied stress of 800 MPa. The observed segregation effects can be rationalized through bridging the solute partitioning behavior across the γ/γ' interface and the pipe diffusion mechanism along the core of the dislocation line. This understanding can provide new insights enabling improved alloy design.

cond-mat.mtrl-sci↗

Segregation assisted grain boundary precipitation in a model Al-Zn-Mg-Cu alloy

Understanding the composition evolution of grain boundaries and grain boundary precipitation at near-atomic scale in aluminum alloys is crucial to tailor mechanical properties and to increase resistance to corrosion and stress corrosion cracking. Here, we elucidate the sequence of precipitation on grain boundaries in comparison to the bulk in a model Al-Zn-Mg-Cu alloy. We investigate the material from the solution heat treated state (475{\textdegree}C), through the very early stages of aging to the peak aged state at 120{\textdegree}C and further into the overaged regime at 180{\textdegree}C. The process starts with solute enrichment on grain boundaries due to equilibrium segregation accompanied by solute depletion in their vicinity, the formation of Guinier--Preston (GP) zones in the solute-enriched grain boundary regions, and GP zones growth and transformation. The equilibrium segregation of solutes to grain boundaries during aging accelerates this sequence compared to the bulk. Analysis of the ~10 nm wide precipitate-free zones (PFZs) adjacent to the solute-enriched grain boundaries 2 shows that the depletion zones are determined by (i) interface equilibrium segregation; (ii) formation and coarsening of the grain boundary precipitates and (iii) the diffusion range of solutes in the matrix. In addition, we quantify the difference in kinetics between grain boundary and bulk precipitation. The precipitation kinetics, as observed in terms of volume fraction, average radius, and number density, is almost identical next to the depletion zone in the bulk and far inside the bulk grain remote from any grain boundary influence. This observation shows that the region influenced by the grain boundaries does not extend beyond the PFZs.

cond-mat.mtrl-sci↗